castor oil reportnov2010

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CastorOil.in -‐ Home of Castor Oil

Comprehensive Castor Oil Report

Comprehensive Castor Oil Report A report on castor oil & castor oil derivatives

(Updated November 2010)

CastorOil.in

A5C, Anugraha Apartments, 41 Nungambakkam High Road

Chennai 600034, Tamilnadu, India Phone: +91-‐44-‐45590142

Mobile: +91-‐98413-‐48117 Email: [email protected] Web: www.castoroil.in

Copyright: All material & content contained in this document are the copyright of Clixoo.

mailto:[email protected]

http://www.castoroil.in/

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Table of Contents 1-‐ Castor Oil Manufacturing .................................................................................................. 5 1.1 Key Manufacturing Processes for Castor Oil & Derivatives ........................................... 6 1.1.1 Castor Oil Manufacturing Processes -‐ Summary .................................................... 6 1.1.2 Castor Oil & Derivatives Manufacturing Processes -‐ Details ................................ 10 1.1.2.1 Castor Oil Extraction -‐ Details ....................................................................... 10 1.1.2.2 Castor Oil Filtration Details ........................................................................ 18 1.1.2.3 Castor Oil Refining -‐ Details .......................................................................... 21 1.1.2.4 Typical Processes & Equipments of Castor Oil Refinery Plants ...................... 24 1.1.2.5 Castor Oil Grades & Derivatives Production ................................................. 25

1.2 Indicative Costs for Setting up Small and Medium Scale Castor Oil & Derivatives Manufacturing Plants ...................................................................................................... 34

2 -‐ Castor Oil Market ........................................................................................................... 36 2.1 Value Chain for the Castor Industry ........................................................................... 37 2.2 The Castor Oil Market ................................................................................................ 37 2.3 Supply & Demand of Castor Oil .................................................................................. 39 2.4 Indian Castor Oil Industry .......................................................................................... 44 2.4.1 Castor Oil Exports -‐ Historical Scenario ............................................................... 44 2.4.2 Castor Oil Exports Current Scenario ................................................................. 47 2.4.3 Castor Seed Production and Acreage in India ...................................................... 48 2.4.4 India-‐wide Data from Castor Crop Survey 2009-‐10.............................................. 50 2.4.5 Cropping Season in India ..................................................................................... 53 2.4.6 Castor Cultivation & Yields in India -‐ Points ......................................................... 53

.................................................... 53 2.5 Demand -‐ Supply Estimates for Castor Oil Derivatives ............................................... 55 2.5.1 Current Demand-‐Supply Estimates for the Various Grades of Castor Oil and Derivatives .................................................................................................................. 56 2.5.2 Future Demand-‐Supply Estimates for the Various Grades of Castor Oil and Derivatives .................................................................................................................. 57

3 -‐ Castor Oil Chemicals & Derivatives ................................................................................. 61 3.1 Introduction .............................................................................................................. 62 3.2 Properties & Chemical Composition of Castor Oil ...................................................... 62 3.3 Chemical, Physical Properties & Specifications of Castor Oil Grades & Derivatives .... 65

4 Castor Oil Prices............................................................................................................. 77 4.1 Historical & Current Price Data for Various Grades of Castor Oil, Castor Seeds .......... 78 4.2 Castor Oil & Castor Seed Price Volatility .................................................................... 81 4.3 Factors that Affect Prices ........................................................................................... 83 4.4 Castor Oil Futures Market .......................................................................................... 84

5 -‐ Castor Cultivation ........................................................................................................... 87 5.1 Introduction to Castor Crop ....................................................................................... 88 5.2 Castor Crop Sowing ................................................................................................... 88 5.3 Castor Crop Growth ................................................................................................... 90

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5.4 Castor Crop Harvest ................................................................................................... 93 5.5 Castor Cultivation Seasons ......................................................................................... 93 5.6 Hybrid Castor Seeds & Genetic Engineering of Castor Plant ....................................... 94 5.7 Yields for Castor Seeds and Castor Oil from Seed ..................................................... 102 5.8 Castor Cultivation FAQ ............................................................................................. 103

6 -‐ Castor Oil End-‐uses ....................................................................................................... 107 6.1 Current End Uses for Castor Oil & Derivatives.......................................................... 108 6.1.1 End Uses by Castor Oil Grade / Derivative ...................................................... 108 6.1.2 Castor Oil & Castor Oil Derivatives Uses By Industry ...................................... 122 6.1.3 Use of Castor Oil in High-‐end Derivatives .......................................................... 129

6.2 Future Possible End-‐uses and End user Industries for Castor Oil and Derivatives ..... 139 6.2.1 Biopolymers and Castor oil ............................................................................... 139 6.2.2 Castor Oil as Feedstock for Biodiesel ................................................................. 146 6.2.3 Other Possible Future End Uses for Castor Oil & Derivatives ............................. 164

7 -‐ Castor Seeds ................................................................................................................. 166 7.1 Introduction to Castor Seeds ................................................................................... 167 7.2 Castor Seeds Production & Supplies ........................................................................ 167 7.3 Castor Seeds Prices & Trends ................................................................................... 168 7.4 Castor Seeds Packaging & Storing ............................................................................ 168 7.5 Castor Seeds Varieties & Hybrids ............................................................................. 168 7.6 Castor Seed Factoids................................................................................................ 169

8 -‐ Castor Meal .................................................................................................................. 170 8.1 Castor Meal Uses ..................................................................................................... 171 8.2 Castor Meal Composition ........................................................................................ 171 8.3 Castor Meal Supply & Demand ................................................................................ 172 8.4 Toxicity in Castor Meal ............................................................................................ 173 8.5 Energy Content in Castor Meal ................................................................................ 174 8.6 Castor Meal Other Points ...................................................................................... 175

9 -‐ Castor Oil Distribution & Logistics ................................................................................ 176 9.1 Castor Oil Storing & Packaging ................................................................................. 177 9.1.1 Castor Oil Storage ............................................................................................. 177 9.1.2 Packaging.......................................................................................................... 177 9.1.3 Shelf Life ........................................................................................................... 177

9.2 Castor Oil Transportation & Logistics ....................................................................... 177 9.2.1 Distribution from Farms to Refinery .................................................................. 177 9.2.1 Transport .......................................................................................................... 178 9.2.2 Cargo Handling ................................................................................................. 178 9.2.3 Density & Volume Expansion ............................................................................ 178 9.2.4 Cargo Securing .................................................................................................. 179 9.2.5 Risk Factors and Loss Prevention ...................................................................... 179

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10 -‐ Prominent Castor Oil & Derivatives Producers............................................................ 182 10.1 Prominent Castor Oil & Derivatives Producers in India........................................... 183 10.2 Prominent Castor Oil & Derivatives Producers in China ......................................... 192 10.3 Prominent Castor Oil & Derivatives Producers in Brazil .......................................... 193 10.4 Other Prominent Suppliers .................................................................................... 194

Appendix 1 ........................................................................................................................ 195 1. Demand -‐ Supply Estimates for Sebacic Acid .............................................................. 195 2. Price of Sebacic Acid .................................................................................................. 196 3. Sebacic Acid Companies and Suppliers ...................................................................... 196

Appendix 2 India Export Details on Castor Derivatives .198

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1 -‐ Castor Oil Manufacturing This chapter comprises the following topics

Key Manufacturing Processes for Castor Oil & Derivatives -‐ 1.1 o Castor Oil Manufacturing Processes Summary -‐ 1.1.1 o Castor Oil & Derivatives Manufacturing Processes Details -‐ 1.1.2

Castor Oil Extraction Details -‐ 1.1.2.1 Castor Oil Filtration Details -‐ 1.1.2.2 Castor Oil Refining Details -‐ 1.1.2.3 Typical Sections & Sub-‐sections of Castor Oil Refinery Plants -‐ 1.1.2.4 Castor Oil Grades & Derivatives Production -‐ 1.1.2.5

Indicative Costs for Setting Up Small and Medium Scale Castor Oil & Derivatives

Manufacturing Plants -‐ 1.2

HIGHLIGHTS

Castor seeds contain about 48-‐50 percent oil by weight.

The overall castor oil & derivatives manufacturing process is: Sowing -‐> Cultivation -‐> Harvest -‐> Seed Dehulling & Cleaning -‐> Oil Extraction -‐> Oil Filtration & Purification -‐> Oil Refining -‐> Production of Castor Oil Grades & Derivatives.

While castor oil by itself is used in diverse applications, chemical derivatives of castor

oil find further uses in industrial applications and their domains of use are increasing rapidly.

The global market for generation II castor oil derivatives is estimated at about $300

million. For generation III derivatives, where half of the generation II derivatives are converted, the estimated market worth is close to $350 million.

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1.1 Key Manufacturing Processes for Castor Oil & Derivatives Castor Oil Production Overall Concept Castor plant grows wild in many tropical countries wher it is considered native. It is grown commercially in plantations for oil, in countries like India, China and Brazil. The seeds contain about 48-‐50 percent oil by weight. To extract the oil they must be crushed and pressed. The oil thus extracted is purified, and the purified oil is further refined. Modification of the refined oil to produce various grades and derivatives is achieved by a variety of chemical processes including oxidation, hydrogenation and thermal treatments to produce derivatives for specific applications. The four main stages thus in the production of castor oil, castor oil grades and derivatives are:

a. Extraction of oil b. Purification of the extracted oil c. Refining the purified oil d. Performing chemical reactions on the refined oil to produce various grades and

derivatives This chapter dwells into each of the above four in depth. 1.1.1 Castor Oil Manufacturing Processes -‐ Summary This section provides a summary of each of the four processes, viz., Extraction, Filtration/Purification, Refining, and Grades & Derivatives Production. The following section provides extensive details on each of the four. Castor Oil Extraction -‐ Summary Extraction of oil from castor seeds is done in a manner similar to that for most other oil seeds. The ripe seeds are allowed to dry, when they split open and discharge the seeds. The seeds are dehulled after harvesting. Dehulling can be done by hand (laborious) or, more commonly, by machine. Small-‐scale hand-‐operated dehullers are also available. The dehulled seeds are cleaned, cooked and dried prior to oil extraction. Cooking is done to coagulate protein (necessary to permit efficient extraction), and for efficient pressing. The first stage of oil extraction is pre-‐pressing, normally using a high pressure continuous screw press called the expeller. Extracted oil is filtered, and the material removed from

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the oil is fed back into the stream along with fresh material. Material finally discharged from the press, called castor cake, contains 8-‐10% oil. It is crushed into a coarse meal, and subjected to solvent extraction with heptane to extract further oil. Castor Oil Filtration & Purification -‐ Summary Once the oil has been extracted from the seed, it is necessary to remove impurities present in the oil. The filtration systems are designed to remove particulates, water, dissolved gases, and acids. The equipment that is normally used for filtration is a filter press. Castor Oil Refining -‐ Summary The filtered oil (called the crude or unrefined oil) is sent to the oil refinery. The steps to refine the crude oil include: Settling and Degumming of the Oil -‐ Done to remove the aqueous phase from the lipids,

and to remove phospholipids from the oil. Neutralization -‐ The neutralization step is necessary to remove free fatty acids from the

oil. Bleaching -‐ Bleaching results in the removal of coloring materials, phospholipids and

oxidation products. Deodorization of the oil -‐ Deodorization results in the removal of odour from the oil Production of Castor Oil Grades & Derivative Chemicals -‐ Summary Using a variety of chemical reactions and/or processes, the refined castor oil is transformed into its various grades and a plethora of useful chemical derivatives. Examples of the chemical reactions used: Hydrolysis, Esterification, Alcoholysis, Saponification, Halogenation, Oxidation, Polymerization, Hydrogenation, Epoxidation, etc. Examples of processes used: Degumming, Bleaching, Dehydration, Splitting & Distillation, Evaporation etc. The chemical reactions and processes used to prepare various grades and derivatives will be discussed in detail later in this chapter. So, the overall castor oil & derivatives manufacturing process is: Sowing -‐> Cultivation -‐> Harvest -‐> Seed Dehulling & Cleaning -‐> Oil Extraction -‐> Oil Filtration & Purification -‐> Oil Refining -‐> Production of Castor Oil Grades & Derivatives

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Representative Diagram for Jatropha Oil Extraction & Filtration

Intake

Seed cleaner

Dehuller

Seed pretreatmen

t

Screw or hydraulic press

Breaker crusher

Solvent extraction plant

Oil filter press

Oil filter press

Hammer or attrition mill

Meter

Meter Meter scale

To storage tanks and refinery Meal for fertilizer

First grade crude oil

Press cake

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Process Flow for a Typical Oil Refining Plant

CRUDE OILS AND FATS

Storage crude oils

tank Other services

Soap stock Neutralisation section

BLEACHING

Sterin separation section

Sterin

DEODORISER Sterin Storage

tank

Refined Oil Distilled Fatty Acid

Deoderiser Steam Distillation

Refined Oil Final Packing

Pretreatment

Byproduct processing

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1.1.2 Castor Oil & Derivatives Manufacturing Processes -‐ Details 1.1.2.1 Castor Oil Extraction -‐ Details Castor oil extraction can be divided into two main stages:

1. Pre-‐extraction 2. Extraction

1. Pre-‐extraction Seed Cleaning & Preparation Seed Cleaning The castor beans have some foreign materials and dirt that get separated by hand picking. The seed cleaner pictured below is a basic type of seed cleaner for efficient cleaning of seeds.

More sophisticated and mechanised seed cleaners are available in the market, and some of these seed cleaners have capacities of over 10 T / hour. Drying, Heating & Conditioning The cleaned beans are sun dried in the open, until the casing splits and sheds the seeds. The beans are further dried in the oven at 60°C for seven hours to a constant weight in order to reduce their moisture content, which initially would have been about 5 to 7%. Pre-‐heating or drying the seeds prior to expelling also improves the release of the oil by breaking the cell walls and by thinning the oil. In some cases, drying is achieved by spreading the seeds outside, exposed to the heat of the sun. In other cases stoves or pans are used for pre-‐heating. There is a likelihood that the seed will burn while using a pan, which will not happen if a double-‐boiler is used. A double-‐boiler is an arrangement in which one pan is placed inside a larger pan without touching the bottom or sides. Water is placed at the bottom of the larger pan and is heated to produce steam that heats the seed in a more controlled manner, preventing it from burning.

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Shelling / Dehulling & Winnowing Most oil-‐bearing seeds need to be separated from their outer husk or shell. This process is referred to as shelling, dehulling or decorticating. Shelling increases the oil extraction efficiency and reduces wear in the expeller as the husks are abrasive. A wide range of manual and mechanical decorticators are available. In general some 10% of husk is added back prior to expelling as the fibre allows the machine to grip or bite on the material. After dehulling, the shell may have to be collected separately from the kernels by winnowing. At small scale this can be done by throwing the material into the air and allowing the air to blow away the husk. At larger scales mechanical winnowers are available. Milling & Grinding Milling: Milling is carried out to reduce the size of particles and improve the efficiencies of extracting oil. Grinding: Mortar and pestle are normally used to crush/grind the beans into paste (cake). This process weakens or ruptures the cell walls for oil extraction. 2. Oil Extraction Oil Yield from Different Oil Seeds

Typical oil yields from 100 kg. of oil seeds

Oilseed Yield Castorseed 43 kg Sunflower 32 kg Copra 62 kg Cottonseed 13 kg Linseed 42 kg Mustard 35 kg Soybean 14 kg Groundnut Kernel 42 kg Rapeseed 37 kg Palmfruit 20 kg Palm Kernel 36 kg Sesame 50 kg

The cleaned and prepared castor seeds are sent for extraction. Oil extraction is done usually in two stages.

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1. The first stage employs pressing the seeds for oil this stage is also called expelling 2. The second stage uses a solvent extraction method to extract the remaining oil.

Pressing / Expelling Expellers -‐ Old Method The old and traditional expellers comprise a pestle and mortar that is traditionally animal powered. Its capacity is approximately 50 kg a day although this will vary depending on the size, strength and number of animals used. Animals need to be replaced after 3 or 4 hours work as they tire. The old methods are rarely used these days except by small processors. Expellers -‐ New Methods New methods of oil expelling use presses to extract the oil from the seed. Small presses like the Bielenberg ram press can be powered by hand, by one or several operators. Capacity is then typically 1-‐10 kg/h of seeds. Larger capacity presses, especially the screw presses, are powered by engines. The strainer type press has its oil output in the form of strainers. The strainers are built up in the form of bars, and their inter-‐spacings (gaps) are adjustable. The whole press tube mostly consists of the strainer. The diameter of the screw increases over the length to get a rising compression of the seed. Sections with changing diameter can be found several times on the screw. During the flow of the seed through the press, the oil is drained via the strainer, which surrounds the pressing space. The choke size can be adjusted to press the seed harder. With some types of strainer presses it is possible to change segments at the worm screw in order to change the compression of the seed. Other manufacturers offer extra screws. In addition the choke size and the rotation speed should be adjusted when pressing different kinds of seed. Strainer presses exist in a wide capacity range from approximately 15 to 2000 kg/h of seed. The press cake comes out of the choke formed as flat plates. Broadly, the expellers / presses used currently can be classified into two types:

Manual Presses Motor Driven Expellers

Manual Presses Small-‐scale manual presses have been promoted by a number of organisations. As these machines do not require any power source their running costs are minimal. Types of manual presses include:

Spindle press

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Bridge press, also known as a screw press Ram press Hydraulic press

Manually powered spindle presses are usually small table mounted devices with a capacity of around 2 to 5 kg per hour. The bridge press comprises a cylinder that contains the seed. The seed is compressed by rotating a screw down onto it. The screw is held in place by a frame that bridges over the seed container. As the seed is compressed the oil drains through holes in the cylinder onto a collection tray. The process is relatively slow as the cylinder needs to be filled, compressed and then the remaining cake needs to be removed Ram presses use a lever mechanism to produce high pressures on a piston that forces the oil out of the seed. Manual ram presses can be tend to be hard work Hydraulic presses use a hydraulic pump to exert a high pressure on the seed. The process is similar to a screw press, in that the seed has to be loaded into a cylinder and then pressed to extract the oil, which runs onto a collection tray. Once the seed has been pressed the remaining cake needs to be removed. Motor Driven Expellers Motorised expellers, usually screw-‐type expellers, are now common in the oilseeds industry worldwide. Motor driven expellers are now very common in the Indian castor oil industry as well. The running costs of the equipment are reasonable. The oil yield is relatively high at around 60%, although production is slow. In India in particular a number of efficient small or "baby" motorised expellers are available with a capacity of up to 100 kg/hr. A typical machine has a central cylinder or cage fitted with eight separate sections or "worms". This flexible system allows single or double-‐reverse use and spreads wear more evenly along the screw. When the screw becomes worn only individual sections require repair, thus reducing maintenance costs. As the seed passes through the expeller the oil is squeezed out, exits through the perforated cage and is collected in a trough under the machine. The solid residue, oil cake, exits from the end of the expeller shaft where it is bagged. Screw type expellers have capacities ranging from 1 T / day to 10 T per day.

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Picture of a Typical Oil Expeller with Cooking Kettle

Large Scale Oil Expellers Single Chamber & Double Chamber Oil Expellers Medium and large-‐scale castor oil processors use motor driven oil expellers that are of the single or double chamber model.

Single Chamber Design Oil Expeller

Capacity range

Capacity of single chamber machine varies between 1 ton to 25 tons a day. Some giant single chamber oil expellers can reach a maximum capacity of over 400 T per day.

Single chamber machine has the capability to crush all kinds of seeds including castor. Other seeds that can be crushed are: palm kernel, nut cotton seeds, copra, rape seeds, sunflower, canola, ground nuts.

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Components of Single Chamber Design Cooker Cooker includes steam kettle, mounted on the expeller for pre-‐heating of seeds. Gear Box Double reduction, heavy duty gear box is used to stand radial casting gear which increases durability and efficiency of machinery. Main Shaft Steel shaft with water cooling arrangements is used to control the temperature of chamber. Worm Assembly For ensuring long life of machinery high grade carbon steel that is especially hardened is normally used. Electrical Components Electric motors are used to make single chamber design, including reversible switch panel board to give an easy restart.

Double Chamber Design Oil Expeller

Capacity Range

1. Capacity of double chamber design machine ranges between 5 tons to 100 tons per day. Some giant double chamber oil expellers can reach a maximum capacity of over 700 T per day.

2. Double chamber machine is suitable for pre-‐pressing and complete full pressing in

one expeller. It also includes a benefit of better oil recovery by providing double crushing

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Components Worm Assembly High grade and hard facing carbon steel is used in this expeller. This increases durability and life of machinery. Gear Box Heavy duty gear box is used for double reduction; this also increases the efficiency of machinery. Cooker Cooker installed in machinery includes steam kettle which preheats seeds. The cooker is also used for recovery & bottle pressing of seeds. Electrical Components Reversible switch panel board is used to restart machine after power failure or overloading. Main Shaft Special steel main shaft with water cooling arrangements is used to control the pungency of chamber. Typical Features of Presses / Oil Expellers

Cast iron bodies & base Foundation frame Single reduction gear box with spur gears Fabricated chambers with multiple sections Case hardened worm assembly Oil expeller chamber cage Thickness of cake can be changed while running the oil expeller Oil pump Tapper roller bearings.

Special Facilities in New Expellers

Thickness of cake can be changed to find and adjust cone at the point of optimum Traditional oil pump is replaced by a vacuum one. Due to ready foundation frame, no foundation of any machine required in the

ground. In addition, you can shift the machine from one place to another as and when required.

Tapper roller bearings make expeller very sturdy and durable. No ball bearing fitted anywhere.

As some of the expellers are very compact, it is today possible and economical to import them by air.

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Solvent Extraction Solvent extraction is a process that is used to recover a component from either a solid or liquid. In this process, the material in which the component of interest is present is contacted with a solvent that will dissolve the solutes of interest. Solvent extraction is of major commercial importance to the chemical and biochemical industries, as it is often the most efficient method of separation of valuable products from complex feedstock or reaction products. In the case of castor oil extraction, the solvent extraction stage comes after the expeller stage. The cake that leaves the expeller has about 10% of oil remainig in it. This is taken to the hexane solvent extraction stage, where the remaining oil is recovered. The crushed castor seeds that come from the expeller are mixed with a solvent in a commercial extractor. Solvents used for extraction include heptane, hexane and petroleum ethers. Hexane is the most commonly used solvent from the above. The castor oil dissolves in the solvent, and the pulp is filtered out from the solution. The oil and solvent are separated by means of fractional distillation. Fractional distillation is the separation of a mixture into its component parts by heating them to a temperature at which several fractions of the compound will evaporate. Hexane Solvent Extraction Schematic Diagram (Haas et al., 2002)

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Castor Oil Extraction Other Points

Over the past three decades, the markets have shunned Brazilian castor beans, due to the allergens found in the oil extracted from them. However, a new processing technique could overcome this problem. The main task is to develop a new processing technique: single acetone extraction of oil from crushed beans. This technique should reduce or even eliminate allergy problems and produce better quality oils and presscake at a lower cost. It has already been tested successfully in the laboratory, and it would be worth backing up its validation on an industrial scale with varietal research to develop an allergen-‐free clone. (Reference: Revitalizing the castor bean sector in Brazil -‐ Jan 2006 -‐ http://www.cirad.fr/en/actualite/communique.php?id=356 )

1.1.2.2 Castor Oil Filtration Details

seed, castor oil contains 1-‐13% solids by weight. These solids need to be separated from oil. The filtration stage of castor oil achieves this objective. The solids can be separated from the oil by means of sedimentation, filtration or centrifugation, or by a combination of these processes. Castor oil filtration process could comprise one or more of the following steps:

Filtration Clarification Sedimentation

Centrifugation

Filtration Filtration can be achieved by allowing the oil to stand and then filtering the clear oil by gravity through fine cloth. A better but more expensive method is pumping the crude oil through a filter press The basic principle of filtration is blocking any particle in the oil against a membrane. The easiest way of filtering is using a cloth. Using filter cloth in home made devices can give very good filtering results. As the filtering processes are not pressurized, purification is very good though speed is low. For home users and small factories (up to some liters per hour) this can be an attractive low-‐cost option as the process can run unattended without purchasing special hardware. It is recommended to sediment the oil for some days before filtering to avoid short changing interval of the filter cloth.

http://www.cirad.fr/en/actualite/communique.php?id=356

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While filtering using a filter cloth is a fairly simple and cost-‐effective method, it might not be suitable for large-‐scale producers. The professional and organized sector in the castor oil industry today uses filters that are more automated. These are called filter presses. Filter Press Filter presses are separation devices used for solid or liquid separation. These work on feed pressure or squeeze pressure to filter solid content in a product. The filter presses also use filter cloth for the filtering process, but they are far more mechanized than manual filtering using filter cloth alone. The professional and large-‐scale oil processors use more efficient methods -‐ filter presses using plate or leaf filters.

Picture of a filter press

Plate Filter Presses Plate filter presses are the most widespread types of filter presses used despite their relatively high investment cost. A filter comprises a set of vertical, juxtaposed recessed plates, presses against each other by hydraulic jacks at one end of the set. The pressure applied to the joint face of each filtering plate must withstand the chamber internal pressure developed by the oil pumping system. This vertical plate layout forms watertight filtration chambers allowing easy mechanisation for the discharge of solids. Filter clothes finely or tightly meshed are applied to the two grooved surfaces in these plates. Orifices feed the crude oil to be filtered under pressure in the filtration chamber. They are usually placed in the center of the plates allowing a proper distribution of flow, right pressure and better drainage of oil within the chamber. Solids gradually accumulate in the

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filtration chamber. The filtrate is collected at the back of the filtration support and carried away by internal ducts. Plate filters are flexible and can be extended by adding more frames for bigger capacities. Filtered cake discharging can be manual or automatic. Features of Filter Presses Capacity The widely used filter press has a capacity of filtering oil from 1 ton to 50 tons a day. Pump Special plunger pump is used for transfer of oil from storage tank to filter press. Filter Cloth Filter cloth includes special polyester filter cloth which does a fine filtration of oil. Plates Adjustable plates are used so that filter cloth can be cleaned easily. Clarification Filtering will remove insoluble contaminants such as fibre but the remaining oil will also contain moisture, resins and colorants from the seed. Clarification is a relatively simple method of removing these unwanted elements and can be done by letting the oil stand undisturbed for a few days and then separating the upper layer, or by using a clarifier in which the oil is held in a tank with a heat source. The oil is boiled to drive off water and to destroy naturally occurring enzymes and contaminating bacteria. After heating the oil is allowed to stand and the contaminants separate out. The oil is filtered through a cloth and is reheated to ensure that all the moisture has been removed Sedimentation

of the sedimentation process, the solids settle at the bottom of the tank. It is a cheap cleaning method because no hardware has to be purchased, only a storage tank large enough to keep the oil about a week with little or no flow. This process is however only recommended for small processing capacities of about one ton of seed per day.

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Centrifugation Centrifugation is a process that involves the use of the centrifugal force for the separation of mixtures. More-‐dense components of the mixture migrate away from the axis of the centrifuge, while less-‐dense components of the mixture migrate towards the axis. Centrifugation is a much faster method for particle separation than sedimentation. It must be noted however that centrifugation hardware is relatively expensive for small scale processors. At the end of the above steps in the filtration process, the castor oil is ready for refining. 1.1.2.3 Castor Oil Refining -‐ Details The Refining Process Filtered Castor Oil De-‐gumming Neutralization Dewaxing Bleaching & Deodorizing In some markets further refining of castor oil beyond the filtration stage is not required as the complex flavours of unrefined oils are preferred. International markets in many developed countries tend to prefer oil that has been refined further. The main aim of refining is to remove impurities such as colloidal matter, free fatty acid, colouring and other undesirable constituents, thus making the oil more resistant to deterioration during storage. The general method of refining used for edible oils is applicable to castor oil. The main processes involved in castor oil refining are:

Degumming, Neutralization, Dewaxing, Bleaching & Deodorizing

Degumming Gums in edible vegetable oil must be removed to avoid color and taste reversion during subsequent refining steps. The removal of phospholipids (referred first step in the process of refining castor oil. The process usually involves a single-‐stage phosphoric acid treatment and a single-‐stage hot water treatment, followed by continuous removal of the hydrated gums in a de-‐gumming centrifuge.

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Neutralization

Neutralizer

Neutralization is a reaction between acids and bases to produce salts. All crude vegetable oils prepared for human consumption are neutralized to remove free fatty acids and latex-‐like matter and then washed to reduce the soap content of neutral oil. Neutralization produces a more stable product. Effective neutralization results in enhanced effectiveness of subsequent steps, such as bleaching, deodorizing and furthermore, results in high yields of a quality product. Neutralization also aides in the removal of phosphatides, removal of free fatty acids, mineral and color bodies. Neutralization can be done in one of two ways: (a) Alkali (Chemical) (b) Steam Stripping (Physical). In the Alkali/Chemical method, caustic soda (alkali) is mixed in the proper amounts with castor oil at 66-‐77oC and the aqueous solution is removed, leaving the neutral oil behind. Some plants use sodium carbonate or potassium hydroxide for alkali. The alkali reacts with the free fatty acids to form soap, which is an important byproduct. Processors remove the traces of soap and moisture through water washing and vacuum drying. In some cases, centrifuges separate neutral oil from soap-‐stock and wash water. Steam stripping is done under vacuum, to remove moisture, free fatty acids, odour elements, and other impurities from the oil. As it is performed under vacuum conditions, the oil can be kept at a low temperature, preserving its chemical structure by not subjecting it to temperatures in which undesirable dehydration reactions can occur. De-‐waxing De-‐waxing refers to the removal of high melting point waxes extracted from castor oil. While the wax does not negatively affect the functionality of products the presence of wax

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does affect the appearance of product. The de-‐waxing process that has proved most effective & efficient is to reduce the temperature down to 23-‐24oCelsius within cooling tanks known as crystallizers, and then filtering out the wax crystals either in a rotary drum vacuum filter or in filter presses made out of polypropylene plate & frame filters. Bleaching & Deodourizing Bleaching The appearance of dark colour oil can be lightened by bleaching. Bleaching, the process for removing these pigments from fats and oils, occurs when 1% bleaching clay is added to oil under vacuum at approximately 107-‐110oCelsius. The oil is later agitated and filtered to remove the clay. The high temperature drives moisture from the clay to absorb the pigments. Some systems also use activated carbon in the place of clay. A high-‐tech bleaching plant may be equipped with hermetic leaf filters and operates under vacuum to prevent oil oxidation. The oil is cold-‐mixed with metered quantities of bleaching earth and/or other bleaching agents, heated to the correct temperature and pumped to a bleaching chamber operating under vacuum where an adequate retention time is provided to ensure effective bleaching. The oil/earth slurry is further pumped through hermetic leaf filters operating in sequence to enable continuous bleached oil (filtrate) discharge. Deodorization Volatile compounds present in the oil that produce bad odours can be eliminated through the process of deodorization. Deodorization represents the last major processing step in refining of castor oil. It separates out the impurities and creates three groups of compounds: 1. Saponifiable compounds: free fatty acids, partial glycerides, esters, and gummy constituents. 2. Unsaponifiable compounds: parafinic hydrocarbons, olefinic and polyolefinic materials, sterols, triterpenic alcohols, and 3. Oxidative reaction products: aldehydes, ketones & peroxides. This highly specialized process uses a type of steam distillation under high vacuum to remove objectionable volatile components. The bleached oil pumps through a de-‐aerator where the pretreated oil is de-‐gassed. This de-‐aerated oil passes through a heat exchanger where the oil is heated by exchanging the heat of the deodorized oil. Deodorization further heats the oil to the stripping temperature in a pre-‐heater. The oil then flows to a flash chamber and thereafter to an oil distributor inside falling film deodorizer. The oil descends counter-‐current to the stripping steam in the form of a very thin film and becomes completely deodorized. The process condenses cools and stores the distilled fatty acids.

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The deodorized oil pumps through a heat exchanger to the polishing filter and thereafter passes through a cooler. 1.1.2.4 Typical Processes & Equipments of Castor Oil Refinery Plants

Process Methods Involved Equipments Used

Degumming

Single stage Phosphoric acid treatment

Single stage hot water treatment Gums tank

Neutralization Alkali/ Chemical method Steam Stripping

Neutralizer Soap/gums tank Water/oil/gravity separator Lye/brine/hot water tank Neutralized oil tank Oil pump Soap stock pump Hot water pump

Dewaxing Removal of high melting point

waxes

Crystallizers Rotary drum vacuum filter Filter presses made out of polypropylene plate Frame filters

Bleaching Removal of pigments from fats and

oils

Bleacher Barometric condenser Earth dozer Bleached oil tank Filter press Filter pump Vacuum pump

Deodorization Steam distillation under high

vacuum

Falling film deodorizer Storage tank Cooler Polish filter Pump Vacuum system

Other Equipments in a Castor Oil Refinery Plant

Reactor Centrifuge Tray drier Crystallizer Pressure filter Distillation assembly Air compressor

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Elevators Conveyors Pressing worm and gears Worm wheel Plunger pumps Electrical/cables Pipe, valves, fittings Instruments/gauges Insulation Cooling tower

1.1.2.5 Castor Oil Grades & Derivatives Production While castor oil by itself is used in diverse applications, chemical derivatives of castor oil find numerous uses in industrial applications and their domains of use are increasing rapidly. The global market for generation II castor oil derivatives, which include sebacic acid, undecyclenic acid, heptaldehyde, polyols and dimer acid, is estimated at about $300 million. For generation III derivatives, where half of the generation II derivatives are converted, the estimated market worth is close to $350 million. Generation III derivatives include the esters and salts of generation II derivatives as well as derivatives such as methyl-‐12-‐hydroxystearate while generation I derivatives include hydrogenated castor oil, 12-‐hydroxy stearic acid, dehydrated castor oil acid, and ethoxylated castor oil among others. Quite naturally, the prices and profit margins of higher generation castor derivatives are significantly higher than the basic grades. The generation I derivatives such as HCO and 12-‐HSA respectively cost about 20% and 50% more than the basic castor oil grades.

Key Derivatives of Castor Oil, Starting Products & Methods of Production

Product Name Starting Product Method of Production Commercial Castor Oil Castor Seed Crushing & Expelling First pressed Degummed Grade Castor Oil Commercial Castor Oil Degumming Refined Castor Oil (F.S.G./B.S.S.) Commercial Castor Oil Bleaching Refined Castor Oil (Extra Pale Grade) Commercial Castor Oil Bleaching Refined Castor Oil (Pale Pressed Grade) Commercial Castor Oil Neutralization and Bleaching Neutralized Castor Oil Commercial Castor Oil Neutralization and Bleaching Refined Castor Oil (DAB-‐10) Commercial Castor Oil Neutralization and Bleaching Castor Oil Pharmaceutical (I.P/B.P./U.S.P.) Commercial Castor Oil Neutralization

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Turkey Red Oil Commercial Castor Oil Sulphonation and Neutralization

Blown Castor Oil (10 to 250 Poise)

Refined Castor Oil (F.S.G./B.S.S.) Oxidation

Ricinoleic Acid Refined Castor Oil (F.S.G./B.S.S.)

Saponification and Acidification

Methyl Ricinoleate Refined Castor Oil (F.S.G./B.S.S.) Esterification

Hydrogenated Castor Oil (Flakes/Powder/Granules)

Refined Castor Oil (F.S.G./B.S.S.) Hydrogenation

12-‐Hydroxy Stearic Acid (12-‐H.S.A.) (Flakes/Powder/Granules)

Hydrogenated Castor Oil Liquid

Saponification and Acidification

Methyl-‐12-‐Hydroxy Stearate (Flakes) Methyl Ricinoleate Hydrogenation Urethane Modified Castor Oil (UMCO)

Refined Castor Oil (F.S.G./B.S.S.) Urethane Reaction

Glyceryl-‐Tri-‐(12-‐Acetyl Ricinoleate)

Refined Castor Oil (F.S.G./B.S.S.) Acetylation

Dehydrated Castor Oil (Commercial) Commercial Castor Oil Dehydration

Glycerin Spent Glycerin Lye Treatment, Evaporation and Distillation

Generic Chemical Reactions of Castor Oil for Manufacture of Various Grades & Derivatives

Reaction Type Nature of Reaction Added Reactants Type of Products

Ester Linkage Hydrolysis

Acid, enzyme or Twitchell reagent catalyst Fatty acids, glycerol

Esterification Monohydric alcohols Esters

Alcoholysis

Glycerol, glycols, pentaerythritol, and other compounds

Mono-‐ and diglycerides, monoglycols, etc.

Saponification Alkalies, alkalies plus metallic salts

Soluble soaps, insoluble soaps

Reduction Na reduction Alcohols

Amidation

Alkyl amines, alkanolamines, and other compounds Amine salts, amides

Double Bond Oxidation, polymerization

Heat, oxygen, crosslink agent Polymerized oils

Hydrogenation

Hydrogen (moderate pressure) Hydroxystearates

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Epoxidation Hydrogen peroxide Epoxidized oils Halogenation Cl2, Br2, I2 Halogenated oils

Addition reactions S, maleic acid Polymerized oils, factice

Sulphonation H2SO4 Sulphonated oils

Hydroxyl Group

Dehydration, hydrolysis, distillation Catalyst (plus heat)

Dehydrated castor oil, octadecadienoic acid

Caustic fusion NaOH Sebacic acid, capryl alcohol

Pyrolysis High heat Undecylenic acid, heptaldehyde

Halogenation PCl5, POCl3 Halogenated castor oils

Alkoxylation Ethylene and/or propylene oxide

Alkoxylated castor oils

Esterification

Acetic-‐, phosphoric-‐, maleic-‐, phthalic anhydrides

Alkyl and alkylaryl esters, phosphate esters

Urethane reactions Isocyanates Urethane polymers

Sulphation H2SO4 Sulphated castor oil (Turkey red oil)

Details of Manufacture for Specific Castor Oil Grades & Derivatives Industrial / Commercial Castor Oil Industrial castor oil is obtained from a mixture of the first pressing and the second phase of production -‐ solvent extraction First Special Grade Castor Oil Castor oil FSG is produced by refining commercial grade castor oil using bleaching and filtering processes. Cold Pressed Castor Oil Cold pressed castor oil is a virgin form of castor oil extracted in its natural form by pressing

healing properties. The cold pressed grade is considered a valuable laxative in the pharma industry. Pale Pressed Castor Oil The Pale Pressed Grade of Castor Oil is obtained from the first pressing of the castor bean

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Pharma Grade Castor Oil Pharmaceutical grade castor oil is produced from the first pressing of castor seed in which the oil does not lose any medicinal qualities. Produced as per USP, JP, BP, EP, IP, DAB pharmacopoeia, it is used as emollient for pharmaceutical creams and lotions. Dehydrated Castor Oil Castor oil has only one double bond in each fatty acid chain and so is classified as non-‐drying oil. However, it can be dehydrated to give semi-‐drying or drying oil which is used extensively in paints and varnishes. Being a polyhydroxy compound, its hydroxyl functionality can be reduced through dehydration or increased by inter-‐estirification with a polyhydric alcohol. The dehydration process is carried out at about 250oC in the presence of catalysts (e.g., concentrated sulphuric acid, activated earth) and under an inert atmosphere or vacuum. Under this condition of dehydration, the hydroxyl group and adjacent hydrogen atom from the C-‐11 or C-‐13 position of the ricinoleic acid portion of the molecule is removed as water. This yields a mixture of two acids, each containing two double bonds but in one case, they are conjugated. The presence of an acid containing conjugated double bonds results in an oil resembling tung oil in some of its properties. Thus, castor oil, which is non-‐drying, can be treated and converted into a semi-‐drying or drying oil known as dehydrated castor oil. DCO Fatty Acid DCO can be converted to dehydrated castor fatty acid by hydrolysis and distillation.

vegetable oil would break down the triglycerides into their constituent fatty acids. The fatty acids are then distilled from the mixture. Hydrogenated Castor Oil Hydrogenated castor oil or castor wax is a hard, brittle wax. It is produced by addition of hydrogen to castor oil (hydrogenation process) in the presence of a nickel catalyst. This is done by bubbling hydrogen gas into the castor oil, during which the ricinoleic acid becomes fully saturated to give a viscous waxy like substance with a melting point of 61-‐69oC. High catalyst concentration is required for the good results. A temperature range of 125-‐135oC and pressure range of 2-‐2.5 kg/cm is required for the saturation of double bond. The object of the hydrogenation is not only to raise the melting point but also to improve the keeping qualities, taste and odor. As the reaction itself is exothermic, the chief energy requirements are in the production of hydrogen, warming of the oil, pumping and filtering.

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12-‐Hydroxy Stearic Acid 12-‐Hydroxy Stearic Acid is a waxy hydroxyl fatty acid. The source for the production of 12-‐hydroxy stearic acid is castor oil which contains up to 85% ricinoleic acid in the form of triglycerides. To produce 12-‐HSA, castor oil is subjected to hydrogenation, and as a result of it, the ricinoleic acid gets saturated at the place of the double bond and transforms into 12-‐ hydroxyl stearic acid. This process is carried out at room temperature under a pressure of 40 psi with alcohol as a solvent. In the hydrogenation process, the castor oil transforms into a solid mass, hydrogenated castor oil (HCO). The HCO consists of saturated glycerides of 12 HSA (upto 80%), ricinoleic (2-‐4%), stearic with traces of palmitic (10-‐15%), and oleic with traces of linoleic (1-‐4%) acids. 12 HSA is isolated from HCO by saponifying the latter with a 20-‐25% NaOH solution, followed by decomposing the soaps obtained with hydrochloric acid. Properties of hydrogenated castor oil and of 12 HSA isolated from it depend substantially on the quality of castor oil, conditions of its hydrogenation, saponification of hydrogenated castor oil, decomposition of soaps by hydrochloric acid, washing, drying and storage of commercial 12 HSA. Sulfonated Castor Oil Sulfated castor oil, also known as turkey-‐red oil, represents one of the earliest chemical derivatives of castor oil. The traditional method of preparing turkey-‐red oil is to add concentrated sulfuric acid at a controlled rate to castor oil over a period of several hours with constant cooling and agitation of the reaction mass to maintain a temperature of 25-‐30oC. After acid addition is complete, the reaction mass is washed then neutralized using an alkali solution or an amine. Castor oil sulfation results largely in sulfuric acid esters in which the hydroxyl group of ricinoleic acid has been esterified. However, the other reactions can also take place. For example, the double bond can be attacked to produce an ester or the hydroxysulfonic acid. Hydrolysis of the sulfuric acid esters occurs during the reaction and subsequent treatment forming hydroxy acids and sulfuric acid. These hydroxyl acids can be further sulfated. Commercially sulfated castor oil contains ca 8.0-‐8.5 wt % combined SO3, indicating that the surfactant properties result from the sulfation of only one of the reactive points in the unmodified triglyceride. The sulfate group acts as a hydrophile imparting excellent wetting, emulsification, and dispersing characteristics to the oil. The anion-‐active product is used in the textile industry for fiber wetting ability and as dye agent to obtain bright, clear colors. Sulfonation of castor oil using anhydrous SO3 yields a product having better hydrolytic stability than that from the sulfuric acid reaction. The organically combined SO3 is low compared to the amount of SO3 introduced to the reation: the final product contains only

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8.0-‐8.5 wt % combined SO3 although 17 wt% SO3 is added. The product contains less inorganic salts and free fatty acids than the sulfuric acid product. Blown Castor Oil Blown or oxidized castor oil is prepared by blowing air or oxygen into it at temperatures of 80 1300C, with or without catalyst to obtain oils of varying viscosity .The process is called oxidative polymerization. This increases the viscosity and specific gravity of the oil. Blown castor oil is the potential replacement for phthalates, and an important drying oil used in surface coating, lubricants, adhesive for inks and lacquers. Blown castor oil is available in the standard viscosity 5-‐10 poise, 20-‐25 poise, 30-‐35 poise, 45-‐55 poise, 90-‐110 poise. Ricinoleic Acid Ricinoleic acid (12-‐ hydroxy-‐9-‐cis-‐octadecenoic acid) is an unsaturated omega-‐9 fatty acid that naturally occurs in mature castor plant (Ricinus communis L., Euphorbiaceae). About 90% of content in castor oil is the triglyceride formed from ricinoleic acid. Ricinoleic acid is obtained from castor oil through hydrolysis, usually carried out under basic conditions, by treating it with NaOH.

Castor oil + NaOH Ricinoleic Acid + Glycerol (hydrolysis)

Industrially, ricinoleic acid is manufactured by saponification or fractional distillation of hydrolyzed castor oil. When this acid is pyrolyzed (heated in the absence of air), it breaks down to give undecylenic acid and n-‐heptaldehyde. Methyl 12-‐HSA Methyl 12 HSA is formed by direct esterification of 12 HSA with methanol. Esterification is the chemical process for making esters, which are compounds of the chemical structure R-‐COOR', where R and R' are either alkyl or aryl groups. The most common method for preparing esters is to heat a carboxylic acid, R-‐CO-‐OH, with an alcohol, R'-‐OH, while removing the water that is formed. A mineral acid catalyst is usually needed to make the reaction occur at a useful rate. Sebacic Acid Sebacic acid, a 10-‐carbon dicarboxylic acid, can be synthesized from phenols and cresols,

Sebacic acid is manufactured by heating castor oil to high temperatures (about 250oC) with alkali. This treatment results in saponification of the castor oil to ricinoleic acid that is then

31



cleaved to give capryl alcohol (2-‐octanol) and sebacic acid. Although the sebacic acid yields are low, this route has been found to be cost competitive. Ricinoleic Acid -‐-‐> Alkali Fusion @ 250 deg C -‐-‐> 2-‐Octanol CH3(CH2)5CH(OH)CH3+ Sebacic Acid COOH(CH2)8COOH+ H2 The complete reaction is as follows: The process is based on the caustic oxidation of castor oil. The modern method, which also claims higher yields, uses castor oil and molten caustic. The type of reaction used affects the purity of the sebacic acid, and the modern conversion technology is reported to yield sebacic acid with a higher purity. Pyrolysis of ricinoleic acid results in heptaldehyde and undecenoic acid. Alkali fusion of this mixture results in 10-‐hydroxydecanoic acid. With 10-‐hydroxydecanoic acid, an increase to two moles of alkali/mole ricinoleate and at temperatures of 250 to 275oC produces capryl alcohol (also called 2-‐Octanol -‐ C8H18O) and sebacic acid. In the actual reaction, the castor oil and caustic are fed to a reactor at a temperature of 180 to 270 oC where the ricinoleic acid undergoes a series of reactions with evolution of hydrogen to give disodium sebacate and capryl alcohol.

Alkali Fusion @ 250 degrees C

Pyrolysis

Alkali Fusion @ 200 deg C

CH3(CH2)5CH(OH)CH2CH:CH(CH2)7COOH Ricinoleic Acid

CH3(CH2)5CHO + CH2=CH(CH2)8COOH Heptaldehyde Undecenoic Acid

CH3(CH2)5COCH3 + CH2(OH)(CH2)8COOH 2 Octanone 10-Hydroxydecanoic Acid

CH3(CH2)5CH(OH)CH3 ) + COOH(CH2)8COOH + H2 2-Octanol Sebacic Acid

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When the reaction is complete, the soaps are dissolved in water and acidified to a pH of about 6. At this pH, the soaps are converted to free acids that are insoluble in water. The disodium sebacate is then partialy neutralized to the half acid salt which is water soluble. The oil and aqueous layers are separated. The aqueous layer containing the half salt is acidulated to a pH of about 2, causing the resulting sebacic acid to precipitate from the solution. It is then filtered, water washed, and finaly dried. A number of process improvements have been described, which include the use of white mineral oil having a boiling range of 300 to 400 oC or the use of a mixture of cresols. These materials act to reduce the reaction mixture's viscosity, thus improving mixing. Higher sebacic acid yields are claimed by the use of catalysts such as barium salts, cadmium salts, lead oxide, and salts. Production of Sebacic Acid from Adipic Acid An electro oxidation process was developed by Asahi Chemical Industry in Japan and was also piloted by BASF in Germany. It produces high purity sebacic acid from adipic acid. The process consists of three steps:

1. Adipic acid is partially esterfied to the monomethyl adipate 2. Electrolysis of the potassium salt of monomethyl adipate in a mixture of methanol

and water gives dimethyl sebacate 3. The last step is the hydrolysis of dimethyl sebacate to sebacic acid

Overall yields are reported to be about 85% for this process. Undecylenic Acid The pyrolysis of castor oil at 700oC under reduced pressure has been used to obtain heptaldeyde and undecylenic acid. (Pyrolysis is the chemical decomposition of organic materials by heating in the absence of oxygen or any other reagents, except possibly steam.) Heptaldehyde can be further hydrogenated to produce alcohol for use as a plasticizer. Another method is via the hydrolysis of Methyl Undecylenate. Methyl Undecylenate is hydrolysed to give Undecylenic Acid. (CH2=CH (CH2)8COOCH3) Methyl Undecylenate H2O Undecylenic Acid (CH2=CH (CH2)8COOH) Methyl Ricinoleate The crude castor oil is transesterified, in the presence of excess methanol and traces of sodium methylate acting as a catalyst. The reaction takes place at 80oC in an agitated

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jacketed reactor. The reactor is fed continuously to maintain the methanol/ester molar ratio at 3/1. At the end of the reaction, methyl ricinoleate and glycerol are formed and the methyl ricinoleate is separated from glycerol phase by settling. The glycerol, which represents 9% of weight of the oil treated, is recovered. The methyl ester is washed with water to remove the last traces of glycerin. Castor Oil Methanolysis Methyl Ricinoleate. Methyl Undecylenate Methyl ricinoleate is pyrolyzed at high temperature, yielding heptaldehyde, methyl undecylenate and a small amount of fatty acids. Pure heptaldehyde and methyl undecylenate are isolated by fractional distillation. CH3-‐(CH2)5-‐CH (OH)-‐CH2-‐CH=CH-‐(CH2)7-‐COOCH3 (Methyl Ricinoleate) Heat n-‐Heptaldehyde (CH3 (CH2)5CHO) + Methyl Undecylenate (CH2=CH (CH2)8COOCH3) 2-‐Octanol Caustic fusion of castor oil in the presence of NaOH results in sebacic acid and 2-‐Octanol (also called Capryl alcohol) CH3-‐(CH2)5-‐CH(OH)-‐CH2-‐CH=CH-‐(CH2)7-‐COOH (Ricinoleic Acid) + NaOH 133oC air HOOC-‐(CH2)8-‐COOH (Sebacic Acid) + CH3-‐(CH2)5-‐CH(OH)-‐CH3 (2-‐Octanol) Heptaldehyde, Heptanoic Acid & Heptyl Alcohol Heptaldehyde & Heptanoic acid are produced by the pyrolysis of castor oil. Castor Oil is pyrolyzed in the presence of 0.5% benzoyl peroxide. The operating parameters are optimized to obtain high yields of heptaldehyde and undecylenic acid. Ricinoleic Acid -‐-‐> (pyrolysis) -‐-‐> Heptaldehyde CH3 (CH2)5CHO+ Undecylenic acid CH2=CH (CH2)8COOH Heptaldehyde is oxidized to form heptanoic acid in liquidphase, employing oxygen as oxidizing agent. Hydrogenation of heptaldehyde with nickel catalysts will yield heptyl alcohol. The optimum conditions found for quantitative conversion of heptaldehyde to heptyl alcohol are temperature -‐ 100°C, nickel catalyst concentration -‐ 2% based on heptaldehyde (w/w), hydrogen pressure -‐145 psig and reaction time of about 1 hour. Details for the Production of 10-‐Undecenoic Acid (Undecylenic Acid) and Heptaldehyde by Pyrolysis

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For the production of 10-‐Undecenoic Acid and Heptaldehyde by pyrolysis of castor oil, batch process is seldom used for the reaction. The starting material could be either castor oil, riciloneic acid or its methyl ester. In general, the reaction is carried out in a tubular reactor, empty or packed, at 450 to 600o

C and 1 atm with the residence time of less than 1 min. gaseous reaction products containing primarily 10-‐Undecenoic acid and Heptaldehyde are condensed. If castor oil is used as the starting material, acrolein formed by the decomposition of glycerol part of the triglyceride is evolved along with the other products. Acrolein is highly poisonous and should be handled with the utmost care. Depending upon the recovery of acrolein, it is probably desirable to use acids rather than the oil as the starting material. If this is done, glycerin can also be removed. Many workers have carried out the reaction at reduced pressure (40 to 100 mmHg) which

polymerization of the residual mass. This spongy mass, if formed, will clog the reactor. Reactors of different material such as Fe, Cu, porcelain, and silica, have been used. It is expected that these materials will catalyze the decomposition of the triglyceride. Devaux and Sornet claimed higher yields of 10-‐Undecenoic Acid and Heptaldehyde by heating castor oil at 300 to 320o C by means of dry or superheated steam or hot inert gas. Some information is available regarding the effect of temperature and the reactor material of construction/packing on the yields of 10-‐Undecenoic Acid and Heptaldehyde. Vernon and Ross investigated the properties of the Pyrolysis products of castor oil as a function of temperature. Most of the decomposition occurs in the temperature range of 400 to 500o C from their experiment it is deducted that the glyceryl portion of the molecule is broken off around 425o C, giving off acrolein. 1.2 Indicative Costs for Setting up Small and Medium Scale Castor Oil & Derivatives Manufacturing Plants The earlier section provided detailed inputs on equipments and processes required in the manufacture of castor oil and derivatives. We provide brief inputs here on the cost of setting up a castor oil and castor oil derivatives plant. Please note that these are indicative costs based on experiences of setting up similar plants in India. All costs are based on inputs provided in the year 2009. Typical cost structures for castor oil plants are provided below. These are only indicative numbers provided solely for completeness. A detailed costing of castor oil plant details is beyond the scope of this report.

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Notes: TPD = Tons per Day, TCI is Total Capital Investment = Plant, Machinery & Factory Infrastructure + Working Capital Sources for data:

Internal databases of eSource India comprising past quotations and commercial data Government of India and State Government of Gujarat Investment data

Assumptions & observations for the above cost table: Starting products will be procured from the best prices from outside and need not be

prepared internally. The reason behind TCI increasing disproportionately between 1 TPD and 10 TPD is owing

to the fact that a large part of work for a 1 TPD plant is done manually, which requires less capital expenses. For higher production volumes, there are increased expenses on machinery and automation that leads to a disproportionate increase in capital expenses and hence TCI.

Capital Investment Costs include factory costs and cost of real estate

SUMMARY

Castor oil manufacturing is similar to that of other oil seeds and hence the oil can be manufactured utilizing the existing equipments that are locally available. The castor seeds contain about 48 to 50 percent oil by weight, and the extracted castor oil can be further processed to derive a number of derivatives, currently used in numerous industrial applications.

Name Capacity TCI Cost -‐ US $ Mill Castor Oil 1 TPD 0.05-‐0.06 Castor Oil 2 TPD 0.10 Castor Oil Commercial 10 TPD 1.0 Castor Oil Commercial 30 TPD 2.75 Hydrogenated Castor Oil 10 TPD 0.7 Sebacic Acid from Castor Oil 0.5 TPD 0.1 Dehydrated Castor Oil 1 TPD 0.08 Castor Oil Emulsifier 0.2 TPD 0.03

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2 -‐ Castor Oil Market This chapter comprises the following topics

Value Chain for the Castor Industry 2.1 The Castor Oil Market -‐ 2.2 Supply & Demand of Castor Oil 2.3

o Castor Oil Supply Data 2.3.1 o Demand & Consumption of Castor Oil 2.3.2

Indian Castor Oil Industry 2.4 o Castor Oil Exports -‐ Historical Scenario -‐ 2.4.1 o Castor Oil Exports -‐ Current Scenario 2.4.2 o Castor Seed Production & Acreage in India 2.4.3 o Indiawide Data from Castor Crop Survey 2007-‐08 2.4.4 o Cropping Season in India 2.4.5 o Castor Cultivation & Yields in India Points 2.4.6

Demand-‐Supply Estimates for Castor Oil Derivatives 2.5 o Current Demand-‐supply Estimates for the Various Grades of Castor Oil and

Derivatives 2.5.1 o Future Demand-‐supply Estimates for the Various Grades of Castor Oil and

Derivatives 2.5.2

HIGHLIGHTS

Castor oil has a worldwide demand that is rising 3 to 5 % per annum.

The world production of castor oil crop is concentrated in a few countries. As a result, there are only a few large exporters of castor oil fulfilling a significant portion of world demand.

The world castor seed production is about 1.4 million tons per annum. India is a

major producer with about 70% share, followed by China and Brazil with about 20% and 10 % respectively.

European Union imports over 1,00,000 tons of castor oil annually, and almost all its

imports are from India.

The total amount of castor oil production worldwide is relatively very low when compared to other oilseeds.

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2.1 Value Chain for the Castor Industry The following figure shows the value chain of the castor industry with different layers in the market structure. The chart clearly indicates that the value chain involves many intermediaries. These intermediaries prevent efficient price discovery and price dissemination.

Value Chain for Castor Industry

2.2 The Castor Oil Market The world production of castor oil crop is concentrated in the hands of few countries and that is why there are just a few exporters of castor oil fulfilling a large level of demand of the world. The major exporters of castor oil are the leading producing countries of it namely India, China and Brazil of which only India has been successfully meeting the domestic and the world requirements. The country holds a share of 70% in the total exports. The other two countries have experienced an increase in their domestic demand and hence are not capable of exporting a high quantity of oil. In Nov 2009, the Nigerian government

Producer

Commission Agent

Commission Agent

Stockist

Private Agency

Government Agency

Processor

Oil Wholesaler

Industrial Users

Other Consumers

Exporters

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announced that it was paying special attention to castor cultivation. It announced that the Raw Materials Research and Development Council of Nigeria would collaborate with farmers to boost castor production, while urging government to establish castor seed plantation in the different states. Nigeria has a lot of castor seed which has great market potential but the challenge is need of a factory to produce castor oil1. Characteristics of Castor Seed and Oil Market

Castor Seed Production -‐ The world castor seed production is over 1 million tons

per annum. India is major producer with about 70% share, followed by China and Brazil with about 20% and 10 % respectively.

Minor Players -‐ Some of the other countries that are minor players in the castor oil market are: Ecuador, Mexico, Paraguay, Pakistan, Philippines, Sudan, Indonesia, Thailand & Russia

Increasing Demand -‐ Castor oil has a demand worldwide that is constantly rising at 3 to 5 % per annum.

American Imports -‐ America imports over 90% of their consumption. Castor plants have not been farmed on a commercial scale in the United States since the early 1970s. (During the 1950s and 1960s, approximately 85,000 acres of castor were grown annually in the United States. Since then domestic production decreased and was abandoned in 1972).

Uncertain Supply -‐ The world castor seed production has fluctuated between 1.2 and 1.5 million tons in the period of 2001 to 2007. India's production ranged between 0.8 and 1.1 million tons during the same period.

Substitutes -‐ Recent developments of artificial substitutes of castor oil in the world market has subjected the demand to large fluctuations. As castor seed production presents some problems (toxicity of the seed, allergic reactions), Lesquerella species were proposed as a valuable source in the USA (up to 70% in the oil) of ricinoleic acid and also of lesquerolic acid, the C20 homologue of ricinoleic acid. It must be noted however that this species is still in the preliminary stage of use.

Hoarding & Long Storing Period -‐ It is a common practice for the castor seed growers and crushers to hoard the commodity before selling in expectation for better prices

Spot Market There is a well-‐developed and organized spot market in India Volatile Prices in the Indian Castor Oil Market Castor seed and castor oil prices

are highly volatile with wide price fluctuations, and the uncertain market conditions discourage buyers from making long-‐term commitments. Indian prices are not only unsteady, but there is also no way overseas buyers can take a view of the market beyond the short-‐term. There is excessive speculation rampant in the futures market which finds a ready reflection in the spot market. Unless buyers are assured of steady and foreseeable prices, the dependence on India as a source of castor oil supply could be diluted over time, according to some experts.

1 http://234next.com/csp/cms/sites/Next/Money/Business/5481131-147/story.csp

http://234next.com/csp/cms/sites/Next/Money/Business/5481131-147/story.csp

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Brazil and China -‐ traditional producers of castor seed and the only competitors to India -‐ the two countries have started to show signs of expanding their production base. Brazil has a National Biodiesel Strategy which proposes castor as one of the feedstocks for biodiesel production. Planting of Mamona (castor bean plant) is being promoted especially in the northeast and the country has launched a biodiesel blending obligation program which proposes 2% by 2007 (800 M l/y), 5% by 2013 (2 B l/y), and goal of 20% by 2020 (12 B l/y). A total of 23 companies were chosen by auction as biodiesel suppliers. Analyzing the raw materials used by the companies, castor oil is used by 8 companies.

European Market Consumers -‐ Servicing the fastidious European market -‐ mainly coating industry -‐ is not easy. Most buyers were highly demanding in terms of very specific, tailor-‐made quality and delivery schedule including the time at which the lorry must enter the factory premises and unload goods. This is not easy for Indian castor oil suppliers.

-‐ There is a distinct lack of investment in research and development of castor oil in India. Experts feel that much of research and development work for newer application of castor oil is mainly taking place in Europe and elsewhere.

Major Castor Growing Countries in the Future While it is currently just three countries India, Brazil & China that are the top producers of castor seeds and oil, there are a few countries that could become significant players in future. These include Ethiopia, Vietnam, Thailand, Philippines, Sri Lanka and Tanzania.

Because of widely fluctuating world supplies and the structure of the world market, prices for castor oil vary considerably. This affects cash flow, makes corporate planning difficult, and discourages investment in new products for many companies. These factors have encouraged many companies to start finding substitutes for castor oil. For instance, in the USA, commercial production of transgenic canola containing 15% ricinoleic acid has been explored.

Market Influencing Factors in Castor Trade

Variations in castor seed domestic acreage, based on yield and price realization Indian, Chinese and Brazilian crop sizes Crop development based on monsoon progress in key growing regions Domestic demand for castor oil from Indian companies Comparative prices with other vegetable oils in the domestic market

2.3 Supply & Demand of Castor Oil Castor Oil Production ( 000 T)

Countries Jan-‐Dec 2009

Jan-‐Dec 2008

Jan-‐Dec 2007

Jan-‐Dec 2006

Jan-‐Dec 2005

Russia 1.0 1.0 1.0 1.0 1.0 Ethiopia 2.3 2.4 2.0 1.5 1.5 Brazil 42.5 52.3 43.3 48.7 70.2 China,PR 81.4 83.1 81.5 90.2 101.7

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India 375.8 413.0 367.6 351.2 335.2 Thailand 5.4 5.7 5.6 5 4.5 Oth countries 24.4 23.8 22.5 21.9 21.2 Total 531.8 580.3 522.6 518.5 534.3

Source CastorOil.in and derived from data obtained from sources such as Oilworld -‐ www.oilworld.biz Observations from the Above Table Major countries producing castor oil are India, China, and Brazil. There is a significant difference in castor oil production among countries: India is by far

the largest producer of castor oil, contributing over 70% of the total production in 2009. China and Brazil together contribute 23% of the total world production in castor oil during 2009.

Castor Oil Imports ( 000 T)

Countries Jan-‐Dec 2009

Jan-‐Dec 2008

Jan-‐Dec 2007

Jan-‐Dec 2006

Jan-‐Dec 2005

Belgium-‐Lux 0.9 0.5 0.3 0.4 0.3

Bulgaria 0.1 0.2 0.3 0.4 0.3

Czech Republ

0.1 0.2 0.3 0.2

Denmark

0.4 0.9 0.3 0.5

Finland 0.7 0.4 0.5 0.6 .

France 17.8 85.3 48.9 43.9 66.3

Germany 33.6 34.3 32.6 27.4 22.8

Ireland

0.1

Italy 1 0.6 1.3 3.6 6.5

Netherlands 24.6 15.3 19.3 14.8 15.3

Poland 0.1 0.2 0.2 0.2 0.1

Portugal 0.1 0.1 . . .

Slovenia . 0.1 . . .

Spain 2.4 2.5 3.5 3 3.3

Sweden 0.7 . 0.3 -‐ .

U.K. 5.2 3.5 5 5.5 4.6

EU-‐27 87.2 143.5 113.3 100.4 120.2

Norway 0.1 0.1 0.1 0.1 0.1

Switzerland 4 5.6 5.6 5.8 4.2

Croatia 0.1 0.1 0.1 0.1 0.1

Serbia/Monten 0.1 0.2 0.1 0.2 0.1

Other Europe 4.3 6 5.9 6.2 4.5

Russia 1.8 2.4 2.2 2.2 3

http://www.oilworld.biz/

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Ukraine 0.6 0.7 1 0.7 1.2

C.I.S 2.4 3.1 3.2 2.9 4.2

S.Africa,Rep 2.1 2.4 2.8 2.2 1.9

Canada 5.5 4.6 2.9 3.3 2.2

U.S.A 32.1 48.8 44.3 45.9 41.8

Mexico 2.1 1.9 1.8 1.8 1.3

Brazil 8.8 6.8 3.7 . .

China,PR 124.2 73.4 70.4 79.5 53.6 Japan 13 19.4 19 17.6 26

Korea,South 4.4 5.8 4.6 3.9 4.5

Taiwan 2.1 2.8 3.7 2.9 2.9 Thailand 12 16.8 10.6 11.4 15

Turkey 2.1 4.8 2.7 2.1 1.9 Oth countries 10 8.7 9.9 8.7 8.5

Total 312.3 348.8 298.8 288.8 288.5 Source CastorOil.in and derived from data obtained from sources such as Oilworld -‐ www.oilworld.biz Observations from the Above Table Of the countries listed above, China was found to be the largest importer of castor oil. China imports about 40% of the total imports, followed by Europe (28%)

Castor Oil Exports ( 000 T)

Countries

Jan-‐Dec 2009

Jan-‐Dec 2008

Jan-‐Dec 2007

Jan-‐Dec 2006

Jan-‐Dec 2005

Belgium-‐Lux 0.2 0.1 0.2 0.2 0.3 France 0.1 0.1 0.1 0.1 0.1 Germany 0.9 0.8 0.4 0.4 0.3

Netherlands 0.5 0.4 0.6 0.3 0.5 Spain 0.1 0.3 0.2 0.1 0.1 U.K. 0.1 0.1 0.2 0.1 0.1 EU-‐27 1.9 1.8 1.8 1.2 1.6 U.S.A 6.7 6.8 3.9 4 2.5 Brazil 0.9 0.2 0.7 4.2 11.8 India 280 315.5 270 255 245

Oth countries 20.9 22.7 20.7 23.2 26.2 Total 312.3 348.8 298.8 288.8 288.5

Source CastorOil.in and derived from data obtained from sources such as Oilworld -‐ www.oilworld.biz



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Observations from the Above Table

India is by far the largest castor oil exporter worldwide and it exports 70-‐75 percent of its total production.

Compared to 2008, exports from India decreased by more than 10 percent in 2009. Summary of Production, Imports and Exports from Prominent Countries/Regions

000 Tons)

Country Production India 375.8 China 81.4 Brazil 42.5 Total 499.7

Country Imports China 124.2 Europe (27) 87.2 USA 32.1 Japan 13 Thailand 12 Total 268.5

Country Exports India 280 USA 6.7 EU (27) 1.9 Brazil 0.9 Total 289.5

Source CastorOil.in and derived from data obtained from sources such as Oilworld -‐ www.oilworld.biz

Castor seed -‐ World Area, Production and Productivity

Country

Harvest Season

Production ('000 T) Yield (T/ha) Harvest Area ('000/ha)

09-‐10(F)

2008-‐09 2007-‐08

09-‐10(F)

2008-‐09

2007-‐08

09-‐10 (F)

2008-‐09

2007-‐08

Brazil Jun-‐Sept 92 123 94 0.58 0.76 0.6 158 163 156

China PR

Sep Jan 190 190 170 0.9 0.86 0.81 210 220 210

India Nov Mar 880 975 990 1.06 1.08 1.15 830 900 860

Other Countries 115 117 112 0.62 0.63 0.61 185 186 183 Total 1277 1405 1366 0.92 0.96 0.97 1383 1469 1409

Source: ISTA Mielke, Oil World, Germany, F-‐ Forecast


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The US Supply Scenario Caschem and Arizona Chemical Company were the major producers of castor oil derivatives in the US. Caschem produced almost all castor oil derivatives except for undecyclenic acid where Arkema (earlier Atofina) is the lone producer. Arkema produces undecyclenic acids and heptaldehyde mostly for pharmaceutical and cosmetic niche applications. Undecyclenic acid is also used in the manufacture of fuel, air and brake tubing. Arizona's castor derivative product lines included methyl-‐12-‐hydroxystearate, 12-‐hydroxy stearic acid, hydrogenated castor oil, specialty ricinoleate esters, specialty dimer acids, sebacic acid and capryl alcohol. The US sebacic acid industry changed significantly with the exit of the two players (in 2003) and the entrance of a newcomer. Both the companies opted to leave the market under pressure from low-‐priced sebacic acid imports from China and high production costs. Arizona Chemical permanently shuttered its Dover, Ohio, sebacic acid facility. The manufacturing of hydrogenated castor oil derivatives for the lubricating grease and coatings industries were not affected. CasChem, a subsidiary of Cambrex Corp., also emptied its sebacic acid inventories and mothballed its highly automated sebacic acid plant in Bayonne, N.J. The company began producing sebacic acid in early 2000 using proprietary processing technology. Like Arizona Chemical, Cas-‐Chem considers the domestic market unprofitable because of pressure from cheaper Chinese imports. However, Cas-‐Chem will continue to produce sebacate esters, which is said to be more profitable and where the market tends to focus more on. Undaunted by the competitive pressures of Chinese imports and the currently flat market situation, Genesis Chemicals Inc. has entered the US sebacic acid market. A privately held company, Genesis started full-‐scale production of sebacic acid at the end of 2002 at its new plant in Loveland, Ohio. The company has a full-‐scale manufacturing facility for castor oil derivative production through a joint venture in China. Genesis Chemi-‐cals' Chinese venture also grows its own castor crops in Northern China for captive use. Meanwhile, even though there are only few major producers of castor oil derivatives in the US, supply is adequately maintained as there are quite a few brokers who outsource from several offshore suppliers. Castor crop has not been grown on a large-‐scale in the United States since the early 1970s. During the 1950s and 1960s, approximately 85,000 acres of castor were grown annually in the United States. Since then domestic production decreased and was abandoned in 1972. Source: USDA. To restart domestic production, it is felt that industries in the United States and administration need to focus on the following:

Sufficient number of special built harvesters to harvest the seed from plants after a killing frost.

Contractual agreements by the processor to market castor oil over a period of years. Detoxification and deallergenation of castor meal to allow use in livestock feeds.

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Development of improved hybrids to increase yield and oil percentage of castor seed.

Development of breeding lines with improved disease and insect resistance, drought tolerance, and shatter resistance.

Mutagenesis and genetic research to eliminate ricin, the toxic seed protein. Acquisition and preservation of germplasm useful to a breeding program.

Castor Oil Production from Minor Producing Countries The following data for 2009 provides an idea of the quantum of supplies from countries that are only minor suppliers of castor oil:

Country Production in Jan Dec 2009 (1000T)

% of world supply

Ethiopia 2.3 0.43 Russia 1.0 0.18 Thailand 5.4 1.01 Others 24.4 4.58 Source CastorOil.in and data derived from sources such as Oilworld -‐ www.oilworld.biz 2.4 Indian Castor Oil Industry India is the largest producer of castor seed and oil. It contributes about 1 million tons of castor seed with and over 4,00,000 tons of castor oil to the world total production. The annual domestic consumption of castor oil in India is only about 80,000-‐1, 00,000 tons. Of this, the soap industry consumes about 25,000 tons, the paint and allied industries 35,000 tons and the lubricant and derivatives industry 20,000 tons. In terms of % split between castor oil and derivatives, about 40% of castor oil consumption in India is in the form of derivatives and 60% for the various castor oil grades. About 85% of total castor oil consumed in India is sold in bulk, the rest (about 15%) in retail. 2.4.1 Castor Oil Exports -‐ Historical Scenario Castor crop plays an important role in the agricultural economy of the earning substantial foreign exchange through export of castor beanoil production (over 70 per cent) is exported. The country annually exports about 300 thousand tons of castor oil thereby earning foreign exchange worth US$ 170 200 million. India is the first country in the world to exploit hybrid varieties on a commercial scale in this crop. Major markets include Europe, USA, Japan and now China and Thailand.

Region-‐wise Export Statistics of Castor Oil (including derivatives, US$ Millions) Region 2000-‐01 2001-‐02 2002-‐03 2004-‐05 2005-‐06 2006-‐07 East Asia 53.7 41.1 28.8 85.8 70.8 90.6 South Asia 1.2 0.5 1.0 0.7 1.4 0.9 West Asia 1.7 2.0 2.6 2.6 3.8 4.9 Africa 2.3 1.6 2.1 2.8 3.3 4.4


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East Europe 13.6 13.7 7.0 3.3 3.4 3.1 West Europe 110.1 65.1 57.7 113.5 88.9 102.4 North America 39.4 18.4 14.4 30.4 36.5 33.6 Latin America 0.3 0.6 0.6 0.5 0.8 0.8 Total 221.6 145.1 120.9 239.5 208.9 240.9

Source: Pharmexcil India Note: Values derived based on US$/Re exchange rates at respective years.

Castor Oil and its Fractions Exports

S.No. Country Values in Rs. Lacs Quntity in thousands

2008-‐2009 2009-‐2010 %Growth 2008-‐2009 2009-‐2010 %Growth

1 AFGHANISTAN TIS

36.57 54

2 ARGENTINA 39.97 137.62 244.3 65 216 232.31 3 AUSTRALIA 858.12 637.04 -‐25.76 1,276.42 982.27 -‐23.04 4 BAHARAIN IS 5.88 22.83 288.37 6 38 533.33 5 BANGLADESH

PR 3.23 17.31 436.66 3 24.65 721.67

6 BELGIUM 509.31 1,651.20 224.21 808.01 2,813.44 248.19 7 BRAZIL 1,524.27 4,188.98 174.82 2,659.12 8,037.13 202.25 8 BULGARIA 9.17 8.75 -‐4.61 10 10 0 9 CANADA 83.95 9.86 -‐88.26 131.14 15.43 -‐88.23 10 CHILE 24.29 26.16 7.71 35 34.27 -‐2.07 11 CHINA P RP 45,908.00 79,627.04 73.45 82,241.39 1,47,430.05 79.27 12 COLOMBIA 36.14 79.22 119.22 54 122 125.93 13 CONGO P REP 1.83 2.12 15.53 3.33 3.6 8.01 14 COTE D' IVOIRE 0.13 0.31 132.02 0.3 0.95 216.67 15 DENMARK 169.28 12.19 -‐92.8 249 20 -‐91.97 16 EGYPT A RP 177.45 297.55 67.69 255 493.16 93.4 17 EQUTL GUINEA 0.04 0.06 18 FIJI IS 0.9 1 19 FINLAND 270.52 248.97 -‐7.97 457 476 4.16 20 FRANCE 45,033.10 22,087.66 -‐50.95 76,865.00 41,868.70 -‐45.53 21 GERMANY 2,991.16 1,370.59 -‐54.18 4,641.23 2,196.69 -‐52.67 22 GHANA 0.02 9.18 59,896.08 0.19 15.2 7,987.23 23 GREECE 46.47 64 24 GUATEMALA 3.24 2.1 -‐35.28 7.8 3.51 -‐54.97 25 GUYANA 0.64 1 26 HONG KONG 108.85 78.04 -‐28.31 167.4 125.04 -‐25.31 27 INDONESIA 251.89 15.48 -‐93.85 348.02 24.08 -‐93.08 28 IRAN 643.13 349.64 -‐45.63 928.8 550.32 -‐40.75 29 IRAQ 152.3 261.01 71.38 229 412.6 80.17 30 ISRAEL 155.02 124.68 -‐19.57 197 168.6 -‐14.41

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31 ITALY 811.01 694.67 -‐14.34 1,145.80 931.31 -‐18.72 32 JAPAN 9,763.09 6,004.31 -‐38.5 16,395.81 10,679.92 -‐34.86 33 JORDAN 79.51 34.29 -‐56.88 105 48 -‐54.29 34 KENYA 187.59 24.44 -‐86.97 277.6 36.17 -‐86.97 35 KOREA RP 3,621.03 2,583.76 -‐28.65 8,320.59 4,347.94 -‐47.74 36 KUWAIT 139.19 83.75 -‐39.83 182.2 139.94 -‐23.19 37 LATVIA 136.62 113.61 -‐16.84 198 169 -‐14.65 38 LEBANON 44.42 23.77 -‐46.48 64 34 -‐46.88 39 LIBERIA 1.11 1.53 37.63 2.4 3.89 61.99 40 LITHUANIA 53.7 36.72 -‐31.62 85 65 -‐23.53 41 MALAYSIA 449.85 895.95 99.17 677.08 964.94 42.51 42 MALDIVES 0.14 0.14 43 MAURITIUS 9.36 1.55 -‐83.44 23.65 3.16 -‐86.64 44 MEXICO 224.68 649.6 189.13 338.9 1,068.33 215.23 45 MOROCCO 13.73 38.04 177.12 18 56.34 212.99 46 MOZAMBIQUE 12.35 15.73 27.3 18 22.31 23.96 47 NEPAL 31.92 29.28 -‐8.27 66.75 66.66 -‐0.13 48 NETHERLAND 36,283.48 33,881.18 -‐6.62 61,772.22 65,273.80 5.67 49 NEW ZEALAND 16.36 13.02 -‐20.38 19.15 15.98 -‐16.58 50 NIGERIA 78.15 30.1 -‐61.48 128.79 53.6 -‐58.38 51 NORWAY 11.26 16 52 PANAMA

REPUBLIC 0.1 0.2

53 PERU 48.07 13.59 -‐71.74 65.09 18 -‐72.35 54 PHILIPPINES 94.34 30.87 -‐67.27 144 51 -‐64.58 55 POLAND 86.23 27.29 -‐68.35 129 50.09 -‐61.17 56 QATAR 13.44 17 57 REUNION 1.65 1.22 -‐25.89 2.69 2.66 -‐1.04 58 RUSSIA 1,766.29 1,098.33 -‐37.82 2,535.00 1,777.67 -‐29.87 59 SAUDI ARAB 349.41 278.18 -‐20.38 495.83 425.67 -‐14.15 60 SENEGAL 0.36 1 61 SINGAPORE 297.57 377.12 26.73 410 578.29 41.05 62 SLOVENIA 42.88 66 63 SOUTH AFRICA 1,659.30 1,038.89 -‐37.39 2,543.43 1,689.26 -‐33.58 64 SPAIN 989.37 289.73 -‐70.72 1,693.00 591.7 -‐65.05 65 SRI LANKA DSR 78.69 90.56 15.08 121.67 192.82 58.47 66 SWEDEN 0.14 378.18 278176.53 0.1 764 763899.99 67 SWITZERLAND 31.99 57 68 SYRIA 146.21 310.82 112.59 225.09 520.5 131.24 69 TAIWAN 1,265.03 1,130.25 -‐10.65 1,952.40 1,859.35 -‐4.77 70 TANZANIA REP 0.03 17.24 64,714.29 0.05 27.2 54,296.00 71 THAILAND 8,182.90 8,334.34 1.85 13,018.32 15,592.00 19.77 72 TRINIDAD 5.61 2.52 -‐55.08 18.58 3 -‐83.85 73 TUNISIA 1.61 2 74 TURKEY 1,802.49 1,435.07 -‐20.38 2,787.79 2,463.10 -‐11.65

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75 U ARAB EMTS 1,020.79 581.37 -‐43.05 1,471.10 953.49 -‐35.19 76 U K 3,181.60 3,121.34 -‐1.89 5,215.14 5,631.41 7.98 77 U S A 21,473.59 22,177.55 3.28 36,159.06 42,224.54 16.77 78 UGANDA 0.6 1.01 79 UKRAINE 515 277.92 -‐46.03 771 442.5 -‐42.61 80 UNSPECIFIED 53.06 1,186.54 2,136.16 84.04 2,330.30 2,672.97 81 UZBEKISTAN 3.32 2 82 VENEZUELA 12.58 12.11 -‐3.74 16 18 12.5 83 VIETNAM SOC

REP 45.41 75.34 65.93 69 128.1 85.65

84 YEMEN REPUBLC

0.94 1.38 46.56 2.89 2.2 -‐24.01

85 ZAMBIA 4.54 9.89

Total 1,94,165.03 1,98,732.03 2.35 Source: Ministry of Commerce, India Note: For India Export of Castor Derivatives, refer Appendix 2

2.4.2 Castor Oil Exports Current Scenario

Indian Export of Castor Oil (Excluding Derivatives)

Year Volume (MT) Value (Rs Crore ) Value per T (Rs / T)

1998-‐99 193,913 595.98 30734 99-‐00 234,824 897.56 38223 00-‐01 227,033 806.07 35505 01-‐02 204,877 556.22 27149 02-‐03 163,862 520.85 31786 03-‐04 161,619 603.27 37327 04-‐05 208,176 788.56 37879 05-‐06 182,159 627.43 34444 06-‐07 195,610 653.05 34995 07-‐08 176,177 757.29 42985 08-‐09* 308,625 1821.57 59022

Notes: (1) 1 $US= Rs 45 approx. in Mar 2010. There have been significant fluctuations in the US$/INR rate during

this period; * -‐ including bulk and container (2) Please note that all the above data are for exports that do not include the castor oil derivatives, but

only the main grades of castor oil. Castor Oil Current Data -‐ Countries Exported to by India Countries that currently import castor oil from India are

European Union USA Japan

48



Thailand China

Castor Oil Export Percentages to Various Regions from India (2006-‐2007) (excluding

derivatives)

Region % Exports Volume of Exports (MT) W Europe 45 87750 E Asia 25 48750 N America 20 39000 E Europe 5 9750 Africa 3 5850 Latin America 2 3900 Break-‐ An approximate estimate is provided below for the break-‐up of castor oil & castor oil derivatives exports. This % has been ts over the last 5 years.

Castor oil grades: 80% Castor oil derivatives: 20%

2.4.3 Castor Seed Production and Acreage in India Castor Growing Areas in India & its Production Castor grows under tropical conditions. It needs heat and humidity and does best in regions where both are ample. India, gifted with an ideal climatic condition, has recorded the largest produce of castor seed in the last few decades. The states in India that are the major producers of castor are

Gujarat Andhra Pradesh Rajasthan Karnataka Orissa Tamil Nadu Maharashtra

The Indian state of Gujarat produces over 65% of the total castor seeds in India followed by Andhra Pradesh and Rajasthan which contribute about equal share. In Gujarat, Castor cultivation comprise 6 districts of North Gujarat, viz., Mehsana, Banaskantha, Sabarkantha, Gandhinagar, Ahmedabad and Kutch, with the first two being the two most important. Andhra Pradesh relies on the districts of Nalgonda, Mehboobnagar, Prakasam, Guntur and Ranga Reddy for the production of castor seeds.

49



State % Share of Production of Castor Oil in India (2006 07, estimate)

State % Share of Production Gujarat 66 Rajasthan 14

Andhra Pradesh 12.5 Karnataka 3.2 Tamilnadu 1.4 Maharashtra 1.6

Major Trading Centers of Castor in India The major trading centers of castor and its derivatives in India are:

Rajkot (Gujarat) Ahmedabad (Gujarat) Gondal (Gujarat) Gadwal (Gujarat) Bhabar (Gujarat) Disa (Gujarat) Kadi (Gujarat) Jedcherla (Andhra Pradesh) Yemignoor (Andhra Pradesh)

Castor Seed Acreage and Production in India

Year Area ('000 ha) Production ('000 tonnes) Yield (kg/ha) 1985-‐86 637 308 480 1990-‐91 810 716 880 1995-‐96 880 930 1060 1996-‐97 776 770 990 1997-‐98 810 800 990 1998-‐99 835 840 1070 1999-‐00 782 765 979 2000-‐01 1080 883 818 2001-‐02 716 652 911 2002-‐03 583 428 733 2003-‐04 712 796 1111 2004-‐05 743 793 1068 2005-‐06 864 990 1146 2006-‐07 628 762 1213 2007-‐08 786 1053 1339 2008-‐09 840 1114 1326

Source: Ministry of Agriculture, GOI

50



2.4.4 India-‐wide Data from Castor Crop Survey 2009-‐10

Gujarat Total area under Castor crop in Gujarat for the year 2009-‐10 is 4.37 lakh hectares. It has

decreased by 3% as compared to previous year. Area under Castor crop has increased in all the major castor growing districts except Ahmedabad, Patan, Rajkot, Surendranagar and Vadodara.

Estimated total production of Castor Seeds in Gujarat for the year 2009-‐10 is 7.34 lakh

tonnes, it has increased by merely 1% as compared to previous year. However this growth is mainly in the districts such as Vadodara (28%), Ahmedabad (24%), Rajkot (19%), Patan (16%) districts and Sabarkantha (8%).

Average yield for the year 2009-‐10 is 1679 kg/hectare as against 1608 kg/hectare during

the year 2008-‐09.

District wise Area, Yield and Production of Castor Seeds in Gujarat (2009-‐10)

District

Estimated Area Under Crop * ('000 ha.)

Estimated Production * ( '000

tonnes)

Estimated Yield * (Kg/ha.)

2008-‐ 09

2009-‐ 10

% Change 2008-‐ 09

2009-‐ 10

% Change 2008-‐ 09

2009-‐ 10

% Change

Ahmedabad 12.00 14.26 19% 19.89 24.60 24% 1657 1725 4% Banaskantha 102.41 97.93 -‐4% 180.72 178.24 -‐1% 1765 1820 3% Bharuch 7.20 6.81 -‐5% 11.14 9.60 -‐14% 1547 1409 -‐9%

Gandhinagar 30.40 29.24 -‐4% 53.62 55.25 3% 1764 1890 7% Jamnagar 12.36 10.36 -‐16% 21.60 17.77 -‐18% 1748 1716 -‐2% Kachchh 67.88 52.21 -‐23% 73.18 61.19 -‐16% 1078 1172 9% Kheda 13.10 10.83 -‐17% 20.36 17.04 -‐16% 1554 1574 1%

Mahesana 53.37 52.09 -‐2% 93.29 98.22 5% 1748 1886 8% Panchmahal 2.35 1.95 -‐17% 3.51 2.76 -‐21% 1494 1414 -‐5%

Patan 37.50 41.22 10% 62.92 72.77 16% 1678 1765 5% Rajkot 12.81 15.20 19% 19.80 23.59 19% 1546 1552 -‐-‐

Sabarkantha 54.81 54.33 -‐1% 94.98 102.35 8% 1733 1884 9% Surendranagar 29.11 34.87 20% 46.62 43.07 -‐8% 1602 1235 -‐23%

Vadodara 11.00 11.42 4% 15.69 20.02 28% 1426 1754 23% Others 4.80 4.65 -‐3% 7.84 7.81 -‐-‐ 1597 1679 5% Total 451.10 437.37 -‐3% 725.16 734.28 1% 1608 1679 4% * Nielsen India estimates Source: http://www.seaofindia.com/castoroil_data/Castor%20Crop%20Survey_2009-‐10.pdf

Rainfall -‐ This year, Castor producing districts of Gujarat state have received 478 mm, which is 31% lower than average rainfall in these districts. About 56% farmers perceived that the rainfall during sowing period was favourable this year.

http://www.seaofindia.com/castoroil_data/Castor%20Crop%20Survey_2009-10.pdf

51



Rajasthan

Total area under Castor crop in Rajasthan for the year 2009-‐10 is 1.18 lakh hectares. It has decreased by 7% as compared to previous year. This year, area under Castor crop has mainly decreased in Hanumangarh (43%) and other major district is Sirohi (4%). Where as the area under crop is increased in Pali district by 10%.

Estimated total production of Castor Seeds in Rajasthan for the year 2009-‐10 is 1.26

lakh tonnes. It has decreased by 8% as compared to previous year. Production in Hanumangarh and Sirohi district has decreased by 66% and 18% respectively as compared to previous year. As against this, the production in Pali, Jodhpur, Barmer and Jalore districts has increased this year.

Average yield for the year 2009-‐10 is 1065 kg/hectare, which is 1% lower than

previous year. Yield has mainly decreased in Hanumangarh and Sirohi districts. Last year also yield was lower than the average yield of Rajasthan

District wise Area, Yield and Production of Castor Seeds in Rajasthan (2009-‐10)

District


Estimated Production * ( '000

tonnes)


2008-‐ 09

2009-‐ 10

% Change 2008-‐ 09

2009-‐ 10

% Change 2008-‐ 09

2009-‐ 10

% Change

Barmer 6.01 5.98 -‐1% 6.33 6.60 4% 1053 1104 5% Hanumangarh 17.93 10.18 -‐43% 13.60 6.07 -‐66% 758 597 -‐21%

Jalore 49.11 48.85 -‐1% 56.81 58.13 2% 1157 1190 3% Jodhpur 15.84 15.94 1% 16.83 17.67 5% 1062 1108 4% Pali 3.58 3.92 10% 3.66 4.12 13% 1021 1052 3% Sirohi 27.93 26.94 -‐4% 32.40 26.48 -‐18% 1160 983 -‐15% Others 7.27 6.65 -‐7% 7.80 7.08 -‐9% 1076 1065 -‐1% Total 127.67 118.46 -‐7% 137.41 126.16 -‐8% 1076 1065 -‐1%

* Nielsen India estimates Source: http://www.seaofindia.com/castoroil_data/Castor%20Crop%20Survey_2009-‐10.pdf

Rainfall -‐ This year, Castor Seeds producing districts of Rajasthan state have received 214 mm average rainfall, which is 43% less than average rainfall in these districts. Almost all farmers opined that rainfall during sowing and post sowing was inadequate this year. Andhra Pradesh

Total area under Castor crop in Andhra Pradesh for the year 2009-‐10 is 1.35 lakh

hectares. It has decreased by 30% as compared to previous year. Area under Castor crop has decreased in all other districts of Andhra Pradesh this year except Kurnool. Similar trend has observed in last year also. Since last 2-‐3 years, area under Castor crop in Andhra Pradesh is continuously decreasing.


52



Estimated total production of Castor Seeds in Andhra Pradesh for the year 2009-‐10 is 0.44 lakh tonnes. It has decreased by 38% as compared to previous year due to decrease in area and yield.

Average yield for the year 2009-‐10 is 325 kg/hectare, which is 12% lower than the

previous year.

District wise Area, Yield and Production of Castor Seeds in Andhra Pradesh (2009-‐10)

District


Estimated Production *

( '000 tonnes)


2008-‐ 09

2009-‐ 10

% Change 2008-‐ 09

2009-‐ 10

% Change 2008-‐ 09

2009-‐ 10

% Change

Kurnool 14.85 18.53 25% 6.59 6.17 -‐6% 444 333 -‐25% Mahbubnagar 118.29 79.25 -‐33% 41.20 24.55 -‐40% 348 310 -‐11% Nalgonda 33.05 18.36 -‐44% 13.53 6.83 -‐49% 409 372 -‐9% Rangareddy 5.34 4.24 -‐21% 1.94 1.56 -‐20% 363 367 1%

Other Districts

20.16

14.15

-‐30%

7.44

4.61

-‐38%

369

326

-‐12%

Total 191.70 134.53 -‐30% 70.70 43.72 -‐38% 369 325 -‐12% * Nielsen India estimates Source: http://www.seaofindia.com/castoroil_data/Castor%20Crop%20Survey_2009-‐10.pdf

Rainfall -‐ This year, all the Castor Seeds producing districts of Andhra Pradesh state have received 460 mm average rainfall, which is 10% lower than average rainfall in these districts. Except Nalgonda district, all other districts have received Normal rainfall this year. Heavy rainfall during last week of Sept and 1st week of October washed out crop at many places, mainly in Kurnool and Mahboobnagar districts. All India

Total area under Castor crop in India for the year 2009-‐10 is 7.40 lakh hectares. It has decreased by 10% as compared to previous year.

Estimated total production of Castor Seeds in India for the year 2009-‐10 is 9.34 lakh

tonnes. It has decreased by 4% as compared to previous year.

Average yield for the year 2009-‐10 is 1261 kg/hectare as against 1180 kg/hectare during the year 2008-‐09. It has increased by 7% as compared to previous year.


53



State wise Area, Yield and Production of Castor Seeds in India (2009-‐10)

District


Estimated Production *

( '000 tonnes)

Estimated Yield *

(Kg/ha.)

2008-‐ 09

2009-‐ 10

% Change

2008-‐ 09

2009-‐ 10

% Change

2008-‐ 09

2009-‐ 10

% Change

Gujarat 451 437 -‐3% 725 734 1% 1608 1679 4%

Rajasthan 127 118 -‐7% 137 126 -‐8% 1076 1065 -‐1% Andhra Pradesh

192

135

-‐30%

71

44

-‐38%

369

325

-‐12%

Other States #

56

50

-‐11%

43

30

-‐30%

760

600

-‐21%

Total 826 740 -‐10% 976 934 -‐4% 1180 1261 7% * Nielsen India estimates; # Secondary source Source: http://www.seaofindia.com/castoroil_data/Castor%20Crop%20Survey_2009-‐10.pdf

2.4.5 Cropping Season in India Castor is planted during July or August and harvested around December or January. The seedpods are dried, de-‐podded and brought to the market yards during January for trading. 2.4.6 Castor Cultivation & Yields in India -‐ Points

Despite phenomenal increase witnessed in the production and productivity of castor over the last ten years, there still exist wide regional disparities in the per hectare yields of castor.

With the exception of Gujarat, where the per hectare yields (1630 kg/ha) have registered three fold increase since 1970, the general productivity levels of castor in all other parts are around 500 kg/ha. A multitude of factors such as its cultivation in sub-‐marginal and marginal lands under rainfed conditions with practically little or no inputs, use of poor quality seed and inefficient crop management are responsible for such dismal yield.

The area under castor in Andhra Pradesh has gradually declined in the last five decades.

Ruling varieties and hybrids of castor in India include Aruna, Sowbhagya, Bhagya, Kranti and GCH-‐4.

2.4 Global Castor Oil Industry As mentioned earlier, India is the undisputed leader in castor oil production. India supplies over 70% of the total production of castor oil in the world.

-‐08 were about $ 170 million, which is not a very large value given the potential for this industry.


54



There are two reasons for this low quantum of export revenues: The total amount of castor oil production worldwide (and thus by India), is relatively

very low when compared to production of other seed-‐oils.

little value addition. Low Volumes of Castor Oil Production The worldwide production of castor oil is about 500,000 T per annum. A look at the table below will show how small this quantity is when looked at from a larger perspective.

Worldwide Production of Fixed Oils

Oilseed Approximate Annual

Production (in million T)

Soybean Oil 34 Palm Oil 35 Rapeseed Oil 17 Sunflower Oil 10 Cottonseed Oil 4 Groundnut Oil 4 Palm Kernel Oil 3.5 Coconut Oil 3 Corn Oil 2 Sesame Oil 0.7 Linseed Oil 0.5 Castor Oil 0.5

Note: Figures for 2005-‐06 The total volume of oils and fats produced was about 145 million T in 2007-‐08, among which oils from oilseeds would be about 120 MT (CastorOil.in estimate). One can see that castor oil has less than 0.5% of total world market for oils from oilseeds. Admittedly, one cannot compare castor oil volumes with the volumes of oils such as palm oil or soybean oil because these are edible oils and hence they have much larger usage and demand in the food market. However, the fact that an oil with use as versatile as that of castor oil has a share of less than 0.5% shows what tremendous potential it has for future growth. Low Value Addition by the Indian Castor Oil Industry The basic grades of castor are the commercial grade, first special grade etc.

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The basic and generation I derivatives are essentially considered commodities and incorporate small value additions, and provide thin margins (in the range of 5%). The value additions and profit margins for generation II & III derivatives are significantly higher and these are very attractive. The combined revenue potential from the generation II & III derivatives is about $650 million. Data based on 2007-‐08 exports show that generation II & III derivatives accounted for less

derivatives alone will be almost an insignificant percentage of the total Indian castor oil exports. What is the Existing & Current Potential that the Indian Castor Industry Should Capitalize On? Compare $650 million to $175-‐200 million -‐ -‐ and the value is India is losing out becomes clear. In spite of being the largest castor oil exporter by far (75% of global exports), India is able to capture only about 25% of the total value from the market. Thus, while India could gain a lot more from both higher production of castor oil as well as higher value addition, it is most likely that a higher focus on value added products will be the most optimal method for the short and medium term, owing to a number of structural and market related factors. 2.5 Demand -‐ Supply Estimates for Castor Oil Derivatives According to the industry nomenclature, generation I derivatives include hydrogenated castor oil, 12-‐hydroxy stearic acid, dehydrated castor oil acid, and ethoxylated castor oil among others. Generation II castor oil derivatives include sebacic acid, undecyclenic acid, heptaldehyde, polyols and dimer acid. Generation III derivatives include the esters and salts of generation II derivatives as well as derivatives such as methyl-‐12-‐hydroxystearate. The global market for generation II castor oil derivatives is estimated at $300 million (based on 2007 data). For generation III derivatives, where half of the generation II derivatives are converted, the estimated market worth is close to $350 million (based on 2007 data). Overall, the castor oil and derivatives industry have shown an average demand growth of about 4% per annum for the period 2000-‐2007. While the demand for castor oil and castor oil derivatives is on the increase, except for some of the derivatives such as HCO, 12-‐HSA, the demand is quite relatively low in quantities for reliable data availability. Data availability for demand and supplies for many of these derivative chemicals is sparse as well. The following table provides qualitative estimates of worldwide demand and demand-‐supply gaps for the various grades and derivatives of castor oil. While we have made an attempt at quantifying the qualitative benchmarks at the end of the table, the numbers

56



should be taken more as intelligent estimates rather than as official data, because there are no official data available for specific grades and derivatives of castor oil. It is requested that the following data hence be considered as approximate and qualitative estimates. These have been computed based on secondary data, industry interactions, and transactions done by CastorOil.in in the past 4 years. 2.5.1 Current Demand-‐Supply Estimates for the Various Grades of Castor Oil and Derivatives

Product Demand Current Demand

Supply Gap Castor Seed High Medium Castor Meal / Castor Residue High High Hydrogenated Castor Oil (HCO) Medium Medium 12 Hydroxy Stearic Acid (12 HSA) Medium Medium Methyl 12 HSA (Hydroxy Stearate Acid) Low-‐Medium Medium Blown Castor Oil Low-‐Medium Medium Sulfated/Sulfonated Castor Oil, Turkey Red Oil Medium Medium COLM (Urethane Grade) Medium-‐High Medium-‐High Commercial Grade Castor Oil Very High Medium BP Grade Castor Oil Medium Medium Deodorized/Deodourised Castor Oil Medium Medium European Pharmacoepia Grade Castor Oil Medium Medium Extra Pale Grade Caster Oil Low Medium Pale Pressed Grade (PPG) Grade Caster Oil Medium Medium First Pressed Degummed Castor Oil Medium-‐High Medium First Special Grade (FSG) Castor Oil Very High Medium United States Pharmacopia (USP) Castor Oil High Medium Dehydrated Castor Oil (DCO) Medium-‐High Medium Ethoxylated Castor Oil Medium High C 3 Derivatives of Castor Oil Glycerine Very High Low C-‐7 Derivatives of Castor Oil Heptanoic Acid Low Medium Heptaldehyde Low Medium Heptyl Alcohol (Heptanol) Low Medium C 11 Derivatives of Castor Oil Undecylenic Acid Very High1 Very High1 Undecanoic Acid Low NA Undecylenic Aldehyde Low NA Undecylenic Alcohol Low NA Calcium Undecylenate Low NA Zinc Undecylenate Low NA Allyl Undecylenate Low NA Sodium Undecylenate Low NA

57



Methyl Undecylenate Low NA Ethyl Undecylenate Low NA C 18 Derivatives of Castor Oil Esterols Not known NA Ricinoleic Acid Medium Medium Methyl Ricinoleate Low-‐Medium Medium Sebacic Acid Very High2 Medium-‐High 2-‐Octanol Low Medium 1 A very large percentage of Undecylenic Acid is used by Arkema to manufacture Nylon 11 2 Large percentage of Sebacic acid is used for the manufacture of Nylon 6 Notations for Demand Very High: 50,000 T and above per year High: 30,000 -‐ 50,000 T per year Medium-‐High: 15,000-‐30,000 T per year Medium: 5,000-‐15,000 T per year Low-‐Medium: 1,000-‐5,000 T per year Low: Less than 1,000 T per year Notations for Demand-‐Supply Gap Medium: There exists some demand over and above supply, but there has not been a significant amount of demand that has gone unmet Medium-‐High: There have been some instances where a significant demand has gone unmet High: There have been many instances where a significant demand in the market has gone unmet Low: There have been very few instances when a significant demand has gone unmet NA: denotes that info on demand supply gap is not available owing to the negligible demand volumes 2.5.2 Future Demand-‐Supply Estimates for the Various Grades of Castor Oil and Derivatives Growth of Key End-‐User Segments The major end-‐use industries for castor oil derivatives castor oil are:

Lubricants & Greases Coatings Personal Care & Detergent Surfactants Oleochemicals

58



Growth of Key End-‐user Industry Segments for Castor Oil Derivatives

Industry % Growth (CAGR), based on 2005 data

Potential

Lubricants & Greases 2 44 million T by 2012 Coatings 4.9% (about 11% in Asia!) -‐ Personal Care & Detergent 6% $375 billion by 2012 Surfactants 4% $16.65 billion by 2012 Oleochemicals 4% 8.5 million T by 2012

Over the past one decade, the growth in demand for castor oil and derivatives has been about 4-‐5% per annum (CAGR). If one looks at the table above, this % growth seems to be in line with the CAGR for the various industries. However, one must remember than a very large percentage of the high value added derivatives are produced by companies outside India, and India simply supplies the commodity oils to them. That is, while the demand in quantity for Indian castor oil has been growing at 4-‐5%, India gets a small share of the actual profits that result from high value add. Apart from this, there are other emerging segments that could hold even more significant potential for castor oil derivatives.

Growth Prospects for Bio-‐based Products A McKinsey & Co. 2006 survey provides the following data for the potential for bio-‐based materials in 2010

Market segment Market size in 2010

($billion) Growth % 2005-‐10

CAGR 2005-‐10

Biofuels 42 100 15% Plant extracts 23 20 3.7% Pharma ingredients 20 100 15% Bulk chemicals and polymers 15 50 8.5% Food ingredients 11 35 6.1% Oleochemicals 8 6 1.1% Enzymes 4 100 15%

An analysis of the above table shows that there are some market segments that have much higher growth potential and in which castor oil could play a significant role. Among the segments in the table above, it is doubtful whether castor oil can have a

small quantities of castor oil produced when compared to the massive volumes required for transportation fuel. However, in high growth segments such as pharma ingredients, biopolymers and food ingredients castor oil could have a considerable role to play. While in

59



some of these segments (pharma for instance), castor oil already is a contributor, it is expected that there will be many more segments within pharma as well as the other two in which castor oil can significantly increase its presence. Demand-‐Supply Estimates Based on its research, CastorOil.in makes following estimations for future demand of various products. Please note that most of these are based on qualitative inputs as scarce official inputs are available for some of the derivatives mentioned

Product Future Demand Current Demand Castor Seed Very High High Castor Meal / Castor Residue Very High High Hydrogenated Castor Oil (HCO) Very High Medium 12 Hydroxy Stearic Acid (12 HSA) Very High Medium Methyl 12 HSA (Hydroxy Stearate Acid) Medium-‐High Low-‐Medium Blown Castor Oil Medium Low-‐Medium Sulfated/Sulfonated Castor Oil, Turkey Red Oil

Medium-‐High Medium

COLM (Urethane Grade) Very High Medium-‐High Commercial / Industrial Grade Castor Oil Very High Very High BP Grade Castor Oil Medium-‐High Medium Deodorized Castor Oil Medium-‐High Medium European Pharmacoepia Grade Castor Oil

High Medium

Extra Pale Grade Castor Oil Low Low Pale Pressed Grade (PPG) Grade Castor Oil

Medium-‐High Medium

First Pressed Degummed Castor Oil Medium-‐High Medium-‐High First Special Grade (FSG) Castor Oil Very High Very High United States Pharmacopia (USP) Castor Oil

High High

Dehydrated Castor Oil (DCO) Very High Medium-‐High Ethoxylated Castor Oil High Medium C 3 Derivatives of Castor Oil Glycerine Very High Very High C-‐7 Derivatives of Castoroil Heptanoic Acid Low Low Heptaldehyde Low Low Heptyl Alcohol (Heptanol) Low Low C 11 Derivatives of Castor Oil Undecylenic Acid Very High Very High Undecanoic Acid Low Low Undecylenic Aldehyde Low Low Undecylenic Alcohol Low Low Calcium Undecylenate Low Low

60



Zinc Undecylenate Low Low Allyl Undecylenate Low Low Sodium Undecylenate Low Low Methyl Undecylenate Low Low Ethyl Undecylenate Low Low C 18 Derivatives of Castor Oil Ricinoleic Acid High Medium Methyl Ricinoleate Low-‐Medium Low-‐Medium Sebacic Acid Very High High 2-‐Octanol Low Low

Notations for Demand Very High: 25,000 T and above per year High: 10,000 25,000 T per year Medium-‐High: 5,000-‐10,000 T per year Medium: 2,500-‐5,000 T per year Low-‐Medium: 1,000-‐2,500 T per year Low: Less than 1,000 T per year

SUMMARY There is a significant demand supply gap for castor oil and its derivatives in the market. The demand for castor oil is increasing at the rate of 3 to 5 percent per annum, but only three countries, namely India, China and Brazil are currently supplying to the world market. In addition, castor oil has less than 0.5 percent of the total world market for oils from seeds. In the context of castor oil derivatives, relatively few companies are involved in production. This shows the significant potential for new entrepreneurs in this sector.

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3 -‐ Castor Oil Chemicals & Derivatives This chapter comprises the following topics

Introduction 3.1 Properties & Chemical Composition of Castor Oil 3.2 Chemical, Physical Properties & Specifications of Castor Oil Grades & Derivatives

3.3 HIGHLIGHTS

Castor oil and derivatives find applications in diverse industries.

The high viscosity makes the oil useful as a component in blending lubricants.

Because of its higher polar hydroxyl groups, castor oil is not only compatible with but will also plasticize a wide variety of natural and synthetic resins, waxes, polymers and elastomers.

Castor oil has excellent emollient properties as well as a marked ability to wet and

dispeapplication versatility is further enhanced.

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3.1 Introduction While castor oil is popular in itself, its various derivatives and their unique properties and consequent applications make castor oil even more important in the plant and vegetable oils hierarchy. Castor Plant Chemistry Leaves: Per 100 g, the leaves are reported to contain on a zero-‐moisture basis, 24.8 g protein, 5.4 g fat, 57.4 g total carbohydrate, 10.3 g fiber, 12.4 g ash, 2,670 mg Ca, and 460 mg P. Seeds: The seed contains about 5% moisture, 12.0 16.0% protein, 45.0 50% oil, 3.0 7.0 NFE, 23 27% CF, and 2.0 2.2% ash. Seeds are high in phosphorus, 90% in the phytic form. Also present in the seed are 60 mg/kg uric acid and 7 ppm HCN. The seeds also contain a powerful lipase, employed for commercial hydrolysis of fats, and amylase, invertase, maltase, endotrypsin, glycolic acid, oxidase, ribonuclease, and a fat-‐soluble zymogen. Sprouting seeds contain catalase, peroxidase and reductase. Summary List of Key Derivatives of Castor Oil Commercial Castor Oil First Pressed Degummed Grade Castor Oil Refined Castor Oil -‐ F.S.G./B.S.S. Refined Castor Oil -‐ Extra Pale Grade Refined Castor Oil -‐ Pale Pressed Grade Castor Oil Pharmaceutical (I.P/B.P./U.S.P.) Sulfonated Castor Oil -‐ Turkey Red Oil Blown Castor Oil Ricinoleic Acid Hydrogenated Castor Oil 12-‐Hydroxy Stearic Acid (12-‐H.S.A.) Methyl-‐12-‐Hydroxy Stearate Methyl Ricinoleate Urethane Modified Castor Oil Dehydrated Castor Oil (DCO) Glycerine Urethane Grade Ethoxylated Castor Oil Sebacic Acid Heptaldehyde 2-‐Heptanol Undecylenic Aldehyde Methyl Undecylenate 2-‐Octanol Undecanoic Acid Undecylenic Acid Calcium Undecylenate Zinc Undecylenate Zinc Ricinoleate Heptanoic Acid 3.2 Properties & Chemical Composition of Castor Oil Castor oil's chemical formula is: CH

3-‐(CH

2)5-‐CH(OH)-‐CH

2-‐CH=CH-‐(CH

2)7-‐COOH

It is a fatty acid with 18 carbon atoms, a double bond between the ninth and tenth carbons, and is hence also known as Dodecahydroxyoleic Acid. No other vegetable oil contains such a diverse and high proportion of fatty hydroxyacids.

63



Unique to castor oil is that regardless of where the beans are grown, the chemical composition remains constant. It is this consistency that has allowed castor oil to be used as the absolute standard for viscosity by the Bureau of Standards. Castor oil has a molecular weight of 298, a low melting point (5°C) and a low solidification point (12°C to -‐18°C). It is a monounsaturated fatty acid, soluble in pure alcohol, insoluble in water and has some miscibility in petroleum aliphatic solvents. It resists heat and leaves virtually no residue. Castor Oil Chemistry and Composition Castor oil is unique among all fats and oils in that:

It is the only source of an 18-‐carbon hydroxylated fatty acid with one double bond Ricinoleic acid (12-‐Hydroxyoleic Acid) comprises approximately 87% of the fatty acid

composition

Product uniformity and consistency are relatively high for a naturally occurring material

It is a toxic, biodegradable, renewable resource

64



Castor Oil Composition vs. Composition of Other Vegetable Oils

Crop % A vg. Oil Content

Oleic Acid

Linoleic Acid

Linolenic Acid

Ricinoleic Acid

Castor 45% 3% 4.2% 0.3% 90% Rape Seed 42% 32% 19% 7% -‐0-‐ Linseed 38% 20% 16% 50% -‐0-‐

Sunflower 48% 26% 62% -‐0-‐ -‐0-‐ Soybean 18% 27% 53% 7% -‐0-‐ Palm 52% 40% 8% -‐0-‐ -‐0-‐

Like other vegetable oils and animal fats, castor oil is a triglyceride, which chemically is a glycerol molecule with each of its three hydroxyl group esterified with a long chain fatty acid. Apart from ricinoleic acid, the other fatty acids present are linoleic (4.2%), oleic (3.0%), stearic (1%), palmitic (1%), di-‐hydroxystearic acid (0.7%), linolenic acid (0.3%), and eicosanoic acid (0.3%). The chemistry of castor oil is centered on its high content of ricinoleic acid and the three points of functionality existing in the molecule. These are: (1) The carboxyl group which can provide a wide range of esterifications; (2) The single point of unsaturation which can be altered by hydrogenation or epoxidation or vulcanization; and (3) The hydroxyl group which can be acetylated or alkoxylated, may be removed by dehydration to increase the unsaturation of the compound to give semi-‐drying oil. The hydroxyl position is so reactive that the molecule can be split at that point by high-‐temperature pyrolysis and by caustic fusion to yield useful products of shorter chain length. The presence of hydroxyl group on castor oil adds extra stability to the oil and its derivatives by preventing the formation of hydroperoxides. Properties Density @ 20°C 0.956-‐0.963g/ml Refractive Index 1.477 -‐1.479 Saponification Number 177-‐187 Iodine Value 82-‐88 Unsaponifiable Matter 0.3-‐0.5% Hydroxyl Number 160mm Viscosity @ 20°C 9.5-‐10.0 dPa.S

65



Crude castor oil is pale straw in colour but turns colourless or slightly yellowish after refining and bleaching. Like all other vegetable oils, castor oil has different physical and chemical properties that vary with the method of extraction. Cold-‐pressed castor oil has low acid value, low iodine value and a slightly higher saponification value than solvent-‐extracted oil, and it is lighter in colour. The oil is characterized by high viscosity, unusual for a natural vegetable oil. This behaviour is due largely to hydrogen bonding of its hydroxyl groups. The high viscosity makes the oil useful as a component in blending lubricants. The hydroxyl groups in castor oil account for a unique combination of physical properties:

Relatively high viscosity and specific gravity Solubility in alcohols in any proportion Limited solubility in aliphatic petroleum solvents

The uniformity and reliability of its physical properties are demonstrated by the long-‐term use of castor oil as an absolute standard for viscosity. Because of its higher polar hydroxyl groups, castor oil is not only compatible with but will plasticize a wide variety of natural and synthetic resins, waxes, polymers and elastomers. Castor oil also has excellent emollient and lubricating properties as well as a marked ability to wet and disperse dyes, pigments and

enhanced. Although castor oil is a unique naturally-‐occurring polyhydroxy compound, a limitation of the oil is the slight reduction of its hydroxyl value and acid value on storage; both values may change by about 10% if stored for about 90 days. The reduction of these values is due to the reaction between hydroxyl and carboxyl groups in the oil molecule to form estolides. 3.3 Chemical, Physical Properties & Specifications of Castor Oil Grades & Derivatives Commercial Grade Castor Oil Appearance Pale Dark Yellow

ond 30 units max. Iodine Value 82 90 Saponification Value 177 187 Hydroxyl Value 160 min. Acid Value 2.0 max. Moisture & Volatiles 0.50% max. Specific Gravity @ 20o C 0.954 0.967

66



BP Grade Castor Oil CAS Number 8001-‐79-‐4 EINECS 292-‐293-‐8 Colour Nearly Colourless or Faintly Yellow Relative Density at 20ºC 0.952-‐0.965 Moisture 0.3% max. Iodine Value 82-‐90 Saponification Value 176-‐187 Acid Value 2.0 max. Unsaponfiables w/w 0.8% max. Optical Rotation between +3.5º and 6.0º Hydroxyl Value 150 min. Peroxide Value 5.0 max Light Absorption 1.0 max Pale Pressed Castor Oil CAS Number 8001-‐79-‐4 Flash Point >440oF, >227oC HCC V6 Boiling Point >450oF,>232oC Vapour Density >Air Colour Gardner 2 Max Acid Value 1.5 % Moisture & Volatile 0.25 Max Hydroxyl Value 160-‐168 Iodine Value 83-‐88 Saponification Value 175-‐185 Viscosity @ 25oC 6.3-‐8.9 Castor Oil U.S.P CAS Number 8001-‐79-‐4 Flash Point 229oC (444oF) CC Autoignition Temperature 449oC (840oF) Appearance Light yellow viscous liquid Odor Slight characteristic odor Solubility Negligible (< 0.1%) Specific Gravity 0.961-‐0.963 @ 15.5oC % Volatiles by volume @ 21oC (70oF) 100 Boiling Point 313oC (595oF) Melting Point -‐10oC (14oF)

67



Dehydrated Castor Oil CAS Number 61789-‐45-‐5 Appearance Viscous liquid Colour Gardner 6 Max Acid Value 5 Max Iodine Value 123 Min Hydroxyl Value 25 Max Saponification Value 185 194 Viscocity at 30 ºC 1.6 to 2.5 (poise 61 sec B4 cup) Viscocity Gardner G J Refined Castor Oil FSG (First Special Grade) Appearance Pale Yellow, Viscous, Clear liquid M .I .V. 0.25 % max. F.F.A. (as oleic) 1.00 % max. Acid Value 2.00 % max. Iodine Value (Wijs) 82 90 Saponification Value 177 185 Hydroxyl Value 158 163 Colour on lovibond in 5.2 Y-‐ 20.0 Max. R -‐ 2.0 Max. Castor Oil BSS Grade (British Standard Specifications) Specific Gravity at 25° C 0.954-‐0.960 Acid Value 2.0 Max. Saponification Value 175.0 Min. Iodine Value 81-‐90 Hydroxyl Value 158 Min. Colour Gardner 2.0 Max.

Blown Castor Oil

Colour Gardner Acid Value

Hydroxyl Value

Iodine Value

Saponification Value

Viscosity Gardner-‐

Holdt/Strokes Z-‐1 6 Max 12-‐16 151-‐158 69-‐73 200-‐220 Z-‐1/25-‐35 Z-‐6 12 Max 10-‐17 130-‐140 56-‐65 210-‐230 Z-‐5,6/100-‐150 Z-‐8 16 Max 11-‐16 125-‐135 58-‐66 220-‐245 Z-‐8/450-‐600

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Urethane Grade

Color

Gardner Acid Value

% Moisture & Volatile

Equivalent Weight

Hydroxyl Value

Iodine Value

Sapon Value

Viscosity @ 25º C

COLM 2 Plus Max 2.0 Max 0.02 Max 342 160-‐168 83-‐88 175-‐185 6.3-‐8.9

Ethoxylated Castor Oil Synonyms -‐ Castor oil polyoxyethylene ether Typical properties of Ethoxylated Castor Oil (the properties given are for EO-‐36) CAS Number 61791-‐12-‐6 Appearance Clear or light yellow liquid Density ( g / cm-‐3) @ 25oC 1.05 pH (5% in water) 5 7 Cloud point, °C 68 75 Hydroxyl Value, mg KOH/g 37 45 Moisture, Percent Max 0.5 12 HSA 12 HSA (12 Hydroxy Stearic Acid) is a wax-‐like, odourless and tasteless compound. The basic form of 12 HSA is a flake. CAS Number 106-‐14-‐9 Formula C18H36O3 Appearance White Colour Flakes Acid Value 175 Min. Iodine Value 3.5 Max. Melting Point 75°C Min. Saponification Value 180-‐190 Hydroxyl Value 155 Min. Colour Gardner (G) 5G Max. Moisture 0.5 % Max. Turkey Red Oil CAS Number 8002-‐33-‐3 Appearance Brownish yellow oil Sp.Gravity 0.98 Melting Point < 0°C Boiling Point > 150°C

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Chemical Character Anionic pH 7 ~ 8 Sulfonation Degree Minimum 4.0 Solubility Miscible in water giving milky emulsion HCO -‐ Hydrogenated Castor Oil CAS Number 61788-‐85-‐0 Hydroxyl Value 158 Iodine Value 3 Saponification Value 180 Acid Value 2 Melting Point °C 86 Specific Gravity 25°C 1.02 Color White to pale yellowish Appearance @ 20°C: Solid (mobile liquid @ 30°C) Odor Almost none Flash Point °C 242 C DIN ISO 2592 Solubility in Water @ 20°C 100G/L pH @ 100G/L H2O 6 7 Ricinoleic Acid Ricinoleic Acid (12-‐hydroxy-‐9-‐octadecenoic acid) is obtained by the hydrolysis of Castor Oil. It is a light coloured liquid with a ricinoleic content of approximately 90%. Primary uses include, coatings, plastics, inks and cosmetics Biochemical studies have revealed that ricinoleic acid is produced in castor by the direct hydroxylation of the common fatty acid, oleic acid (18:1). The hydroxylation reaction is catalysed by a single, highly efficient enzyme, the fatty acid hydroxylase.

IUPAC Name -‐ (E)-‐12-‐hydroxyoctadec-‐9-‐enoic acid Synonyms -‐ 12-‐hydroxy-‐(cis)-‐9-‐octadecenoic acid CAS Number 5323-‐95-‐5 Chemical Formula C18H34O3 Mol Wt. 298.46 Physical State Viscous yellow liquid Melting Point 5.5oC Boiling Point 245oC

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Specific Gravity 0.94 Solubility in Water Insoluble Vapour Density 10.3 Flash Point 224oC Stability Stable under ordinary conditions Appearance Viscous yellow liquid Acid Value 175 min Hydroxyl Value 150 min Iodine Value 80-‐91 Saponification Value 180 min Colour, Gardner 8 max Methyl 12 HSA -‐Methyl 12 Hydroxy Stearate Hydroxyl Value 160+ Iodine Value 3 Saponification Value 175+ Acid Value 1.2 Melting Point °C 52 Specific Gravity 25 °C 1.02 Sebacic Acid Sebacic acid is a dicarboxylic acid.

Chemical, Physical Properties & Specifications of Sebacic Acid

Chemical Names

Decanedioic acid 1,8-‐Octanedicarboxylic Acid Dicarboxylic acid C10

Chemical Formula C10H18O4 CAS Number 111-‐20-‐6

Physical State and Appearance White flake or powdered crystal in its pure state

Molecular Weight 202.24 g/mole Color Colorless to light yellow Odour Mild odor of fatty acid. Boiling Point Decomposes

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Melting Point 132°C (269.6°F) Specific Gravity 1.207 (Water = 1) Density at 25oC 1.209 g per cubic centimeter

Dispersion Properties See solubility in water, methanol, diethyl ether, acetone

A Sample Producer Specification for Sebacic Acid -‐ Form: Powder

Parameter Values

Special High-‐grade High-‐grade I High-‐grade II Sebacic Acid Content (%) 99.5 min 99.5 min 99.5 min

Ash Content (%) 0.02 max 0.03 max 0.05 max Moisture Content (%) 0.3 max 0.3 max 0.3 max

Alkaifusion Specific Color (Platinum-‐Cobalt Color

No.) 5 max 15 max 25 max

Melting Point Range oC 131 to 134.5 131 to 134.5 131 to 134.5 Form: Grain

Parameter Value

Sebacic Acid Content (%) 99.5 min

Ash Content (%) 0.03 max

Moisture Content (%) 0.1 max

Alkali Fusion Chromaticity (Platinum-‐Cobalt Color No.) 25 max

Melting Point Range, oC 131 to 134.5

Granularity (%) 95 and higher

Heptaldehyde Synonyms: Enanthal, enanthaldehyde, enanthole, heptyl aldehyde, enanthic aldehyde, n-‐heptaldehyde, heptanal, n-‐heptanal CAS Number 111-‐71-‐7 Molecular Formula C7H14O Appearance Colourless Liquid Melting Point -‐43oC Boiling Point 40 42oC Density (g cm-‐3) 0.818 Flash Point 35oC Explosion Limits 1.1 -‐ 5.2% Water Solubility Slight

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2-‐Heptanol Synonyms: Amyl methyl carbinol, 5-‐heptyl alcohol, heptan-‐2-‐ol, methyl amyl carbinol, 1-‐methylhexanol CAS Number 543-‐49-‐7 Molecular Formula C7H16O Appearance Colourless Liquid Boiling Point 160 162oC Density (g/cm3) 0.817 Flash Point 64oC Undecylenic Aldehyde Synonyms: 10-‐Undecenal; C-‐11 Aldehyde, undecylenic; 1-‐Undecen-‐10-‐al; 10-‐Undecylenaldehyde; Undecylenaldehyde CAS Number 112-‐45-‐8 Molecular Formula C11H20O Molecular Weight 168.28 Appearance Clear, colorless to pale yellow liquid. Flash Point 76oC ( 168.80oF) Physical State Liquid Appearance Clear, colorless to pale yellow Odor Rose-‐like Vapour Density 5.8 Boiling Point 235oC Freezing/Melting Point 7oC Solubility Insoluble Specific Gravity/Density 845 g/ml Methyl Undecylenate CAS Number 5760-‐50-‐9 Formula C12H22O2 Molar Refractivity 59.47 ± 0.3 cm3 Parachor 521.5 ± 4.0 cm3 Index of Refraction 1.444 ± 0.02 Surface Tension 29.5 ± 3.0 dyne/cm Density 0.886 ± 0.06 g/cm3 Polarizability 23.57 ± 0.5 10-‐24cm3 Molecular Weight 198.3018800 Odor Type Earthy Odor Strength Medium Odor Description at 100.00% Earthy Fungal Rose Fatty Floral Substantivity 24 Hour(s)

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Appearance Colorless to pale yellow clear liquid Assay 98.00 -‐ 100.00 % Specific Gravity 0.87900 -‐ 0.88900 @ 25.00 °C Optical Rotation -‐2.00 to +2.00 Melting Point -‐28.00 -‐ -‐27.00 °C. @ 760.00 mm Hg Boiling Point 247.00 -‐ 248.00 °C. @ 760.00 mm Hg Boiling Point 159.00 -‐ 160.00 °C. @ 50.00 mm Hg Acid Value 1.00 max. KOH/g Shelf Life 24.00 month(s) or longer if stored properly Flash Point ( oF. ) > 200.00 °F. TCC (> 93.33 °C.) 2-‐Octanol Synonyms: capryl alcohol, caprylic alcohol, ethylpentylcarbinol CAS Number 123-‐96-‐6 Molecular Formula C8H18O [ Structural CH3(CH2)5COHCH3 ] Appearance Colourless liquid with a pungent odour Melting Point -‐38oC Boiling Point 174 181oC Vapour Pressure 0.15 mm Hg at 25oC Specific Gravity 0.819 Flash Point 71oC (closed cup) Glycerine Synonyms: Glycerol; 1,2,3-‐Propanetriol; Glyceritol; Glycic Alcohol; 1,2,3-‐Trihydroxypropane; 1,2,3-‐Propanetriol CAS Number 56-‐81-‐5 Molecular Formula C3H8O3 Molecular Weight 92.0542 Physical State Liquid Appearance Clear Odor Faint odour Vapour Pressure .0025 mm Hg @ 5 Vapour Density 3.17 (H2O=1) Boiling Point 290oC Freezing/Melting Point 20oF Autoignition Temperature 400oC ( 752.00 deg F) Flash Point 193oC ( 379.40 deg F) Decomposition Temperature 290oC Solubility Miscible in water. Insoluble in chloroform Specific Gravity/Density 1.4746

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Undecanoic Acid Synonyms: 1-‐decanecarboxylic acid, hendecanoic acid, undecoic acid, undecylic acid, N-‐undecoic acid, hendecanoic acid, N-‐undecylic acid, 1-‐decane carboxylic acid, N-‐undecanoic acid CAS Number 112-‐37-‐8 Chemical Formula C11-‐H22-‐O2 Appearance Colourless to light yellow liquid or solid Odour Waxy, creamy, coconut odour

Physical State and Appearance

Solid. (Low Melting Point Solid. Above 28.5oC it is a colorless to slightly yellow liquid)

Flash Points Closed Cup: >93.333°C (200°F) Molecular Weight 186.3 g/mole Boiling Point 228°C (442.4°F) Melting Point 28.5°C (83.3°F) Appearance Colourless crystals Undecylenic Acid Synonyms: 10-‐Hendecenoic; 10-‐Henedecenoic acid; 10-‐Undecylenic acid; Undecyl-‐10-‐enic acid CAS Number 112-‐38-‐9 Chemical Formula C11-‐H20-‐O2 Auto-‐Ignition Temperature 275°C (527°F)

Flash Points Closed Cup: 148°C (298.4°F). Open Cup: 160°C (320°F)

Physical state and appearance Solid (low melting point solid) Odour Fruity. Rosy Molecular Weight 184.28 g/mole Colour Yellow. (Light.)

Boiling Point 232 -‐235oC.@ 182 mm Hg; 230 235oC.@ 130 mm Hg.

Melting Point 24.5°C (76.1°F) Specific Gravity 0.9072 (Water = 1) Decomposition Temperature 275°C (527°F) @ 760 mm Hg

Calcium Undecylenate CAS Number 1322-‐14-‐1 Chemical Formula C22H38O4Ca Physical state and appearance Solid Molecular Weight 406.62 g/mole Melting Point Decomposes

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Zinc Undecylenate Synonyms -‐ Zinc diundec-‐10-‐enoate; Undecylenic acid zinc salt CAS Number 557-‐08-‐4 Chemical Formula C22H38O4Zn Physical state and appearance Solid Molecular Weight 431.92 g/mole

Zinc Ricinoleate Zinc Ricinoleate 13040-‐19-‐2 Melting Point 160oF pH 6.6 Specific Gravity Approx. 600 kg/m3 Solubility in Water Insoluble Appearance & Odour Beige pellets with characteristic odor Flash Point >482oF Auto Ignition Temperature Approx. 824.00oF Heptanoic Acid Synonym: 1-‐Hexanecarboxylic acid; Enanthic acid; Enanthylic acid; Heptylic acid; n-‐ Heptoic acid; n-‐Heptylic acid; Oenanthic acid; Oenanthylic acid CAS Number 111-‐14-‐8 Chemical Formula CH3-‐(CH2)5-‐COOH Flammability of the Product May be combustible at high temperature Auto-‐Ignition Temperature 289°C (552.2°F) Flash Points Closed Cup: >112°C (233.6°F) Flammable Limits Lower: 1.1% Upper: 10% Products of Combustion Carbon oxides (CO, CO2) Physical State and Appearance Liquid (Oily liquid) Odour Disagreeable. Rancid. Faint Tallow-‐like Molecular Weight 130.19 g/mole Colour Clear pH (1% soln/water) Acidic Boiling Point 222.2°C (432°F) Melting Point -‐7.5°C (18.5°F) Specific Gravity 0.92 (Water = 1) Vapour Density 4.49 (Air = 1)

Water/Oil Dist. Coeff. The product is more soluble in oil; log(oil/water) = 2.4

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SUMMARY

Unique properties of castor oil make it versatile industrial oil with varied applications.

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4 Castor Oil Prices This chapter comprises the following topics

Historical & Current Price Data for Castor Oil, Castor Seeds 4.1 Castor Oil and Castor Seed Price Volatility 4.2 Factors that Affect Prices 4.3 Castor Oil Futures Market 4.4

HIGHLIGHTS

Castor oil prices are highly volatile.

There is a wide intra and inter seasonal price variation. The price in US$ is made even more volatile due to the volatility of the Indian Re. against the US $.

There is a price variation of about 30% between planting and harvesting seasons.

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4.1 Historical & Current Price Data for Various Grades of Castor Oil, Castor Seeds Castor oil prices are highly volatile. An example of volatility is seen in seed prices There is a wide intra and inter seasonal price variation. The price in US$ is made even more volatile due to the volatility of the Indian Re. against the US $. The price increase of castor seeds has been quite dramatic since the middle of 2007. It increased by over 30% between June 2007 and June 2008. Usually, the prices of castor seeds firm up during the planting period that is Jul Aug due to lesser availability. It eases down during the harvesting period (Jan Feb) as a result of increase in supply. There is a price variation of about 30% between planting and harvesting seasons. Factors to watch out for regarding castor oil prices:

Production constant since 2-‐3 years World demand for castor oil is increasing @ 3-‐5 % per annum Export demand expected to increase significantly in future

Some other points to note about castor oil prices:

It is generally believed that being a versatile industrial oil with varied applications, demand for castor oil is price inelastic. There is invariably a minimum quantity of this commodity that is consumed annually by advanced countries irrespective of price.

Between 2006 and 2009, prices have fluctuated in a wide range between a low of $650 a ton and the present high of $ 1,500 a ton.

Castor Seed

Average Prices for Castor Seeds (all prices in US$, FOB Mumbai)

Year Prices -‐ $ / MT 2004 400 2005 410 2006 350 2007 475

2008 (Jan -‐ June) 575 2008 (Jun Dec) 675

2009 (Jan -‐ Jun) 515 2009 (June Dec) 589

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Monthwise Castor Seed Price (Average) (US$/T, NCDEX)

2006 2007 2008 2009 2010

Jan 318 434 511 524 629

Feb 325 449 546 487 627

Mar 336 462 594 489 640

Apr 325 486 580 519 663.5

May 316 473 580 539 695

Jun 317 470 612 532 731

Jul 342 481 699 543 804.5

Aug 344 479 707 574 819

Sep 368 477 698 592 889

Oct 391 478 662 592 812

Nov 404 497 651 639

Dec 398 513 637 648

Note: 1 US$= 45 Rs. Castor Seed Price (Average)

Castor Oil

Castor Oil Prices (average price for commercial grade) US$/T, FOB Mumbai

Year Price 2002 675 2003 925 2004 850 2005 925

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2006 775 2007 1025

2008 (Feb) 1160 2008 (June) 1350 2009 (Jan) 1050 2009 (June) 1104 2010 (Jan) 1330

Monthwise Castor Oil Price (Average)

(US$/T, MCX)

Month 2006 2007 2008 2009 2010

Jan 692 950 1077 1050 1330

Feb 695 975 1161 1055 1314

Mar 723 1005 1282 1038 1367

Apr 711 1045 1288 1091

May 695 1011 1299 1115

Jun 697 991 1355 1104

Jul 737 1015 1471 1123

Aug 761 1021 1527 1195

Sep 804 1022 1501 1253

Oct 867 1025 1421 1250

Nov 909 1071 1413 1344

Dec 896 1092 1378 1390 Note: 1 US$= Rs 45

Castor Oil Price (Average)

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A Snapshot of Castor Seed, Castor Oil & Castor Cake Prices in Jul/Aug 2008 and Jan 2009 do later Jul/Aug 2008 All castor products hit a record high in Jul/Aug 2008. A look at the average prices below will tell the story. All prices in US $ / Metric Ton, FOB India

Product Price Castor seed 700 Castor oil 1500 Castor cake 110

These prices were 20% higher than the already high prices existing in May 2008 (in the middle of May 2008, castor seed prices were quoting at US $ 575-‐600 per MT). In spite of such a sharp increase, industry professionals and traders have said that the demand had not decreased considerably. Jan 2009 The data for average prices in Jan 2009 tell an entirely different story. All prices in US $ / Metric Ton, FOB India

Product Price Castor seed 500 Castor oil 1050 Castor cake 65

It can be observed that there is a dramatic reduction in prices across all the castor products. In spite of these low prices, suppliers say there is much less demand, primarily because of the global economic downturn. 4.2 Castor Oil & Castor Seed Price Volatility Monthly Price Volatility of Castor Seed and Oil in Mumbai Market (based on data between 2000 and 2006)

Monthly Var % 0-‐2 months 2-‐5 months 5 & above months Castor seed 24 % 43 % 35 % Castor Oil 25 % 40 % 35 %

Maximum Variation in Mumbai Markets in % Terms

Period Castor Seed Castor Oil Daily 3.2 3 Weekly 7.8 7.2 Monthly 16 15

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Pricing Pattern The price of castor seed is influenced by climatic conditions, prices of castor oil in the world trade, production in India and Rotterdam prices in Europe. An analysis of spot prices for the past few years clearly indicates that the commodity price is volatile.

Rationale for the Castor Seed Contract Some of the main reasons for introducing the futures contract in castor seed are: Fluctuating production of castor seed in India: There is significant fluctuation in the production of castor seeds in India. The market participants like the farmers, traders, oil millers, exporters and industries which produce value added derivatives face an eternal price risk due to fluctuating production. Hence it is imperative to introduce a hedging mechanism for efficient price discovery and price dessimation.

Volatile commodity: Market research done by NCDEX shows that the Annualized Price Volatility is 15%.

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Wide usage of castor products: Castor oil and its derivatives are used as raw materials in many industries like Paint, Lubricant, Textile, Pharmaceutical etc. They form a large part of the variable cost for the production of the above products. Any negative fluctuations in the price of the raw material may erode their profits. Hence, an efficient hedging mechanism is essential to combat the price risk. Large number of market participants: There are many intermediaries in the castor distribution chain. These intermediaries prevent efficient price discovery and price dissemination for the farmer. Hence the need for an effective market intelligence platform, so that farmers take informed decisions. Limited hedging options: Due to lack of transparency in the unorganized forward markets, there is counter party risk, default and quality issues. Hence a genuine hedging tool needs to be put forth for the castor industry. More than 80% of production is exported: India exports nearly 80% of its production and is highly vulnerable to the world prices set by other trading countries. Hence, there is a need for futures contract to hedge their price risk. Importance of Castor Seed and Castor Oil Futures The following points underscore the importance of futures trading in castor seed and castor oil

Uncontrolled and uncertain supply Fluctuating and uncertain demand Wide and unforeseen price variation Wide intra and inter seasonal price variation Homogenous nature and well-‐defined grades Long storing period Well-‐developed and organized spot market

4.3 Factors that Affect Prices

Characteristics of Castor Seed and Oil Market

Uncertain supply -‐ The world castor seed production has fluctuated between 1.2 and 1.8 million tons since 1997 to 2001. India's production ranged between 0.8 and 1.1 million tons during the same period.

Recent developments of artificial substitutes development of substitutes for castor oil has subjected the demand to fluctuate in the world market (especially Lesquerella fendleri)

Long storing period & hoarding -‐ It is a common practice for the castor seed growers and crushers to hoard the commodity before selling in expectation for better prices.

Well-‐developed and organized spot market in India

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Market Influencing Factors in Castor Trade The following factors influence castor oil prices, export volumes and overall castor trading:

Crop development based on monsoon progress in key growing regions Domestic demand for castor oil from the major Indian cities & export

demand of castor oil Variations in castor seed domestic acreage worldwide and specifically in

India, based on yield and price realization Indian, Chinese and Brazilian crop sizes Comparative prices of other vegetable oils in the Indian and global markets The castor seed price tends to firm up during the planting period and eases

down during the harvesting period. Prices tend to show significant inter-‐seasonal variations

Castor seed growers and crushers hoard the commodity before selling in expectation of better prices.

During some years (as it happened in 2006), due to better price realization in cotton and pulses, farmers had shifted from castor thus reducing the total area under castor.

Floods and drought in major castor growing states such as Gujarat and Andhra Pradesh had also adversely affected the crop in some years (eg: 2006)

4.4 Castor Oil Futures Market A few years back, the Government of India has removed all restriction on futures trading in almost all commodities under the Forward Contracts Regulation Act (FCRA), and this includes agricultural commodities such as castor seed and castor oil. Since then, there has been a vibrant futures trading in castor seed and oil. Castor Oil Futures Contract Specifications on the MCX (Multi Commodity Exchange, India)

Trading Unit 1 MT Quotation / Base Value Rs / 10 Kg Maximum Order Size 50 MT Tick Size (Min Price Movement) 10 paise per 10 Kg Daily Price Limits 3% Price Quotes Ex Kandla

Max Allowable Open Position

For a client 20000 MT For a member collectively for all clients 25% of the open position of the market @ any point of time

Delivery Delivery Unit 10 MT (with tolerance limit of 250 Kg) Delivery Centers Kandla Quality Specifications

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Appearance @ 25% C Clear and free from suspended matters Odour Slight

Lovibond Tintometer / AOCS CC 13B-‐45 20 yellow maximum / 2 red maximum Free Fatty Acid (AOCS CA 5A-‐40) 1% max Hydroxyl Value (AOCS CD 13 -‐6) 160-‐168 Moisture and Volatile Values (AOCS CA 2C -‐25) 0.25% max Insoluble Impurities (AOCS CA 3 -‐46) 0.02% max Ricinoleic Acid Content (ISO 5508 & 5509) 85% minimum Density @ 30 C (ISO 6883 1995 CORR. 1/1996) 0.952 minimum

Solubility in alcohol @ 20oC Completely without turbidity in 2 volumes of specially denatured alcohol formula 3A (95%)

Flash Point 280oC minimum Iodine Value 82-‐90 RI @ 40oC 1.47 1.474 Specific Gravity @ 30 C 0.954-‐0.96 Test for presence of other oils Negative Castor Seed Futures Contract Specifications on the MCX (Multi Commodity Exchange, India)

Trading Unit 10 T Quotation / Base Value 20 kg Maximum Order Size 500 MT Tick Size (Min Price Movement) 10 paise Daily Price Limits 3%

Price Quotes

For a client 20000 MT For a member collectively for all clients 25% of the open position of the market @ any point of time

Max Allowable Open Position Delivery Delivery Unit 10 MT (+/-‐ 1%) Delivery Period Margin 25% Delivery Centers Babhar, Disa, Pathan, Palanpur, Visnagar Quality Specifications Gujarat small castorseeds packed in 75 Kg bags. Delivery samples will have to certified by the Exchange designated quality surveyor Oil content (on clean seed basis) Min 47%, Acceptable (45-‐47%)

Foreign matter and impurities

Stones, earth, straw or chaff including castor husk / pod maximum % by weight is specified and checked

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Notes from MCX, India Cash v/s Futures Prices Relationship: In general, futures markets compensate an individual for the cost of purchasing a commodity today, storing it and delivering it in future. As a result, one would ordinarily expect to see an upward trend in prices as contract months go further out. Such a condition is known as Contango and is typical of many futures markets. However, in castor seed & castor oil the flows of demand and production are not synchronized. Stored inventories absorb demand fluctuations in periods between production times. There is a likelihood of shortage in the physical market and peak arrival months in the future. This may cause the spot price to rise above the futures price between production times. Backwardation is a condition in which spot price is higher than futures or the futures price is lower in the distant delivery months than in the near delivery months.

SUMMARY The castor oil market price experiences significant volatility. Uncertain oil supply, recent development of substitutes, long storing periods & hoarding are the main reasons for the price fluctuations. In spite of these factors, there is invariably a minimum quantity of this commodity that is consumed annually by advanced countries.

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5 -‐ Castor Cultivation This chapter comprises the following topics

Introduction 5.1 Castor Crop Sowing -‐ 5.2 Castor Crop Growth 5.3 Castor Crop Harvest 5.4 Castor Cultivation Seasons 5.5 Hybrid Castor Seeds & Genetic Engineering of Castor Plant 5.6 Yields for Castor Seeds and Castor Oil from Seed 5.7 Castor Cultivation FAQ 5.8

HIGHLIGHTS

The most suitable soils for castor are deep, moderately fertile, with slightly acidic conditions, well drained, sandy loams.

The fertilizer dose recommended for castor is 40 N-‐40 P-‐20 K kg/ha.

The minimum rainfall needed by the castor crop is 38-‐50 cm (15-‐20 in.)

Some of the high yielding castor varieties used in India are NPH-‐1 (Aruna), GAUCH-‐4,

and TMVCH.

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5.1 Introduction to Castor Crop The castor plant is a coarse perennial, about 10 ft tall in the tropics, with the stem 7.5 15 cm in diameter. Though it is a perennial, it usually behaves as an annual in the temperate regions. Its stems are succulent, and the plant is herbaceous. Its leaves are alternate, orbicular, and palmately compound, with 6 11 toothed lobes. Its flowers are numerous in long inflorescences, with male flowers at the base and female flowers at the tips. Petals are absent in both sexes, sepals number 3 5. Its stamens are numerous, 5 10 mm long. Its ovary is superior, is 3-‐celled with a short style and 3 stigmas.

spiny, green that turns to brown on ripening. The fruit usually contains 3 seeds. The seeds are ovoid, tick-‐like and shiny. They are 0.5 1.5 cm long, carunculate, vari-‐color with base color white, gray, brownish, yellow, brown, red, or black. The outer patterns on the fruit are gray or brown to black, the pattern varying from fine to coarse, and in shape the outer patterns vary from veined or finely dotted to large splotches. While castor is an important crop known for its versatility of uses, in many parts of the western world, including the US, the crop is not planted on a large scale. The main reason for this is the ricin, a toxin present in the seed coat. Besides the ricin toxin, there's another compelling reason why this crop has fallen out of favor with growers. The shiny, beetle-‐shaped seeds contain powerful allergens. People who work with the off-‐white meal ground from castor beans may develop allergic reactions, such as hives or asthma. 5.2 Castor Crop Sowing Soil Castor does well in the soil which is not fit for valuable commercial and food crops. It can be grown on a wide range of soils, provided they are fairly deep and well drained. The most suitable soils for castor are deep, moderately fertile, with slightly acidic conditions, well drained, sandy loams. While castor prefers deep sandy loam soil with a pH of around 6, it can be cultivated on soils with pH range of 5 -‐ 8. The recommended soil pH requirements are:

6.1 to 6.5 (mildly acidic) 6.6 to 7.5 (neutral)

In India, it is equally successful in light and heavy loams of other states. The red sandy loams and shallow light textured black soils of Andhra Pradesh state, Karnataka state and deep/medium sandly loams of North Gujarat state and Rajasthan state are the principal soil types on which castor is currently grown. Heavy clays, with poor drainage, and marshy soils are unsuitable, as they favour excessive vegetative growth at the expense of seed yield. In general castor genotypes cannot tolerate

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alkalinity or salinity, hence, avoid such problematic soils. It is highly intolerant of water-‐logging and requires free draining soils. Land Preparation The land is repeatedly ploughed in summer, as and when the rains are received, and with the onset of monsoon rains the clods are crushed by working a country plough or harrow to bring the soil into proper tilth. For good growth, castor requires a well pulverised seed bed with loose subsoil upto 45 cm depth. For annual varieties the seedbed must be weed free as young plants are delicate. Good weed control is essential, both pre-‐ and post-‐emergence. It does not require fine tilth, but for germination it requires adequate moisture for a longer period in seed bed, preferably to a depth of 15-‐20 cm. Deep ploughing is found to be advantageous in many regions of India as this practice helps in absorption and conservation of more rain water. It is also a common practice on light soil areas to plough the land once in summer months, followed by harrowing once or twice with the receipt of pre-‐monsoon rains. In clay loams only harrowing is done by blade harrows two to three times to bring the soil to proper tilth. In laterite soils, deep ploughing is especially advantageous to break the compact layers in sub soil. Sowing Castor bean is usually planted at the start of the rainy season during the latter part of May and early June, or at the end of the rainy season in the late September and early October. Sow in such dates / periods as to avoid wet weather in 2nd half of the crops life. Castor bean seeds for planting must be healthy, vigorous, hardy and come from prolific mother plants. After the seedbed has been deeply cultivated, seeds in mechanized countries are planted 47.5 cm deep in rows 1 m apart; and about 50 cm apart within rows (some varieties can be planted just 25 cm apart). For unmechanized societies that prefer larger varieties, seeds are planted 60 by 90 cm apart, 2 4 seeds per hole, and then thinned to one plant. The seed is sown either in the plough furrow, with a seed-‐drill or by hand-‐dibbling. For an increased production of seeds, castor should be planted on fallow land, and should not follow small grains or another castor crop. In India it is rotated with groundnuts, cotton, dryland chillies, tobacco or horsegram.

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5.3 Castor Crop Growth Fertilizers The fertilizer dose recommended for castor is 40 N-‐40 P-‐20 K kg/ha.

Nitrogen Recommendations for Castor Beans

Soil Organic Matter % Nitrogen Application Rate lb/acre < 2 100

2 4.9 80 5 10 60 > 10 40

Castor exhausts the soil quickly. So 45 135 kg/ha of nitrogen is added in split applications in some areas. Leaves, stalks and seed hulls are disked into the field following harvest. In India 89 kg/ha of nitrogen gives the highest yields. Where phosphorus is deficient, 40 50 kg/ha of P2O5 is recommended. Castor bean needs plenty of nitrogen especially during its early development. A hectare with 1,600 hills requires complete fertilizer (14-‐14-‐14) at planting time at the rate of 30 grams per hill. Thirty days after the plant emerges, apply 125 grams of nitrogenous fertilizer (45-‐0-‐0) per hill. Just before flowering, apply 16-‐20-‐0 at the rate of 250 grams per hill. Please note however that unbalanced nitrogen application encourages growth of foliage at the expense of flower and seed formation. Water Castor, being a deep rooted crop, is fairly resistant to drought. Rainfall The castor plant is a tropical/sub-‐tropical species and grows in areas of low rainfall. It is sensitive to extreme climatic changes, especially extreme changes in rainfall distribution. The minimum rainfall needed by the castor crop is 38-‐50 cm (15-‐20 in.). In India satisfactory yields have been obtained on sandy soils receiving a rainfall of 30-‐50 cm, using the varieties with capacity for extremely quick root growth. In the Indian state of Andhra Pradesh, a rainfall of 50-‐60 cm is considered optimum for producing good yields on red loams. Castor can withstand long dry spells as well as heavy rains but is highly susceptible to water logged conditions. The ideal pattern of rainfall distribution for optimum growth will be approximately 10 cm in each month evenly distributed during the crop growth period. There should not be heavy and continuous rains during flowering. Continuous rains prior to

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planting are also not desirable as it will lower the soil temperature effecting the germination and increase the fungal diseases. Hail storms do considerable damage to the crop especially during the seedling stage. Defoliation due to hail prior to flowering will have little effect on final yield, but hail storm during flowering and capsule formation will cause considerable damage to the final yield. Irrigation The crop must have sufficient moisture during its growing period. In Brazil 2,400 cu m of water is applied during the 3 months between flowering and harvest, with about 400 cu m being applied at 15 day intervals. Furrow irrigation is preferred, but adoption of sub-‐irrigation has been found to reduce weed problems. Normally, irrigation commences after plants have 6 8 leaves. Over-‐irrigation on heavy soils should be avoided; final irrigation should be 3 4 weeks before harvest. Climate Castor is essentially a warm season crop, cultivated in tropical, subtropical and temperate regions. Its cultivation is largely confined to countries lying between 400N and 400S latitudes. It grows in tropical and subtropical regions as a perennial plant and in temperate climate as an annual plant. A frost free growing period of 140-‐190 days depending on variety is highly essential for obtaining satisfactory yields. The regions in which castor may be grown as a commercial crop are restricted by this lack of frost tolerant types and the need for high temperatures (optimum 20 -‐ 25C, over 4.5 -‐ 6 months) and low atmospheric humidity to achieve good yields. In Europe, only the southern part is potentially suitable for castor production. A moderate temperature of 20-‐26oC is highly favourable during crop period for obtaining higher yields. The plant also grows in temperatures of 26.7-‐40.6oC. Temperatures above 41oC, even for a relatively short period, results in the blasting of flowers and poor seed set. The effect is more marked if it coincides with moisture stress. A low temperature (less than 15oC) in the seed bed prolongs the emergence of seedlings, and makes the seed more liable to attack by fungal diseases and insects. The crop grows best at an elevation of 460 meters (140.24 feet) above the sea level. In India it is being cultivated up to an attitude of 2500m, but in regions where frosts are common during the crop season, its cultivation is restricted to altitudes of 500 m. Crop Protection Diseases seldom do much damage though leaf spot (Cercospora reicinella), Rust (Melampsora oricini) and Alternaria Leaf spot may occur.

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The seedling blight and Alternaria blight cause serious losses to this crop. The sowing of the crop in low-‐lying and water-‐logged areas should be avoided to prevent the seedling blight from appearing. Pests that are Harmful to Castor Plant Several insects are pests for castor crop. In India the Capsule borer (Dichocrocis punctiferalis) bores into young and ripening capsules; and the Castor semilooper (Achoea janata) is a pest too. In Tanganyika, the damage by capsid and myrid bugs is a limiting factor causing immature fruits to drop. Green stinkbugs, leaf-‐hoppers, leaf-‐miners and grasshoppers are pests that feed on the leaves. In Africa there is a great variety of pests. Up to 50 species of insect can damage castor, including grasshoppers, various larvae, and the more serious pests: capsid bugs, green stink bugs, lygus bugs, Helopeltis. Sucking pests cause damage by puncturing, rather than actual sucking. Whether these would also be a problem in Europe is unknown. The most troublesome fungus for castor in Europe is thought to be Alternaria ricini. Most of these insects may be controlled by insecticides. Dusting BHC 10% in early stages or spraying 0.1% Carbaryl on the crop will give an effective control on these pests. Weed Control Weed control for castor crop is based on a pre-‐sowing application of trifluraline and a pre-‐emergence application of linuron. Due to lack of selectivity, both products are usually applied by farmers before sowing. Harrowing is generally carried out when plants have between 2 and 5 leaves in order to improve chemical weed control. Some pre-‐emergence herbicides may be suitable for weed control but subsequent measures will also be likely required. Castor Growth Other Points

Defoliation speeds up maturity and makes the harvest easier. Pruning castor plants is necessary for them to grow more productive branches. Start pruning 2-‐3 months after the plants sprout or when it is already one foot high.

In case of seed production of castor, climatic conditions prevailing in a season has

profound influence on sex expression. High temperatures coupled with humidity provide an ideal climate for producing more male flowers, and low temperatures are most conducive for production of female flowers. This is one reason why winter is the most ideal season for taking up hybrid certified seed production.

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5.4 Castor Crop Harvest The first harvest is on the 6th month and every other month thereon. Harvesting may be done by hand methods or be completely mechanized. In the tropics most harvesting is by hand; the spikes are cut or broken off, the capsules stripped off into a wagon or sled, or into containers strapped on the workers. Unless the capsules are dry, they must be spread out to dry quickly. The improved varieties mature in about 150 to 180 days. When one or two capsules in a bunch show signs of drying, the whole cluster is generally removed and stacked, covered and weighed in a corner of the field or in a pit. The harvesting of unripe capsules in this manner has an adverse effect on the oil content of the seed and hence should be avoided. It is preferable to collect the fruits, as and when they ripen. When the whole crop is gathered, it is dried in the sun for a few days and the threshing is done either by beating the dried capsules with a stick or by treading them under the feet of bullocks. Winnowing is done in the usual manner. Harvesting -‐ Additional Points

A new system for dehusking the seeds during harvesting has been designed. About 90% of the husks are removed by the combine harvester. Although such a system avoids an additional cost, the cost of the harvester modification remains too high and harvesting capacity too low. Improvement of the harvester is currently going on but an increase of the crop area should be necessary to reduce costs.

5.5 Castor Cultivation Seasons

Sowing, Growth & Harvest Stages for the Castor Crop -‐ India

State Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar

Guj Sow Sow Grow Grow Grow Grow Harv Harv Harv

AP Sow Sow Grow Grow Grow Grow Harv Harv Harv

World Castor Seed Harvest Seasons

Country Main Harvest Season India Dec -‐ Mar China Sep -‐ Jan Brazil May Sep

Paraguay May Sep

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5.6 Hybrid Castor Seeds & Genetic Engineering of Castor Plant Genetic improvement of castor has mostly been confined to the exploitation of naturally occurring genetic variability available in the base population and limited to selection for high yield, desirable branching type, non-‐shattering capsules and seeds with higher oil content. Mass selection and pedigree methods have been largely employed for developing genotypes with desirable attributes. Based on the exotic pistillate line TSP-‐10R (Classen and Hoffman 1950), the first hybrid castor, GCH-‐3 was developed. Subsequently the development of andigenous pistillate line, VP-‐1 which is based on TSP-‐10R, gave new impetus to hybrid castor development programmes and resulted in the release of three hybrids, GAUCH-‐1, GCH-‐2 and GCH-‐4. However, extensive cultivation of the varities and hybrids under high inputs, without proper scientific management and crop rotation, has made them vulnerable to a number of biotic and abiotic stresses. Diseases, such as wilt, root rot, bacterial blight, botrytis grey rot, seedling blight, and insects such as semilooper, capsule borer, spodoptera litura, red hairy caterpillar, jassids, white fly, cause considerable damage to castor. New sources of disease and pest resistance and tolerance to stress environments are in constant demand by the breeders. Ricinus is considered to be a monotypic genus and R. communis is the lone species encompassing the many polymorphic types known in the world (Weiss 1983). Several of these types were designated as species (R.communis, R. macrocarpus, R. microcarpus) but they are intercrossable and fertile and are not true species as usually defined in other plants. All the castor varities that have been investigated cytologically are diploids with a 2n number of 20 and is reported to be a secondary balanced polyploidy with a basic number of x = 5 (singh 1976). The great variability within the single species of this genus has not been correlated with any observable cytological differences, inversions, duplications etc, rather than to change in the whole chromosome complement (Perry 1943). Success in breeding of castor with yield stability is thus limited by a lack of exploitable genetic variability for productivity traits and sources for resistance to diseases and pests. Breeders have to resort to alternative approaches like mutations, wide (intergeneric) hybridization and biotechnology for the creation of genetic variability and incorporation of desired traits into castor. The effect of irradiation on castor seed and seedlings has been the subject of a number of studies, aimed at producing mutatnts with specifically required characters. In most of the studies various neutron-‐induced morphological abnormalities have been described (Shivraj and Ramanarao 1963). The importance of induced mutatuions in castor is well demonstrated in the development of productive semi-‐dwarfs with high yield potential an early maturity and identification of variants for sex expression (Kulkarni and Ankineedu 1966 et al., 1968). However, mutation technique using radiations could not be exploited for the development of genotypes resistant/tolerant to biotic stresses. Intensive studies on plant regeneration and transformation have led to the production of transgenic plants in many crop plants. However, techniques for tissue culture and gene transfer in castor as well as other Euphorbiaceous plants, with the expectation of Cassara and Herea brasiliensis, are less advanced. The introduction of foreign genes by genetic

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engineering techniques requires an efficient in vitro regeneration system for the desired plant species. Such a system must be rapid, reliable and applicable to a broad range of genetypes. However, regeneration of plants from callus cultures of castor has been problematic. There are only a few reports of plantlet differentiation in castor and in most of the cases regenerated plantlets were obtaine from apical meristems and shoot tip callus, and the plantlets had poor survival in the soil (Athma and Reddy 1983; Reddy et al., 1986; Genyu 1988; Sangduen et al., 1987). Efficient protocols of plant regeneration have been developed for jatropha species (Sujatha and Dhingra 1993; Sujatha and Mukta 1996; Sujatha et al., 2005) but lack of a reliable system of regeneration in castor is a major bottleneck for parasexual hybridization between the two economically important genera. This review presets the progress and future prospects of tissue culture and genetic transformation in castor. Castor Varities in India The varities of castor recommended for different states of India are:

State Variety Hybrid

Andhra Pradesh

Aruna, Bhagya, sowbhagya, Kranti (PCS-‐4), Jwala, DCS-‐9 (Jyothi), kiran (PCS-‐136), Haritha (PCS-‐124).

Uttar Pradesh Kalpi-‐6, T-‐3, T-‐4

Gujarat GAUC-‐1, VI-‐9, S-‐20, J-‐1and GCH 7

CH-‐1, GCH-‐2, GCH-‐3, GCH-‐6, SHB-‐145, GCH-‐7 and (SKP 84 x SKI 215

Tamil Nadu

TMV-‐1, TMV-‐2, TMV-‐3, TMV-‐5, SA-‐1, SA-‐2, TMV-‐4, Jyothi, CO-‐1 TNAUCH-‐1 and TMVCG*

Karnataka Jwala (48-‐1), RC-‐8, Jyothi Maharashtra AKC-‐1, Girija GCH-‐6 Rajasthan GCH-‐6, RHC-‐1 Haryana CH-‐1 Punjab Pb. No.1

For all states Gujarat castor-‐2

DCH-‐32 (Deepti) DCH-‐177 (Deepak) GCH-‐4, GCH-‐5, DCH 519

For entire country DCH 519 M 574 x DCS 78 * Castor hybrid recommended for cultivation in Tamil Nadu is TMVCH by Oilseeds Research Station of the Tamil Nadu Agricultural University (TNAU) Tindivanam. This hybrid matures in 160-‐170 days. Its seeds contain 51.7% oil. It is moderately susceptible to semilooper pest and moderately resistant to wilt and grey mould. Source: Indian Agricultural Research Institute, 2008. Gujarat is the largest castor seed production in India. As a result of intensive hybridization and selection programme research center, the following castor hybrids / varieties have been developed and released for commercial cultivation in Gujarat State.

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I. GCH -‐ 3 After the introduction of female line TSP-‐10-‐R from USA, it was utilized extensively in hybridization programme. As a result first castor hybrid GCH-‐3 (TSP-‐10-‐R x JI-‐15) was found to give 88 per cent higher yield than local variety. It was released as first castor hybrid in the state for general cultivation in 1968. It, however, had the shattering characteristic. II. J-‐1 By intensive selection, a number of inbred lines were isolated from local materials from which a promising inbred line, JI-‐44 was released as J-‐1 in 1968 which gave 11% higher yield than local variety, S-‐20. III. GAUC-‐1 It was developed by selection from S-‐20, a local variety, which showed superiority over improved variety J-‐1 by yielding 23.4% higher yield. It has green stem, double bloom, flat leaves and early maturity. It was released for general cultivation in Gujarat in 1973. IV. GAUCH-‐1 After development of female line VP-‐1, it was utilized extensively in hybridization programme for developing superior hybrids. Among a number of single crosses made and tested, VBH-‐44 (VP-‐1 x VI-‐9) was found superior to GCH-‐3. It was released for general cultivation as GAUCH-‐1 in 1973. It possesses green stem, triple bloom, with 16% higher yield over GCH-‐3 and non-‐shattering habit. V. GCH-‐2 It was developed from a cross, VP-‐1 x J1-‐35 in Gujarat state. It has shown superiority over GAUCH-‐1 by way of giving 13% more seed yield and was released for general cultivation in 1984. It has green stem with reddish tinch, possesses triple bloom and tolerance to root rot. VI. GCH-‐4 It involves VP-‐1 as female and 48-‐1 as male parent. It was tested as SHB 18 and released as GCH-‐4 for general cultivation in 1985. It is resistant to wilt and gives 13.25 and 9.30% higher yields over GAUCH-‐1 and GCH-‐2, respectively. This hybrid was released as a national hybrid in the year 1987. It possesses mahogany stem, triple bloom and flat leaf and it is highly suitable for irrigated condition. VII. GC-‐2 The variety was developed from the cross "1-‐21 x VI-‐9" following selection. This variety possesses Jassids and wilt tolerance and early maturity. On the basis of results of

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coordinated trials, the variety was released at national level in 1994. It has showed 15% yield superiority over check variety, GAUC-‐1. VIII. GCH-‐5 In involves Geeta as a female and SH-‐72 as a male parent. It was tested as SHB-‐145. It is resistant to wilt and it showed 13% yield superiority over GCH-‐4. The hybrid has been released for irrigated and medium condition at national level in 1995 and for Gujarat state in 1997. IX. GCH-‐6 It involves JP 65 as female and JI 96 as pollinator. It gives 11.58% and 14.13% higher yield than GCH-‐4 under irrigated and rainfed situation, respectively. It is resistant to root rot and tolerant to wilt. X. GCH-‐7 A high yielding wilt complex resistant hybrid has recently been identified. Development of Pistillate Lines2

The research center has developed a versatile pistillate line of castor, VP-‐1, which is derivative of (TSP-‐10-‐R x J-‐1) F2 x (JP-‐5 x 26006) F2. This is one of the most versatile pistillate line, used as female in most of the presently cultivated hybrids and it is being used in all castor growing states of India for developing hybrids and also for the development of pistillate lines. As a part of development of new pistillate lines, through single, double and three way crosses, a number of new pistillate lines are developed such as SKP-‐1 to SKP-‐117. Out of these, SKP-‐4, 6, 13, 16, 19, 23, 42,72, 84, 106, 108,112,113 and 114 appear to be promising in respect of resistance to wilt disease as well as these lines possess sex stability. A new pistillate line Geeta has been developed from the male parent of castor hybrid GCH-‐4, which is resistant to wilt. Another pistillate line JP-‐65 having NES mechanism has been developed at Junagadh, Gujarat, India. Development of Promising Inbred Lines and Hybrids3

With a view to develop new inbred lines, intensive and extensive hybridization programme was undertaken. As a result, 321 inbred lines have been isolated from segregating materials. The most promising inbred lines are SKI-‐80, 90, 147, 160, 215, 217, 218, 225, 237, 202 269 232, 266, 267, 271, 280,283,285,291, 294, 306,314; and JI-‐122, 102, 106, 220, 227, 244, 256, 258, 263, 273, 303, 314, 319 and 320, while the most promising hybrids are SHB 706, SHB 725 , SHB 754, SHB 758, SHB 765, SHB 795, and JHB 665, JHB 882, JHB 887, JHB 888, JHB 905 and JHB 921. Many of these lines are resistance to wilt, root-‐rot, reniform nematode and nematode-‐wilt complex.

2 http://www.sdau.edu.in/ 3 http://www.sdau.edu.in/

http://www.sdau.edu.in/

http://www.sdau.edu.in/

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International Germplasm Center A search of International Germplasm collections on the Bioversity web site combined with the USDA-‐ARS castor germplasm at Griffin, GA (USA) identified 12 major sources of germplasm and a total of 6,588 accessions. Extensive germplasm collections are held in Brazil, China, Ethiopia, India, Kenya and the former USSR, but availability of these germplasm resources is not known. Additional castor germplasm can be obtained from public breeders in South America including Brazil and Columbia. The feral castor can be a valuable source of germplasm especially for adaptation to localized diseases, pests and environmental conditions.

Major Germplasm Collections of Castor (Ricinus communis L.) as Listed by the Bioversity International Directory (October 14. 2008)

Country Collection Agency Accessions Reported

Brazil CENERGEN/EMBRAPA 360

Brazil Centro Nacional de Pesquisa de Algodao (CNPA) 199

Brazil Ernpresa Baiana de Desenvolvimento Agricola S.A. 528 Brazil Instituto Agronomico de Campinas (l.A.C.) 200 China Institute of Crop Science (CAAS) 1,689

China Institute of Oil Crops Research (CAAS) 1,652

Ethiopia Biodiversity Conservation and Research Institute 232

India Region Station Akola, National Bureau of Plant Genetic Resources (NBPGR) 290

Kenya National Dryland Farming Research Station, Kenya -‐

Kenya National Genehank of Kenya. Crop Plant Genetic Resources Centre, KARl 43

Romania Agricultural Research Station Teleorman -‐

Russia N.I. Vavilov All-‐Russian Scientific Research Institute of Plant Industry 423

Serbia Maize Research Institute 69

Serbia Institute of Field and Vegetable Crops 43

Ukraine institute for Oil Crops 255 United States USDA-‐ARS-‐PGRCU 364

World 39 Institutes Source: National Agriculture Library, United States Department of Agriculture

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Castor Seed Varieties & Hybrids -‐ Salient Points Castor beans are graded based on moisture content, percentage of cracked and

broken seeds, and amount of foreign material. The allowable moisture content is 6 per cent.

The varieties of castor differ in the branching habits of plant, colour of the stem and branches (red and green), the nature of capsules (smooth or shiny), duration (early or late) and the size of seed.

One of the aspects usually considered while discussing grades and varieties is the location where the castor seed was grown and harvested.

The most commonly traded varieties in India are Gujarat small seed and Andhra Pradesh big seed

The Gujarat seed has oil content up to 48-‐50% which is more than that for the Andhra variety.

Bangkok variety has two types -‐ Bangkok brown & Bangkok white. Bangkok brown spotted type is generally adapted to the Philippine conditions. Its seed has few small chestnut light on its back side and large spots on the abdominal side. Bangkok white spotted type, on the other hand, has few small chestnut white spots scatted on its bask side.

The Brazilian is another common variety. It grows 1.83-‐2.44 meters (6-‐8 feet) high depending on the soil type. The stalks are dark brown, 2.5 centimeters (1 inch) in diameter, while internodes measure 10-‐20 cm (4-‐8 inches) long. This variety has an oil content of 49.3 per cent.

An early maturing variety with 49 per cent oil content is Ethiopian. Its red seed is big with small white dots on both sides.

The Lamao Red variety grows 1.83-‐2.44 meters (6-‐8 feet) tall. The stalks is more than an inch in diameter at the middle portion, reddish brown from the base to the tip, with internodes measuring 2.54 cm (1-‐4 inches).

Other castor bean varieties include Cimaron, Connex, Baker No.1, Baker 195 and the Iranian variety.

Some of the high yielding castor varieties used in India are NPH-‐1 (Aruna), GAUCH-‐4, and TMVCH.

A castor hybrid specifically recommended for cultivation in Tamil Nadu is TMVCH. This hybrid matures in 160-‐170 days. Its seeds contain 51.7% oil. It is moderately susceptible to semilooper pest and moderately resistant to wilt and grey mould.

In Brazil, the plant has also been bred to mature at a shorter height. Whereas the castor-‐oil plant traditionally reaches three meters in height, making mechanised harvest difficult, there are now varieties that grow to just 1.7 meters. More information is available with the state-‐run Brazilian Enterprise for Agricultural Research (EMBRAPA) (May 2008)

A list of hybrid seed developments from across the world: South Africa -‐ Varieties Baker 44, Baker 22, II23 and UC53 India

Tamil Nadu Research Centre for TMV 5 & TMV 6 Andhra Pradesh for Kranti Kiran and Jyothi

Brazil -‐ EMBRAPA

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Some Short Term (annual) Varieties Tested in East Africa

Variety Time To Maturity II23 7-‐10 Months UC53 7-‐10 Months

Baker 44 5-‐7 Months Baker 22 5-‐7 Months Lynn 5-‐7 Months

Advantages of annual varieties: Higher yield potential, seeds seldom shatter and have uniform hull strength and thickness. Disadvantages of annual varieties: Pest susceptibility Castor Genetic Engineering Salient Points

While experiments with producing genetically modified castor plants and seeds are in their early stages, scientists and researchers are confident that with the availability of molecular-‐breeding tools, there is a possibility for developing castor as a reasonably safe crop. To this end, some scientists have developed methods to genetically transform castor, and the implementation of some of the molecular-‐breeding approaches could provide significant reduction of harmful components present in the crop. For example, antisense gene technology has been successful in reducing expression of specific proteins by greater than 99%.

Transgenic plants expressing the gene for the enzyme Oleoyl-‐12-‐hydroxylase -‐ which is directly responsible for synthesis of ricinoleate -‐ produce limited amounts of hydroxy fatty acid. To aid in development of transgenic substitutes for castor, scientists are trying to determine which steps in the pathway lead to accumulation of ricinoleate in the oil. This and other techniques have allowed scientists to identify other enzyme activities from castor that lead to the high level of ricinoleate in its seed oil. According to one research study, the steps leading to high production of ricinoleate and incorporation into triacylglycerol include: (i) lyso-‐phosphatidylcholine acyltransferase (LPCAT), which transfers oleate from oleoyl-‐CoA into the sn-‐2 position of phosphatidylcholine (PC) for hydroxylation; (ii) oleoyl-‐12-‐hydroxylase, which hydroxylates the sn-‐2 oleate to form sn-‐2 ricinoleoyl-‐PC for hydrolysis; (iii) phospholipase A#, which preferentially removes ricinoleate from the sn-‐2 position and releases lyso-‐PC for re-‐incorporation of oleate by LPCAT; (iv) diacylglycerolacyltransferase (DAGAT) preferentially incorporates ricinoleate to form diricinoleins and triricinolein. Using process insights such as these, scientists are making efforts to find suitable substitutes for the castor plant that do not have

(Reference: http://www.biochemsoctrans.org/bst/028/0972/0280972.pdf )

Scientists are also aiming to build and insert slightly different versions of genes into the castor plant, to block the action of the ricin and allergen genes. For example, they want to construct antisense genes, which are genes that make nonsense copies of the authentic ricin or allergen genes.

http://www.biochemsoctrans.org/bst/028/0972/0280972.pdf

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Epoxy Oil from Castor? -‐ Genetic engineering might someday be used to tweak oil-‐producing mechanism so that it could yield another valuable oil, known

as epoxy. An epoxy-‐based paint, for example, offers all the advantages of a premium, oil-‐based paint, yet does not give off certain volatile chemicals that pollute the atmosphere. That's unlike the solvents in oil-‐based paints, which can be an environmental hazard. Some scientists think that production of epoxy oil by castor plants is possible, because the chemical structure of epoxy oil is very similar to that of castor oil. The modification that's needed to cue the castor plant to make epoxy oil instead of castor oil is minor, compared to genetically engineer a corn plant or a soybean plant to make epoxy oil, because the oils that those plants make are very unlike epoxy oil.

Other aspects that have been identified while researching genetic modification for castor seeds -‐ Oleoyl-‐12-‐hydroxylase is the enzyme responsible for ricinoleate biosynthesis in castor (Ricinus communis). The hydroxylase introduces the mid-‐chain hydroxyl group, resulting in a fatty acid with numerous chemical uses. Other factors involved in the high level of ricinoleate production by castor are the steady increase in hydroxylase activity throughout development and the decline in oleoyl desaturase. The glycol lipid oleoyloxyethyl phosphocholine is an effective inhibitor of hydroxylase activity, and should prove to be a useful tool in following the movement of labelled fatty acids through lipid pools.

Thomas A. McKeon of ARS' Western Regional Research Center in Albany, California and colleague Grace Q. Chen, both in the Crop Improvement and Utilization Research Unit, are some of the first in the world to genetically engineer castor plants. In preliminary experiments, McKeon and Chen used marker genes to determine whether their tactics for shuttling new genes into plants actually worked. Now the scientists want to give the plants other genes -‐ ones that could, among other things, block production of ricin poison and the powerful allergens. (a 2001 report, URL: http://www.ars.usda.gov/is/AR/archive/jan01/plant0101.htm )

Castor plants are gradually revealing the secrets of how they make this prized substance. Scientists with the Agricultural Research Service (ARS) in Albany, Calif., are delving into the mostly-‐mysterious mechanisms. The researchers' probing has revealed, for the first time, the starring role that a gene called RcDGAT may play in directing the castor plant to put the oil's most important component, its ricinoleate. ARS research chemist Thomas A. McKeon did the work at the ARS Western Regional Research Center in Albany along with research chemist Jiann-‐Tsyh Lin and ARS research associate and molecular biologist Xiaohua He. The scientists right now are continuing to slip the newly identified gene into yeasts in laboratory experiments that will determine more about how to harness RcDGAT's oil-‐making prowess. (based on a Dec 2005 report)

In the United States, administrators and researchers are considering the large-‐scale reintroduction of castor this is largely driven by a desire to replace the significant annual importation of castor oil with a reliable, cost-‐effective, domestic supply of ricinoleic acid. Failing reintroduction of castor, efforts are afoot to so that crops that produce high levels of oleic acid, such as sunflower or rape-‐seed, are being engineered to contain the gene required to produce hydroxyleic acid, thereby yielding the desired ricinoleic acid in an established agronomic crop. Over the near term the acreage of traditional crops will continue to dwarf that of new crops. In the

http://www.ars.usda.gov/is/AR/archive/jan01/plant0101.htm

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long-‐term, alternative and possibly genetically engineered crops can make important contributions in the industrial and agricultural sectors if they can compete in the marketplace with traditional crops.

Atofina (now Arkema) to introduce genetic varieties of castor-‐oil plant (March, 2002) -‐ The French chemicals group Atofina, is negotiating with the Brazilian Embrapa (Empresa Brasileira de Pesquisa Agropecuaria) and with EBDA (Empresa Baiana de Desenvolvimento Agricola) the introduction of new genetic varieties of castor oil plant in Irece, the major producer of the Bahia state.

Atofina (now Arkema) FDL Co-‐operation for hybrid castor seeds -‐ FDL has set up a castor seed joint venture project with Atofina (now Arkema) in China to try to

and reduce the raw material cost of castor oil for Atofina. FDL has supplied castor oil to Atofina for many years predominantly from India but also from Brazil and China. FDL set up a joint venture with a partner in China to encourage experimentation, research and development of castor seed planting within China for the past six years. FDL America for the development of high yield hybrid seeds, and has utilised their knowledge for the identification of suitable hybrid seeds for experimentation within China. These hybrid seeds have been shipped to China and plantation studies have been carried out across various regions of China for identification of the most successful hybrids for Chinese soil and climatic conditions. (Fuerst Day Lawson (FDL) press release, date not published)

Commercial production of transgenic canola containing 15% ricinoleic acid is currently under way.

5.7 Yields for Castor Seeds and Castor Oil from Seed Castor Seed Yield Average seed yields range from 900 1000 kg/ha under irrigation, and 500 kg/ha without adequate moisture. Some improved open-‐pollinated varieties in Brazil yield 1,300 kg/ha, with exceptional yields up to 5,000 kg/ha. Average Indian yields are about 1000 kg/ha. Under exceptional circumstances in the state of Gujarat in India, seed yields of 6000 Kg / hectare have been recorded, but it should be noted that these yields have been registered only for some limited growth areas. FAO Data for castor seed yields (2006)

India: 973 Kg / hectare China: 960 Kg / hectare Brazil: 671 Kg / hectare

Castor Oil Yield The Indian variety of castor has 48% oil content of which 42% can be extracted, while the cake retains the rest.

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5.8 Castor Cultivation FAQ We have provided brief answers to some frequently asked questions related to castor crop cultivation.

Why is castor an annual crop while it is actually a perennial?

o It has been found that of the castor crop is grown as a perennial, the yield

decreases significantly over the years. As a result, castor has primarily been used as an annual crop.

Is harvesting done manually or is it automated?

o Most harvesting done in India is manual in nature.

Intercropping of castor with other plants?

o Intercropping refers to growing more than one crop at the same place at the

same time. While crop rotation is done in a significant manner, there have not been any significant instances of intercropping in the context of castor.

What are the safety laws that are followed in the castor industry especially in

areas where people come in contact with the seeds and/or castor meal?

o Based on observations at castor farms and oil mills in India, no specific safety procedures have been found, except in cases where people come in direct contact with castor meal. Even in these cases, based on observations, it can be said that the safety precautions taken are only minimal.

Is spreading castor meal as fertilizer not a problem to those who spread it?

o In some cases, farmers use the castor meal as a fertilizer and in these cases

they spread the meal in the farms. From our interactions with the farmers, it can be said that there is no major risk for the person using the castor meal as a fertilizer, though it is advisable to wear safety gloves and any other protection required by law.

How resistant is the crop to salinity?

o The castor crop can grow in soils with a reasonable amount of salinity.

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What are the fertilizers commonly used for castor crop cultivation?

o The fertilizers used most commonly are Diammonium Phosphate and Urea.

Provide more details on castor meal as fertilizer

o It is used extensively as fertilizer. Countries that use castor meal as fertilizer

in a significant way are countries such as Korea, Taiwan etc. Is organic castor oil produced anywhere?

o Based on interactions CastorOil.in has had with vendors in the last few years,

it can be stated that few, if any, companies have made efforts to produce organic castor oil.

How is soil fertility maintained?

o The two primary activities understaken for soil fertility are the use of

fertilizers & crop rotation Is there a danger to the flora and fauna in the region owing to the toxicity of castor

beans?

o Castor beans need to be consumed in order for the toxicity to affect human benigs or animals. From our interactions and discussions with the castor oil industry professionals, there have been few, if any, cases of human or animal mortality owing to accidental consumption of castor beans.

What are the spacing recommendations for sowing castor?

o After the seedbed has been deeply cultivated, seeds in mechanized countries are planted 4 7.5 cm deep in rows 1 m apart; and about 50 cm apart within rows (some varieties can be planted just 25 cm apart).

o For unmechanized societies that prefer larger varieties, seeds are planted 60

by 90 cm apart, 2 4 seeds per hole, and then thinned to one plant.

Is direct sowing preferred for castor? If yes, how deep should we sow?

o Castor plant can be raised by direct sowing or by planting of nursery raised seedlings. In direct sowing, the seeds are usually planted in a row with a depth of 4-‐7 cm.

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What are the recommendations with regard to water management and irrigation

for castor cultivation?

o Castor is usually grown under rainfed conditions. However, it has been observed that it responds very well to irrigation. Castor, being a deep-‐rooted crop, can extract water from considerable depth in the soil. Irrigation may thus be relatively heavy and less frequent. For good yields, wherever possible two to three heavy irrigations may be given. In case of soil moisture deficiency at flowering stage, essentially one irrigation may be provided. In heavy rainfall areas proper drainage is essential.

o Furrow irrigation is preferred, but adoption of sub-‐irrigation has been found

to reduce weed problems.

When does the first flowering start for the castor plant?

o Flowering starts early in the life of castor. The first flowers normally open 4070 days after sowing.

When does the first harvest start for castor?

o The first harvest is on the 6th month and every other month thereon.

What are the average seed yields from the castor plant?

o Average seed yields range from 900 1000 kg/ha per annum under irrigated

conditions, but some states such as Gujarat have reported yields in excess of 5000 Kg/ha. The official data for India suggests an average yield of about 1000 kg of seeds per hectare per year.

What is the lifespan of the castor plant?

o For all commercial purposes, castor is an annual plant. Though it is a

perennial, it usually behaves as an annual in the temperate regions and its seed yield decreases significantly after the first year. As a result, the plant is used as an annual crop.

What is the average oil content in castor seed?

o The seeds contain about 48-‐50 percent oil by weight.

To what extent are inputs such as fertilizer, water, and pesticides are required for

the castor crop when compared to other energy and food crops?

o Castor crop requires significantly less inputs than many other energy and food crops. For instance, it requires only about half the amount of fertilizers

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required for sunflower (for a similar area) and less than 20% of fertilizers required for crops such as groundnuts or sorghum.

Are the seeds used for sowing of special grade/ variety, different from the seeds

harvested? If yes, what are these grades and what are the prices?

o The seeds that are used for sowing for the castor crop are different, and belong to the high yield variety (usually hybrid seeds).

SUMMARY Castor does well in the soil which is not fit for valuable commercial and food crops. It can be grown on a wide range of soils, provided they are fairly deep and well drained. However, to produce good yield, the plant requires, a minimum amount of water, fertilizer and maintenance. Average seed yields range from 900 1000 kg/ha under irrigation, though higher yields have been reported.

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6 -‐ Castor Oil End Uses This chapter comprises the following topics

Current End Uses for Castor Oil and Derivatives 6.1 o End Uses by Castor Oil Grade / Derivative 6.1.1 o Castor Oil & Castor Oil Derivatives Uses By Industry 6.1.2 o Use of Castor Oil in High-‐end Derivatives 6.1.3

Future Possible End-‐uses and End User Industries for Castor Oil and Derivatives 6.2 o Biopolymers and Castor oil -‐ 6.2.1 o Castor Oil as a Feedstock for Biodiesel 6.2.2 o Other Possible Future Uses 6.2.3

HIGHLIGHTS

Castor oil and its derivatives today find major application in soaps, lubricants, grease,

hydraulic brake fluids, paints, polymers, perfumery products, surfactants, surface coatings and inks, telecom & engineering plastics, pharma, rubber chemicals, polishes, flypapers, and cosmetic derivatives.

Companies such as BASF produce plastics from renewable resources which contains

about 60 per cent sebacic acid a derivative of castor oil.

Castor oil is increasingly finding application in the manufacture of polyurethane foams. The polyurethane is produced from polyols based on castor oil.

The world's largest single use of castor oil in one product, outside the lubricants

markets, is in the manufacture of polyamide 11 (Nylon 11). The commercially available polyamide made from castor oil is Arkema's (earlier Atofina) Rilsan Nylon 11.

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6.1 Current End Uses for Castor Oil & Derivatives Castor oil's application range is very wide. From the attractive uses such as cosmetics to the areas of national security involving engineering plastics, jet engine lubricants and polymers

industry. The chemical structure of castor oil affords a wide range of reactions to the oleochemical industry and the unique chemicals that can be derived from it. Some of these derivatives are on par with petrochemical products for use in several industrial applications. In fact, they are considerably superior since they are from renewable sources, bio-‐degradable and eco-‐friendly. Castor oil and its derivatives today find major application in soaps (bind ingredients in cosmetic and soap formulas, humectant for soap products), lubricants (jet engine lubricants), grease, hydraulic brake fluids, paints (varnishes ), polymers (basic ingredient in the production of nylon 11, nylon 6-‐10, polyurethanes), perfumery products, surfactants, surface coatings and inks, telecom & engineering plastics (polyamide 11), pharma, rubber chemicals, polishes, flypapers, in addition to other chemical derivatives and medicinal, pharmaceutical and cosmetic derivatives.

-‐wise Castor Oil Consumption by End-‐use Industry

Industry Percentage Soaps 30 Paints 40 Lubricants & Derivatives 30 Total 100

Source: based on data from 2005 to 2007; of the total consumption of about 85000 T per year, soaps, paints and lubricants industries consume approximately 25000 T, 35000 T and 25000 T respectively. 6.1.1 End Uses by Castor Oil Grade / Derivative Blown Castor Oil Blown castor oil is a potential replacement for phthalates and is used primarily as a plasticizer for lacquers, inks, adhesives, hydraulic fluids and leathers. Castor oil has been long used as a plasticizer for celluloid and in lacquers but the blown oil has been discovered to perform better. Sulfonated Castor Oil Sulfonated castor oil is castor oil that has been treated so that it is fully dispersible in water, thus making it perfect for bath oil products. Also called Sulfated castor oil and Turkey Red

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Oil, it was the first synthetic detergent after ordinary soap. It is also used in formulating lubricants, softeners, and dyeing assistants. Being an anionic surfactant, it is an active wetting agent (a chemical agent capable of reducing the surface tension of a liquid in which it is dissolved). As such, it is used extensively in dyeing and in finishing of cotton and linen. Generally, the ability of castor oil and some of its derivatives to wet surfaces make them useful as excellent carriers of pigments and dyes. It is of medium viscosity and is usually used in bath oil recipes along with fragrance or essential oils, or in shampoos. It is the only oil that will completely disperse in water. It is a surfactant and therefore makes a wonderful base for bath oil as it mixes well with water, producing a milk bath. For instance, it is used to emulsify essential oils so that they will dissolve in other water-‐based products or for super-‐fatting liquid soap if you want the soap to remain transparent. This means that the oil will combine with the water in the tub, and not leave those little oil bubbles floating on the top of the water. Sulfonated castor oil is also used in agriculture as organic manure, in paper industry for defoaming, in pharmaceuticals as undecylenate, in paints, inks and in lubricants. Alternatives to sulfonated castor oil Recent research has shown that, on sulfonation to the hydroxyl group, long-‐chain alkyl ricinoleates produce surface-‐active compounds. Tetradecyl ricinoleate, for instance, shows the best surface-‐active behavior and seems to be much better than that of sulfonated castor oil. Urethane Grade Castor Oil Urethane Grade Castor Oil is a refined grade of castor oil for specific applications that require minimum moisture. Typical applications include use in making urethane coatings, adhesives and inks. This grade also finds use in urethane blowing and urethane molding. BP Grade Castor Oil This grade is used in pharmacy & medicinal applications in Great Britain European Pharmacopia Grade European Pharmacopia Grade refers to the castor oil specifications as laid down by the European Pharmacopia standards. This grade is used in pharmacy & medicinal applications in the European Union.

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Castor Oil USP Castor Oil USP Grade refers to the castor oil prepared in conformity with the USP norms. It is the grade used by the pharmaceutical industry in the USA. First Pressed Degummed Grade Castor oil that is first pressed, filtered and then degummed has the unique lubricating properties of castor without the excessive buildup and carbon. This grade is hence used in the lubricant industry in a significant manner. Dehydrated Castor Oil DCO can be used to improve the quality of house paints, enamels, caulks, sealants and inks. It is used as primary binder for house paints, enamels, caulk sealant, and making varnishes. This oil also works well in clear varnishes and hard finish coatings. By far the most important coatings use of castor oil is in the form of dehydrated castor. In commercial manufacture of dehydrated castor oil, the aim is to produce the most valuable material for use as a drying oil. Dehydrated castor oil is now recognized as an individual drying oil with its own characteristic properties and advantages. The drying oils owe their value as raw materials for decorative and protective coatings to their ability to polymerize

abrasion resistance films. The advantages claimed in surface coating applications include excellent odor and heat bleachability, good drying properties, more uniform polymer structure, and lack of after-‐yellowing. DCO has advantages over tung oil because it is non-‐yellowing. DCO can be converted to dehydrated castor fatty acid by hydrolysis and distillation. This (dehydrated castor fatty acid) is used in the manufacture of alkyd resins, coatings, appliance finishes, primers and inks. Alkyd resins in turn are used for paints, enamels, lacquers and varnishes with high gloss, good adhesion and wetting qualities. The vulcanization of DCO with sulphur has been reported: factice, the resulting product, has been found to be a rubber additive with anti-‐ozonant and good flow properties. If DCO is epoxidized, the product can be evaluated in poly (vinyl) compounds as a plasticizer/stabilizer giving rise to the possibility that epoxidized castor oil may be capable of replacing epoxidized soybean oil. Ethoxylated Castor Oil

Ethoxylated castor oil is a nonionic surfactant having many industrial applications. Used in polymer coating applications

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Used in the wool scouring industry, as it is an excellent cleaning agent for grease and oil

Used in corrosion lubricants HCO Hydrogenated castor oil (HCO) or castor wax is a hard, brittle wax that is insoluble. It is produced by adding hydrogen in the presence of a nickel catalyst. Hydrogenation of castor oil accounts for the largest single use of castor oil for a standard commodity. The HCO is insoluble in water and most organic solvents, but it is soluble in hot solvents. It is water resistant while retaining lubricity, polarity and surface wetting properties. It is this insolubility that makes HCO valuable to the lubricants markets. It is perfect for metal drawing lubricants and multipurpose industrial greases. Thus it is no surprise that HCO is mainly used for coatings and greases where resistance to moisture, oils and other petrochemical products is required. The early use of HCO in greases was to improve texture and oxidative stability of greases exposed to high sheer stress with little effect on structure or consistency. HCO made its debut in greases as a replacement for traditional soap thickeners, sodium, potassium and calcium. Hydrogenated castor oil is also utilized in the manufacture of waxes, polishes, carbon paper, candles and crayons. In addition, it finds use in cosmetics, hair dressing, ointments, and in the preparation of hydroxyl-‐stearic acid and derivatives. Sometimes, HCO is used as a paint additive, pressure mould release agent in the manufacture of formed plastics and rubber goods. Some new uses of HCO: HCO based rheology modifiers see the web page -‐ http://www.crayvallac.com/inks/download/Castor_Wax_Tec_Bulletin.PDF 12-‐HSA 12 HSA is used in grease manufacture, plastics lubrication and as a raw material for the synthesis of more complex chemicals. It is used as a high hydroxyl castor based wax, as a wax ingredient. When reacted with an ester, 12 HSA provides a hard finish for the automotive and small appliance industries. Both HCO and 12 HSA have enjoyed popularity with the growth of lithium complex greases, which are growing to be the largest segment of the grease market. These greases have excellent heat tolerance like the sodium greases and the water resistance of calcium greases. The addition of 12 HSA enhances the overall performance with better texture, improved heat stability and improved dropping points. It simplifies the grease manufacturing process because it no longer requires milling and homogenization steps that were normally used with lithium type greases.

http://www.crayvallac.com/inks/download/Castor_Wax_Tec_Bulletin.PDF

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12 HSA soaps are used in mineral oil-‐based multipurpose greases making it possible for grease to fill the requirements of a variety of needs in the automotive and truck greases. In cosmetics: 12 HSA may be used for gelling liquid petroleum to produce brilliance. It may be incorporated into cold creams and vanishing creams to give a jelly-‐like feeling. In paints: 12-‐HSA is reacted with acrylic esters to produce hard, durable thermosetting polymers used in high-‐quality automotive, industrial appliance and metal decorative finishes. In rubbers: 12-‐HSA functions as an activator and internal lubricant for natural and synthetic rubbers. Undecylenic Acid Undecylenic acid has a long history as antifungal drug. It is used to treat some types of fungus infections. Undecylenic acid is a natural fungicide and is FDA approved in over-‐the-‐counter medications for skin disorders or problems. It is the active ingredient in medications for skin infections, and relieves itching, burning, and irritation. For example, it is used against fungal skin infections such as athlete's foot, ringworm, and Candida albicans. It is also used in the treatment of psoriasis. Most organic fatty acids are fungicidal and have been used for centuries as antimicrobial agents, originally in the manufacture of soaps. In the last 50 years, however, they have found use both in vitro as yeast and mold inhibitors in food stuffs, and as topical and systemic antifungals. Undecylenic acid is an economical antifungal agent and is the active ingredient in many topical over-‐the-‐counter antifungal preparations. Undecylenic acid has been shown to be approximately six times more effective as an antifungal than caprylic acid, and is effective in maintaining a healthy balance of intestinal and vaginal flora. When undecylenic acid is treated with hydrogen bromide in a non-‐polar solvent in the presence of peroxide, reverse Markownikoff addition occurs and the main product is x-‐bromoundecanoic acid. The product is then treated with ammonia to give x-‐aminoundecanoic acid, which is a crystalline solid. Aminoundecanoic acid is the starting material for nylon-‐11. Related Chemical Reactions (CH2=CH(CH2)8COOH) Undecylenic Acid HBr BrCH2.CH2(CH2)8COOH BrCH2.CH2(CH2)8COOH NH3 H2N(CH2)10COOH (w-‐Aminoundecanoic Acid) Specific applications of undecylenic acid:

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An active ingredient in many topical over-‐the-‐counter antifungal preparations like the (tinea pedis), diaper rash, and effective against denture stomatitis and herpes. Several studies have demonstrated that undecylenic acid is 4-‐5 times as powerful an antifungal agent as caprylic acid in the same dosage.

Undecylenic acid and its derivatives have a bi-‐functionality: surfactant as well as natural bio-‐resistance properties.

Biocide in soaps and deodorants Surfactant in hair lotions. Starting material for Nylon-‐11 Malodorous/foul smelling paper mill effluents can also be deodorized by treating

them with an effective deodorizing amount such as an alkyl or polyoxyalkylene ester of undecylenic acid, for example methyl undecylenate or polyoxyethylene undecylenate.

Malodorous animal feeds can be deodorized by treating them with an effective foodstuff deodorizing amount of polyoxyalkylene ester of undecylenic acid.

There are instances where malodorous liquid animal manures & sewage sludges are deodorized by treating the sample with a polyoxyalkylene ester of undecylenic acid.

Biochemistry and Pharmacokinetics for Undecylenic Acid Wyss et al demonstrated more than 50 years ago that the greater the number of carbon atoms in the fatty acid chain, the greater the fungicidal activity, up to the point exceeding eleven carbon atoms, where solubility becomes the limiting factor. Although the fungistatic and fungicidal effects of fatty acids have been well documented, they can be somewhat irritating to mucous membranes in certain people, and commonly used fatty acids such as caprylic and undecylenic acids have an objectionable taste and odor. Consequently, the calcium, magnesium, and sodium salts of these fatty acids have been offered as reasonable alternatives. Undecylenate salts have been shown to possess as much as four times the fungicidal effect of undecylenic acid, and may be over 30 times more effective than caprylic acid. Unfortunately, the antifungal effects of these fatty acid salts are more sensitive to pH than the free fatty acids. When tested over a pH range from 4.5 to 6.0, the antifungal activities of both undecylenic acid and calcium undecylenate are quite pronounced; the minimal inhibitory concentration of calcium undecylenate against Candida albicans is 200 ppm at pH 6.0. However, above pH 6.0, the calcium salt is less active than the free acid, perhaps due to the suppression of ionization of the salt at higher pH levels. Mechanism of Action At least one of the mechanisms underlying its anti-‐fungal effect is its inhibition of morphogenesis of Candida albicans. In a study on denture liners, undecylenic acid in the liners was found to inhibit conversion of yeast to the hyphal form. Hyphae were associated with active infection. The authors speculated on possible mechanisms including interference with fatty acid biosynthesis, which can inhibit germ tube (hyphae) formation. Medium-‐chain fatty acids have also been shown to disrupt the pH of the cell cytoplasm by being proton carriers.

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Undecylenic Acid for Specific Clinical Applications Vaginal/Gastrointestinal Candidiasis -‐ Undecylenic acid has been shown to be effective in preventing fungal overgrowth associated with vaginal and gastrointestinal candidiasis via its fungicidal activity. Thrush -‐ Since undecylenic acid acts systemically, oral administration can inhibit or even prevent oral candidiasis, or thrush. Dermatomycoses -‐ Undecylenic acid is the active ingredient in Desinex[R] cream and a number of other over-‐the-‐counter antifungals. It is responsible for the antifungal effect of these medications against such organisms as Candida albicans, Trichophyton species, Epidermophyton inguinale, and Microsporum audouini. Herpes Simplex Infection -‐ Undecylenic acid has been shown to have antibacterial and antiviral properties in vitro and is effective topically against the herpes simplex virus in both animals and humans. Denture Stomatitis -‐ Candida albicans is a major cause of denture stomatitis, an inflammation of the tissues underlying dentures. The organism exists in two cellular morphologies -‐-‐ the round yeast form found in asymptomatic carrier states and the branching hyphal form found in active infections. Resilient liners are frequently used to treat denture stomatitis, and it has been demonstrated that liners containing undecylenic acid completely inhibited the conversion of the yeast form of Candida albicans to the hyphal form, thereby inhibiting proliferation of the yeast. Undecylenic Acid Minor Derivatives (Source: Arkema Inc)

Undecylenic Acid -‐ Ammonium Derivatives o Undecylenamidopropyl betaine: C11 betaine.

A very mild, active surfactant with a dual water and oil solubility. Especially suited to use in anti-‐dandruff shampoos. A good viscosity regulator.

Undecylenic Acid -‐ Ethanolamide Derivatives o Ethanolamide derivatives are both oil-‐ and water-‐soluble and hence can

easily be formulated: High water solubility and high surfactant properties for haircare uses.

Undecylenic Acid -‐ Undecylenamide MEA o Good fungicidal and bactericidal properties, that can be added to:

Shampoos and other products to provide foam stabilization, viscosity control...

Soaps to provide emolliency, firmness and fungicidal properties Pharmaceutical creams and oils where fungicidal properties are

important

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Bubble bath products and shampoos, especially anti-‐dandruff shampoos

Shaving creams and after-‐shave lotions.

Undecylenic Acid -‐ Undecylenamide DEA o Same applications as for undecylenamide MEA, and additionally, any use in

which increased water solubility is required Thickener and refatting agent for special formulations Foam stabilization and viscosity control of detergent formulations Suitable for foot and skincare preparations Additive for anti-‐dandruff shampoos.

Undecylenic Acid -‐ Sulfosuccinate Derivatives o Disodium Undecylenamido MEA-‐Sulfosuccinate

Contains the powerful solubilizing sulfonate group A very mild anionic surfactant both to skin and eyes recommended for

application in baby shampoos and cleaning creams for its good skin compatibility

Anti-‐dandruff activity: 2% active disodium mono-‐undecylenamido MEA-‐sulfosuccinate is effective in the reduction of itching, scaling and dandruff associated with seborrhea capitis.

Methyl 12-‐HSA Methyl 12-‐HSA is an ester that is efficient in extending the lubrication life of grease. Greases made with the product can be formulated to higher drop points, and they experience both less bleeding and improved oxidative stability .The development of these products was most beneficial in the grease processing area due to avoidance of milling and homogenizing, less shearing and overall uniform consistency. Methyl 12-‐HSA is usually sold in the liquid form and is widely used in the continuous grease process. It has a lower melt point than 12-‐HSA and is, therefore, easier to handle in the liquid form. Main Applications

Solid pigment dispersant for colour concentrates used in plastics, inks and coatings Mold lubricant and release agent in plastic extrusion, molding and calendaring Plasticizer -‐ coupling agent for hot melt adhesives and textile printing compounds Processing aid for rubber, plastics and polymers Used in high temperature greases

Heptaldehyde Undecylenic acid and Heptaldehyde are starting materials for a number of perfumery compounds & for flavours and fragrances

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Uses o Chemical intermediates for perfumes and flavours o Used in perfumery in the form of compounds jasmine aldehyde (alpha amyl

cinnemic aldehyde) and coconut aldehyde o Also used in the manufacture of heptyl alcohol, heptonoic acid etc., which

have subsequent usage in various industries o Used in rubber industry in the preparation of vulcanization accelerators o Used as solvent in rubber & plastics industries o Also used for emulsifiers & plasticizers o Heptaldehyde & undecylenic acid are used to make key aroma chemicals

used in perfumes. An important aroma chemical is undecylenic aldehyde, reportedly even used in Chanel perfumes.

Heptyl Alcohol

Used as chemical intermediates for:

Perfumes and flavours (with fruit taste) Polymer plasticizer

Used in toilet preparations and detergents. Undecanoic Acid

Used as chemical intermediates for perfumes/flavors, for instance, macrocyclic musks

Used to prepare ointments with dermatophilic activity. Undecylenic Aldehyde Undecylenic acid is an unsaturated carboxylic acid. Undecylenic aldehyde is used to formulate perfumes. Undecylenic aldehyde is one of the commonly used ingredients in perfumery. Its end applications include soaps, detergents, beauty care products & household products. Undecylenic Alcohol Undecylenic alcohol is a common ingredient in flavours and fragrances. Odour description: floral, ozone, waxy. Calcium Undecylenate Calcium undecylenate is the calcium salt of undecylenic acid. It is derived by the vacuum distillation of castor oil. The antifungal properties of medium chain fatty acid increase as the chain lengthens, and peak at 11.

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An 11 carbon mono-‐unsaturated fatty acid, calcium undecylenate is an extremely effective, broad-‐spectrum antifungal. Both zinc & calcium undecylenate salts are used as fungicides. The fungicidal effect of undecylenate salts have been shown to be four times higher than that of undecylenic acid. Calcium undecylenate is an extremely effective, well-‐tolerated, broad-‐spectrum antifungal. Topical calcium undecylenate is specifically used on the skin to treat fungus infections. Zinc Undecylenate Undecylenic acid and its zinc salts are used for the treatment and prevention of superficial fungus infections of the skin, primarily tinea pedis, as well as relieves itching, burning and irritation For both zinc and calcium undecylenate salts The fungicidal effect of undecylenate salts have been shown to be four times higher than with undecylenic acid.

Excellent skin bio-‐affinity due to their amphiphile structure. No side effects or adverse reactions with preparations containing undecylenic acid

and its zinc salt (formulations of foot powder with 20% ZnUDA and 2% UDA in talcum).

(Source: Arkema Inc)

Methyl Undecylenate Used as chemical intermediates for:

Cosmetics/pharmaceuticals Anti-‐odor formulations

Ethyl Undecylenate

Used as a flavouring agent Esterols Esterols are used in/for:

Bitumen emulsions (Esterol 11) Machining oils, due to their capacity to fix sulphur Metal working fluids (lubricity for anti-‐wear additive when sulfurized) Fat liquors for leather treatment Concrete mold release agents Grease and lubrication formulations Anti-‐foam agents

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Ricinoleic Acid Castor oil's effectiveness is probably due in part to its unusual chemical composition -‐ a triglyceride of fatty acids with almost 90 percent of that fatty acid content consisting of ricinoleic acid. Ricinoleic acid is not found in any other substance, and the high concentration of this unusual, unsaturated fatty acid is thought to be responsible for castor oil's remarkable healing abilities. Ricinoleic acid is shown to be synthesized in the immature castor bean seed only after 3-‐4 weeks from the time of fertilization. Synthesis occurs both in the isolated embryo and the endosperm. While known chiefly as a purgative a few decades ago, this fatty acid now affords a wide range of reactions enabling the formation of several derivatives. These chemicals are on par with petrochemical products for use in several industrial applications. Primary uses include, coatings, plastics, inks and cosmetics. Poly (anhydrides) is hydrolytically degradable polymers which have been used as

vehicles for controlled delivery of drugs. A new class of biodegradable polyanhydrides based on ricinoleic acid has been synthesized

Ricinoleic acid is effective in preventing the growth of numerous species of viruses, bacteria, yeasts, and molds. It's successful as a topical treatment for ringworm, keratoses, skin inflammation, abrasions, fungal-‐infected finger-‐ and toenails, acne, and chronic pruritus (itching). Generally, for these conditions the affected area is wrapped each night in a castor oil-‐soaked cloth. Ricinoleic acid is used also as a bactericide. Hence, washing wounds with ricinoleic acid at prescribed dilution levels is sometimes recommended.

Ricin acts as a blood coagulant Macrolactones and polyesters can be derived from ricinoleic acid Ricinoleic acid has been used in contraceptive jellies Used in soaps, amine compounds, esters in cutting oils, industrial lubricants, emulsifiers,

metal working compounds. Ricinoleate soaps have been patented as algaecides for aquaculture systems. Used in dispersion of pigments and dyes. Used in resins, thermosetting acrylics and non-‐drying plasticizing esters. Quaternary ammonium compounds based on ricinoleates and hydroxy stearates have

been used in for cosmetics skin and hair care, personal products, germicides and textile processing agents.

Methyl Ricinoleate Alkyl ricinoleates and alkyl 12-‐hydroxy stearates such as methyl ricinoleate are

important ingredients in various cosmetics and toiletries Some microorganisms can transform methyl ricinoleate int -‐decalactone, a valuable

aroma compound Methyl ricinoleate has the potential to be used as a fuel additive to enhance the

performance of environmentally friendly fuels. As part of ongoing research efforts on

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biodiesel fuels, methyl ricinoleate has been tested as a potential lubricity additive for petroleum diesel.

Methyl ricinoleate is a low-‐temperature plasticizer for rubber polymers, and for epoxy resin systems

Zinc Ricinoleate The zinc salt of ricinoleic acid, zinc ricinoleate finds use in the deodorants industry as a sensitizer. Like a sponge, zinc ricinoleate traps and absorbs the odour molecules produced by skin bacteria. Zinc ricinoleate does not inhibit normal perspiration, and will not interfere with the natural flora of the skin. Instead, it so that they cannot be released into the atmosphere and cause the characteristic sweaty smell. In other words, it chemically binds unpleasant odorous substances in such a way that they are no longer perceptible. The precise mechanism of this process is not known. Based on some simulation studies, the following were observed: In the vacuum and oil phase structures, the Zn2+ ion is almost completely shielded by the oxygen ligands. Structural transitions are caused by the interaction of Zinc ricinoleate with water-‐solvent molecules, and this results in a weakening of the electrostatic shield. While Zinc ricinoleate is in aqueous solution, it is possible for the nucleophilic attack of odor-‐active compounds to the relatively unprotected Zn2+ atom. This results in a structural change, and this structural change, it is surmised, results in an increase of the solubility and adsorption activity of Zinc ricinoleate. Zinc ricinoleate is also used as a fungicide, emulsifier and stabilizer Sebacic Acid Sebacic Acid was named from the Latin sebaceus (tallow candle) or sebum (tallow) in

reference to its use in the manufacture of candles One of the largest uses of Sebacic Acid is in the manufacture of Nylon 6-‐10. Sebacic acid and

hexamethylene diisocyanate react through condensation polymerization to produce Nylon 6-‐10.

Sebacic Acid and its derivatives such as Azelaic acid have a variety of industrial uses in plasticizers, lubricants, hydraulic fluids, cosmetics, candles, etc. They are used in the synthesis of polyamide and alkyd resins. An isomer, isosebacic acid, has other applications in the manufacture of extrusion plastics, adhesives, polyesters, polyurethane resins and synthetic rubber.

Sebacic Acid is also used as an intermediate for aromatics, antiseptics and painting materials. A large number of esters can be obtained from thousands of potential starting materials.

It is used as a corrosion inhibitor in metalworking fluids and as a complexing agent in greases. When mixed with amines, Sebacic acid can give a very effective water soluble corrosion inhibitor for metal working fluids.

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Lithium hydroxystearate complex greases often utilize dibasic acids such as sebacic acid for the more unusual performance parameters. These greases require the esters of sebacic acid, which were developed for specific performance criteria under varying conditions. Examples: DOS (dioctyl sebacate) is very functional in low temperature formulations and DSS (disodium sebacate) has been used to replace sodium nitrites in aluminum greases. Its fine particle size allows it to be added to the grease during the cool down period with no additional processing. DMS/DBS (dimethyl sebacate/dibutyl sebacate) are synthetic base stocks that can replace the mineral oils for environmentally friendly applications. DOS or DMS in complexed greases improve workability and low temperature properties particularity for applications in aircraft, trucks, automobiles and equipment exposed to arctic conditions.

The esters of sebacic acid also are used as plasticizers for vinyl resins and in the manufacture of dioctyl sebacate -‐ a jet lubricant and lubricant in aircooled combustion motors.

Two derivatives of sebacic acid are used in a range of applications as well. Dibutyl Sebacate (DBS) -‐ Di-‐n-‐bibutyl Sebacate (DBS), is a transparent oil liquid, dissolves ethanol and ether. This product is widely used as rocket propellant. Being non-‐toxic, used in food & pharma industry as packing material It is also used as cold resistant plasticizer for synthetic resin and synthetic rubber. Dioctyl Sebacate (DOS) -‐ Dioctyl Sebacate (DMS) a transparent light yellow oil liquid with a distinct smell This product with low volatility and high-‐resistant, lightproof, and electrical insulation dissolve in hydracarbons, alcohol, ether, benzene and other organic solvents. It is mainly used by PVC, chloroethylene copolymer, nitrocellulose, ethyl cellulose and synthetic rubber industries as plasticizer and suitable for cold resistant cables, leatherette, thin film, sheet material, etc. Sebacic Acid Summary of Applications

Application sector Nature of application

Nylon Nylon 6,10 Plasticizer

Dimethyl sebacate Dioctyl sebacate Dibutyl sebacate Diisopropyl sebacate

Lubricant

Heat resistance lubricant oil Epoxy solidified agent Sebacic anhydride Synthetic lubricating grease

Derivatives

Azelaic acid Isosebacic acid(Isomer)

Miscellaneous Perfumery Pharmaceuticals

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2-‐Octanol

2-‐Octanol is the main raw material for some esters. It is used as a solvent, dehydrater and antibubbling agent

In coal industry, it is used as floatation agent; finds uses as a frother in mineral flotation.

In farming chemical industry too, it is used as floatation agent & for producing emulsifiers

In chemical fiber industry, it is used as fiber oil Used in producing the plastic plasticizer and synthetic perfume. The refined

derivative can be used to produce plasticizers such as dioctanol phthalate (DCP), dioctanol adipate (DCA).

It can be used as a possible alternate for 2-‐ethylhexanol or isooctyl alcohol in the preparation of diesters, monomeric and polymeric plasticizers.

The refined 2-‐Octanol is used as a raw material to produce caproic acid. In some countries the caproic acid is used to produce ethyl caproate -‐ a kind of flavor.

N-‐Heptanoic acid

n-‐heptanoic acid is used primarily:

in the form of esters: industrial lubricants (aviation, refrigeration, etc.), plasticizers for laminated glass, tracer for butter etc.

in the form of salts: for aqueous anticorrosion. as raw material for perfume, medicine and lubricating grease. as chemical intermediate in the synthesis of emollient agents:

o in personal care: propylene glycol diheptanoate & stearyl heptanoate o in pharmaceutical gel: neopentylglycol diheptanoate.

Allyl Undecyclenate

A white, water-‐soluble powder that decomposes above 200°C, it is used in cosmetics and pharmaceuticals as a bacteriostat and fungistat

Used in pet flea shampoo Glycerine Glycerine is used in cosmetics, foods, pharmaceuticals, and a variety of personal care and oral care products, as well as in other applications including animal seed, antifreeze and certain energy uses. Uses of glycerine by industry

Food and beverages -‐ Humectant, solvent, sweetener, and preservative. Pharmaceuticals -‐ Solvent, moistener, humectant, and bodying agent in tinctures,

elixirs, ointments, and syrups; plasticizer for medicine capsules; other uses include

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suppositories, ear infection remedies, anesthetics, cough remedies, lozenges, gargles, and carrier for antibiotics and antiseptics.

Cosmetics and toiletries -‐ Humectant, vehicle, and emollient in toothpaste, skin creams and lotions, shaving preparations, deodorants, and makeup.

Tobacco -‐ Keeps tobacco moist and soft to prevent breaking and crumbling during processing; ensures freshness in packaged cigarettes and other tobacco products.

Surface coatings -‐ Used in the manufacture of alkyd resins, which are important components of surface coatings.

Paper and printing -‐ Plasticizer, humectant, and lubricant in the manufacture of paper; used with other ingredients in specialty treatments such as grease-‐proofing; alkyd resins also an important constituent of many printing inks.

Lubricants -‐ Because of its nontoxic character, used in lubricants for food and other machinery where product purity is essential.

Textiles -‐ Conditioning agent used widely in lubricating, sizing, and softening yarn and fabric; lubricates many kinds of fibers in spinning, twist setting, knitting, and weaving operations.

Rubber and plastics -‐ Lubricant and plasticizer for plastic. Urethane polymers -‐ Fundamental chemical component of polyethers for urethane

foams. Electrical and electronics -‐ Widely employed in manufacturing electrolytes for

electrolytic condensers, which are used in radios and neon lights, and in processes for electrodeposition and treatment of metals.

Nitration -‐ Used to make nitroglycerine, which is the usual explosive in dynamite and a cardiovascular agent.

6.1.2 Castor Oil & Castor Oil Derivatives Uses By Industry Castor oil has over 1000 patented industrial applications. It is used in the following industries: automobile, aviation, cosmetics, drug, electrical, electronics, food, manufacturing, plastics, and telecommunications. Details of industry used in & the castor products used in that industry. Agriculture Used in

a. Fertilisers Organic Fertilisers Castor Products & Derivatives Used

a. Castor Meal Food Food grade castor oil is used in additives, flavorings, candy (e.g., chocolate), as a mold inhibitor, and in packaging. Cremophor, also known as polyoxyethylated castor oil, is also used in the foodstuff industry.

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Used in a. Surfactants b. Viscosity Reducing Additives c. Flavourings d. Food Packaging

Castor Products & Derivatives Used

a. Food Grade Castor Oil b. Polyoxyethylated Castor Oil

Textile Chemicals Used in

a. Textile Finishing Materials b. Dyeing Aids c. Nylon, Synthetic Fibers & Resins d. Synthetic Detergents e. Surfactants, Pigment Wetting Agents


a. Ethoxylated Castor Oil b. Sulfonated Castor Oil / Turkey Red Oil c. Methyl 12-‐HSA

Paper Used in

a. Flypapers b. Defoamer c. Water Proofing Additive d. Paper Coatings


a. Methyl 12-‐HSA b. Glycerine

Plastics & Rubber Used in

a. Polyamide 11 (Nylon 11) b. Polyamide 6 c. Polyurethane Foam d. Plastic Films e. Adhesives f. Synthetic Resins g. Plasticizers h. Coupling Agents

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i. Polyols Castor Products & Derivatives Used

a. 12-‐HSA b. Heptaldehyde c. Ricinoleic Acid d. Methyl Ricinoleate e. Sebacic Acid f. Undecylenic Acid g. Glycerine

Cosmetics & Perfumeries Castor oil and derivatives are used in soaps, creams (tretinoin), shampoos, perfumes, lip gels, lipsticks, hair oil's (increases hair luster), deodorants, lubricants, sunscreens, and many other personal hygiene and beauty products. Castor oil has been used in skin care products for centuries, and continues to play an important part in the production of soaps and cosmetics. Cosmetic manufacturers use castor oil and its derivatives in formulating non-‐comedogenic cosmetics (cosmetics that don't exacerbate or contribute to acne) and emollients (softens). Undecylenic acid is also used in cosmetics and is the active ingredient in over-‐the-‐counter medications for skin infections and relieves itching, burning, and irritation. Used in

a. Perfumery Products b. Lipsticks c. Hair Tonics d. Shampoos e. Polishes f. Emulsifiers g. Deodorants


a. Castor Oil b. Castor Oil Esters c. Undecylenic Acid d. Castor Wax e. Zinc Ricinoleate f. Heptaldehyde g. Heptanoic Acid h. Undecylenic Acid i. Heptyl Alcohol j. Ethyl Heptoate k. Heptyl Acetate

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Electronics & Telecommunications Used in

a. Polymers for Electronics & Telecommunications b. Polyurethanes c. Insulation Materials


a. Castor Oil Esters b. Polyols

Pharmaceuticals Used in

a. Antihelmintic b. Antidandruff c. Cathartic d. Emollient e. Emulsifiers f. Encapsulants g. Expectorant h. Laxatives & Purgative i. Additives & Excipients


a. Glycerine b. Undecylenic Acid c. Zinc Undecylenate d. Enanthic Anhydride e. Calcium Undecylenate f. Hydrogenated Castor Oil

Paints, Inks & Additives Used in

a. Inks b. Plasticizer for Coatings c. Varnishes d. Lacquers e. Paint Strippers f. Adhesive Removers g. Wetting & Dispersing Additives


a. Polyols b. Glycerine c. Dimer Acid

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d. Ricinoleic Acid e. Castor Oil f. Dehydrated Castor Oil (DCO)

Lubricants Vegetable oils, due to their good lubricity and biodegradability are attractive alternatives to petroleum-‐derived lubricants, but oxidative stability and low temperature performance limit their widespread use. Castor oil has better low temperature viscosity properties and high temperature lubrication than most vegetable oils, making it useful as a lubricant in jet, diesel, and race-‐car engines. Castor oil is the preferred lubricant for bicycle pumps, likely because it doesn't dissolve natural-‐rubber seals. Castor oil is also one of the preferred lubricants for model aircraft. The lubricants company Castrol took its name from castor oil. For most of the lubrication purposes, the degummed variety of castor oil is the preferred grade. Used in

a. Lubricating Grease b. Aircraft Lubricants c. Jet Engine Lubricants d. Racing Car Lubricants e. Hydraulic Fluids f. Heavy Duty Automotive Greases g. Fuel Additives h. Corrosion Inhibitors


a. Dimer Acid b. Ricinoleic Acid c. Castor Oil Esters d. Blown Castor Oil e. Heptanoic Acid f. Hydrogenated Castor Oil g. Hydroxy Amide Waxes h. 12 Hydroxy Stearic Acid i. Sebacic Acid j. Ethoxylated Castor Oil

Bio-‐fuels Castor oil, owing to its chemical structure can be used as a bio-‐fuel in place of petrol-‐based fuels. Biotransformation of vegetable oils through the use of enzymes as catalysts has been a matter of intense investigation nowadays. Furthermore, the possibility of using biodiesel as an additive to mineral diesel, to result in a sulfur-‐free, with a higher-‐cetane number fuel

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from a renewable resource has motivated the biomodification of vegetable oils towards the reduction of environmental investments and import needs. Other End Products Where Castor Oil & Derivatives are Used Sealants Components for Shatterproof Safety Glass Embalming Fluid Metallic Salts Since it is has a relatively high dielectric constant (4.7), highly refined and dried castor oil

is sometimes used as a dielectric fluid within high performance high voltage capacitors. Castor based benzoate esters -‐ Castor-‐based benzoate esters, including benzoate esters

of castor oil, benzoate esters of hydrogenated castor oil, benzoate esters of cetyl ricinoleate, and benzoate esters of octyl hydroxy stearate are used in a number of industries. These benzoate esters of ricinoleic acid and hydroxy stearic acid are double esters having a fatty acid group at the respective -‐-‐COOH group and a benzoate group at the -‐-‐OH group. These esters are useful as vehicles or carriers, emollients or solubilizers for toiletry, cosmetic, hair and skin care formulations.

One of the key ways of using castor oil is to produce conjugated linoleic acids (CLAs). There is growing interest in these molecules, due to their nutritional and therapeutic properties. Of the many ways of producing synthetic CLAs, the most attractive is chemical conversion of castor oil, which is rich in ricinoleic acid (a hydroxylated fatty acid), by simple dehydration of the acid. This is a direct way of producing triglycerides, the natural matrix of fats and oils. Converting crude CLA-‐rich castor oil should be possible on an industrial scale, near production sites.

Medicinal Uses of Castor Oil The United States Food and Drug Administration (FDA) has categorized castor oil as "generally recognized as safe and effective" (GRASE) for over-‐the-‐counter use as a laxative, with its major site of action the small intestine. Therapeutically, modern drugs are rarely given in a pure chemical state, so most active ingredients are combined with excipients or additives. For instance, Cremophor EL is a registered trademark of BASF Corp. for its version of polyethoxylated castor oil. It is prepared by reacting 35 moles of ethylene oxide with each mole of castor oil. Cremophor EL is a synthetic, nonionic surfactant. Its utility comes from its ability to stabilize emulsions of nonpolar materials in aqueous systems. Cremophor EL is an excipient or additive in drugs. Therapeutically, modern drugs are rarely given in a pure chemical state, so most active ingredients are combined with excipients or additives such as Cremophor EL Castor oil, or a castor oil derivative such as Cremophor EL, is added to many modern drugs, including:

Miconazole, an anti-‐fungal agent

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Paclitaxel, a mitotic inhibitor used in cancer chemotherapy Sandimmune (cyclosporine injection, USP), an immunosuppressant drug widely used

in connection with organ transplant to reduce the activity of the patient's immune system

Nelfinavir mesylate, an HIV protease inhibitor Saperconazole, a triazole antifungal agent (contains Emulphor EL -‐719P, a castor oil

derivative) Prograf, an immunosuppressive drug (contains HCO-‐60, polyoxyl 60 hydrogenated

Castor oil) Xenaderm ointment, a topical treatment for skin ulcers is a combination of Balsam

Peru, Castor oil, and trypsin Aci-‐Jel, a gel used to create or maintain the acidity of the vagina (comprises acetic

acid/oxyquinoline/ricinoleic acid vaginal) Polyethylene glycol (PEG): Peg-‐40 is a hydrogenated Castor oil used in pegylation.

Pegylation is now an established method for increasing the circulating half-‐life of protein and lipsomal pharmaceuticals. Pegylation agents are beneficial for patients with cancer.

Emulphor: A polyethoxylated castor oil drug vehicle. Taxol (paclitaxel) Sandimmune (cyclosporine injection, USP) Diazepam injection; superseded by lipid emulsion alternative (Diazemuls) Vitamin K injection

Anti-‐cancer Drugs

An obstacle to successful chemotherapy and cancer treatment is multidrug resistance (MDR). Cremophor from castor oil is a chemomodulator and a MDR reversing agent used in anti-‐cancer drugs.

Teniposide (VM-‐26) has been widely used in the treatment of small cell lung cancer, malignant lymphoma, breast cancer, etc., and the main ingredient of VM-‐26 solvent (vehicle) is PECO (Cremophor).

Cremophor minimizes the negative effects of radiation chemotherapy. Cremophor EL is a Castor oil surfactant used as a vehicle for formulation of a variety

of poorly water-‐soluble agents, including paclitaxel. The efficacy of paclitaxel against some tumors may be aided by its administration in a vehicle solution containing Cremophor.

Fulvestrant is a pure antiestrogen. In in vivo and in vitro breast cancer models, fulvestrant has anticancer activity at least as good as tamoxifen, and is superior to tamoxifen in some models. Fulvestrant requires intramuscular administration in a proprietary formulation of Castor oil and alcohols.

Antifungal Drugs

Undecylenic acid is the active ingredient in over-‐the-‐counter medications for skin infections, and relieves itching, burning, and irritation. For example, it's used against fungal skin infections (mycosis) such as athlete's foot, ringworm, candida albicans, etc. It's also used in the treatment of Psoriasis. Undecylenic acid also has anti-‐

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bacterial and anti-‐viral properties that are effective on viral skin infections such as the herpes simplex virus, cold sores, warts, etc.

Cutaneous alternariosis treated with miconazole and 10 ml of Cremophor EL. Heart & Blood Pressure Drugs

Digoxin with Cremophor helps the heart and is used to treat certain heart conditions. The diluent Cremophor contributes to the antiproliferative effects of the taxane

paclitaxel Human Immunodeficiency Virus (HIV) Protease Inhibitors

Saquinavir (SQV) with Cremophor is a HIV specific protease inhibitor. Organ Transplant Drugs

Cyclosporin is considered to be the best immunosuppressive molecule in transplantation (10A) and it gets help from its vehicle Cremophor.

Use of Castor Oil to Encourage Onset of Labour Castor oil has a long history of being used by women to encourage the onset of labour during pregnancy. It is thought to act in one of several possible ways. By creating strong and spasmodic cramps of the intestines (which lie around and above the uterus at the end of pregnancy) it might cause a reflexive cramping and spasms of the uterine muscle, which might then turn into labor. It might also work by having a dehydrating effect, which causes uterine irritability and then labour. It could also encourage the onset of labour by stimulating the release of prostaglandins from the inflammation of the intestines. And, lastly, it may have no real connection to the onset of labor at all, and be merely an unpleasant placebo. While the effectiveness of castor oil to encourage the onset of labor is scientifically questionable, it is generally considered safe, although there are some who believe that it increases the risk of meconium passage in the infant. This application of castor oil has not been well studied surprising considering how long this old remedy has been in use. 6.1.3 Use of Castor Oil in High-‐end Derivatives There are a few companies that use castor oil to develop a range of derivatives. Some prominent companies and their use of castor oil derivatives are given below: Arkema Main Line of Business: Industrial and speciality chemical company Corporate Headquaters: Cedex, France

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Background: Arkema is made up of three business segments; Vinyl Products, Industrial Chemicals and Performance Products. It is present in over 80 countries with 13,800 employees and sales of around Euro 4.4 billion (2010) The vinyl products unit includes chlorine/soda and PVC, vinyl compounds and pipes and profiles (Alphacan). Industrial chemicals business is involved in acrylics, polymethyl methacrylate (PMMA), thiochemicals, fluorochemicals and hydrogen peroxide. Performance products unit is involved in technical polymers, additives, speciality chemicals (Ceca), and organic peroxides. Castor Oil End Use: Nylon 11 Polyamide 11 (PA 11) or Nylon 11 is a polyamide bioplastic and is produced by Arkema under the tradename Rilsan from castor beans. Pebax® stands for polyether block amide. This high durability thermoplastic elastomer, is partially made from non-‐edible renewable resource, castor oil, Pebax® is plasticizer free and belongs to the engineering polymers family. The pebax® range enables to bridge the gap between thermoplastics and rubbers. Pebax® Rnew is made up of block copolymers consisting of a sequence of polyamide 11 and polyether segments. It can be used pure, as an additive or in blends with other polymers or rubbers. It can also be reinforced with various fillers. Arkema also uses many alcohols, acids and other by-‐products of the Rilsan® and Pebax Rnew® manufacturing processes, which can be used by the perfumes and cosmetics, food, pharmaceutical or leather industries. Rilsan® PA resins have earned a preferred material status in the most demanding applications due largely to their excellent combination of thermal, physical, chemical and mechanical properties resulting in an outstanding cost performance ratio. Processing ease is another major benefit of Rilsan® polyamide resins. Supplied in powder or pellet form, Rilsan® PA resins can be processed by injection molding, extrusion, blown film extrusion, extrusion blow molding or rotomolding. These properties have led designers to select Rilsan® polyamides for industries as diverse as electrical cables, automotive, and pneumatic and hydraulic hose. Here's a detailed page (PDF) on Rilsan PA 11 properties and specifications, and comparisons with other polymers for specific applications http://www.solarplastics.com/solarplastics/client/materials_pdf/Elf_Atofina_Nylon_11-‐12_pro.PDF

Prominent users of Arkema : SCARPA, Mizuno, Smith Optics.

Pebax Rnew® to manufacture its sports equipment. Arkema and Scarpa Research & Development teams have closely collaborated on the design of a ski boot more eco-‐aware: the Scarpa Hurricane.

http://www.solarplastics.com/solarplastics/client/materials_pdf/Elf_Atofina_Nylon_11-12_pro.PDF

http://www.solarplastics.com/solarplastics/client/materials_pdf/Elf_Atofina_Nylon_11-12_pro.PDF

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This prototype was presented at the ISPO 08 and it was the first biobased ski boots of the market. MIZUNO, a leader in running footwear and apparel technology, has announced the use of the Inspire 5, Wave Creation 10, and Wave Nirvana 5. Smith Optics, an eyewear manufacturing company has unveiled new sunglasses collection that uses Rilsan® Clear G830 Rnew. A total of 20 newsunglass frame models are made entirely of Rilsan® Clear G830 Rnew, a bio-‐renewable sourced polymer derived from castor oil.

Sony has leveraged its expertise in material research to make a unique soccer ball built to ains, in which Pebax® Rnew is used. This ball features a dual

layered surface, one of them being in Pebax® Rnew, which brings 1.6 times higher durability than conventional soccer balls. These footballs will be distributed by NGOs -‐ UNDP (United Nations Development Programme) and JICA (Japan International Cooperation Agency) -‐ during and after the 2010 World Cup.

Website: www.arkema.com BASF Main Line of Business: Chemical Company Corporate Headquarters: New Jersey, USA

Background: six Verbund sites and close to 385 production sites worldwide serves customers and partners in almost all countries of the world.

In 2009, BASF posted .7 billion and income before special items of approximately .

The BASF portfolio comprises:

Chemicals Plastics Performance Products Functional Solutions Agricultural Solutions Oil & Gas

Castor Oil End Use: Ultramid® BALANCE, Poly etherol BASF produces the following two products from castor oil: Ultramid® BALANCE, a polyamide 6.10. This is based to the extent of about 60 per cent on sebacic acid, a renewable raw

http://www.arkema.com/

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material derived from castor oil. This established and now revitalized material combines product properties such as good lowtemperature impact resistance with a relatively low density for a polyamide, which in automotive construction, for example, allows savings in weight, associated costs and emissions. Besides Ultramid®, BASF and Elastogran research and development experts have succeeded in the development of a poly etherol made of castor oil, is called Lupranol® BALANCE 50 It is the only NOP that can be used as a 100% drop-‐in for any other conventional slab polyol. Lupranol Balance 50 is based on a content of 31 % castor-‐oil. This means that up to 25 per cent of the weight in the polyure thane slabstock foam can be replaced with renewable resources. A large part of this biomass is used in the production of Mattresses by Elastogran. Mattresses made up of almost 25% renewable raw material. The new product is made up of 31% castor oil. A finished mattress made with Lupranol® BALANCE contains up to 24% by weight of castor oil, without impairing the performance of the foam. This very high percentage of renewable raw material in the finished product is a breakthrough in the realm of polyurethane base products. Website: www.basf.com Rhodia Main Line of Business: Specialty Chemical Producer Corporate Headquarters: Boulogne-‐Billancourt, Paris. Background: Rhodia develops and produces specialty chemicals. It provides added-‐value products and high-‐performance solutions to diversified markets, including automotive, electronics, flavors and fragrances, health, personal and home care, consumer goods and industrial, through its six global enterprises. Rhodia currently generates thirty one percent of its sales with products that respond to the desire of customers and consumers for sustainable solutions. Castor Oil End Use: Nylon 6/10, Technyl® eXten In Nov 2009, Rhodia SA introduced a new nylon 6/10 range of materials made in part from castor oil.

significant reduction in the environmental impact related to its production from raw materials of plant origin (i.e. a 50% reduction in greenhouse gas emissions).

-‐performance alternatives, specifically suited to the manufacture of flexible tubes for the power-‐assisted control systems market and fittings and adapters for the engine fuel systems market.

http://www.basf.com/

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In April 2010, Rhodia announced the launch of Technyl® eXten using polyamide 6.10, produced in part from castor oil. Technyl® eXten has has a higher level of performance than conventional engineering plastics. It has also reduced carbon footprint: the production of a ton of this product requires 20% less non-‐renewable resources than the production of a ton of conventional polyamide with equivalent performance properties. According to the company, Technyl®eXten, is already helping Rocket Electric Co. Ltd. one

increase the service life of its AA and AAA ranges of alkaline batteries by up to 50%. Website: www.rhodia.com DSM Main Line of Business: A life sciences and materials sciences company Corporate Headquaters: Heerlen, Netherland Background -‐ Royal DSM N.V. creates solutions that nourish, protect and improve performance. Its end markets include human and animal nutrition and health, personal care, pharmaceuticals, automotive, coatings and paint, electrical and electronics, life protection and housing. DSM has annu22,700 people worldwide. The company is headquartered in the Netherlands, with locations on five continents. DSM is listed on Euronext Amsterdam. Castor Oil End Use: , an engineering plastic In A -‐based, high-‐performance engineering plastic. The product is involved in final approvals by several customers in the automotive industry. -‐chain polyamide whose properties make it suitable for demanding applications such as those in the automotive and electrical markets. Approximately 70% of the polymer consists of building blocks derived from castor oil as a renewable resource. The new material, which is based on polyamide (PA) 410, has been developed by DSM, and is now set to be commercialized.

-‐performance polyamide with excellent mechanical properties. It combines the benefits of a high melting point of ca. 250oC, with a high rate of crystallization enabling high productivity. The material has low moisture absorption and excellent chemical and hydrolysis resistance, which makes it highly suitable for various demanding applications, for instance in the automotive and electrical markets. A good example is its very good resistance to salts, such as calcium chloride. Because of its low moisture absorption,

The company is targeting auto industry with the new bio-‐based performance materials in response to demand from auto customers for more environmentally friendly materials.

http://www.rhodia.com/

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Website: www.dsm.com Fujitsu Limited Main Line of Business: ICT-‐based business solutions provider Corporate Headquarters: Tokyo, Japan Background: Fujitsu is a provider of ICT-‐based business solutions for the global marketplace. With approximately 170,000 employees supporting customers in 70 countries, Fujitsu combines a worldwide corps of systems and services experts with reliable computing and communications products and microelectronics to deliver added value to customers. Headquartered in Tokyo, Fujitsu Limited reported consolidated revenues of 4.6 trillion yen (US$50 billion) for the fiscal year ended March 31, 2010. Castor Oil End Use: Polyamide-‐11 (PA-‐11) Fujitsu Limited and Fujitsu Laboratories Limited have developed a new polymer with a high bio-‐content that uses castor oil extracted from the seeds of the castor bean. The new bio-‐based polymer features superior flexibility that can withstand repeated bending. This new bio-‐based polymer is used for small components of notebook PCs and mobile phones, such as connector cover. In 2002, Fujitsu started using bio-‐based polymers based on polylactic acid, made from materials including corn, in the chassis of the FMV-‐BIBLO notebook PC. However, in order for plant-‐based materials to be used more widely in Fujitsu products, what has been needed is the development of a new bio-‐based polymer with a higher bio-‐content that features superior flexibility and is suitable for mass-‐production. To address this need, Fujitsu and Fujitsu Laboratories worked with a major French chemical company, Arkema, and succeeded in developing a new bio-‐based polymer plastic that has as its principal component polyamide-‐11 (PA-‐11), which is derived from castor oil. By weakening the interaction of the chain molecule in PA-‐11 and relaxing the stereo-‐regularity of their organization, the resulting new material has sufficient flexibility to withstand repeated bending without causing the whitening that often occurs when such materials are strained. Moreover, Fujitsu has succeeded in developing a prototype of certain notebook PC-‐cover components with an exceptionally high bio-‐content of 60-‐80%. Even after adding high-‐density fillers to increase strength, the polymer maintains good impact-‐resistance and thus it is hoped that the material could eventually be used in PC chasses and other larger components. Website: www.fujitsu-‐general.com

http://www.dsm.com/

http://www.fujitsu-general.com/

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DENSO Main Line of Business: Supplier of advanced automotive technology, systems and components Corporate Headquarters: Aichi prefecture, Japan Background: DENSO, a supplier of advanced automotive technology, systems and components for all the world's major automakers, operates in 33 countries and regions with approximately 120,000 employees. Global consolidated sales totaled US$32.0 billion for fiscal year ended March 31, 2010. Castor Oil End Use: DENSO Corporation has developed a plant-‐derived resin radiator tank using an organic compound derived from castor-‐oil tree. DENSO started mass-‐producing this new product in the spring of 2009 for vehicles sold worldwide. "In addition to increasing installations of the new radiator tank to more vehicles, DENSO aims to incorporate the new resin into a wide range of products in an effort to reduce the use of limited oil resources, reduce CO2 emissions during a product's life cycle and help prevent global warming," said Akio Shikamura, managing officer responsible for DENSO's Thermal Systems Business Group. The eco-‐friendly polymer -‐ DuPont Kabushiki Kaisha, is produced by a chemical reaction between two organic compounds that are derived from castor-‐oil tree and petroleum. An additive, such as glass fiber, is then added to the substance to produce the resin. Plant-‐derived ingredient comprises about 40 percent of the eco-‐friendly resin. Since engine compartment components, such as the radiator tank need to be extremely heat resistant and durable, it was previously difficult to develop a resin with a high percentage of plant-‐derived ingredients.

Generally, the cost increases for on-‐board devices that need to be resistant to calcium-‐chloride, which is contained in large amounts in snow-‐melting agents dispensed on the road in many colder regions. The newly developed radiator tank is more than seven times more resistant to calcium chloride and can be produced at lower cost compared to conventional products designed for cold regions, according to the company. The plant-‐derived resin radiator end tank which can be found in some 2009 Toyota Camrys has earned the Most Innovative Use of Plastics award in the Environment Category from the Society of Plastics Engineers (SPE) Automotive Division for Toyota and partners DENSO and DuPont Automotive. Website: www.globaldenso.com

http://www.globaldenso.com/

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Dow India Main Line of Business: Production of specialty chemical, advanced materials, agrosciences and plastics. Corporate Headquarters: Michigan, USA Background: The Dow Chemical Company is an American multinational corporation. As of 2007, it is the second largest chemical manufacturer in the world by revenue (after BASF) and as of February 2009, the third-‐largest chemical company in the world by market capitalization (after BASF and DuPont).

polystyrene. Dow opened its first representative office in New Delhi in 1963. Dow later extended its operations to include the automotive and agricultural sectors along with a Polyurethane system development center and other commercial offices. Castor Oil End Use: In 1995, the Dow Chemical Company set important goals to improve environment, health and safety performance. In this backdrop, the company is using more ecofriendly products in chemical production and one of the products under research for producing chemicals is castor oil. Dow Chemicals along with Royal Castor Products Ltd., a Gujarat-‐based company have signed a commitment to conduct research in sustainable bio-‐based products and solutions using castor oil. Royal Castor has has a joint venture with a Japanese company for manufacturing high-‐end castor derivatives and an exclusive tie-‐up with an Italian company for speciality products. ALTANA Main Line of Business: Specialty chemical producer Corporate Headquarters: Germany

Background: The name ALTANA represents a global specialty chemical group. It com-‐prises the holding company ALTANA AG and four operating divisions: BYK Additives & Instruments, ECKART Effect Pigments, ELANTAS Electrical Insulation, and ACTEGA Coatings & Sealants. They have currently 43 operational companies and 47 application and research laboratories worldwide.

Foreign business accounts for 84% of its total turnover. Products made by companies in the ALTANA Group are sold in over 100 countries worldwide. ALTANA develops, produces and sells innovative products in the specialty chemicals business. ALTANA offers matching speciality products for coating manufactures, paint and plastic processors, the printing and cosmetic industries, and the electrical and electronic industry. The product range includes additives, special coatings and adhesives, effect

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pigments, sealants and compounds, impregnating resins & varnishes, and testing and measuring instruments. Castor Oil End Uses: Polyurethane and Lipstick

materials in some of the products they produce. ACTEGA Rhenania (www.actega.com) has developed a novel series of solvent-‐free polyurethane adhesives for laminates to be used in packaging. Raw material involved in polyurethane is castor oil derivative. ECKART (www.eckart.net) is a manufacturer of metallic pigments for the paints and coatings industry, the graphic arts industry, the plastics, lightweight concrete industries and the cosmetics industry. The company uses castor oil as one of the ingredient in its lipstick. Website: www.altana.com BioSolar Main Line of Business: Solar cell manufacturer. Corporated Headquarters: California, USA Background: BioSolar, Inc. has developed a breakthrough technology to produce bio-‐based materials from renewable plant sources that will reduce the cost per watt of solar cells. Most of the solar industry is focused on photovoltaic efficiency to reduce cost. BioSolar is the first company to introduce a new dimension of cost reduction by replacing petroleum-‐based plastic solar cell components with durable bio-‐based components. Through the advanced manipulation of bio-‐based polymers, BioSolar intends to produce robust bio-‐based components that meet the stringent thermal and durability requirements of current solar cell manufacturing processes. BioSolar materials can be used directly in conventional manufacturing systems, such as injection molding and thin-‐film roll-‐to-‐roll, to create superstrate layer, substrate layer, backsheet as well as module and panel components. Whether solar cells are produced using crystalline silicon, amorphous silicon or other solar technologies, BioSolar can help reduce the cost per watt through the use of its lower cost bio-‐based materials. By removing petroleum from solar cells, BioSolar makes solar energy a true green source of energy. Castor Oil End Use: BioBacksheet Backsheets, which are a protective layer on photovoltaic solar modules, are typically made from petroleum products. these backsheets are made from a biobased polyamide resin made from castor beans and cotton. According to the company, their backsheets will cost 25 percent less than conventional backsheets, which cost between $0.70 and $1 per square foot. The company

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claims that in addition to being less expensive and more sustainable, its single-‐layer construction avoids the delamination problem conventional petroleum-‐based backsheets may have. The proces starts with used cotton rags and turns them into a film of cellulose, a natural fiber and then the film is blended with a type of nylon made from castor beans. The tests conducted by the company at the National Renewable Energy Laboratory shows that flexible plastic backsheet lasts longer. Website: www.biosolar.com Castor Derivatives in Deodorants and Body Lotions The castor derivative zinc ricinoleate is used as a key ingredient in the manufacturing of deodorants and body lotions. Prominent companies that use zinc ricinoleate as a key ingredient are: Lavera, Avene & Janson Lavera Main Line of Business: Organic cosmetic company Corporate Headquarters: Washington, USA Background: Lavera is natural cosmetics manufacturer that offers a complete system of skin and body care specially formulated for allergy sufferers and sensitive skin (Neutral). They use plant based products in their products. They received the "Innovation Prize of the Year" award in Europe at the Biofach the largest natural product expo worldwide several years in a row. Castor Oil End Use: Zinc ricinoleate and hydrogenated castor oil The company uses zinc ricinoleate as one of the ingredients in its deodorant and body lotion. It uses hydrogenated castor oil in its sunscreen lotion production. Website: www.lavera.com Avene Main Line of Business: Dermatology and hydrotherapy Corporate Headquarters: New Jersy, USA Background: Since 1743, when the first Hydrotherapy Center was built near the Sainte-‐Odile spring, the vocation of Avène has never changed: The Hydrotherapy Center is entirely dedicated to dermatology. The therapeutic properties of Avène Thermal spring water have been used at the Hydrotherapy Center to address a variety of dermatological conditions such as atopic dermatitis, psoriasis, eczema and burns. Castor Oil End Use: Uses zinc ricinoleate in its deodorant production

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Website: www.aveneusa.com Jason Main Line of Business: Natural cosmetics Corporate Headquarters: Boulder, Colorado Background: Since 1959, JASON Natural Products has been the leading purveyor of pure and natural products for skin, body, hair and oral health for the whole family, giving consumers effective, environmentally-‐friendly alternatives to mass-‐produced, synthetic chemical products. It features over 200 products which are manufactured using pure organic ingrediants. Castor Oil End Use: Uses zinc riciloneate in hand and body lotion and deodorants. Website: www.jason-‐natural.com 6.2 Future Possible End-‐uses and End user Industries for Castor Oil and Derivatives 1. Biopolymers 2. Biofuels 3. Others 6.2.1 Biopolymers and Castor oil The use of oleochemicals in polymers has a long tradition. One can differentiate between the use as polymer materials, such as linseed oil and soybean oil as drying oils, polymer additives, such as epoxidized soybean oil as plasticizer, and building blocks for polymer, such as dicarboxylic acids for polyesters or polyamides. Considering the large market for polymers, the share of oleochemically based products is relatively small -‐ or, in other terms -‐ the potential for these products is very high.

Oleochemicals for Polymers -‐ Selected Examples

Product/Use Source

Polymer materials Polymerized soybean oil, castor oil Drying oils Soybean oil, Castor oil Polymerized linseed oil Linoleum Linseed oil Polymer additives Epoxides Stabilizers, Plasticizers Soybean oil Soaps (Ba/Cd, Ca/Zn) Stabilizers Stearic acid Fatty acid esters, -‐ amides, Lubricants Rapeseed oil

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waxes Building blocks for polymers

Dicarboxylic acids Polyamides, Polyesters, Alkyd Resins Tall oil, Soybean oil, Castor oil

Ether-‐/ester polyols Polyurethanes Sunflower oil, Linseed oil, Oleic Acid

Source: Karlheinz Hill, Pure Appl. Chem., Vol. 72, No. 7, pp. 1255 1264, 2000 Building Blocks for Polymers-‐based on Natural Oils

Karlheinz Hill, Pure Appl. Chem., Vol. 72, No. 7, pp. 1255 1264, 2000

Development of new bio-‐materials and applications continues at a strong pace despite practical obstacles such as high prices, limited production capacity, and the lack of an infrastructure for effective composting. New materials and modifying agents are expanding biopolymers' reach, particularly in the case of polylactic acid (PLA). Efforts are focused on boosting mechanical and thermal properties so biopolymers can be effective alternatives to less costly commodity materials. Polylactic acid (PLA), a biopolymer originating from corn sugar fermentation is one of the most popular biopolymers. Two other biopolymers with a much longer commercial history are latex rubber and nylon-‐11 (made from a by-‐product of castor oil). The latter two are applied in only a small fraction of the millions of polymer products in global commerce. The good news is that more biopolymers are approaching commercial viability for a long list of familiar and unfamiliar objects.

Caustic Oxidation

Ozonolysis Dimerization Oxidation/Epoxidation Epoxy Ring Opening E Oleochemical Polyois

Linoleum

Radiation Curing Acrylates

Dimer Fatty Acid

Azelaic Acid Sebacic Acid

Oleic Acid

Natural Fats and Oils

Polyurethanes Polyamides Nylon 6.9 Nylon 6.6.9

Polyurethanes Laminating

Adhesives

Polyamido amines Epoxy curing agents

Non-nylon Polyamides Hotmelt Adhesives Printing Ink Resins

Modification of Epoxy Resins

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Europe is the largest market for biopolymers, with 60% of total production centered there. Average global growth is 12.6% per year, and the overall market is expected to grow from 114 million lb in 2005 to 206 million lb by 2010. Most of that usage will still be in two applications: compost bags and loose-‐fill packaging. The quest for bio-‐sourcing of plastics has also brought back a castor oil-‐sourced polyamide. For instance, BASF produced a nylon 6.10 about 50 years ago but the product was discontinued. Now, with growing interest in producing plastics from renewable resources, the company has reintroduced the material. It contains about 60 per cent sebacic acid -‐ derived from castor oil. It has a relatively low density for a polyamide, good low temperature impact strength and good dimensional stability because of its low water absorption and BASF says it is suitable for typical nylon 6 applications. 6.2.1.1 Biopolymers in Durables While biodegradable plastics such as PLA have made strong penetration so far in disposable consumer packaging, durable applications may not be that far behind. Japanese companies are using biopolymers in auto interior parts and cell phone and computer housings. Mitsubishi Motors Corp. and the Aichi Industrial Technology Institute have developed a biopolymer of polybutylene succinate (PBS) and bamboo fiber for auto interiors. PBS is made from 1,4-‐butanediol (a petrochemical) and succinic acid (a product of fermenting sugar cane or corn). The fiber-‐reinforced material is said to provide greater rigidity and strength. Meanwhile, Fujitsu Ltd. and Fujitsu Laboratories Ltd., Tokyo, have chosen Rilsan nylon 11 from Arkema for notebook PCs and cell phones. Based on castor oil, nylon 11 is typically used in automotive tubing and air-‐brake hose. Formulations contain 60% to 80% nylon 11 with high-‐density fillers for increased strength. Previously, the Fujitsu companies developed a notebook PC housing based on PLA and PLA/polycarbonate blends (the latter in cooperation with Toray Industries). This was its FMV BIBLO notebook PC series, which it had manufactured using a material called Ecodear. For its current product, Fujitsu is developing a castor oil derived PA 11 plastic with Arkema, which is more flexible and will help expand its use of bio-‐plastics in notebook computers. The material can withstand repeated bending thanks to scientists weakening the interaction of the chain molecule in PA 11 and relaxing the stereoregularity of their organisation. The improved durability means its prototypes of PC cover components consist of 60-‐80 percent of the new bioplastic, an unprecedented achievement to date. (Reference URL from Fujitsu -‐ http://www.fujitsu.com/global/news/pr/archives/month/2006/20061207-‐01.html & based on a July 2007 news report) In Dec 2008, Toyota announced plans to use plant-‐derived plastic in more vehicle models, starting with hybrids next years. The company said that it will use a variety of materials (polylactic acid, plant-‐derived polyester, castor oil derivatives and more) to make seat cushions, sun visors, trunk liners, door trim, scuff plates and other interior parts. In 2009, the company hopes for bioplastic to account for 60 percent of the interior parts of vehicles it's used in.

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In Dec 2008, solar cells manufacturer BioSolar announced that it planned to use biomass in solar panel components in an effort to reduce the costs of solar cells, thus replacing petroleum-‐based solar panel components with durable biomass-‐based plastic materials. According to BioSolar, one of its first product offerings, a BioBacksheet, is in the pre-‐production phase. The product forms the bottom layer of most crystalline silicon (c-‐Si) solar cells a layer traditionally comprised of petroleum-‐based plastics. BioSolar will use primarily recycled cotton in combination with natural polymers derived from castor bean oil in its BioBacksheet product, according to the company. In Jan 2009, Icynene Inc. ( www.icynene.com ), a manufacturer of opencell foam insulation products introduced castor-‐based spray foam insulation. ICYNENE LD-‐R-‐ -‐based foam insulation and air barrier material that reduces the need for petroleum-‐based polyols. The product was made using castor oil and exceeds United States Department of Agriculture (USDA) requirements for a rapidly renewable product. In Feb 2009, Keetsa, a San Francisco retailer that calls itself "the eco-‐friendly mattress store," announced it was selling mattresses made from a material it enthusiastically promotes as "BioFoam". This contains a polyurethane foam that partially utilized castor oil (The other 88 percent, though, is still petroleum-‐based) After two years of research and development, French nylon yarn specialist SOFILA announced in March 2010 that it had developed a new commercially available range of high performance nylon yarns, produced using bio-‐polymers derived from the castor oil plant.

yarns. These yarns have been presented at Premiere Vision in Paris last year and were under trial (as of March 2010) by major French and European textile brands, for instance in hosiery and socks. With the growth in the biopolymers industry, it is expected that there will be a simultaneous demand for the suitable grades of castor oil. 6.2.1.2 Castor Oil Polyurethane Castor oil is increasingly finding application in the manufacture of polyurethane foams. The polyurethane is produced from polyols based on castor oil. Polyols are compounds in which multiple hydroxyl functional groups are available for organic reactions. A molecule with two hydroxyl groups is a diol, one with three is a triol, and one with four is a tetrol and so on. The main use of polymeric polyols is as reactants to make other polymers. Polyols can be reacted with diisocyanates to make polyurethanes. An isocyanate is a functional group of atoms N=C=O (1 nitrogen, 1 carbon, 1 oxygen). Any organic compound which contains an isocyanate group may also be referred to in brief as an

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isocyanate. An isocyanate may have more than one isocyanate group. An isocyanate that has two isocyanate groups is known as a diisocyanate. These diisocyanates are reacted with castor oil polyols in the production of polyurethanes. Polyurethane is ultimately used to make elastomeric shoe soles, fibers, foam insulation for appliances, adhesives, mattresses, automotive seats and so on. There are a limited number of naturally occurring vegetable oils (triglycerides) which contain the unreacted hydroxyl groups that account for both the name and important reactivity of these polyols. Castor oil is the only commercially-‐available natural oil polyol that is produced directly from a plant source: all other natural oil polyols require chemical modification of the oils directly available from plants. The hope is that using renewable resources feedstocks such as castor oil for polyols and subsequently polyurethane production will reduce the demand on non-‐renewable fossil fuels currently used in the chemical industry and reduce the overall production of carbon dioxide, the most notable greenhouse gas. Features of Castor Oil Based Polyurethane Superior to PPG (Polypropylene Glycol) or polyester in water and hydrolysis resistance Superior to PPG or polyester in insulation Lower viscosity than Polybutadiene or Polyester One of the most challenging issues of polyurethane flooring is heat and humidity. The

urethane produced from castor oil is stable under high heat and humidity. A typical polyurethane formulation: Composition Polyol: 61.4 % Extender pigment: 23.1 % Pigment: 5.0 % Dehydrating agent: 10.0 % Deformer: 0.3 % Wetting agent: 0.3 % Crosslinker: 100.0 Formulation rate: 3/1 6.2.1.3 Nylon Nylon 11 The world's largest single use of castor oil in one product, outside the lubricants markets, is in the manufacture of polyamide 11 (Nylon 11). The commercially available polyamide made from castor oil is Arkema's (earlier Atofina) Rilsan Nylon 11.

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The world's only producer of polyamide 11 using amino-‐undecanoic acid, Arkema controls the entire production chain for Rilsan ® A and B thanks to the resources of TotalFinaElf, its parent company, and Costacem, its subsidiary specialising in the production of seeds for castor plants. With its extensive and wide-‐ranging properties, Rilsan ® has become a pioneer in many diverse areas, and remains the choice polymer of high tech industries for the manufacture of parts requiring optimum reliability. Wide-‐ranging powders and application processes accommodating various types of support have made Rilsan ® the choice material for coating. Uses of Rilsan ® include:

Polyamides 11 and 12 (Rilsan ®): automotive parts (fuel lines, pneumatic brake lines for heavy goods vehicles, sheathing for control cable, air-‐conditioning ducts); components for precision mechanical and electrical industries; flexible tubing for compressed air, hydraulics and oil industry (offshore extraction); aviation parts (alkaline battery trays).

Thermoplastic polyamide coating powders (Rilsan ®): protection of automotive parts (clutch controls, bumpers, brake lines), protection of materials for construction and public works (cladding, aluminium profiles, heating pipes and fittings, soundproofing walls, stadium seating, etc.), printing components (press rollers), water pipes, pipelines and various equipment (dishwasher baskets, refrigerator shelves, garden furniture, screws, nuts and bolts, haberdashery (hooks, buckles), etc.

Nylon 11 has been produced from 11-‐aminoundecanoic acid. The process to make Nylon 11 from castor oil is quite involved and includes several reaction steps, but briefly, it is as follows: Castor oil is converted to methyl ricinoleate by treatment with methyl alcohol. Methyl ricinoleate is pyrolysed at high temperature yielding heptaldehyde, methyl undecylenate and a small amount of fatty acids. Methyl undecylenate is hydrolysed to produce undecylenic acid. When undecylenic acid is treated with hydrogen bromide in a non-‐polar solvent in the presence of peroxide, reverse Markownikoff addition occurs and the main product is x-‐bromoundecanoic acid. This is then treated with ammonia to give x-‐aminoundecanoic acid, which is a crystalline solid. Aminoundecanoic acid is the starting material for nylon-‐11. (CH2=CH(CH2)8COOH) Undecylenic Acid HBr BrCH2.CH2(CH2)8COOH (x-‐bromoundecanoic acid) BrCH2.CH2(CH2)8COOH NH3 H2N(CH2)10COOH (w-‐Aminoundecanoic Acid) Compared to its predecessors, Nylon 6, 6-‐6 and 6-‐10, Nylon 11 has the lowest melting point, lowest specific gravity and the lowest moisture absorption. It is also resistant to acid and alkaline reagents or oxidizing agents. These qualities of castor oil are of particular importance in its use in high quality engineering plastics and in durable protective coatings.

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Structure of Nylon-‐11 / Polyamide-‐11.

Arkema has now extended the technology into TPEs (thermo plastic elastomers) by producing a grade of its Pebax polyether block amide with the nylon block using the nylon 11 chemistry. The new grade is being sold as Pebax RNew in 25 to 72D hardness. Polyamide from BASF The quest for bio-‐sourcing of plastics has brought back a castor oil-‐sourced polyamide from BASF's old chemistry notebooks. Produced from Sebacic acid, this has a relatively low density for a polyamide, with good low temperature impact strength and good dimensional stability because of its low water absorption, and BASF says it is suitable for typical Nylon 6 applications and those where nylon 6 has shown limitations. Nylon 6/10 At the end of 2009, the company announced that it was introducing a new nylon 6/10 range of materials made in part from castor oil. Research & Trends in Castor Oil Based Biopolymers

Castor oil based polyurethane adhesives for wood-‐to-‐wood bonding -‐ Most adhesives are polymeric adhesives, and if made from renewable sources they will have low cost and biodegradability which are of importance. In view of these properties research is being done on polyurethane (PU) adhesives from different polyester polyols obtained from castor oil.

Lactic Acid and Ricinoleic Acid Based Copolyesters -‐ Copolyesters based on purified ricinoleic (RA) and lactic (LA) acids with different RA:LA ratios have been synthesized by thermal polycondensation and by transesterification of high molecular weight poly(lactic acid) (PLA) with ricinoleic acid and repolyesterification. Transesterification of high molecular weight PLA with pure ricinoleic acid and repolymerization of those oligomers by condensation resulted in multiblock P (PLA-‐RA) copolyesters of molecular weights between 6000 and 14000.

Ricinoleic acid-‐based biopolymers as drug carriers -‐ Polyanhydrides synthesized from pure ricinoleic acid half-‐esters with maleic and succinic anhydrides have been shown to possess desired physicochemical and mechanical properties for use as drug carriers. Biocompatibility studies have demonstrated their toxicological inertness and biodegradability.

Millable polyurethane elastomers based on difunctional castor oil and poly (propylene glycol), 2,4-‐toluene diisocyanate and 1,4-‐butane diol were prepared and cured using toluene diisocyanate dimer as crosslinking agent. All elastomers were characterized by conventional methods. Physical, thermal and mechanical properties

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of elastomers were studied. Investigation of these properties showed that the elastomers could be tailor made in order to fulfill industrial needs (based on a 2003 research paper).

Modification of the biopolymer castor oil with free isocyanate groups to be applied as bioadhesive -‐ June 2006 -‐ Surgical adhesives have been used for several applications, including haemostasis, sealing air leakages and tissue adhesion. Recently, efforts have been made to develop a biodegradable urethane-‐based bioadhesive based on castor oil containing free isocyanate groups. This material presents the advantage of being biodegradable, biocompatible and having the capacity of reacting with amino groups present in the biological molecules.

Polyesteramide resins from dehydrated castor oil and various dibasic acids -‐ Attempt has been made in this study, to utilize castor oil in the preparation of polyesteramide resins. Castor oil was first converted into dehydrated castor oils (DCO) to improve drying characteristics. DCO was then converted into diethanolamide {(N, N-‐ bis hydroxethyl) castor oil amide} of mixed fatty acids using 0.5 per cent sodium methoxide as a catalyst and converted to polyesteramide resins after reacting with various dibasic acids such as phthalic anhydride, sebacic, succinic and adipic acids in presence of xylene as azeotropic solvent. The resins obtained were then analysed for its physico-‐chemical, film performance properties and resistance to various chemicals (Source: Author(s): Pradeep G. Shende, Abhijit B. Jadhav, Shrikant B. Dabhade; Journal: Pigment & Resin Technology, Year: 2002)

Electrical characterization of castor-‐oil resins -‐ Several Brazilian research works have shown that new materials, based on polyurethane resins derived from castor oil, have had great success in the medical field. This could in fact be expected because of their stable physical and chemical properties. In this work, using the same fabrication techniques, thin films and circular plates of 1-‐2 mm thickness, of these resins were made and electrically characterized. Tests for a.c. electrical breakdown, permittivity, d.c. insulation resistance and dissipation factor show that these materials are very good insulators. Internal insulators and conductor covers are among their main applications. Their mechanical properties are also presented and discussed (Source: Gonzaga, D.P.; Murakami, C.R.; Chierice, G.O.; Altafim, R.A.C. Electrical Insulation, 1998. Conference Record of the 1998 IEEE International Symposium on Volume 1, Issue , 7-‐10 Jun 1998 Page(s):181 -‐ 185 vol.1)

6.2.2 Castor Oil as Feedstock for Biodiesel Castor oil, owing to its chemical structure has the potential to be used as a bio-‐fuel in place of petrol-‐based fuels. In the last few years, there has been a growing debate on whether castor oil can be an effective biofuel (biodiesel) stock. This section analyses this issue in detail. Can castor oil become an efficient bio-‐fuel and bio-‐diesel? This question is answered by analyzing the following: Characteristics of oils or fats affecting their suitability for use as fuel Characteristics of efficient bio-‐fuels and bio-‐diesels

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How does the bio-‐diesel derived from castor oil rate on the above aspects?

Characteristics of Oils Affecting their Suitability for Use as Fuel The following aspects need to be considered while evaluating a plant oil feedstock for biofuel. Calorific Value, Heat of Combustion Heating Value or Heat of Combustion, is the amount of heating energy released by the combustion of a unit value of fuels. Melt Point or Pour Point -‐ Melt or pour point refers to the temperature at which the oil in solid form starts to melt or pour. In cases where the temperatures fall below the melt point, the entire fuel system including all fuel lines and fuel tank will need to be heated. Cloud Point -‐ The temperature at which oil starts to solidify is known as the cloud point. While operating an engine at temperatures below cloud point, heating will be necessary in order to avoid waxing of the fuel. Flash Point (FP) -‐ The flash point temperature of diesel fuel is the minimum temperature at which the fuel will ignite (flash) on application of an ignition source. Flash point varies

inimum flash point temperatures are required for proper safety and handling of diesel fuel. Iodine Value (IV) -‐ Iodine Value (IV) is a value of the amount of iodine, measured in grams, absorbed by 100 grams of given oil. Iodine value (or Iodine number) is commonly used as a measure of the chemical stability properties of different biodiesel fuels. The Iodine value is determined by measuring the number of double bonds in the mixture of fatty acid chains in the fuel by introducing iodine into 100 grams of the sample under test and measuring how many grams of that iodine are absorbed. Iodine absorption occurs at double bond positions -‐ thus a higher IV number indicates a higher quantity of double bonds in the sample, greater potential to polymerise and hence lesser stability. Iodine Numbers for some plant oils (before conversion into biodiesel)

Coconut oil: 10 Rapeseed oil: 94-‐120 Soybean oil: 117-‐143 Sardine oil: 185 Castor oil: 60-‐70

Iodine Numbers after conversion to biodiesel through transesterification (approximate values):

Rapeseed Methyl Ester (Rapeseed Biodiesel): 97 Rapeseed Ethyl Ester (Another variety of Rapessed biodiesel): 100

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Soy Ethyl Ester (Soy biodiesel variety 1): 123 Soy Methyl Ester (Soy biodiesel variety 2): 133 Castor methyl ester: 60 (estimate)

One can hence see that the process of transesterification (conversion of plant oil into biodiesel) reduces the iodine value by a small extent. Viscosity Viscosity refers to the thickness of the oil, and is determined by measuring the amount of time taken for a given measure of oil to pass through an orifice of a specified size. Viscosity affects injector lubrication and fuel atomization. Fuels with low viscosity may not provide sufficient lubrication for the precision fit of fuel injection pumps, resulting in leakage or increased wear. Fuel atomization is also affected by fuel viscosity. Diesel fuels with high viscosity tend to form larger droplets on injection which can cause poor combustion, increased exhaust smoke and emissions. Aniline Point/Cetane Number (CN) -‐ Is a relative measure of the interval between the beginning of injection and autoignition of the fuel. The higher the cetane number, the shorter the delay interval and the greater its combustibility. Fuels with low Cetane Numbers will result in difficult starting, noise and exhaust smoke. In general, diesel engines will operate better on fuels with cetane numbers above 50. Density Is the weight per unit volume. Oils that are denser contain more energy. For example, petrol and diesel fuels give comparable energy by weight, but diesel is denser and hence gives more energy per litre. The aspects listed above are the key aspects that determine the efficiency of a fuel for diesel engines. There are other aspects/characteristics which do not have a direct bearing on the performance, but are important for reasons such as environmental impact etc. These are: Ash Percentage -‐ Ash is a measure of the amount of metals contained in the fuel. High concentrations of these materials can cause injector tip plugging, combustion deposits and injection system wear. Ash content for bio-‐fuels is typically lower than that for most coals, and sulfur content is much lower than that for many fossil fuels. Unlike coal ash, which may contain toxic metals and other trace contaminants, biomass ash may be used as a soil amendment to help replenish nutrients removed by harvest. Sulfur Percentage -‐ The percentage by weight, of sulfur in the fuel Sulfur content is limited by law to very small percentages for diesel fuel used in on-‐road applications. Potassium Percentage -‐ The percentage by weight of potassium in the fuel Characteristics of Efficient Bio-‐fuels and Bio-‐diesel What are the most desirable values for biodiesel, for the above characteristics? This section provides the details.

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Biodiesel is noteworthy for its similarity to petroleum-‐derived diesel fuel, while at the same time having negligible sulfur and ash content. Bioethanol has only about 70% the heating value of petroleum distillates such as gasoline, but its sulfur and ash contents are also very low. Both of these liquid fuels have lower vapor pressure and flammability than their petroleum-‐based competitors an advantage in some cases (e.g. use in confined spaces such as mines) but a disadvantage in others (e.g. engine starting at cold temperatures). Despite their wide range of possible sources, biomass feedstocks are remarkably uniform in many of their fuel properties, compared with feedstocks such as coal or petroleum. For example, there are many kinds of coals whose gross heating value ranges from 20 to 30 GJ/T (gigajoules per metric ton). However, nearly all kinds of biomass feedstocks destined for combustion fall in the range 15-‐19 GJ/T. For most agricultural residues, the heating values are even more uniform about 15-‐17 GJ/T (6450-‐7300 Btu/lb); the values for most woody materials are 18-‐19 GJ/T (7750-‐8200 Btu/lb). However, in contrast to their fairly uniform physical properties, biomass fuels are rather heterogeneous with respect to their chemical elemental composition. Most biomass materials are more reactive than coal, with higher ignition stability. This characteristic also makes them easier to process thermochemically into higher-‐value fuels such as methanol or hydrogen. Engine Manufactures Association (EMA) Recommended Guideline on Diesel Fuel

Property Test Method FQP-‐1A EMA #1 DF(1)

FQP-‐1A EMA #2 DF(1)

Flash Point, °C min. D 93 38 52 Water, ppm max D1744 200 200 Sediment, ppm max D2276 or D5452 10 10 Distillation % Vol. Recovery, °C D 86 90%, max. 272 332 95%, max. 288 355 Kinematic Viscosity, 40 °C D 445 1.3 -‐ 2.4 1.9 -‐ 4.1 Ash, % max. D 482 0.01 0.01 Sulfur, % max. D 2622 0.05 0.05 Copper Corrosion, max. D 130 3b 3b Cetane Number, min. D 613 50 50 Cetane Index, min. D 4737 45 45 Rams Carbon, 10% residue max. D 524 0.15 0.15 API Gravity, max. D 287 43 39 Lubricity, g. min. D6078(2) 3100 3100 Accelerated Stability, mg/L max. D 2274 15 15 Detergency -‐ L10 Injector CRC Rating <10 <10 Depositing Test % Flow Loss <6 <6 Low Temperature Flow, °C D2500 or D4539 (3) (3) Microbial Growth (4) (4)

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Biodiesel Requirements (ASTM, 2003a) Properties Test Methods Limits Units Flash Point (closed cup) D 93 130.0 minimum oC Water & Sediments D 2709 0.050 maximum % volume Kinematic Viscosity (40oC) D 445 1.9-‐6.0 mm2/s Sulfated Ash D 874 0.020 maximum % mass Sulphur D 5453 0.05 maximum % mass Cetane Number D 613 47 minimum

Cloud Point D 2500 Higher than that for petro-‐diesel oC

Carbon Residue D 4530 0.050 maximum % mass Acid Number D 664 0.80 maximum mg KOH/g Free Glycerine D 6584 0.020 % mass Total Glycerine D 6584 0.240 % mass Phosphorus Content D 4951 0.001 maximum % mass Distillation Temperature (atmospheric equivalent temperature, 90% recovered) D 1160 360 maximum oC How does bio-‐diesel derived from castor oil rate on the above aspects? This section looks at the values for biodiesel derived from castor oil for each of the characteristics described in the previous sections. Iodine Value: The transesterified castor oil has an iodine value of about 85. This is quite an acceptable value for biodiesel. The lower the iodine value, the better the fuel will be as a biodiesel. While most countries do not have mandatory upper limits for iodine value, in some countries of Europe the upper limits have been stipulated at around 120. One can hence see that castor oil biodiesel easily passes this test (while soy biodiesel, whose iodine value is about 120, perhaps does not). Cetane Number: The higher the cetane number, the better is the fuel as a diesel. The Cetane Number of most biodiesel fuels are higher than petro-‐diesel (cetane number of petro diesel is about 45, while for most biodiesel, the cetane number falls in the range 45-‐65), and the cetane number of castor oil biodiesel is in acceptable range for diesel engines. In fact, castor oil has one of the highest cetane numbers amongst vegetable oils (about 42), and all the other biodiesel contenders amongst vegetable oils have cetane numbers slightly lower than that for castor oil

Oil Cetane Number Linseed 27.6 Bay 33.6

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Walnut 33.6 Cottonseed 33.7 Almond 34.5 Peanut 34.6 Wheat 35.2 Poppyseed 36.7 Sunflowerseed 36.7 Rapeseed 37.5 Corn 37.5 Soybean 38.1 Sesameseed 40.4 Safflowerseed 42 Castor 42.3 Olive 49.3 Hazelnut 52.9

Note: These numbers were determined using ASTM D163

Melting Point: 5ºC. This is acceptable for diesel engines.

Solidification Point Castor oil has a very low solidification point (-‐12ºC to -‐18ºC). This is a positive characteristic for colder climates, since it implies that the biodiesel from castor oil solidifies fewer times than those biodiesels with higher solidification points.

Density: Castor oil, before transesterification has a density of 0.956-‐0.963 g/ml (@ 20 degrees C. The conversion into alkyl esters decreases the density by a small extent, hence one can expect the castor oil based biodiesel to have a density of about 0.9 g/ml. (Comparative values are approx 0.74 g/ml for gasoline and 0.85 g/ml for diesel). While the castor oil biodiesel has a density somewhat higher than petro-‐diesel, this is unlikely to be a bottleneck as the difference is not very high.

Flash Point: 260oC. It compares favourably with other vegetable oils.

Cloud Point: < -‐7oC; within acceptable range. Pour Point: At a pour point of about -‐32 degrees C, it compares well with other plant oils, and is acceptable in diesel engines. Ash content: Castor oil has an ash content of about 0.02% Sulfur %: is less than 0.04% Potassium: Negligible Heating value: 39.5 GJ/T. At this number, it compares favourably with most vegetable oils. Petro-‐based diesel & gasoline have heating values of approximately 45 GJ/T. Hence, one could say that most biodiesel, including that from castor, have heating values that are about 10% lower than that for gasoline or petro diesel.

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Water, ppm max Biodiesel prepared from castor oil have a water content of about 1300 ppm. This is much higher than the maximum limit prescribed by EMA for diesel fuel (200 ppm). Sediment Refined castor oil grades are available that have sediment at less than 10 ppm API Gravity With a specific gravity of 0.96, castor oil has an API Gravity of about 15.9 Lubricity Numerous studies on the effects of vegetable oil methyl esters on diesel fuel lubricity have shown an increase in lubricity associated with the addition of these esters. Castor oil and its esters are known for their excellent lubricity, and it is above the EMA minimum specification limit. Carbon Residue A B100 from castor oil has a carbon residue % of 0.037% Acid Number Castor oil has a maximum acid number of 1.5 mg KOH/g, and experiments suggest that some specific grades of castor oil can have acid numbers less than 0.8 (around 0.6). Phosphorus Content Castor oil has less than 0.001 % phosphorus by weight Distillation Temperature Castor oil boiling point is 313oC, which is less than the maximum distillation temperature required by ASTM (360oC) Free Glycerine Based on some tests done on biodiesel from castor (both methyl and ethyl esters), the biodiesel contains about 1% free glycerine. This is much higher than the maximum prescribed by ASTM (0.02%) Viscosity: Castor oil in its raw form is one of the most viscous of oils (9.5 10.0 dPa.s @ 20 degress C about 990 cP; Viscosity, St by test method ASTM D1545 is in the range of 6.3 -‐ 8.9). The other plant oils, in themselves, have viscosities much higher than those for gasoline and petro-‐diesel. Castor oil has a viscosity of over 100 times that of petro-‐diesel! Absolute or Dynamic Viscosity of Some Common Fluids Absolute or dynamic viscosity of some common liquids at a temperature of 27oC is indicated below: Fluid Absolute Viscosity (N s/m2, Pa s) Alcohol, ethyl (ethanol) 0.0011 Alcohol, methyl (methanol) 0.00056 Alcohol, propyl 0.0019 Benzene 0.0006 Castor Oil 0.650 Ether 0.00022 Ethylene Glycol 0.016

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Glycerine 0.950 Heptane 0.00038 Kerosene 0.0016 Linseed Oil 0.033 Octane 0.00051 Propane 0.00011 Propylene 0.00009 Toluene 0.00055 Turpentine 0.0014 Water, Fresh 0.00089 From the above analysis, one can hence see that viscosity could be a major bottleneck in castor oil becoming a biodiesel. However, this high viscosity can be considerably reduced by subjecting the vegetable oils to the process of transesterification. Transesterification is the process most commonly used for converting plant oil into biodiesel. We have some data for the kinematic viscosity of transesterified castor oil. One study has estimated that the B100 biodiesel from castor oil has a kinematic viscosity of 15.98 mm2/s. Another study puts the kinematic viscosity of castor oil methyl esters and castor oil ethyl esters in the same range (13.23 and 16.14 mm2/s respectively). The kinematic viscosity numbers for castor biodiesel is significantly higher than what it is for other vegetable oils that are biodiesel contenders, as well as much higher than what is specified by ASTM (1.9-‐6 mm2/s). At the same time, it has been said that if the castor oil biodiesel is blended with petro-‐diesel in suitable ratios, the overall viscosity should be within acceptable range. A B10 and B20 castor oil biodiesel are estimated to have 4.54 and 4.97 mm2/s respectively as the kinematic viscosity. (Reference URLs: http://www.icrepq.com/full-‐paper-‐icrep/222-‐barajas.pdf , http://www.biodiesel.org/resources/reportsdatabase/reports/gen/20000501_gen-‐308.pdf ) A research done in 2006 says the following about COEE (castor oil ethyl esters) and COME (castor oil methyl esters) defined by the standard EN 14 214. The viscosities are more than twice as high as the limit

biodiesel that has been produced from plant oils) (Reference URL: (http://www3.interscience.wiley.com/journal/112724331/abstract?CRETRY=1&SRETRY=0 ) At the same time, from the news articles and information gathered from around the world (and especially from Brazil), it does appear that the viscosity of biodiesel prepared from castor oil is within acceptable limits for use in diesel engines. Some studies (done in 2007) have also thrown up questions on the thermal and oxidative degradation of castor oil biodiesel. The heating of vegetable oils can cause complementary decomposition reactions, in which the results can also lead to the formation of polymeric compounds. Research was carried out to study the degradation process of biodiesel in different temperatures and exposure times. The degradation process of biodiesel affected its thermogravimetric and calorimetric profiles, indicating the formation of intermediary compounds. The spectroscopic data of degraded biodiesel suggested oxidative

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polymerization, confirming thermal data. In the degraded biodiesel at 210 C for 48 h, the formation of gum occurred, indicating that oxidative polymerization was completed. This was however a preliminary research and more research needs to be done in order to verify if these results could affect the biodiesel properties overall. Cost of Castor Oil The final, and possibly one of the most important, aspects to be considered is the cost. If one were to take the current prices of the various plant oils as a measure of the input cost, the following is what emerges as data: The following were the spot prices for the various oils in India in June, 2008 in US $ / T (using a conversion of Indian Re / US $ = 43 Rs / US$)

Castor Oil (commercial grade) 1400 Groundnut Oil/Peanut Oil 1150 Mustard Oil 960 Palm Oil 1200 Refined Soy Oil 1400

While the above list does not provide data for all the vegetable oils that are biodiesel

market, and in addition its prices are highly volatile. Evaluation Table for Castor Oil as Biodiesel Candidate A comparison on various parameters is made for castor oil properties with those suggested for suitable diesel fuel as well for biodiesel. Refer to the above section for more details of comparison

Parameter Suitability of castor oil Iodine Value Suitable

Cetane Number Less than minimum prescribed

Melting Point Suitable Solidification Point Suitable

Density

Slightly higher than diesel, but this is unlikely to pose problems

Flash Point Suitable Cloud Point Suitable Pour Point Suitable Ash Content Suitable Sulfur Percetange Suitable Potassium Suitable

Heating Value Slightly less than diesel, but within acceptable limits

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Water Content Higher than prescribed Sediment Suitable API Gravity Suitable Lubricity Suitable Carbon Residue Suitable Acid Number Suitable Phosporus Content Suitable Free Glycerine Higher than prescribed Distillation Temperature Suitable Viscosity Higher than prescribed

From the above table, it can be seen that the four parameters on which castor oil does not have values in the prescribed limits are:

Cetane Numbers Water Content Glycerine Kinematic Viscosity

Of the above, from our studies it appears that the real bottleneck would be the kinematic viscosity, as the other three parameters could possibly be controlled during the transesterification process or by employing other processes. From other studies as well, it is clear that one of the major scientific impediments to castor oil being a biodiesel feedstock is its high viscosity. As noted earlier, some experiments suggest that the transesterified castor oil could be made to have a viscosity that is close to acceptable limits, while there are some others which are not conclusive. Assuming transesterified castor oil biodiesel can have an acceptable kinematic viscosity, based on the above facts and analysis, castor oil can theoretically be a candidate for bio-‐diesel. However, its limited production (less than 1% of the total amount of vegetable oils), rising demand in diverse non-‐fuel applications, and its volatile and high prices make it an unlikely contender to be a significant contributor for the biofuel industry for the foreseeable future. Addendum 1: How is castor oil converted into bio-‐diesel? The most common process of converting castor oil into a product that can be used as diesel is the same as what is used in the case of converting other similar vegetable oils into diesel. The process is called transesterification.

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Transesterification refers to a reaction between an ester of one alcohol and a second alcohol to form an ester of the second alcohol and an alcohol from the original ester, as that of methyl acetate and ethyl alcohol to form ethyl acetate and methyl alcohol. Transesterification largely eliminates the tendency of the plant oils and fats to undergo polymerisation and auto-‐oxidation, and also reduces the viscosity of the oil to about the same as petroleum diesel. Transesterification of castor oil like the transesterification process for other oils is done by the reaction castor oil with methanol (or ethanol) in the presence of a catalyst. Several conventional catalytic systems such as KOH, NaOH, KOCH3, NaOCH3, H2SO4, HCl, K2CO3, and CaCO3 can be considered, though NaOH is one of the most widely used catalysts for transesterification. Results from some recent studies show that acid catalysis is relatively effective for the ethanolysis of castor oil, particularly at short reaction times. In a recent experiment involving the transesterification of castor oil, potassium and calcium carbonates were also tested as catalysts. Although both compounds were insoluble in the reaction medium, the former was a relatively effective catalyst whereas the latter showed no catalytic activity even after almost ten hours of reaction. Some useful research info on biodiesel from castor oil The following is an excerpt from a transesterification research using alternative catalysts, done in 2006: Transesterification of castor oil in the presence of acid and alkali. Several conventional catalytic systems were used (including KOH, NaOH, KOCH3, NaOCH3, H2SO4, HCl, K2CO3, and CaCO3) to obtain an overview of the typical yields of FAEE obtainable from the transesterification of castor oil. In all cases the highest conversion yields were achieved following long (>5 h) reaction times. Among the catalytic systems studied, the use of methoxides or acids produced the highest yields of FAEE and such reactions attained reversibility after ca. 6 8 h, as has already been reported. Methoxide ions appeared to be more efficient catalysts than hydroxide ions although, from a chemical standpoint, the active species in both systems were the ethoxide ions formed by virtue of the large excess of EtOH in the medium. The significant difference between the two catalytic systems is that with hydroxide catalysts, water molecules are produced during the formation of the active species; as a consequence, side reactions, such as hydrolysis and saponification, may diminish the yield of ester. The results clearly show that acid catalysis is relatively effective for the ethanolysis of castor oil, particularly at short reaction times. Potassium and calcium carbonates were also tested as catalysts. Although both compounds were insoluble in the reaction medium, the former was a relatively effective catalyst whereas the latter showed no catalytic activity even after 10 h of reaction.

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Based on the results presented, one may conclude that the production of biodiesel by ethanolysis of castor oil may be improved through further development and optimization of appropriate catalytic systems and processes. Strategies involving acid catalysis might provide a promising solution to this problem since it has recently been demonstrated that on an industrial scale acid-‐catalyzed production of biodiesel can compete economically with base-‐catalyzed processes. Moreover, acid-‐catalyzed transesterification reactions exhibit an important advantage in that the performance of the acid catalyst is not strongly affected by the presence of FFA in the oil. In fact, acid catalysts can simultaneously catalyze both esterification and transesterification Reference: http://www.biodiesel.gov.br/docs/JAOCSMeneghetti2006.pdf Another research done in 2007 on the thermoanalytical characterization of castor oil biodiesel

work wishing to provide a thermoanalytical and physical-‐chemistry characterization of castor oil and biodiesel was done in 2007. Biodiesel was obtained with methyl alcohol and characterized through several techniques. Gas chromatography indicated methyl ester content of 97.7%. The volatilization of biodiesel starts and finishes under inferior temperatures than the beginning and final volatilization temperatures of castor oil. Biodiesel data are very close to the volatilization temperatures of conventional diesel Reference: http://cat.inist.fr/?aModele=afficheN&cpsidt=18403364 Rheological behavior of castor oil biodiesel Jul 2005 Viscosity, the measurement of the internal flow resistance of a liquid, constitutes an intrinsic property of vegetable oils. It is of remarkable influence in the mechanism of atomization of the fuel spray, in other words, in the operation of the injection system. This property is also reflected in the combustion process, whose efficiency depends the maximum power developed by the engine. This work aims at assessing the rheological behavior of castor oil, castor oil biodiesel, and undegraded and degraded biodiesel at different exposure times and temperatures. Castor oil biodiesel presents viscosity higher than diesel oil, but this drawback can be corrected by means of blends of both components at different proportions. The viscosity data indicated that the heat treatment leads to a degradation of the samples accompanied by an increase of the viscosity, probably because of interactions with intermediary compounds. The degraded samples presented a pseudoplastic behavior, once the flow index, m, is smaller than 1.

; -‐ Universidade Federal do Rio Grande do Norte, Departamento de Química, Laboratório de Combustíveis, Natal, Rio Grande do Norte, Lagoa Nova, CEP 59072970, Brazil, and -‐ Universidade Federal da Paraíba, Departamento Química, João Pessoa, Paraíba, Brazil Energy Fuels, 2005, 19 (5), pp 2185 2188; DOI: 10.1021/ef050016g; Publication Date: July 8, 2005) Thermoanalytical characterization of castor oil biodiesel -‐ 2007 A work wishing to provide a thermoanalytical and physical-‐chemistry characterization of castor oil and biodiesel was done in 2007. Biodiesel was obtained with methyl alcohol and

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characterized through several techniques. Gas chromatography indicated methyl ester content of 97.7%. The volatilization of biodiesel starts and finishes under inferior temperatures than the beginning and final volatilization temperatures of castor oil. Biodiesel data are very close to the volatilization temperatures of conventional diesel. (See abstract here -‐ http://cat.inist.fr/?aModele=afficheN&cpsidt=18403364, A 2007 research paper) Addendum 2: Castor Oil as Biofuels Facts, Data, Nuggets While castor oil is unlikely to be a significant contributor to the biodiesel industry for the foreseeable future, as pointed out earlier, in specific cases and regions it could play a limited role as a biodiesel feedstock. This is especially true of poor countries in Africa and South America. Following are some of the initiatives that are being taken in order to explore the viability of castor oil as a biodiesel feedstock.

In Aug 2008, Petrobras Biocombustível of Brazil reaffirmed that it will continue producing Biodiesel from castor oil despite the fact that castor oil does not qualify on 2 of the 22 parameters ( the two being specific gravity and viscosity ) set for biodiesel by the National Petroleum Agency (NPA) of Brazil. In fact, according to reports, the Resolution 7 by the NPA prohibits the usage, in Brazil, of biodiesel produced from castor seed oil. However, Petrobras Biocombustível clarified early Aug 2008 that its plans were not affected by the NPA Resolution dated March 19

al had always been to use, initially, blends of up to 30% castor seed oil as raw material. The usage of 30% castor seed oil

to the company. The company further stated that a few important properties will, in fact, even be improved by the addition of castor seed oil as a raw material. For example, adding 30% castor seed oil to soybean oil improves the quality of the biodiesel that is produced, making it compliant with the European standard, and, thus, viable to be exported to cold European regions.

Alternative Energy in Castor Beans in Brazil -‐ May 2008 -‐ The state-‐run Brazilian

Enterprise for Agricultural Research (EMBRAPA) is experimenting with castor oil as biodiesel feedstock at its labs in the northeastern city of Campina Grande, in Paraíba state. The castor-‐oil plant is easy to grow and is resistant to drought, which makes it an ideal crop for the extensive semi-‐arid region of northeast Brazil. That area holds some four million hectares of appropriate land that could yield up to 1.5 tons of castor beans per hectare, compared to the global average of 750 kilos per hectare. And castor beans could become a farming alternative, providing income for 15 million people in Brazil's poorest region. For decades, Brazil was the world leader in producing and exporting castor oil, but has fallen to third place, behind India and China. Brazilian output of 500,000 tons in the late 1980s fell to about 100,000 tons in 2007. A clear signal that Brazil plans to move towards biodiesel would jump-‐start the recovery of the castor-‐oil crop.

pilot program in castor oil viability as an energy alternative. (May 2008)

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Ivory Coast diversifies into biofuels production (Jul 2008) -‐ Ivory Coast is diversifying

into the booming market for biofuels by growing the jatropha & castor plants. To take advantage of a global trend toward alternatives to fossil fuels, several jatropha projects are underway across the West African nation, which intends to produce enough oil to make biofuel domestically. In Toumdi in centre of the country, the Ivory Coast Reneweable Energies Development Agency (ADERCI), a privately-‐owned firm, is producing seeds for a project to grow jatropha and castor plants on 100,000 hectares from 2009. The project involves around 70,000 farmers, and is seen producing a total of 1.8 million tonnes of jatropha and castor seeds a year, enough to make 705,600 tonnes of biofuel. Oil produced by pressing jatropha and castor seeds will be sold to the Ivorian Refinery Company, and the national petrol firm, Petroci, to make biodiesel. According to the co-‐ordinators, Jatropha and castor oil plants can grow on any type of land and this is a project which will help redress the social imbalance caused by cocoa and coffee, which only grow in some soils. According to them, 5,000 hectares of jatropha or castor oil will be enough to produce between 15 and 23 million litres of biodiesel per year.

Biofuel from Castor Beans in Brazil (March 2008) -‐ Brazil recently launched a major

bio-‐diesel program that will start in 2008 with 2% bio-‐diesel added to fossil fuel-‐derived diesel. Significant incentives are already in place, with emphasis on the production of bio-‐diesel from castor bean oil. Part of the program focuses in the Northeast, the poorest region in the country, where the castor bean is very well adapted to the arid areas. Until now, little attention has been paid to the Amazonian region, in spite of the fact that ther is a high potential for bio-‐diesel production from palm oil to replace fossil diesel that power generators in hundreds of off-‐grid communities (with total subsidies for the transportation of fuel diesel going up to about US$1.2 billion in 2005). Small-‐scale processing of castor beans at a facility owned by the local farmers would allow them to capture the value added from processing. In addition, they would have the option, depending on price, to sell the oil to either bio-‐diesel producers or to those who use the oil for lubrication, thereby avoiding dependence on a single buyer. The project is supporting the creation of access of locally owned small-‐scale renewable energy projects to financial markets, promoting public and private sector investment within the renewable energy market, and collaborating with partners to identify and secure sources of capital and markets.

Fiorello H. LaGuardia Foundation (LGF) has initiated a castor bean oil producers association, training small farmers in Itatira, in the State of Ceara with local partners the AVINA Foundation, Associação Caatinga and the Brazilian National Environment Fund. LGF has also started preliminary work on biodiesel from a native Amazonian palm tree that is under commercial production in the State of Maranhão.

The project is supporting the creation of access of locally-‐ owned small-‐scale renewable energy projects to financial markets, promoting public and private sector investment within the renewable energy market, and collaborating with partners to identify and secure sources of capital and markets.

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The LGF approach will also increase distribution efficiencies through decentralized production of vegetable oil and biodiesel, eliminating long distance transportation of raw agricultural products, and ensuring that the added value of the agricultural residues (fertilizer and animal feed) remains with the small farmers.

Castor biofuel farming started in 2008 in Ethiopia. The initiative is run by energy

company Global Energy Ethiopia, who are also conducting a research and development programme to create new varieties of castor with better yields. In July 2008, Global Energy announced it had successfully completed sowing 5,000 hectares of Chinese hybrid castor seeds for its alternative energy project in Ethiopia. The project entails planting and harvesting castor for the production of non-‐edible oil for the bio-‐diesel industry and for other uses. The castor farming initiative is located in southern Ethiopia, approximately 350 km south of the capital of Addis Ababa. Just six months after launching the project, some 90% of the land has reached a germination stage of over 96%.

Some companies in the Dominican Republic are exploring growing castor and using

castor oil as biodiesel. One of the reasons is that the natural conditions in the country could be suitable for the growth of castor crop. (Based on a 2008 news report)

Jamaica To Use Castor Bean as a Biofuel -‐ August, 2007 -‐ Castor oil has been

identified as a viable biofuel to be produced locally and used as a cost-‐effective way to cut Jamaica's growing energy bill -‐ an opportunity that has not escaped the private sector. Karl James, the chairman of Petrojam Ethanol Limited, noted that, "There are plans for a major commercial plant to be constructed and many persons are now preparing their lands for the castor bean." He added, "We believe that large areas of rural Jamaica could be quickly transformed into attractive economic zones where independent small land owners are engaged in the production of an agricultural good for which there is a ready market at a price that should provide satisfactory return for their efforts." The castor bean is considered complementary to ethanol for many reasons: (1) It is not a food product, (2) It is well known in Jamaican agriculture, (3) It is not prone to larceny, (4) It can be produced on varied scales from large scale farms to cottage industries, involving thousands of small farmers in the rural areas.

African Countries in Co-‐operation with Brazil on Castor Biodiesel -‐ March 2007 -‐

Morocco became the first Arab country in North Africa to establish a partnership with the Brazilian Agricultural Research Corporation (Embrapa) office in Accra, the capital of Ghana. The partnership should be concentrated mainly in the production of biodiesel, which may be obtained from castor seeds and pine seeds, plants of the region that are resistant to lack of rain. Libya is another Arab country that may make use of the Embrapa office in Africa. According to the researcher, the Libyan embassy in Ghana has already shown interest in a partnership in the area of irrigated agriculture.

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A new project has been financed by FEP Ethiopia for castor oil based biodiesel (2007) This is for a castor plant for biofuel production in Oromia State, Ethiopia. FEP Ethiopia PLC, Ethiopia, a fully owned subsidiary of Flora EcoPower Holding AG, Germany, signed a land lease agreement with Oromia State and a collaboration agreement with the peasant Associations (Community Farming), 26 associations in total for all Fedis and Midega Region. The land lease agreement secures the company 8,000 hectares of government land for castor cultivation for 45 years.

Castor Oil is a new source for biodiesel in the USA? (Jun, 2006) -‐ Using grant money

from the federal government, Mississippi State has begun conducting research on a number of alternative crops, including winter annuals like canola, camelina, hesperis, black mustard, crambe and flax, summer annuals such as castor and sunflower and perennials such as tung and tallow trees. Castor has attracted the attention of MSU researchers because with its oil content at 50 percent and its relatively high crop yield of 1,695 pounds per acre, castor beans can supply up to 141 gallons of castor oil per acre. That compares to 50 to 60 gallons per acre for soybeans. (The yield data provided are by the researchers from the USA, officially published figures for castor yield in India are lesser only about 1000 pounds per hectare)

The Myanmar government plans to implement a project to grow castor bean plants

2006 news)

In 2006, Japan showed significant interest in importing castor oil to produce biodiesel.

A December 2004 Report from Brazil -‐

imported diesel, castor bean producers may soon be eligible to sell carbon credits. A Brazilian industry professional estimates that 40 percent of the biodiesel produced in the country in the coming years could come from castor beans. Embrapa is working to develop commercial varieties of castor beans with higher levels of oil output -‐ around 60 percent of the weight of the beans -‐ and is also working on varieties that can be planted below 300 meters above sea level. The northeast state of Bahia is

output. But other states like Paraíba stand to gain from the government bill that will set biodiesel levels in regular petroleum diesel sold at the pump at 2 percent.

Brazil Starts Biodiesel Drive -‐ August 2004 In Aug 2004, Brazil launched efforts to

produce a biodiesel fuel on an industrial scale using the castor-‐oil plant. A pilot project has been underway for two months in Quixeramobim, state of Ceará. Quixeramobim is a town in the semi-‐arid region of the Brazilian Northeast where 70 hectares are being cultivated. At the moment, the project is producing 350 liters daily of biodiesel. When the project is completely operational it will produce 800 liters daily. So far, a total of US$ 508,000 (1.5 million reais) has been invested by the state, local authorities and a consortium of privately-‐owned thermoelectric power plants.

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Gujarat Oleo Chem Ltd (GOCL) based in Mumbai, India, bagged an order for supply of biodiesel worth Rs 25 crore (US$ 6 million) to Indian Oil Corporation (IOC) in Aug 2004. GOCL planned to use castor oil as feedstock for production of biodiesel.

Brazil Northeast region to produce biodiesel with castor oil -‐ March, 2004 -‐ Brasil

EcoDiesel will transform the Brazilian Northeast region into a large biodiesel producer. The company has already started in Canto do Buriti (Piaui), the first of a total of six projects -‐ four in Piaui and two in Ceara states that involve the cultivation of the castor plant, which is a raw material for biodiesel production. Each project demands investments of R$15mil for the cultivation of a 52,000 ha area.

Brazil, the world's second largest producer of soybean, passed a bill (in 2004) making

it compulsory to produce a 2% bio-‐diesel fuel blend, made from castor oil and soy oil.

China is exploring major investments in Brazil to produce both ethanol and castor oil

or biodiesel for shipment to China While specific gravity and viscosity could be some of the issues to be dealt with while

considering castor oil as a biofuel feedstock, the other main issue is its low availability. The total production of castor oil is less than 500,000 T per annum and given its use in a number of industries, the non biofuel consumers of castor oil today are willing to paying for castor oil a price that is above what would be currently economically viable for the fuel segment to pay.

Can castor oil be used in the production of anhydrous ethanol? Castor oil freely

dissolves in alcohol. This means that in theory castor oil can be used in ethanol production to separate the distilled ethanol from the 5% or more of water it will contain, producing anhydrous ethanol that can be used for production of ethyl esters biodiesel. Ethanol needs to be anhydrous for it to be blended with gasoline for fuel use. This method however has not been employed by anyone formally, so one can say this is more a theoretically possibility.

According to one school of thought, castor oil is the best substance for producing

biodiesel because it is the only one that is soluble in alcohol, and does not require heat and the consequent energy requirement of other vegetable oils in transforming them into fuel.

Three Israeli companies -‐ alternative energy company Ormat (www.ormat.com), plant breeding company Evogene (www.evogene.com), and the real estate developer the Lev Leviev Group (www.thelevievgroup.com) signed an agreement, in 2008, to produce biodiesel from castor oil. Leviev already owns mining concessions

substantial experience in biofuel R&D, and Evogene is a world leader in plant genetics and breeding. Evogene Ltd. conducted a Life Cycle Assessment (LCA) of biodiesel production from castor bean varieties. In Apr 2010, the company announced that the LCA of biodiesel produced from castor bean varieties reduced

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greenhouse gases (GHG) emissions by 90% compared to petroleum diesel in the U.S. The results are based on Evogene's objectives for castor bean varieties, aimed at increasing crop yields to 4-‐5 ton/ha on semi-‐arid lands -‐-‐ focusing on Texas and Brazil.

Results showed that Evogene's castor bean biodiesel

Reduces net GHG emissions by 90% in the U.S. and more than 75% in Brazil compared with conventional diesel, if grown in non-‐arable or marginal land.

Exceeds the GHG savings achieved with soybean biodiesel, with reductions for the U.S. of 43% compared to soybean.

Brasil Ecodiesel (www.brasilecodiesel.com.br) according to the ANP, National agency of petroleum. The company maintains six operational plants with a combined annual biodiesel production capacity of 640,000 m3. In order to maintain market leadership in Brazil, the Brazil Ecodiesel has projects for the expansion of the capacity of its plants and which will happen according to the needs of the market. The company has pioneered the production of biodiesel on a commercial scale in Brazil, with castor, jatropha and other vegetable oil as a feedstock. Its activities are based on cost-‐efficient industrial and logistics processes and an innovative and diversified model for the sourcing of raw materials through direct purchases in the vegetable oil market, the development of new intensive agricultural production chains and the encouragement of family farming, with an emphasis on the promotion of human and social development. The company entered into an agreement with the state of Piauí for the installation of a castor plant production center based on family farming. Brasil Ecodiesel also intends to develop new crops of castor plant to achieve greater productivity. The extraction of vegetable oil and the process of producing biodiesel through transesterification have generated by-‐products of significant economic value. The production of vegetable oil from oilseeds intended exclusively for industrial consumption, such as castor plant and jatropha, have generated additional income by marketing them in the form of organic fertilizer and to reduce operating costs by using biomass to generate heat for its own biodiesel production process. The production of biodiesel also generates significant amounts of glycerin that can be used to generate heat or can be sold to third parties for use in cosmetics, petrochemicals and other products.

Fertibom (http://www.fertibom.com.br ) is an agribusiness organisation in Brazil.

technology, resource production processes using internally designed and built equipment. The biodiesel is produced from castor and other oilseeds using ethyl or methyl alcohol through its innovative process called T-‐max.

Kaiima (www.kaiima.com) is a next generation seed and breeding company. The

-‐GMO crops with dramatically improved productivity and improved land and water-‐use efficiencies.

-‐transgenic biotechnology platform developed in 2002 that induces clean polyploidy in plants

http://www.brasilecodiesel.com.br/

http://www.fertibom.com.br/

http://www.kaiima.com/

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(i.e., multiplying the number of chromosomes found in the plant). It includes a proprietary set of protocols and methods that direct the active chemicals used in the genome-‐multiplication process away from the sensitive DNA, which stays unharmed, unlike past methods for inducing polyploidy, thus keeping the plant fertile and genetically stable. The company claims that its technology provides advantages including higher plant yield, greater biomass accumulation, enhanced photosynthesis and other features. proprietary genomic-‐based breeding technologies to develop high-‐yielding energy crops for the production of biodiesel, bioethanol, and biomass energy. The biodiesel strategy involves breeding castor varieties that can yield up to 10 tons of seeds (or 5 tons of oil) per hectare per year compared to the global average of between 1-‐1.5 tons of seeds. The company expects that these high yields, will make fuel from castor we economically competitive with the price of petroleum.

Rahan Meristem (www.rahan.co.il) is an Israeli company with more than 30 years

experience in plant propagation and biotechnology, and in the laboratory production of tissue culture plants. In January 2010, the company was reported to have announced its plans to engage in developing protocols for the mass propagation and genetic transformation of castor beans and jatropha to produce biodiesel. The

market transgenic jatropha and castor bean clones that confer resistance to salinity and drought.

6.2.3 Other Possible Future End Uses for Castor Oil & Derivatives

Castor oil based polyurethane adhesives Lubricant for ethanol fuel -‐ Ethanol has no lubricating characteristics. Castor oil is

one of the few lubricants that blend with alcohol. This might lead to castor oil being a major lubricant for the ethanol fuel market.

Oil-‐modified alkyd type resin based on secondary esters of castor oil Use of castor oil in preparation of oil-‐based binders Use in castor oil in treating some unique gland ailments Acetoacetylated castor oil in coatings applications -‐ Acetoacetate esters from castor

oil are being tried to formulate thermosetting coating compositions. Food Grade Plasticizers In July 2005, Denmark's Danisco A/S announced it has

developed a non-‐phthalate plasticizer based on castor oil. This food-‐grade plasticizer for flexible PVC has been developed as an alternative to phthalates. Grindsted Soft-‐N-‐Safe from is made from fully hardened castor oil and acetic acid. The product has been approved by the EU for food-‐contact applications and is expected to find future uses in toys and medical equipment.

Modification of the biopolymer castor oil with free isocyanate groups to be applied as bioadhesive -‐ Surgical adhesives have been used for several applications, including haemostasis, sealing air leakages and tissue adhesion. Recent research has tried to produce a biodegradable urethane-‐based bioadhesive containing free isocyanate groups. This material presents the advantage of being biodegradable, biocompatible and having the capacity of reacting with amino groups present in the biological

http://www.rahan.co.il/

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molecules. Uurethane based on castor oil (CO) was synthesized by reaction of the molecule with isophorone diisocyanate (IPD) for developing this product.

SUMMARY Castor oil has over a thousand patented industrial applications. It is used in the following industries: automobile, aviation, cosmetics, drug, electrical, electronics, food, manufacturing, plastics, and telecommunications. Recently, castor oil is being investigated for its use in producing bioplastics.

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7 -‐ Castor Seeds This chapter comprises the following topics

Castor Seeds Production & Supplies -‐ 7.1 Castor Seeds Prices & Trends 7.2 Castor Seeds Packaging & Storing 7.3 Castor Seed Varieties 7.4 Castor Seed Factoids 7.5

HIGHLIGHTS

India is the largest producer of castor seeds in the world with China and Brazil being the next two. It exports about 15,000 T of castor seeds per year.

The prices of castor seeds are volatile and this volatility is present intra-‐year as well

as inter-‐year.

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7.1 Introduction to Castor Seeds Although monotypic, the castor oil plant can vary greatly in its growth habit and appearance. It is a fast-‐growing, suckering perennial shrub which can reach the size of a small tree (around 12 m), but it is not hardy. It has large leaves which are long-‐stalked, alternate and palmate with coarsely toothed segments. Terminating stems are panicle-‐like inflorescences of green monoecious flowers, the stalked female flowers above the male flowers below, both without petals. The fruit is a spiny, greenish capsule with large, oval, shiny, bean-‐like seeds with variable brownish motling. The inflorescence of the castor plant consists of an erect panicle with female flowers at the top and male flowers at the bottom. The castor fruits are spherical capsules which become hard and brittle. The seed capsule has thick walls, is spiny and contains 3 cocci. Each coccus contains one seed. 7.2 Castor Seeds Production & Supplies India is the largest producer of castor seeds in the world with China and Brazil being the next two. India is also the largest exporter of castor seeds; it exports about 15,000 T of castor seeds per year, on an average.

World Castor Seed Production

Country Harvest Season

Production ('000 T) Yield (T/ha) Harvest Area ('000/ha)

09-‐10(F) 2008-‐09

2007-‐08

09-‐10(F)

2008-‐09

2007-‐08

09-‐10 (F)

2008-‐09

2007-‐08

Brazil Jun-‐Sept 92 123 94 0.58 0.76 0.6 158 163 156

China PR Sep -‐ Jan 190 190 170 0.9 0.86 0.81 210 220 210

India Nov -‐ Mar 880 975 990 1.06 1.08 1.15 830 900 860

Other Countries 115 117 112 0.62 0.63 0.61 185 186 183 Total 1277 1405 1366 0.92 0.96 0.97 1383 1469 1409

Note: F-‐ Forecast Source: ISTA Mielke, Oil World, Germany.

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7.3 Castor Seeds Prices & Trends The prices of castor seeds are volatile and this volatility is present intra-‐year as well as inter-‐year. Average Prices for Castor Seeds The average spot prices provided for specific months over a 3 year period to demonstrate the increase and volatility in prices

Year Average Price ($ / T) 2005 May 400 2005 Nov 330 2006 Mar 340 2006 Jul 340 2006 Nov 400 2007 Mar 460 2007 Jul 480 2007 Nov 500 2008 Mar 600 2008 Jul 700 2008 Nov 650 2009 Mar 490 2009 Jul 540 2009 Nov 640 2010 Mar 640

The above prices also have factored in the volatility of the Indian Re / US $ which saw a change of over 20% during this period (45 Rs per US $ in 2004 to 39.5 Rs per US$ by end of 2007, back to about 50 Rs per US$ by end of 2008, and hovering about 45 Rs per $ by Mar 2010!) 7.4 Castor Seeds Packaging & Storing

Castor seeds are large and occupy considerable space in the storehouse. The normal packing is either 50 Kgs or 70 Kgs, and the products are usually packed in

gunny bags.

It is recommended that castor seeds be dried to 5-‐6% moisture content before storing.

7.5 Castor Seeds Varieties & Hybrids Please see section 5.5 in chapter 5.

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7.6 Castor Seed Factoids

o Some areas in the state of Gujarat in India claim to produce a yield of 6 T of seeds per hectare (about 2500 Kg per acre), while according to published figures, the average yield in India is only about 1 T per hectare

o It is possible to store castor seeds for about 5 years, as long as the seeds are kept in a cool and dry place

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8 -‐ Castor Meal This chapter comprises inputs on the following topics

Castor Meal Uses 8.1 Castor Meal Composition 8.2 Castor Meal Supply & Demand 8.3 Toxicity in Castor Meal 8.4 Energy Content in Castor Meal 8.5 Castor Meal Other Points 8.6

HIGHLIGHTS

Castor meal is one of the most useful natural manures.

The two primary uses of castor meal today are as fertilizer and as fuel.

India exported about 330,000 MT of castor meal for the period 2007-‐2008. About 1,00,000 tons are consumed within the country, in the form of fertilizers and as fuel.

When compared to other oilseed meals such as rapeseed mean and soymeal, castor

meal is much cheaper.

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8.1 Castor Meal Uses Castor meal -‐ the residue obtained from castor cake -‐ is one of the most versatile natural manures. It is organic manure that enhances the fertility of the soil without causing any damage or decay. It is enriched with the three big elements vital and conducive to the proper growth of crops -‐ Nitrogen, Phosphorus and Potassium. It also has traces of nutrients like Manganese, Zinc and Copper, thus making it a balanced fertiliser. Advantages 1. Provides all the major & minor nutrients necessary for better plant growth 2. Helps in increasing the nutrient uptake by plants 3. Improves soil fertility and productivity; improves yield & quality of the farm produce 4. Protects plants from nematodes and termites Main Uses of Castor Meal The two primary uses of castor meal today are as fertilizer and as fuel 8.2 Castor Meal Composition Nutrient Content of Deoiled Castor Cake / Meal A typical composition of castor residue/meal is as follows:

Organic Matter 80-‐85% (The organic matter consists of proteins about 32-‐33%, fibers about 25-‐30%, ash content about 6%)

Nitrogen 5 %

Phosphourous (as P205) 2 %

Potassium 1.25 % -‐ 1.5 %

Moisture 10% max. approx.

Oil Content 0.7% max. approx.

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It also contains some micro nutrients viz., Calcium, Magnesium, Sulphur, Iron, Zinc, Manganese, Copper etc. (One published manural value for castor cake is: 6.6% N, 2.6% P2O5, and 1.2% K2O -‐ C.S.I.R., 1948 1976). Castor meal is an excellent fertilizer because of high content of N (6.4%), Phosphoric Acid (2.55%), Potash (1%) and moisture retention. The protein content of castor seed meal varies between 21-‐48% depending upon the extent of decortications. It has an ideal amino acid profile with moderately high Cystine, mithionine, and isoleucine. While it is rich in proteins, castor cake cannot be used as cattle fodder because of its toxicity. 8.3 Castor Meal Supply & Demand India exported approximately 2, 00,000 tons of castor meal in 2006-‐2007. About 1,00,000 tons are consumed within the country, in the form of fertilizers and as fuel. While the castor meal exports also fluctuate in tune with the castor oil trading market, India has seen a dramatic increase in the exports of castor meal in the period 2003-‐2008. According to estimates by the industry, the increase has over 400%. Between 2006-‐2007 and 2007-‐2008 alone, the increase has been over 60%! India exported about 330,000 MT of castor meal for the period 2007-‐2008. South Korea and Taiwan are the leading importers of castor seed meal. Vietnam, China, Brazil and Europe are the other major consumers. Most of these consumers, with the exception of Brazil, import almost all their consumption, primarily from India.

Indian Castor Meal Exports

Year Exports (in MT) 2003-‐04 65 2004-‐05 70 2005-‐06 200 2006-‐07 205 2007-‐08 330 2008-‐09 204 2009-‐10 240

Source: http://www.seaofindia.com/oilmeal_data/oilmealdata_march_2010.pdf The price of castor meal ranges between $70-‐$80 per T (FOB), depending on the season and the supply-‐demand scenario.

http://www.seaofindia.com/oilmeal_data/oilmealdata_march_2010.pdf

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8.4 Toxicity in Castor Meal The castor cake is mainly used as a fertilizer. It is unsuitable as an animal feed because of the presence of toxic protein called ricin and toxic allergen often referred to as CBA (castor bean allergen). However, it is noteworthy that none of the toxic components is carried into the oil. Some methods for the detoxification of the cake have been attempted. These include

Treatment with ammonia, caustic soda, lime and heat.

When the cake is steamed, the ricin is detoxified and the allergen is inactivated.

Another method of detoxifying castor seed meal involved the wet mixing with sal seed meal so that the toxic constituents of castor seed were neutralized by tannins.

In addition, some people in parts of South-‐Eastern Nigeria have long developed a

method for treating and detoxifying the unextracted seed. In this case, the method used to detoxify castor seed involves fermentation. The seeds are first dehulled and boiled in water for about 18 hours. The boiled seeds are cooled and wrapped together with leaves and allowed to ferment in the fire place for about five days. The fermented seeds are then mashed by pounding using a mortar and pestle. This is followed by addition of ash from burnt palm kernel husk which gives it a dark colour. The dark, mashed product is allowed to mature for a further period of five days after which it is packaged for sale. It is believed that most of the detoxification takes place during fermentation and it leads to the elimination of the toxic factors. Microbiological studies have shown that the bacteria involved are spore-‐forming bacteria, especially members of the genus Bacillus

Detoxified and deallergenized castor meal (DDCM) is a by-‐product of an extraction

process of the castor bean in Thailand, introduced in the 1990s. It has been claimed that DDCM can be safely used as animal feed. It is claimed that the extraction process is done in such as way that due to the action of heat, together with some base solubles, the castor meal is rendered non-‐toxic.

Although the use of detoxified cake as cattle feed has been reported in a few cases using one or more of the methods explained above, extreme caution and experimentation are desirable before the cake is fed to farm animals. About the ricin The castor seed coat contains ricin, a poison, which is also present in lower concentrations throughout the plant. The toxicity of raw castor beans is well-‐known, though reports of actual poisoning are relatively rare. While children could die from the intake of as few as three beans; adults may require eight or more. When injected, even a small dose of ricin may cause toxic symptoms.

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Ricin is classified as a Type 2 ribosome inactivating protein (RIP). Whereas Type 1 RIPs consist of a single enzymatic protein chain, Type 2 RIPs, also known as holotoxins, are heterodimeric glycoproteins. Type 2 RIPs consist of a Ricin A chain that is functionally equivalent to a Type 1 RIP, covalently connected by a single disulfide bond to a Ricin B chain that is catalytically inactive, but serves to mediate entry of the A-‐B protein complex into the cytosol. Both Type 1 and Type 2 RIPs are functionally active against ribosomes in vitro, however only Type 2 RIPs display cytoxicity due to the lectin properties of the B chain. The Ricin A Chain is an N-‐glycoside hydrolase composed of 267 amino acids. It has three structural domains with approximately 50% of the polypeptide arranged into alpha-‐helices and beta-‐sheets. The three domains form a pronounced cleft that is the active site of RTA. The Ricin B Chain is a lectin composed of 262 amino acids that is able to bind terminal galactose residues on cell surfaces. RTB form a bilobal, barbell-‐like structure lacking alpha-‐helices or beta-‐sheets where individual lobes contain three subdomains. At least one of these three subdomains in each homologous lobe possesses a sugar-‐binding pocket that gives RTB its functional character. Many plants such as barley have the Ricin A chain but not the B chain. People do not fall ill from eating large amounts of such products, as Ricin A is of extremely low toxicity as long as the B chain is not present. Potential medicinal use of ricin Ricins may have therapeutic use in the treatment of cancer, to specifically target and destroy cancer cells: Ricin could be linked to a monoclonal antibody to target malignant cells recognized by the antibody. Modification of ricin is believed to be possible to lessen its toxicity to humans, but not to the cancer cells. Another promising approach is to use the non-‐toxic subunit of ricin as a vehicle for delivering antigens into cells, thus greatly increasing their immunogenicity. Use of ricin as an adjuvant has potential implications for developing mucosal vaccines. 8.5 Energy Content in Castor Meal The calorific value of deoiled castor cake is about 4200 Kcal per kg. Given the fact that the cost of castor meal /cake is lower than those of other equivalents such as soy meal, rapeseed meal etc., and given its reasonably good energy content, castor meal is today used in some cases as a cost effective fuel. However, the limited quantities in which castor meal is available, and the significant demand that emanates for its use as organic fertilizer implies that the impact of castor meal on the biomass/biofuels industry is insignificant.

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8.6 Castor Meal Other Points

For the time being, castor bean presscake is not widely used as it contains toxic proteins and allergens. However, the lipase it also contains could be used for various applications: stereoisomer separation, emulsifier production or edible fat and triglyceride biomanufacturing, which improves the nutritional, rheological and functional properties of fatty acids.

In the last three years (2005-‐2008), according to suppliers in India, castor meal saw a price variation in the range $40-‐$150 per T

The countries to which castor meal is mostly exported from India are Korea and Taiwan.

When compared to other oilseed meals, castor meal is much cheaper than rapeseed meal and soymeal.

SUMMARY Castor meal is an excellent fertilizer because of the high content of nitrogen, phosphoric acid, potash and moisture retention. It is used as fuel as well. India is the largest exporter of castor seed meal, and South Korea and Taiwan are the leading importers. Vietnam, China, Brazil and Europe are the other major consumers. Most of these consumers, with the exception of Brazil, import almost all their consumption, primarily from India.

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9 -‐ Castor Oil Distribution & Logistics This chapter comprises inputs on the following topics

Castor Oil Storing & Packaging 9.1 o Castor Oil Storage 9.1.1 o Castor Oil Packaging 9.1.2 o Castor Oil Shelf Life 9.1.3

Castor Oil Transportation & Logistics 9.2

o Distribution from Farms to Refinery 9.2.1 o Transport 9.2.2 o Cargo Handling 9.2.3 o Density & Volume Expansion 9.2.4 o Cargo Securing 9.2.5 o Risk Factors & Loss Prevention 9.2.6

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9.1 Castor Oil Storing & Packaging 9.1.1 Castor Oil Storage Because the castor oil contains double bonds in its lipid structure, it is prone to an undesirable reaction called lipid oxidation. Lipid oxidation occurs when the double bonds in the fatty acid react with oxygen to form peroxides -‐ this changes the chemical nature of the oil. There are many factors which influence the rate of oxidation in foods: fatty acid composition, free fatty acids versus the corresponding acylglycerols, oxygen concentration, temperature, pro-‐oxidants, radiant energy (visible and ultraviolet light), and the presence of antioxidants. Owing to the above reasons, castor oil is stored in a controlled environment. That includes removing oxygen, storing the oil in a cool place, placing the oil in an opaque container, removal of pro-‐oxidants (e.g., cobalt, copper, iron, manganese, and nickel), and possibly adding antioxidants. 9.1.2 Packaging Packaging Options In retail, castor oil is usually sold in small packs. Sea Transport -‐ Castor oil is usually packed in steel drums (200/225 Kg) while transported by sea in containers. Many suppliers have started using flexibags for packaging as these are significantly less costly than drums.

Bulk Shipping -‐ usually for lots of 500 Metric Tons minimum 9.1.3 Shelf Life Under normal temperatures and conditions, castor oil has a shelf life of about 12 months. Used in retail form, refrigeration after opening is recommended 9.2 Castor Oil Transportation & Logistics 9.2.1 Distribution from Farms to Refinery The process mentioned below is representative of a typical distribution of castor seeds in India.

o Castor seeds are bought to the auction place from the farms o At the auction place, traders buy the castor seeds through an auction process.

There are many traders who do this in each city.

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o Then, there are a few large brokers (far fewer than the number of traders) who interact with the traders and who in turn are contacted by the crushers & refiners for purchase

o The supply chain thus looks as follows: Farmer -‐> Auction Place -‐> Trader -‐> Broker -‐> Crusher

o Pricewise, if X (Rs) is the price per Kg when it is auctioned, the price at which the crusher receives it is about 1.05 X (a 5% increase). This increase results by way of commissions to traders and brokers and for transport costs to the crushing unit.

9.2.1 Transport Castor oil can be transported by ship, truck, or railroad, depending on the factors. A large part of international transportation of castor oil happens by sea. 9.2.2 Cargo Handling Normally, castor oil does not need to be heated, since its solidification point is relatively low. However, should temperatures during voyage happen to be in the solidification range, the following must be noted: to be able to pump the oil out of the tanks, it must be at the required pumping temperature. This is only possible, however, if the oil has been kept liquid during the voyage (above a minimum temperature). If the oil solidifies in the tanks, it cannot be liquefied again even by forced heating. In the vicinity of the heating coils, the oil melts, scorches, discolours and becomes rancid. The oil may also cool too rapidly in the long lines and solid deposits form on the outer walls, which cannot be pumped out and prevent the still liquid cargo from reaching the suction valve. This problem can be solved by appropriate heating or insulation of the lines. Because of the above reasons, loading, travel and pumping temperatures must be precisely complied with, since any change in consistency which occurs during transport may prove irreversible. Where the oil is packaged in barrels, the latter have to be handled with appropriate care. Damaged barrels quickly lead to oil leakage and thus to loss of volume or to damage to other parts of the cargo. 9.2.3 Density & Volume Expansion The density of castor oil is approximately 0.960 cm3

With a rise in temperature, however, density diminishes, thereby leading at the same time to an increase in volume. This behavior is described by the coefficient of cubic expansion and is known as thermal dilatation. The coefficient of cubic expansion amounts to: g = approx. 0.0007°C-‐1

As a rule of thumb, castor oil may be expected to increase in volume by 1% of their total volume for each 14°C temperature increase. So, when filling the barrels or tanks, attention

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must however be paid to the expansion behavior of the cargo in the event of a rise in temperature (risk of bursting of barrels). 9.2.4 Cargo Securing In the case of castor oil (as with most other liquid cargoes), it is important for the space above the cargo to be small, so that only slight movement of the cargo is possible. Movement in liquid cargoes may have a negative effect on the stability of the means of transport (e.g. during cornering in the case of trucks and trains or when ships roll and pitch). Barrels have to be secured in such a way that they cannot slip in the hold or on the loading area and suffer damage. 9.2.5 Risk Factors and Loss Prevention Temperature Castor oil has no particular requirements as to storage climate conditions. The solidification temperature is of considerable significance in the transport of fatty oils and fats. They must remain liquid during loading, during the voyage and during unloading. Chill haze (separation) begins if cooling causes the temperature of the oil to approach solidification point, the oil becoming ointment-‐like and finally solid, and it can no longer be pumped. Separation and the associated change in consistency from liquid to solid occurs more readily upon cooling, the higher is the solidification point. The oil must be heated only by a few °C per day, else the risk of rancidity and other negative changes arises. The following table constitutes a rough estimate of appropriate temperature ranges. Temperatures may deviate from these values, depending on the particular transport conditions.

Designation Temperature range Travel temperature (favorable temperature range) 15°C (12 -‐ 25°C)

Solidification temperature -‐10 to -‐18°C

Pumping temperature 30 -‐ 35°C The travel temperature must be complied with as far as possible during transport, to minimize oxidation processes.

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Humidity/Moisture Castor oil is insoluble in water. However, contact with water may give rise to soluble lower fatty acids and glycerol, which cause rancidity together with changes in colour (yellow to brown), odour and taste as well as gelling and thickening. Castor oil spoils on contact with water. For this reason, the tanks must be absolutely dry after cleaning. Ventilation Ventilation must not be carried out under any circumstances, as it would supply fresh oxygen to the oil, which would promote oxidation processes and premature rancidity. Although castor oil thickens when exposed to atmospheric oxygen, it does not form a skin at the surface. Biotic Activity Castor oil displays 3rd order biotic activity. It belongs to the class of goods in which respiration processes are suspended, but in which biochemical, microbial and other decomposition processes proceed. Care of the oil during the voyage must be aimed at keeping decomposition processes to a low level. Self-‐heating / Spontaneous Combustion The oil may ignite spontaneously in conjunction with sawdust or material residues. Odour

Active ehavior

Castor oil releases an unpleasant odour. Contaminated oil smells like stale water.

Passive behavior

Tanks and barrels must always be odour-‐free, since there is a risk that quality will be diminished in particular where the previous cargo had a strong odour.

Contamination

Active behavior

Leaking oil leads to massive contamination and may make whole cargoes unusable. Of considerable significance with regard to tank cleaning is the iodine value, which is a measure of how strong a tendency the oil has to oxidation and thus to drying. Drying is particularly detrimental to tank cleaning, as the oil/fat sticks to the walls and can be removed only with difficulty. On the basis of drying capacity, oils are divided into nondrying, semidrying and drying oils.

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With an iodine value of 81 -‐ 100, castor oil is a non-‐drying oil, which means that it does not dry significantly on contact with atmospheric oxygen and so the tanks are easily cleaned.

Passive behavior

Castor oil is sensitive to contamination by ferrous and rust particles and water (especially seawater). The tanks or barrels must be clean and in a thoroughly hygienic condition before filling.

Mechanical Influences In the case of transport in barrels, extreme mechanical stresses, such as dropping, tipping over or bumping, may lead to breakage of the barrels and thus to leakage. Toxicity / Hazards to Health Before anyone enters a tank, it must be ventilated and a gas measurement carried out. Oxidation processes may lead to a life-‐threatening shortage of O2. Shrinkage / Shortage In cases where castor oil is packaged in barrels, weight loss from leakage is always to be expected. Losses of up to 0.3% due to adhesion of the cargo to the tank walls may be deemed normal. Insect Infestation / Diseases No risk. Castor Oil Storage during Transportation Maximum duration of storage:

Temperature Max. Duration of storage

12 -‐ 25°C 6 months

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10 -‐ Prominent Castor Oil & Derivatives Producers This chapter comprises inputs on the following topics

Producers in India 10.1 Producers in China 10.2 Producers in Brazil 10.3 Other Suppliers 10.4

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10.1 Prominent Castor Oil & Derivatives Producers in India Following is the list of prominent castor oil and castor derivatives manufacturers in India. The list is based on a number of parameters, the key among which are the size of the

1. Jayant Agro Organics 2. Biotor Industries 3. Ambuja Global 4. Adani Group 5. NK Proteins 6. RPK Agrotech

1. Jayant Agro Organics Main Line of Business: Castor Oil & Derivatives Production Background: Jayant Agro-‐Organics Limited is a public listed company, traded on Bombay Stock Exchange and the National Stock Exchange. It is a 100% Export Oriented Unit, and is one of the leading the Castor based companies in India. The company has a history of almost five decades. It is one of the largest castor oil and derivatives companies in the world. The company has acquired 100 percent subsidiary of Ihsedu Agrochem Pvt Ltd, a crushing unit from Gujarat Agro Industries Corporation Limited. This plant has a crushing capacity of 350 MT oil / day and also has solvent extraction plant. The plant is located in Banaskantha which is one of the largest castor growing districts in Gujarat which alone accounts for 75% of I Products manufactured are Castor Oil Commercial Grade, Castor Oil First Special Grade,Castor Oil Pale Pressed Grade, Castor Oil Extra Pale Grade, Castor Oil Neutralised Grade, Castor Oil Pharma Grade. Notable is the fact that this unit also manufactures all high grade Castor Oils including Castor Oil Cold Pressed. Products: The company had been focusing more on castor grades until a decade back. In the last few years, the company has started climbing the value chain and has a high focus on specialty chemicals. It currently supplies a range of generation I and generation II castor oil derivatives, besides the basic grades. Our estimate is that it will be supplying about 1,00,000 T of castor oil / derivatives, and about 75-‐100,000 T of castor meal per year. For a complete list of their products, please see the following URL http://www.jayantagro.com/products.htm Financials: Revenues of about 125 million US$ 2007-‐2008.

http://www.jayantagro.com/products.htm

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Location: Headquartered in Mumbai Address: Akhandanand, 38, Marol Co-‐Operative Industrial Estate, Off. M. V. Road, Sakinaka, Andheri (E) Mumbai -‐ 400059, India Tel: +91-‐22-‐66970470 www.jayantagro.com 2. Biotor Industries Main Line of Business: Castor Oil & Derivatives Production Background: Previously called Jayant Oil Mills, Biotor is one of the largest integrated castor companies in the world. It operates across the entire value chain, from contract farming of castor seeds to wholly owned retailing operations in Europe and the United States. The company has its manufacturing unit and seed crushing plant at Makarpura in Baroda, Gujarat, for castor oil of various grades and its derivatives. They have also put up an 8000 TPA Sebacic Acid Plant which is located in Ekalbara, Baroda. Products: The company produces all grades of castor oil and is moving up the value chain to focus on much higher value added derivatives such as Zinc Undecylenate, Calcium Undecyclenate, methyl ricinoleate, polyamides, polyols and more. See this URL for the complete list of products: http://www.biotorindustries.com/castor-‐oil-‐products.html The company also announced its intention to invest significantly over next three years to produce high value castor derivatives such as nylon 11, 12 used in automobile and telecom and nylon 6, 10 used in toothbrush, zip fasteners and fishing nets. Biotor has also, over the last three years, launched major initiatives to promote castor cultivation under the framework of contract farming in India. Biotor has already contracted about 100,000 acres in 2008-‐09. It has a 2,20,000 T per annum crushing capacity, and supplies about 1,00,000 T of castor oil and derivatives per year. It has about 25% castor oil and derivatives market share in the world. Castor meal is marketed by Biotor's fertilizer division. Our estimate is that it will be producing about 75-‐100,000 T of castor meal per year. In Dec 2008, Morgan Stanley invested in Biotor. Morgan Stanley Private Equity Asia, the

stake. The partnership is expected to provide Biotor wfranchise and relationships, which we believe will prove invaluable as we aim to increase

http://www.jayantagro.com/

http://www.biotorindustries.com/castor-oil-products.html

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our international presence. Biotor is planning to invest part of this Morgan Stanley investment in its upcoming project at the Bharuch SEZ in Gujarat. The SEZ project will be completed in the first quarter of 2010-‐capacity will account for 45% of the total market in India. Financials: Revenues of about US$ 125 million 2007-‐08 Location: Headquartered in Mumbai Address 13, Sitafalwadi, Dr. Mascarenhas Road, Mazgaon, Mumbai 400 010, India www.biotorindustries.com 3. Gujarat Ambuja Exports Main Line of Business: Agro Processing & Trading Background: Gujarat Ambuja Exports Limited is principally involved in agro-‐processing & trading and has focused on exports, competing in the global market. With a small beginning in 1983, the company has grown with the addition of numerous plants in the agro-‐processing sector, After establishing its first edible oil refinery in 1986, the company set up its wheat flour mill and cattle feed mill in 1987. The company also set up huge capacities in the Solvent Extraction industry backed by vertically integrated projects of edible oil refinery and vanaspati ghee. The company with its focus on international trade has setup a wholly-‐owned subsidiary at Singapore and has recently promoted a vanaspati and oil refinery project in Sri Lanka. Products: One of the products it deals in is castor oil and castor meal. Others are soy, maize, cottonseed, palm, rapeseed, wheat, coconut, sesame and safflower. The total amount of castor oil is estimated to be around 10,000 T per year. Financials: Total group revenues are about US$ 400 million 2007-‐2008 Location: Headquarters -‐ Ahmedabad, Gujarat Address: "Ambuja Tower", Opp. Memnagar Fire Station, Post Navjivan, Ahmedabad 380014, Gujarat) Phone: +91-‐79-‐26423316, 26405535

http://www.biotorindustries.com/

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Fax: +91-‐79-‐26423079 URL: www.ambujaglobal.com URL of the castor division: http://www.ambujaglobal.com/castor_meal.php 4. Adani Group Main Line of Business: Trading & Diversified Background: Adani Group is a large conglomerate of about 4 billion $ in revenues, with a focus on trading activities. Products: Today, the Adani business portfolio is a diverse group with interests in edible oil, logistics, power generation, coal, oil and gas exploration, gas distribution, real estate, ports and more. The group also trades in castor oil and castor meal and is one of the largest exporters of castor products from India. The company exports over 50,000 T of castor oil and castor meal annually. Financials: Adani Group turnover is about 4 billion $ in revenues. (2007-‐08) Location: Headquareters -‐ Ahmedabad, Gujarat Address:

Near Mithakhali Six Roads, Navrangpura, Ahmedabad 380 009 URL: www.adanigroup.com 5. NK Proteins Main Line of Business: Producer of vegetable oils Background: N. K. Proteins was started in 1993 and is today a prominent refiner of vegetable oils in the state of Gujarat. It has a large manufacturing plant for castor oil, derivatives and organic fertilizers from castor meal. The manufacturing plant at situated at Kadi, in the north of the Gujarat state.

http://www.ambujaglobal.com/

http://www.ambujaglobal.com/castor_meal.php

http://www.adanigroup.com/

187



Products: In addition to the basic grades of castor oil, the company also produces ricinoleic acid, hydrogenated castor oil (HCO) and 12-‐HSA. It has the capacity to crush 1000 MT of castor seeds per day, and refining capacity of 400 T of castor oil per day. It also has a solvent extraction plant with a capacity to process 600 T of de-‐oiled castor cake per day For a complete list of their products, please see the following URL http://www.nkproteins.com/index.php?file=caster-‐product Financials: Revenues are about $200 million (2007-‐08). Location: Headquarters: Ahmedabad, Gujarat Address: 2nd / 7th Floor, Popular House, Ashram Road, Ahmedabad -‐ 380009 Gujarat, India www.nkproteins.com 6. RPK Agrotech Main Line of Business: Castor oil and derivatives producer and trader Background: RPK Agrotech was established in 2004 and focusses on castor oil exports. Products: The company focused on producing the basic castor oil grades. The company has also started trading of castor oil derivatives mainly HCO and 12 HSA, which the company gets made on job work basis. The company has a capacity to crush over 9000 MT of castor seed per month. It is currently (Dec 2008) setting up new plant with crushing capacity of castor seed with 250 MT per day. For a complete list of products, please see the following URL http://rpkagrotech.com/products.php Financials: Approximately $25 million Location: The Company operates a manufacturing facility at KSEZ Kandla in the state of Gujarat. The other unit is at Bhachau, also in Gujarat.

http://www.nkproteins.com/index.php?file=caster-product

http://www.nkproteins.com/

http://rpkagrotech.com/products.php

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Address: Plot No 351, 2nd Floor, Sector 1/A, Gandhidham, Gujarat -‐ 370201 www.rpkagrotech.com Other Companies 7. Gokul Overseas Main Line of Business: Gokul Overseas (GO) is producer of castor oil and castor base derivative products in the world Background: Gokul Overseas, a constituent of the Gokul Group is a partnership firm. It is the Flagship Company of US $400 Million Gokul Overseas Group, a conglomerate of diversified activities with major interests in castor oil (FSG, BP, USP, CP, PP, EP, & Comml), edible oils besides castor derivatives. It is an IOCA Members and has been supplying the castor derivatives to international markets since April'2007 covering worldwide customers. The company has firmed up plans to set up a castor seed crushing plant at Gandhidham in Kutch. The new plant will have a capacity of 600 tonnes per day (tpd) and the investment will be in the range of Rs 30 crore to Rs 35 crore, The plant is expected to be operational by November 2009.The company earlier used to outsource crushing of castor seed from other plants. Products: Its castor products include: Castor Oil (FSG / BSS, CP, BP, USP, EP, PP, Grades) Hydrogenated Castor Oil (Flakes-‐Super & Spl.) 12 Hydroxy stearic acid (Flakes-‐Super & Spl) Ricinoleic Acid (Liquid-‐Colour 2 max) of HCO, 12 HSA and Ricinoleic Acid Financials: The company is a 100% Export Oriented Company. It achieved a top line of US$ 73 millions (31.03.2009). Location: economic zone (SEZ) KANDLA in the state of Gujarat. Address: State Highway No. 41, Near Sujanpur Patia,

http://www.rpkagrotech.com/

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Sidhpur, Gujarat-‐ 384151 Phone: +91 2767 222075/ 220 975 Fax: +91 2767 223475 eMail: [email protected] http://www.gokulgroup.com/ 8. Adya Oil & Chemicals Ltd Main Line of Business: A company manufacturing castor oil and it's derivatives. Background: AOCL founded in 1997, has set up world class manufacturing facilities to process commercial castor oil and various down stream products. Products: Its castor products include: Commercial castor oil Castor Oil FSG Castor oil first pressed degummed Castor oil -‐ pale pressed Hydrogenated castor oil 12-‐hydroxy stearic acid For the product specification and application, see the link http://www.adyaoils.com/product.htm Location: The company operates a modern manufacturing facility at Karjan near Baroda in Gujarat Address K-‐20, Ground Floor M.R.Society, Opp. Raheja College Relief Road, Santacruz (West) Mumbai 400 054. INDIA. Tel. 26616172, 26616173 Fax. :( 91-‐22) 26616126 E-‐Mail. : [email protected] www.adyaoils.com


http://www.gokulgroup.com/

http://www.adyaoils.com/product.htm

http://www.adyaoils.com/

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9. Kanak Castor Products Pvt Ltd Main Line of Business: Manufacturing and exporting of castor oil and its derivatives. Background: Apart form castor oil and its derivatives, Kanak Castor Products Pvt. Ltd., is involved in manufacturing and exporting of natural organic fertilizers, neem-‐based pesticides, food additives and emulsifier. Products: For the complete list of products, please see the following link, http://www.kanak.in/products.html Location: The manufacturing unit situated at Mehsana, North Gujarat, India covers more than 80,000 sq. mtrs. land having modern manufacturing facilities Address National Highway No.8, At. Umanagar, Nandasan, Ta. Kadi, Mehsana-‐382 706. (Gujarat -‐ India). Ph: +91 -‐ 2764 -‐ 267611-‐13/15/18-‐20 E Mail: [email protected] http://www.kanak.in/ 10. Royal Castor Products Main Line of Business: Manufacturer, exporter and supplier of a varied range of Castor products and derivatives. Background: Royal Castor Products Limited, promoted by the Standard Greases Group, the largest Grease manufacturer in the private sector In India & Patel Group, conglomerate with a strong base in the construction and manufacturing industries promoted in 1995 has now become a name that is identified with quality in the castor oil derivatives world over. The Indian arm of Dow Chemical International (Dow India) and Gujarat-‐based Royal Castor Products Ltd have signed a commitment to conduct research in sustainable bio-‐based products and solutions using castor oil (Mar 2009) Products: For a complete list of products, see the link http://www.royalcastor.in/html/product.html Location: The facility is located in At. Khali, Sidhpur, Patan,

http://www.kanak.in/products.html


http://www.kanak.in/

http://www.royalcastor.in/html/product.html

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Address: 101, Ketan Apartments, 233, R.B. Mehta Marg, Ghatkopar (East), Mumbai 400 077, INDIA. Tel. No. : +91 22 2509 3641 to 46 Fax No. : +91 22 2510 0384 Email : [email protected] www.royalcastor.in 11. Taj Agro Products Main Line of Business: Manufacture various grades of castor oil & castor seed extraction. Background: Taj agro Products limited, incorporated in the year 1986, is a flagship company of the Taj Group. It established with an objective to manufacture and market various grades of Castor Seed & Castor Oil. The unit is having expelling capacity of 115 MT/day, refining capacity of 50 MT/day and a solvent extraction plant for castor seed extraction meal with a capacity of 100 MT/day. Taj Group has also added one more Solvent Extraction Plant in the year 2005 under the name of Taj Proteins Pvt. Ltd. to produce Rapeseed Extraction Meal with the production capacity of 250 MT/day. In the future, Taj Proteins will also have the Rapeseed Expelling Facility supported by Refinery to back up the captive requirements of its Solvent Extraction Plant and to cater to the ever deficit Indian Edible Oil Market by offering Refined Grade Rapeseed Oil. Products: Taj Group is a manufacturer and exporter of the following grades: Commercial Castor Oil Refined Castor Oil (FSG/BSS) Refined Castor Oil (Pale Pressed Grade) Refined Castor Oil (Extra Pale Grade) Neutralized Castor Oil (N.C.O.) Pharmaceutical Castor Oil (I.P. Grade) Pharmaceutical Castor Oil (B.P. Grade) Pharmaceutical Castor Oil (U.S.P. Grade) Refined Castor Oil (DAB 10) Hydrogenated Castor Oil (HCO) 12-‐Hydroxy Stearic Acid (12-‐H.S.A.) Eco-‐Friendly Fertilizers Castor Seed Extraction Meal (D.O.C.) Bio Organic Fertilizer from Compost Agro Waste Mix Rapeseed Extraction Meal.


http://www.royalcastor.in/

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Address: 434, Laxmi Plaza, Laxmi Industrial Estate, New Link Road, Andheri (W), Mumbai-‐ 400 053. India. Mob: 009930407744 E-‐mail : [email protected] www.tajagroproducts.com

10.2 Prominent Castor Oil & Derivatives Producers in China 1. Tongliao TongHua Castor Chemical Co., Ltd. The company was founded in 1985 and put into operation in 1988. It processes 80,000MT castor seeds annually. Products: Castor oil basic grades, dehydrated castor oil, hydrogenated castor oil, 12-‐HSA, sebacic acid, castor oil fatty acid, dehydrated castor oil fatty acid, pharmaceutical castor oil, blown castor oil, sulphonated castor oil, lithium 12-‐HSA, Magnesium 12-‐HSA, Alumium 12-‐HSA and other stearate products and Dioctyl Stearate (DOS), Dibutyl Sebacate (DBS), Dioctyl Fumarate (DOF), Dibutyl Fumarate (DBF), Dodecanedioic Acid, secondary octyl alcohol, commercial stearic acid, castor meal. http://www.castoroil.cn/MainWeb_EN.htm 2. Zouping County Tianxing Chemical Industry Co., Ltd. This company is located in the Handian Industrial Zone, Zouping, Shandong China. It can produce castor oil basic grades, Sebacic Acid and 12-‐hydroxy stearate. It also is a member of the China Castor Association. It can press the castor seed of 80,000T to the castor oil of 35,000T, Sebacic Acid of 4,000T, 12-‐hydroxy stearate of 10,000T every year Products: Castor oil basic grades, Sebacic acid, Dimethyl sebacate, Dibutyl Sebacate (DBS), 2-‐Octanol, 12-‐Hydroxy Stearic Acid, Castor Cake http://www.tianxingchem.com 3. Liaoyang Huaxing Chemical Co., Ltd. Liaoyang Huaxing Chemical Co., Ltd is equipped with total production capacity of 60,000 tons of nonionic surfactants every year. The company mainly produces three series and more than 100 kinds of nonionic surfactants such as fatty alcohol-‐polyoxyethyleneether, nonylphenol-‐polyoxyethyleneether and polyethylene glycol (PEG), etc. Now, the company


http://www.tajagroproducts.com/

http://www.castoroil.cn/MainWeb_EN.htm

http://www.tianxingchem.com/

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has established long-‐term and close cooperation relation with more than 300 enterprises such as Nanfeng Group, Hangao Company, Guangzhou Libai, Liaoning Whitecat, Zhejiang Nice, etc. Products: It mainly produces three series and more than 100 kinds of nonionic surfactants such as fatty alcohol-‐polyoxyethyleneether, nonylphenol-‐polyoxyethyleneether and polyethylene glycol (PEG), etc. 4. Xingtai Lantian Fine Chemical Co., Ltd. The former Xingtai Industrial Detergent Factory, established in May 1992, is manufacturer of surfactants and other practical products. Their products are: surfactants, pesticide auxiliarg, detergent auxiliary, and textile, printing and dyeing chemicals, altogether about 100 types. It has an annual output of 5,000 tons of external cycle gas-‐liquid contact ethoxylation or propoxylation production lines and advanced PI techniques. The main products are inspected with ISO series standard. In 1999, we came up with innovative production methods for DBS-‐Ca. Its pesticide emulsifier production capacity reaches 4,500 tons. Products: For a complete list of products, please click on the following link http://www.ltchem.com/cgi/search-‐en.cgi?f=contact_en+product_en+company_en_1_&t=product_en&w=product_en&terms=Castor+oil-‐polyoxyethylene+ether+series+&Submit.x=30&Submit.y=4 www.ltchem.com 10.3 Prominent Castor Oil & Derivatives Producers in Brazil

Company Location Production (est.) MT,

2007 Bom Brasil Salvador, BA 25

A.Azevedo Itupeva, SP 6 Enovel Bariri, SP 3

A consolidated list of companies using castor as a biodiesel feedstock and their production quantities has been provided

Producer Location Feedstock

Production Capacity (litres/m³)

Ambra Varginha/MG sunflower, nabo forrageiro and castor bean 2400L

http://www.ltchem.com/cgi/search-en.cgi?f=contact_en+product_en+company_en_1_&t=product_en&w=product_en&terms=Castor+oil-polyoxyethylene+ether+series+&Submit.x=30&Submit.y=4



http://www.ltchem.com/

194



Araguassu Porto Alegre do Norte/MT

soybean, cotton, sunflower and castor bean 100m³

Biocamp Campo Verde/MT castor bean, tallow and jatropha 154m³

Biocapital Charqueada/SP soybean, cotton, peanut, sunflower, palm, jatropha and castor bean 824m³

Brasil Ecodiesel Teresina/PI

castor bean, soybean, cotton and sunflower 2000L

Brasil Ecodiesel Floriano/PI


Brasil Ecodiesel Crateús/CE

castor bean, soybean, cotton and sunflower 360m³

Brasil Ecodiesel Iraquara/BA


Brasil Ecodiesel Rosário do Sul/RS

castor bean, soybean, cotton, sunflower and jatropha 252m³

Brasil Ecodiesel São Luis/MA


Comanche (ex-‐IBR) Simões Filho/BA

Soybean, cotton, tallow, dendê and castor bean 65000L

Dhaymers Taboão da Serra/SP

soybean, babassu, castor bean and tallow 26m³

Nutec (Fundação Núcleo de Tecnologia Industrial do Ceará) Fortaleza/CE castor bean 2400L

Soyminas Cássia/MG castor bean, colza, nabo forrageiro and sunflower 40m³

Source: http://www.iucnael.org/index.php?option=com_docman&task=doc_download&gid=99&lang=en

10.4 Other Prominent Suppliers Fuerst Day Lawson -‐ International Trading Company in Castor Oil Fuerst Day Lawson is one of the leading Castor Oil suppliers in Europe with over 40 years experience buying directly from the producers in India, China and Brazil. The company supplies castor oil into Europe and China, selling approximately 40,000 MT per year via storage tanks in Rotterdam and Marseille, and via direct deliveries in flexitanks and drums. Since the emergence of India as the dominant region of supply more than 15 years ago, Fuerst Day Lawson has gained a significant presence with a regional head office based in Delhi, from where it maintains regular contact with major market players.

http://www.iucnael.org/index.php?option=com_docman&task=doc_download&gid=99&lang=en

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Appendix 1

In recent times, we @ CastorOil.in have had a number of enquiries for details and data about sebacic acid. Owing to this, we are including a special section in this report for sebacic acid. This section comprises the following details on sebacic acid:

1. Demand -‐ Supply Estimates for Sebacic Acid 2. Price of Sebacic Acid 3. Sebacic Acid Companies and Suppliers

1. Demand -‐ Supply Estimates for Sebacic Acid Introduction According to the industry nomenclature, generation I derivatives include hydrogenated castor oil, 12-‐hydroxy stearic acid, dehydrated castor oil acid, and ethoxylated castor oil among others. Generation II castor oil derivatives include sebacic acid, undecyclenic acid, heptaldehyde, polyols and dimer acid. Generation III derivatives include the esters and salts of generation II derivatives as well as derivatives such as methyl-‐12-‐hydroxystearate. The global market for generation II castor oil derivatives is estimated at $300 million (based on 2007 data). For generation III derivatives, where half of the generation II derivatives are converted, the estimated market worth is close to $350 million (based on 2007 data). Overall, the castor oil and derivatives industry have shown an average demand growth of about 4% per annum for the period 2000-‐2007. Current Demand-‐Supply Estimates for Sebacic Acid Global Demand Global demand level: Approximately 140,000 metric tonnes per annum Global supply Global installed capacity: Approximately 150,000 metric tonnes per annum China is currently the primary producer of SBA. The United States and India are also producers.

largest supplier produces 10000 T/yr.

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2. Price of Sebacic Acid

FOB Price (Tianjin, China) $3,584.00/MT -‐ $3,602.00/MT CIF Mumbai (Origin port: Tianjin, China)

$3,648.00/MT -‐ $3,666.00/MT Palletized CIF price: $3,686.00/MT -‐ $3,704.00/MT

Note: All data for Sep 2009

3. Sebacic Acid Companies and Suppliers Main Countries Producing Sebacic Acid

China Japan Brazil India United Kingdom

Top Suppliers of Sebacic Acid Worldwide

Name of the Manufacturer Location Fulida Industry co Hebei China Green International Germany Hengshui Dongfeng Chemical Co China Hengshui Jinghua Chemical Plant China Hengshui OK Enterprises Hebei Inner Mongolia Tianrun

China

Castor Development Co., Ltd China Jiheng Chemical China Mitsu Toatsu Chemicals Japan Persulphate Ltd China Qingdao Great Chemical Inc China Ronas Chemicals Ind. Co., Ltd. Taiwan Shandong Haihua Tianhe Organic Chemical Co., Ltd

China

Shandong Ocean Chemical Group China Shenzhen Pharmaceutical Factory Shenzhen, Guangdong, China Shijiazhuang Jihua, Chemical Textile Co China Sinochem Tianjin, Tianjin, China.

197



Suny Chem International Co., Ltd Yantai Shandong, China Taizhou Donghai Chemical Co.Ltd., Zhejiang Province, China Tianjin No.1 Chemical Reagent Factory Tianjin, China Tianjin Zhonghe Chemical Plant Tianjin, China Tonliao Xinghe Chemical Co., Ltd Inner Mongolia, China Unitchem Co Ltd China Weifang Tianhe Organic Chemical Co., China Zouping County Tianxing Chemical Industry Co., Ltd

China

Source: Derived from various sources

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Appendix 2 India Export Details on Castor Derivatives

Indian Export of 12 HSA and HCO (Unit: KGS)

S.No. Country Values in Rs.

Lacs Values in Rs.

Lacs Quntity in thousands 2008-‐2009 2009-‐2010 %Growth 2008-‐2009 2009-‐2010 %Growth 1 ARGENTINA 55.01 18.03 -‐67.23 50.21 24 -‐52.2 2 AUSTRALIA 395.82 465.55 17.62 473.43 593.34 25.33 3 BAHARAIN IS 11.52 12

4 BANGLADESH PR 1.8 2.91 61.45 2 3 50

5 BELGIUM 2,441.09 2,341.41 -‐4.08 3,150.31 3,213.89 2.02 6 BRAZIL 11.41 413.8 3,525.55 22 567.34 2,478.84 7 BULGARIA 14.97 11.52 -‐23.04 17 16.12 -‐5.19 8 BELARUS 12.25 16.23 9 CANADA 323 337.71 4.55 333.3 426.43 27.94 10 CHILE 16.1 24 11 TAIWAN 120.35 127.61 6.04 188.2 171.15 -‐9.06 12 CHINA P RP 224.21 47.28 -‐78.91 299 70 -‐76.59 13 COLOMBIA 220.36 73.53 -‐66.63 245.39 70 -‐71.47 14 CUBA 72.01 97 15 DENMARK 17.51 24 16 EGYPT A RP 314.9 34.4 -‐89.08 343 51 -‐85.13 17 FRANCE 34.72 131.34 278.29 32 181.47 467.1 18 GERMANY 103.44 146.64 41.76 113.74 213.78 87.96 19 GREECE 36.11 56.58 56.69 53.01 79 49.03 20 HONG KONG 0.77 1 21 INDONESIA 95.56 60.52 -‐36.66 144.63 82.32 -‐43.08 22 IRAN 157.89 2.02 -‐98.72 199.79 2.5 -‐98.75 23 ISRAEL 37.28 50.09 34.35 49.11 68.58 39.66 24 ITALY 617.49 664.71 7.65 801.44 984.5 22.84 25 JAPAN 4,168.66 3,161.24 -‐24.17 4,890.10 4,105.17 -‐16.05 26 JORDAN 42.65 60 27 KENYA 2.04 2.94 28 KOREA RP 1,295.07 791.98 -‐38.85 1,688.71 1,050.95 -‐37.77 29 KUWAIT 10.96 16 30 LITHUANIA 11.9 11.55 -‐2.95 17 17 0 31 MALAYSIA 45.79 62.81 32 MEXICO 83.45 178.34 113.72 89 231.85 160.51 33 NEPAL 45.2 9.44 -‐79.11 102 31.05 -‐69.56 34 NETHERLAND 4,100.16 2,821.66 -‐31.18 4,900.20 3,672.31 -‐25.06 35 NEW ZEALAND 2.02 1.03 -‐49.14 2 0.5 -‐75

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36 PAKISTAN IR 7.68 18.81 37 PERU 13.01 16.23 38 PHILIPPINES 227.1 179.55 -‐20.94 310.58 242 -‐22.08 39 POLAND 361.97 318.35 -‐12.05 460 435.74 -‐5.27 40 RUSSIA 1,073.46 1,016.32 -‐5.32 1,412.63 1,397.75 -‐1.05 41 SAUDI ARAB 491.19 127.96 -‐73.95 610.43 165.86 -‐72.83 42 SINGAPORE 57.58 114.84 99.44 70.88 134 89.05 43 SLOVENIA 12.31 22.7 84.4 16.66 33.32 100 44 SOUTH AFRICA 122.75 221.02 80.06 154 268.93 74.63 45 SPAIN 261.16 215.23 -‐17.58 358.71 292.21 -‐18.54 46 SUDAN 14.12 10.76 -‐23.77 17 15 -‐11.76 47 SWEDEN 98.6 75.27 -‐23.66 108 73 -‐32.41 48 SWITZERLAND 30.29 42 49 SYRIA 17.7 25.48 50 TANZANIA REP 2.88 4 51 THAILAND 300.69 350.17 16.46 364.34 455.38 24.99 52 TUNISIA 59.04 80 53 TURKEY 744.69 441.45 -‐40.72 889.63 590.42 -‐33.63 54 U ARAB EMTS 371.57 502.95 35.36 487.57 698.12 43.18 55 U K 529.72 491.5 -‐7.21 634.11 683.56 7.8 56 UKRAINE 390.19 202.67 -‐48.06 479.54 266.68 -‐44.39 57 U S A 3,951.80 4,264.11 7.9 5,370.45 5,884.61 9.57 58 VENEZUELA 68.78 96

59 VIETNAM SOC REP 57.64 77.54

60 UNSPECIFIED 87.93 184.02 109.29 95 221.99 133.67 Total 24,430.01 20,767.04 -‐14.99

Source: Ministry of Commerce, India

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Export of Azelaic Aci, Sebacic Acid their Salts & Esters from India


2008-‐2009 2009-‐2010 %Growth

2008-‐2009

2009-‐2010

%Growth

1 AUSTRALIA 21.2 12 2 BELGIUM 248.77 168 3 TAIWAN 43.24 0.09 -‐99.78 32 0.03 -‐99.92 4 CHINA P RP 309.77 129.39 -‐58.23 255 64.7 -‐74.63 5 GERMANY 157.09 272.54 73.49 110 216.02 96.38 6 ITALY 88.44 100.02 13.1 80 50 -‐37.5 7 JAPAN 71.71 48 8 KOREA RP 23.22 15 9 NETHERLAND 1,353.46 305.9 -‐77.4 1,031.00 232 -‐77.5 10 SINGAPORE 3.32 3 11 U S A 548.47 377.74 -‐31.13 417.71 279.58 -‐33.07 Total 2,847.49 1,206.88 -‐57.62

Source: Ministry of Commerce, India

Export Data forDehyrdated Castor Oil

CASTOR OIL DEHYDRTD OF EDBILE GRADE Unit: KGS


2008-‐2009

2009-‐2010

%Growth 2008-‐2009

2009-‐2010

%Growth

1 AUSTRALIA 6.3 7.9 2 BRAZIL 24.63 15 3 CHINA P RP 7.3 8 4 GREECE 2.85 40.02 5 MALAYSIA 0.83 1.02 6 SOUTH

AFRICA 10.5 10

Total 44.28 8.13 -‐81.63

Export Data for Hydrogenated Castor Oil

HYDROGNTD CASTOR OIL (OPL WAX) OF EDBLE GRADE Unit: KGS S.No. Country Values in Rs. Lacs Quntity in thousands

2008-‐2009

2009-‐2010

%Growth 2008-‐2009

2009-‐2010

%Growth

1 BELGIUM 239.75 96 2 IRAN 11.8 16

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3 ITALY 8.39 8 4 MOROCCO 13.05 16 5 NEPAL 4.9 7.7 6 NIGERIA 26.04 34 7 PAKISTAN IR 0.12 0.2 8 SAUDI ARAB 11.54 16 9 SINGAPORE 0.01 0.03 10 SOUTH

AFRICA 13.07 16

11 SRI LANKA DSR

32.03 115

12 U ARAB EMTS

12.92 16

13 U K 0.31 0.13 14 U S A 75.88 15.38 -‐79.73 100 20 -‐80

Total 418.56 46.65 -‐88.86

Export Data for Sulphonated or Sulphated or Oxidized or Castor Oils

SULPHONATED OR SULPHATED OR OXIDIZED OR CASTOR ,FISH ,SPARM ,NEATS FOOT OILS Unit: KGS


2008-2009

2009-2010 %Growth 2008-

2009 2009-2010 %Growth

1 ALGERIA 38.87 82.66

2 AUSTRALIA 15.67 3.58 -‐77.18 22.21 4.94 -‐77.75

3 BANGLADESH PR

62.7 56.06 -‐10.59 85.65 74.53 -‐12.98

4 TAIWAN 14.62 25.2

5 COLOMBIA 2.26 4.12

6 EGYPT A RP 10.24 21.58

7 ERITREA 16.41 50.68

8 FRANCE 2.97 1.4

9 GHANA 10.59 50.2

10 GUYANA 8.94 22.6

11 HONG KONG 0.44 0.4

12 INDONESIA 0.24 12.13 4,867.49 0.8 17.25 2,056.00

13 IRAN 8.89 16.62

14 ISRAEL 9.85 13.96

15 KENYA 14.45 15.51 7.31 18.34 16.46 -‐10.26

16 KOREA RP 14.1 14.32

17 KUWAIT 98.69 154.69 56.74 199.92 321.64 60.88

18 MADAGASCAR 3.55 7.16 101.31 20 39.8 99

19 MALDIVES 0.94 0.8

20 MOROCCO 6.73 16.2

202



21 NEPAL 0.1 0.06 -‐43.8 0.2 0.09 -‐55

22 NIGERIA 56.1 13.76 -‐75.47 60.48 15.12 -‐75

23 OMAN 0.31 0.2

24 PAKISTAN IR 1.23 1.51

25 PERU 0.66 1.2

26 PHILIPPINES 7.83 10.55 34.79 10.45 15.77 50.82

27 PORTUGAL 69.65 74.15

28 ROMANIA 0.27 0.6 117.99 0.86 0.08 -‐91.32

29 SAUDI ARAB 17.65 18.83 6.73 16.98 53.28 213.78

30 SINGAPORE 2.07 4.48 116.33 1.52 3.55 133.75

31 SOUTH AFRICA 4.93 25

32 SRI LANKA DSR 266.3 81.91 -‐69.24 705.89 287 -‐59.34

33 SYRIA 0.09 0.1

34 THAILAND 0.48 42.73 8,793.78 1 59.92 5,892.00

35 TURKEY 13.16 25

36 U ARAB EMTS 18.64 3.67 -‐80.31 45.08 13.68 -‐69.65

37 U K 4.09 16.33

38 U S A 17.19 21.58

39 VIETNAM SOC REP

13.95 3.39 -‐75.71 31.62 7.98 -‐74.76

40 YEMEN REPUBLC

90.74 184.23 103.03 195.02 392.04 101.03

41 ZAMBIA 0.29 0.5

42 UNSPECIFIED 17.3 14.19 -‐17.95 8.14 16.17 98.71

Total 848.93 722.75 -‐14.86

203



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castor oil reportnov2010

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