FINAL REPORT

National Agricultural Innovation Project

(Indian Council of Agricultural Research)

A Value Chain on Castor and Its Industrial Products

Main Castor Mustard Research Station

Sardarkrushinagar Dantiwada Agricultural University

Sardarkrushinagar-385506 Distt. Banaskantha Gujarat

2012

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Component-

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2012

1

“A Value Chain on Castor and Its Industrial Products”

, ,

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, 2009

2012 2000

Gangudara, Chodungari,

Kamali, Matpur Garamadi ( )

15.7 23.9 , ,

. 2011 2012 Gangudara, Chodungari, Kamali, Matpur

Kasalpura

, 37.6 .

GCH ,

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, -

12 HAS

hydrolic > ,

ricinoleate ,

,

2

LLE ricinoleate

LLE ricinoleate

N-undecenylethanolamine N,N-diundecenylethanolamine

. N-undecenylethanolamine UDA

ethanolamine

N,N-diundecenylethanolamine UDA ethanolamine

micellar

UDA Quats, N,N-Dimethyl diethanolamine

diundecenoate dimethylsulphate

sodium bisulphate monohydrate

Quats

octanol . octanol

.

Deoiled

.

ricin Deoiled

Deoiled ricin

3

Executive Summary

The project entitled “ A Value Chain on Castor and Its Industrial Products” under NAIP

component II was undertaken by Sardarkrushinagar Dantiwada Agricultural University,

Sardarkrushinagar (Consortia lead Centre), Indian Institute of Chemical Technology, Hyderabad

(CSIR, Institute) and Jayant Agro Organics Ltd.; Mumbai (Private sector), Royal Castor Products,

Siddhpur (Private sector). SDAU, Sardarkrushinagar, the lead centre, is most prestigious research

station engaged in castor agro-research and development. This centre has been credited to

develop six castor hybrid, two castor varieties and production/protection technology for castor

cultivation.

After base line survey of six districts of north Gujarat, in three years two thousand four hundred

demonstrations comprising about 2000 under irrigated and 400 under rainfed conditions

demonstrating different agro-techniques were conducted on farmer’s field during 2009-2012.

Through field demonstration: Total 465 farmers’ field demonstrations were conducted during

2009-10. The yield level of selected villages viz. Gangudara, Chodungari, Kamali, Matpur, and

Garamadi (rainfed) was 19-21, 23-25, 31-33, 33-34 and 6-8 q/ha, respectively. Through the agro

technological demonstration, the results indicated that the range of increase in seed yield of castor

in different selected villages was 15.7 to 23.9 percent. On an average, the magnitude of increase

in yield over present level was 34 percent which was 11.8 per cent more than targeted yield.

During 2011-12 total 672 demonstrations were conducted. The yield level of selected villages viz.

Gangudara, Chodungari, Kamali, Matpur, and Kasalpura was 19-21, 23-25, 31-33, 33-34 and 35-

40 q/ha, respectively. On an average, the magnitude of increase in yield over present level and

targeted yield was 37.6 per cent, respectively.

For value addition in the harvesting and processing it was found that The local sickle, improved

sickle and secator were evaluated for efficient harvesting of castor crop (variety: GCH-7) and

minimum losses. The average harvesting capacity of castor spike was found 65.90 kg/hr for

secator followed 52.99 and 51.24 kg/hr for improved sickle and local sickle respectively. The

higher percent losses were observed for improved and local sickles as compared to secator. Solar

dryer is more suitable for drying of castor crops drying was found 6 to 7 days earlier as compared

to traditional drying method. On the basis of demonstration of farmer's field single groove planter

was found most suitable for sowing castor crop sown at fixed crop geometry.

In order to specific to value chain, various esters were prepared and evaluated with 12 HAS. The

product was made with great efforts, the hydroxyl value of final product was Zero (High hydrolic

stability) and viscosity of > 42. The technical specification of the ester developed was finalized.

Enrichment of Methyl Ricinoleate from Castor Oil Methyl Esters:

4

Using liquid paraffin as a medium, the selectivity in enrichment of methyl ricinoleate from castor

oil methyl esters is good but due to the closer densities of liquid paraffin and aqueous methanol

the contamination of liquid paraffin with the solute was to the extent of 2.5-3.5% which was

determined by TLC and column chromatography. Therefore, the experiments using liquid

paraffin as medium in enrichment of methyl ricinoleate by LLE is not satisfactory.

The method of using refined vegetable oil as medium in enrichment of methyl ricinoleate by

LLE, the selectivity is good and the contamination of oil with solute is less than 0.8% as

determined by TLC and column chromatography. Efforts are on at further minimizing the

contamination. Standardization of up-scaling experimental conditions are in progress. Efforts are

on to explore the possibilities of separation of solute from extract using solvent resistant thin film

composite reverse osmosis membranes. Using the enriched methyl ricinoleate various derivatives

are planned to prepare and compare the properties with respect to the CME. Experiments are in

progress to standardize the experimental conditions.

Further upscaling experiments are being conducted for the enrichment of methyl ricinoleate from

castor oil methyl esters. Adsorbents like celite will be tried in reducing the vegetable oil

contamination in the extract. Centrifugation is another option to be explored in minimizing the

vegetable oil contamination. Thin film composite RO membranes will be explored in separation

of the solute from the solvent of the extract in liquid-liquid extraction process. Efforts are on in

increasing the conjugation in the dehydrated products and methodology for evaluation of

conjugated fatty acid esters in the products by HPLC and Silver ion Thin layer chromatography.

Design and fabrication of Liquid-liquid extraction set-up is under progress.

Preparation of UDA-based Surfactants: Optimized conditions for exclusive preparation of N-

undecenylethanolamine and N, N-diundecenylethanolamine. N-undecenylethanolamine was

prepared by taking 1:1 molar ratio of UDA and ethanolamine and heating the reaction mixture at

170 °C for 2 hrs. The structure of the compound was confirmed by NMR, IR and mass. The cmc

and surface tension at cmc was determined following Kruss Tensiometer. The cmc value was

found to be 3.08×10-4

mM and surface temsion at cmc, is 30.7 mN/m. N,N-

diundecenylethanolamine was prepared by taking 3:1 molar ratio of UDA and ethanolamine and

heating the reaction mixture at 170 °C for 2 hrs. Attempts to determine the micellar properties of

this compound failed as the compound is almost insoluble in water.

UDA-based ester quats, N, N-dimethyl diethanolamine diundecenoate dimethylsulphate was

prepared by esterification in presence of 5% sodium bisulphate monohydrate at 120 °C under

stirred conditions. The cmc value of the ester quat was found to be 3.0 × 10-2

mM/L and surface

tension at cmc, is 25.46 mN/m. Four UDA-based surfactants are synthesized and evaluated for

their surface properties using surface tension and fluorescence probing techniques. Influence of

5

the presence of unsaturation and also its location in the hydrophobic chain on surface properties

of four different ester quats are also studied.

Value added products based on the 2-octanol like phthalate, maleate, fumarate, sebacate, adipate,

benzoate and these can be used as plasticizers in PVC and resins for various applications. 2-

octanol is co-product of the castor industry and based on its such value added products will earn

good returns to the stakeholders. Based on the estimation, the 2-octanol based esters as

plasticizers will be cheaper than the existing products based on 2-ethyl hexanol and isononanol.

Developed process technologies for esters based on 2-octanol will be able to replace petroleum

derived products thus increasing the value of the castor plant & indirectly benefit the farmers due

to increased demand.

Deoiled castor cake is also a co-product of castor industry and it has rich content of protein. Apart

from this it also comprises of other constituents. One of the constituents of castor cake is found

very toxic. Due to this the deoiled castor is not used as foodstuff for live stock in spite of rich

amount of protein. The developed process of extraction and isolation shows the protein from

castor deoiled cake is free from toxic component i.e. ricin. Hence such isolated protein can be

used for industrial applications like adhesive and bio-film and can be partially or fully replaced

by soy protein isolate as this is being used in the food products. Also could be considered for feed

purpose after satisfactory trials

Value addition in castor cake: Among, Fifty one castor genotypes analysed, the protein content

varied from 19.93 to 30.81%. Maximum protein content was noted in GP-415 (30.81%)

genotype. Thirty six castor genotypes were analysed for protein isolation from cake. The protein

isolated from different genotype varied from 11.05to 19.35%. Among all the genotypes, GP-422

(19.35 %) recorded maximum isolated protein content. Thirty seven castor cake samples were

analysed for crude ricin ranging from 1.03-1.92 % in the different DOC samples. GP-420 (1.03

%) showed lowest toxic constituents and GP-460 (1.92%) had the highest toxic constituents.

After the series of treatments for detoxification, resulted in traces or undetectable levels of toxic

constituents were observed. Eighteen castor genotypes were analyzed for lignin and cellulose

content of stem by chemical method. The lignin and cellulose content was noted in the range of

14.1 to18.8 and 34.9 to 45.7% respectively.

Key Words: Castor, Value addiction, Value Chain, Ricinolic acid, Ricin, castor

derivatives

6

Part-I: General Information of Sub-project

1. Title of the sub-project: “ A Value Chain on Castor and Its Industrial Products”

2. Sub-project code:

3. Component: 2 (Production to Consumption System)

4. Date of sanction of sub-project: February 18, 2009

5. Date of completion: June 30, 2012

6. Extension if granted, from: Nil

7. Total sanctioned amount for the sub-project: 393.00 lakh

8. Total expenditure of the sub-project:

9. Consortium leader: S. D. Agricultural University, Sardarkrushinagar 385 506

Dr. K. Sreedharan, Vice Chancellor

S. D. Agricultural University, Sardarkrushinagar 385 506

Phone: 02748 278457 Phone: 02748 278457

E-mail: vc@sdau.edu.in

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

10. List of consortium partners:

Name of CPI/ CCPI

with designation

Name of organization and

address, phone & fax, email

Duration

(From-To)

Budget

(Lakhs)

CPI Dr. P. S. Patel,

Research Scientist

(C&M)

Main Castor-Mustard Research

Station, SDAU,

S. K. Nagar (Gujarat)

Phone: 02748 278457

pspatel8181@gmail.com

March 1, 2009

to June 30,

2012.

266.127/-

CCPI1 Dr. R.B.N. Prasad,

Director

Centre for Lipid Research,

Indian Institutes of Chemical

Technology, Hyderabad, (AP)

March 1, 2009

to June 30,

2012.

61.8384

CCPI2 Dr. Subhash V.

Udeshi.

Director – Technical

M/s.Jayant Agro-Organics Ltd.

38 Marol Co-op. Ind. Estate

Off M. V. Rd, Sakinaka,

Andheri(E), Mumbai-400059

Tel: 022-40271300 – 314-15

Fax: 022-40271399:

subhash.udeshi@jayantagro.com

March 1, 2009

to June 30,

2012.

40.88430/-

(39.2112/-

sanctioned

letter dated

on Feb. 18,

2009)

CCPI 3 Dr. Subhash Polara

Director,

Royal Castor Product

Limited.

M/s Royal Castor Products Limited

At. Khali, Mehsana – Sidhpur

Highway, Sidhpur-384151, Dist –

Patan, Gujarat.

Phone : 02767 – 222905-06,

Fax:02767- 221833 E-mail :

polarasubhash@royalcastor.in

March 1, 2009

to June 30,

2012.

24.9096

CPI-Consortia Principal Investigator; CCPI-Consortia Co-Principal Investigator

7

11. Statement of budget released and utilization partner-wise (in Lakhs):

CPI/ CCPI

Name,

designation

& address)

Total budget

sanctioned

Fund released

(up to closing date)

Fund utilized

(up to closing

date)

CPI Dr. P. S.

Patel,

Research

Scientist

266.127/- 208.75116/- 143.07207/-

CCPI1 Dr RBN

Prasad,

Director, IICT

61.8384/- 51.15588/- 41.91817/-

CCPI2 Dr. Subhash

V Udeshi.

Director –

Technical

40.88430/-

(39.2112/- as

per sanctioned

letter dated on

Feb. 18, 2009)

23.73524/- 23.49770/-

CCPI 3 Mr. Subhash

Polara

24.9096/- 17.43336/- 19.67142/-

Total 393.7593/- 301.0756/- 228.1594/- CPI-Consortia Principal Investigator; CCPI-Consortia Co-Principal Investigator

8

Part-II: Technical Details

1. Introduction

Castor (Ricinus communis L) is a non edible oil seeds crop having high industrial

importance due to presence of unique fatty acid, ricinoleic acid. India is the world leader

in castor seed and oil production and contributes about 55 % of world castor area and

70% of world castor production. In India, Gujarat state holds the first ranks with regards

to area (52 %), production (80 %) and productivity (1833 kg/ha, 2009-10). Other

important states are Rajasthan and Andhra Pradesh. The crop is grown mainly under

irrigated condition in Gujarat and Rajasthan. The castor crop productivity is low due to

various biotic and a biotic factors amongst these wilt caused by Fusarium oxysporium is

the major constraints beside this partial/improper adoption of recommended technology

also led to low productivity of castor.

The adoption of recommended production/protection technologies, are essential to

increase productivity of castor. At present recommended technologies are being adopted

partially or not adopted like application of recommended dose of fertilizer, application of

sulphur, irrigation schedule , spacing and harvesting etc.

The castor seeds produce after harvesting is not properly cleaned and dried, packing

material used are mostly gunny bags and also contains foreign materials like iron nails,

dust, stone etc., such poor quality produce gets less prices for farm produce. The

improved technology for drying cleaning, grading and bulk packaging will improve the

quality of raw material for industrial supply and increase the farmer’s income.

Castor plant grows in tropical, sub-tropical and warm temperate regions, preferring a dry

environment. It is cultivated both as an annual and a perennial, the size of plant and yield

of beans per acre showing very large variation according to cultivation. Castor oil is

obtained by pressing or pressing followed by solvent extraction. Oil content of the beans

averages 45-55%. Pharmaceutical grade oil is highly quality oil derived solely from the

first pressing of beans and account for only a very small percentage of total sales.

India is now the most important producer and its share of world castor oil production has

increased from 46.7 % in 1990 to 64.4 % in 1995. The other castor producers in the rest

of world are Brazil and China. Castor oil is unique in having three reactive functional

groups such as double bond, hydroxyl group and carboxylic group. Pyrolysis of castor oil

or recinoleic acid in the presence of alkali yields 2-octanol and sebacic acid. These

9

oleochemicals are precursors for industrially important plasticizers, surface coatings and

perfumery chemicals.

The residue left behind after extraction of oil is called as deoiled cake or meal. Such cake

is predominantly consisting of proteins, minerals, fibers, etc. However this cake is not

consumed by animal owing to contents of the toxic compounds. Therefore it’s being used

as manure. Since some chemical or heat treatments over come the effect of toxin

henceforth it would be consumed by both poultry and animals. Moreover, the amino acid

profile of the deoiled castor cake is same as soy cake, but difference in their proportions.

The castor deoiled cake contains about 32 % proteins whereas in soy deoiled cake 47 %.

Soy protein isolate or concentrate are being used in various industries such as food,

pharmaceutical, adhesive, furniture, etc. The similar applications can be achieved except

food and pharmaceutical by using castor protein isolate and concentrate following the

same methodologies, which is used for isolation of protein from soy deoiled cake.

2. Overall Sub-project Objectives

1. Production: To increase farmer’s income and castor productivity through

popularization of latest high yielding castor hybrid and its agronomic practices

and innovative farming.

2. Processing: To develop post harvest handling and processing technologies to

improve quality of produce and reduce losses.

3. By-product value addition: To develop products from castor cake (by products of

castor oil extraction) for higher benefit of castor oil extraction units and farmers.

4. Specific to value chain: To develop higher generation castor oil based derivatives

for promotion of export and benefit of all stakeholders.

10

Sub-project Technical Profile

Output Deliverables Targets Achievements

To prepare the Esters like

DCP, DCS, DCM, DCF,

DCA and CB with high

purity (>99%) and light

color appearance

(10-12 M)

Processes have been standardized to prepare DCP,

DCS, DCM, DCF, DCA & CB with consistent quality

>99% conversion of PAN/SA/MAN/FA/AA/BA was

achieved

Completed work as per targeted

Performance evaluation of

DCP and DCS against the

DEHP and DINP in PVC

formulation

(12-14 M) Results indicate that DCP & DCS can replace

partially/completely DEHP and DINP in PVC

formulations

Performance evaluation of

DCM , DCF, DCA and CB

against existing plasticizers

(esters) based on 2EH and

isonanol in PVC formulation

and other resins

(14-20 M)

Performance evaluation work is delayed as per the

target owing to some practical problems.

Enough quantity of esters are prepared for

performance evoluation

To prepare and obtain

maximum conversion of 2-

octanol into symmetrical

(DCE) and asymmetrical

(CGE) ethers

(22-25 M)

Prepared refined Dicapryl ether alongwith co-product

2-octene which can be used for diluents, surfactants,

etc.

Capryl Gycidyl Ether is under preparation and this

will have application in reactive diluents and

intermediate for specialty surfactants

To extract and isolate protein

from deoiled castor cake:

Optimization of the process

parameters for extraction and

isolation of the proteins:

Comparison studies for film

and adhesive based on CPI ,

SPI and a combination of

CPI and SPI

(1-12 M)

97 % of protein extractability of protein was achieved

62 % protein isolated from extract

No ricin toxic constituent was found in CPI

No loss of protein on neutralization of extract with

acid and followed by drying. Could be Castor protein

concentrate

Process optimization work was completed as per

target.

The proteins isolation on large scale was delayed

owing to some practical problems (lack of filtration

media)

Trial batch of the proteins

extraction and isolation

using Ultrafiltration Process

(20-24 M)

Carried out large size batch of protein extraction from

DCC using optimized process parameters

97 % of protein extractability of protein was achieved

Protein enrichment in concentrate using UF found 4-5

time more than initial

No ricin was detectable in CPI & this protein could be

a source of animal/poultry/fish feed after proper trials

In a proposed investigation, the 2-octanol obtained from alkali fusion of ricinoleic acid, and

protein enriched deoiled castor cake are used to develop value added products.

11

3. Baseline Analysis

In six districts of SDAU, Jurisdiction farmer’s income is very less. After

NAIP demonstration and training programme farmers’ income increases 27

per cent under uses of different production technology viz., intercropping,

High yielding variety, drip irrigation system uses.

Farmer’s maximum losses in harvesting technique. After NAIP project

implementation farmers preferred improved sickle and secator uses.

The castor crop sowing method was mainly traditional but after NAIP project

progress farmers adopted castor planter that found more suitable.

Earlier the maximum farmers were sowing of existing variety but after NAIP

progress they sown hybrid high yielding variety of castor.

12

Research Achievements

5.1 Research Achievements of Main Castor Mustard Research Station, SDAU,

Sardarkrushinagar

Improved agro techniques developed for castor cultivation were demonstrated at farmers

field viz.-

Wilt resistant variety: Propagation of newly recommended wilt resistant hybrid

GCH 7.

Drip Irrigation: Drip irrigation system is demonstrated and created awareness to

apply irrigation at requiring intervals.

Sulphur application: Sulphur is essential element for oil synthesis and seed yield

and oil content increases with sulphur application.

Proper stage and means of harvesting: Spikes should be harvested when ½ of the

total capsules appear yellow, harvesting at this stage minimize the shattering losses.

When spikes are cut with sickle, some of the dry capsules shatter and results in low

yield. Using the secater is effective tool for harvesting, which reduce the

harvesting losses.

Intercropping with castor: Irrigated castor is planted at wider spacing and takes

240-270 days for complete harvesting. Pulses and cotton crop are recommended

as intercropped in castor. This practice is beneficial to farmers to increase income

per unit area.

Results of field demonstration:

In 2009-10, farmers’ field demonstrations were conducted in five selected villages to

demonstrate the recommendation practices. At the time of implementation of project,

present yield level of the villages was surveyed. The yield level of selected villages viz.

Gangudara, Chodungari, Kamali, Matpur, and Garamadi (rainfed) was 19-21, 23-25, 31-

33, 33-34 and 6-8 q/ha, respectively. Considering the present yield level the target for

increased the yield level for different villages were fixed. The results indicated that the

range of increase in seed yield of castor in different selected villages was 15.7 to 23.9

percent. On an average, the magnitude of increase in yield over present level was 34

percent which was 11.8 per cent more than targeted yield (Table 5.1).

13

Table 5.1: Average yield, expected yield and actual yield of five selected villages

Village Present yield

status

(q/ha)

Targeted yield

(q/ha)

Actual yield

received (q/ha)

Increase over

present yield

(%)

Gangudara 19-21 23-25 28.18 20.0

Chodungari 23-25 28-30 28.78 20.8

Kamali 31-33 35-37 40.73 12.5

Matpur 33-34 38-40 42.50 16.4

Ratanpur 32-35 40-42 49.38 23.9

Garamadi 6-8 10-12 11.54 15.7

25 30 (20 %) 34.0

14

Field demonstration on demonstration of varietal response:

About 148 farmers were selected to demonstrate the response of newly released wilt resistant and high yielding hybrid GCH 7 in five

selected villages. The results indicated that the magnitude of increase in seed yield under GCH 7 was varied from 17.5 to 33.9 per

cent in different villages over local hybrids/varieties (Table 5.1.1). On an average GCH 7 produced 23.2 per cent higher seed yield

and31.0 per cent higher net returns over local one.

Table 5.1.1: Demonstration of varietal response

Name of village Yield (kg/ha) Total income (Rs/ha) Cost of

cultivation

(Rs/ha)

Net income (Rs/ha) % higher

over local

yield

GCH 7 Local GCH 7 Local GCH 7 Local

Gangudara 2212(24) 1825 (25) 61936 51100 21733 40203 29367 21.2

Chodungari 2878 (39) 2150 (25) 80597 60200 26031 54566 34169 33.9

Matpur 3656 (18) 3050(25) 102368 93800 31847 70521 61720 19.9

Kamali 3506(25) 2985 (25) 98168 83580 30086 68082 53493 17.5

Garamadi 926 (42) 750 (25) 25928 21000 11840 14088 9160 23.5

2636 2152 49486 37782 (31.0) (23.2)

15

Field demonstration on demonstration of varietal response:

About 281 farmers were selected to demonstrate the response of sulphur on castor in five selected villages. The results indicated that

the magnitude of increase in seed yield with sulphur application was varied from 16.2 to 27.4 was recorded with sulpuur application

over control (Table 5.1.2). On an average application of sulphur recorded 21.1 per cent higher seed yield and 27.9 per cent higher net

returns over control field.

Table 5.1.2: Demonstration of response of Sulphur

Name of

village

Yield (kg/ha) Total income (Rs/ha) Cost of cultivation

(Rs/ha)

Net income (Rs/ha) % higher

yield over

without S With S Without S With S Without S With S Without S With S Without S

Gangudar

a

2818 (76) 2212(24) 78904 61936 22380 21733 56524 40203 27.4

Matpur 4250(73) 3656 (18) 119000 102368 32140 31847 86860 70521 16.3

Kamali 4073

(100)

3506(25) 114044 98168 30373 30086 83671 68082 16.2

Garamadi 1154(32) 926 (42) 32312 25928 12620 11840 19692 14088 24.6

3074

2575 61687 48224

(27.9%)

21.1

16

Field demonstration on demonstration of drip irrigation system:

Under this project, Ratanpur village is selected to demonstrate drip irrigation method in castor crop. The results indicated that application of water

through drip system recorded 29.2 percent higher yield over flood irrigation system (Table 5.1.3).

Table 5.1.3: Demonstration of response of drip irrigation system:

Name of

village

Yield (kg/ha) Total income

(Rs/ha)

Cost of cultivation

(Rs/ha)

Net income(Rs/ha) % higher over flood

yield

Drip Flood Drip Flood Drip Flood Drip Flood

Ratanpur 4938

(10)

3823

(10)

138264 107044 31289 27200 106975 79844 29.2

Field demonstration on demonstration of Intercropping:

Under this project 10 demonstrations on intercropping system were conducted in Danta and Kamali villages. Results indicated that intercropping

of castor with pulse as well as cotton found beneficial in respect of generate additional income. Results indicated that intercropping of castor with

urd bean and cotton 10.68 and 76.1 per cent higher net income as compared to sole castor and cotton, respectively (Table 5.1.4).

Table 5.1.4: Demonstration of response of Intercropping:

Name

of

village

Yield

(kg/ha)

Yield Castor +

Urd bean (kg/ha)

CEY

(kg/ha)

Total income

(Rs/ha)

Cost of cultivation

(Rs/ha)

Net income(Rs/ha) % Income

higher over

castor /cotton

sole

Castor

sole

Castor Urd

bean

Cotton

sole

Inter cropping Castor

sole

Inter cropping Castor

sole

Inter cropping

Danta 4389

(4)

4464 475 4973 122885 139235 31026 35655 94900 105033 10.68

13.3 %

Cotton

sole

Cotton Castor Cotton

sole

Intercropping Cotton

sole

Intercropping Cotton

sole

Intercropping

Kamali 3660

(6)

3148 2253 5963 120780 166960 36863 47182 83918 119778 76.4

62.9 %

17

In 2010-11, farmers’ field demonstrations were conducted in all the districts falls under

the jurisdiction of SDAU, Sardarkrusinagar (Table 5.1.5).

Table 5.1.5: District wise selected villages and No. of farmers

Sr.

No.

Name of village No. of

farmers

Selected

Sr.

No.

Name of village No. of

farmers

Selected

District: Banaskantha District: Sabarkantha

1 Gangodara 57 1 Dhamadi 64

2 Chodungari 40 2 Laloda 78

3 Undai 40 3 Mahadevpura 46

Total 137 Total 188

District: Kutchh District: Patan

1 Kamali 208 1 Matpur 78

2 Motidhau 30 2 Ruvavi 22

3 Kherava 38 3 Kanni 29

4 Sunok 27 4 Mithidhariyal 36

5 Shankhalpur 34 5 Ruppur 36

6 Garamadi 68

Total 337 Total 269

District: Kutchh District: Gandhinagar

1 Amardi 40 1 Tintoda 52

2 Nakhtrana 48

3 Kanakpur 28

4 Virani 20

Total 136

Grand total 1112

Total village 22

In this project, 1112 farmers’ field demonstrations were conducted during 2010-11 in

selected villages. The yield level of selected villages viz. Gangudara, Chodungari,

Kamali, Matpur, and Garamadi (rainfed) was surveyed and found 19-21, 23-25, 31-33,

33-34 and 6-8 q/ha, respectively. Looking to the present yield level, the target was fixed

for increasing yield level for different villages. The results indicated that the range of

increase in seed yield of castor in different selected villages was 25.8 to 51.1 percent

(Table 5.1.6). On an average, the magnitude of increase in yield over present level and

targeted yield was 37.6 per cent, respectively.

18

Table 5.1.6: Present yield, expected yield and actual yield of selected villages

S.

No.

Village Baseline

yield

status

(q/ha)

Actual received

yield (q/ha)

Increase

over Baseline yield status (%)

2009-10 2010-11 2009-10 2010-11 Mean

1 Gangudara 19-21 28.18 32.25 40.9 61.3 51.1

2 Chodungari 23-25 28.78 31.60 19.9 31.7 25.8

3 Kamali 31-33 40.73 42.20 27.3 31.9 29.6

4 Matpur 33-34 42.50 45.10 26.9 34.6 30.8

5 Garamadi 6-8 11.54 12.25 64.9 36.1 50.5

23.7 30.35 32.68

(32.52)

36.0 39.1 37.6

19

Demonstration on yield of GCH 7

Primary survey was made to know the present productivity of each selected villages. The

figures indicated that the productivity of selected villages was ranging from 27 to 35 q/ha

with average value of 30.26 q/ha. The result obtained in the demonstrations indicate that

by adoption of improved wilt resistant and high yielding hybrid GCH 7 recorded 12.32 to

46.38 per cent higher seed yield over existing hybrid/varieties (Table 5.1.7). On an

average 28.10 per cent productivity was increased.

Table 5.1.7: Demonstration of yield of GCH 7 over local cultivar

Name of the

village

Productivity

(q/ha)

%

higher

over

local

Name of

the village

Productivity

(q/ha)

%

higher

over

local Local

cultivar

GCH

7

Local

cultivar

GCH

7

Undai 29.00 36.21 24.86 Dhamadi 31.00 36.03 16.23

Motidhau 31.00 39.25 26.61 Laloda 34.50 39.45 14.35

Kherava 33.50 37.64 12.36 Mahadevpura 30.50 38.45 26.07

Shankhalpur 27.50 35.62 29.53 Ruvavi 31.50 37.25 18.25

Sunok 31.50 38.65 22.70 Kanni 30.50 36.84 20.79

Amardi 30.50 42.25 38.52 M. ghariyal 28.00 39.45 40.89

Nakhtrana 29.00 40.52 39.72 Ruppur 29.50 38.00 28.81

Kanakpur 30.50 39.65 30.00 Tintoda 27.50 38.95 41.64

Virani 29.00 42.45 46.38

Mean 30.26 38.62 28.10

20

Demonstration on intercropping

Under this project 28 demonstrations on intercropping system were conducted in Kamali village during 2010-11. Results clearly

indicated that intercropping of castor in cotton found beneficial in respect of generate additional income (Table 5.1.8). On an average

intercropping of castor with cotton gave 50.79 and 58.76 per cent higher cotton equivalent yield and net income as compared to sole

cotton, respectively.

Table 5.1.8: Demonstration on intercropping

Pest observed/leaf –

Cotton: - Jassid 5.25, Thrips 11, Aphids 7 and White fly 10 Castor: - Jassid 3.5, Thrips 7.0, Aphids 2.0 and White fly 8

Year Cotton

sole

Yield Castor + Urd

bean (kg/ha)

CEY

(kg/ha)

Total income

(Rs/ha)

Cost of cultivation

(Rs/ha)

Net income(Rs/ha) % Income

higher

over

castor

/cotton

sole

Cotton Castor Cotton

sole

Inter

cropping

Cotton

sole

Inter

cropping

Cotton

sole

Inter

cropping

2009-10 3660 (6) 3148 2253 5266

(43.88)

183000 263291 35900 42850 147100 220441 49.86

2010-11 3440 (28) 3052 2541 5441

(58.17)

172000 272027 35900 42850 136100 229177 68.39

Mean 3550 3100 2397 5353

(50.79)

177500 267669 35900 42850 141600 224809 58.76

21

In 2010-11, farmers’ field demonstrations were conducted in all the districts falls under the

jurisdiction of SDAU, Sardarkrusinagar (Table 5.1.9).

Table 5.1.9: List of villages selected for demonstrations during 2011-2012

Sr.

No.

Name of village No. of

farmers

Selected

Sr.

No.

Name of village No. of

farmers

Selected

District: Banaskantha District: Sabarkantha

1 Gangodara 50 1 Kheroj 40

2 Chodungari 40 2 Kalwan 36

3 Kasalpura 40

Total 130 Total 76

District: Mehsana District: Patan

1 Kamali 160 1 Matpur 80

2 Badharpura 34

3 Maghapura 32

Total 160 Total 146

District: Kutchh District: Gandhinagar

1 Koday 20 1 Halisa 25

2 Nakhtrana 20 2 Jakhora 25

3 Rapar 20 3 Patelpura 25

4 Paliyad 25

Total 60 Total 100

Total village 16

Grand total 672

Total 672 demonstrations were conducted during 2011-12 in selected villages. At the

time of implementation of project, present yield level of the villages was surveyed. The yield

level of selected villages viz. Gangudara, Chodungari, Kamali, Matpur, and Kasalpura was 19-

21, 23-25, 31-33, 33-34 and 35-40 q/ha, respectively. Looking to the present yield level, the

target was fixed for increased the yield level for different villages. The results indicated that the

range of increase in seed yield of castor in different selected villages was 25.8 to 51.1 percent in

2010-11, but in 2011-12 it was not increased due to chilling injury (due to climatic change). On

an average, the magnitude of increase in yield over present level and targeted yield was 37.6 per

cent, respectively (Table 5.1.10).

22

Table 5.1.10 : Present yield, expected yield and actual yield of five selected villages

Demonstration on varietal response

About 148 farmers were selected to demonstrate the response of newly released wilt resistant and

high yielding hybrid GCH 7 in five selected villages. The results indicated that the magnitude of

increase in seed yield under GCH 7 was varied from 0.38 to 29.10 per cent in different villages

over local hybrids/varieties (Table 5.1.11). On an average GCH 7 produced 18.67 per cent

higher seed yield and 42.85 per cent higher net returns over local one.

Table 5.1.11 : Demonstration on varietal response

Name of

village

Yield (kg/ha) Total income

(Rs/ha)

Cost of

cultivation

(Rs/ha)

Net income

(Rs/ha)

%

increase

in yield

over

locally

grown

cultivars

GCH 7 Local GCH 7 Local GCH

7

Local

Gangudara 2251 1825 67530 51100 21733 45797 29367 23.34

Chodungari 1847 1840 55410 51520 26031 29379 25489 0.38

Matpur 3583 3050 107490 93800 38572 68918 55228 17.47

Kamali 3674 2985 110220 83580 38223 71997 45357 23.08

Kasalpura 3983 3085 119490 92550 43714 75776 48876 29.10

3067 2619 58373 40863 (18.67)

Village Present

yield status

(q/ha)

Actual received

yield (q/ha)

Increase

Over Present status (%)

2010-11 2011-12 2010-11 2011-12 Mean

Gangudara 19-21 32.25 22.51 61.3 12.5 36.9

Chodungari 23-25 31.60 18.47 31.7 -24.24 3.73

Kamali 31-33 42.20 36.74 34.70 8.43 21.6

Matpur 33-34 45.10 35.83 34.6 3.28 18.9

Kasalpura 35-40 45.30 39.83 43.70 16.53 30.11

29.4 39.29 30.67 41.2 3.3 22.24

23

Demonstration on drip irrigation system

Chodungari village was selected to demonstrate drip irrigation method in castor crop. The results

indicated that application of water through drip system recorded 7.28 percent higher yield over

flood irrigation system (Table 5.1.12). The yield is decreasing of castor crop due to chilling

injury.

Table 5.1.12 : Demonstration on drip irrigation system

Name of

village

Yield (kg/ha) Total income

(Rs/ha)

Cost of

cultivation

(Rs/ha)

Net

income(Rs/ha)

%

increase

over

flood

yield

Drip Flood Drip Flood Drip Flood Drip Flood

Chodungari 1844

1720 55320 51600 30228 27200 25092 24400 7.28

Demonstration on Intercropping

Ten demonstrations on intercropping system were conducted in Chodungari and Gangudara

villages. Results clearly indicated that intercropping of castor with ground nut found beneficial in

respect of generate additional income. Results indicated that intercropping of castor with ground

nut 72.01 and 79.21 per cent higher net income as compared to sole castor in Chodungari and

Gangudara, respectively (Table 5.1.13).

Table 5.1.13: Demonstration on Intercropping

Name

of

village

Yield

(kg/ha

)

Yield Castor +

Ground nut

(kg/ha)

Total income

(Rs/ha)

Cost of

cultivation

(Rs/ha)

Net

income(Rs/ha)

%

Income

higher

over

castor

sole

Castor

sole

Casto

r

Grou

nd

nut

Casto

r sole

Inter

croppin

g

Casto

r sole

Inter

croppi

ng

Casto

r sole

Inter

cropping

Chodun

gari

2200

1400 1100 66000 95500 35195 42510 30805 52990 72.01

Gangu

Dara

2175

1325 1185 65250 97725 34241 42182 31009 55573 79.21

24

5.1.13 Value addition to the by-products of the castor

Objective: - To determine protein content in castor cake of different genotypes

Techniques used: - Determination of Total Protein content by Micro-Kjeldahl Method

Results and discussion: - Fifty one castor germplasm genotypes were analysed for protein

content. The protein content was in the range of 19.93 to 30.81% (Table 5.1.13). Maximum

protein content was noted in GP-415 (30.81%) genotype.

Table 5.2.1: Nitrogen and Protein content in cake of castor germplasm

Sr.

No. Sample Name N %

Protein

%

Sr.

No.

Sample

Name N % Protein %

1 GP – 401 4.37 27.31 26 GP – 437 3.36 21.00

2 GP – 402 4.65 29.06 27 GP – 440 3.64 22.75

3 GP – 407 4.24 26.50 28 GP – 444 3.92 24.50

4 GP – 408 3.64 22.75 29 GP – 445 4.34 27.12

5 GP – 409 3.92 24.50 30 GP – 447 4.45 27.81

6 GP – 411 4.84 30.25 31 GP – 460 4.20 26.25

7 GP – 412 4.09 25.56 32 GP – 461 3.92 24.50

8 GP – 413 3.83 23.93 33 GP – 463 3.36 21.00

9 GP – 414 3.69 23.06 34 GP – 466 4.76 29.75

10 GP – 415 4.93 30.81 35 GP – 467 3.64 22.75

11 GP – 416 4.25 26.56 36 GP – 471 4.84 30.25

12 GP – 417 4.49 28.06 37 GP- 473 4.64 29.00

13 GP – 419 4.06 25.37 38 GP – 478 4.37 27.31

14 GP – 420 4.22 26.37 39 GP – 480 4.27 26.68

15 GP – 421 3.22 20.12 40 GP – 481 4.88 30.50

16 GP – 422 3.92 24.50 41 GP – 482 3.92 24.50

17 GP – 423 3.83 23.93 42 GP – 487 4.25 26.56

18 GP – 424 4.45 27.81 43 GP -488 3.73 23.31

19 GP – 425 4.36 27.25 44 GP – 489 3.79 23.68

20 GP – 426 4.20 26.25 45 GP – 490 4.29 26.81

21 GP – 427 3.75 23.44 46 GP – 491 4.25 26.56

22 GP – 428 3.50 21.80 47 GP – 492 3.90 24.37

23 GP – 429 3.66 22.88 48 GP – 493 4.11 25.68

24 GP – 431 3.76 23.54 49 GP – 494 4.17 26.06

25 GP – 435 4.25 26.56 50 GP – 495 3.19 19.93

51 GP – 496 4.09 25.56

25

Objectives: To develop protein estimation and extraction method from castor cake.

Techniques used:- Rebeca Marnoch and Levente L.Diosady (2006) Production of Mustard

protein isolates from Oriental Mustard seed (Brassica juncea L.) JAOCS, 83(1): 65-69

Results and discussion:

Thirty six castor genotypes were analysed for protein isolation from cake. The protein content of

different genotype was in the range of 11.05to 19.35% (Table 5.1.14). Among all the genotypes,

GP-422 (19.35 %) recorded maximum protein content.

Table 5.1.14: Protein isolation and extraction from castor cake.

Sr.

No.

Sample Name Protein (%) Sr.

No.

Sample

Name

Protein (%)

1 GP-401 13.70 19 GP-434 16.82

2 GP-402 11.05 20 GP-435 17.53

3 GP-407 13.57 21 GP-437 17.22

4 GP-408 14.01 22 GP-440 18.86

5 GP-409 12.90 23 GP-441 11.27

6 GP-411 11.89 24 GP-442 16.51

7 GP-412 14.13 25 GP-444 13.38

8 GP-413 13.52 26 GP-445 15.46

9 GP-414 12.10 27 GP-460 14.35

10 GP-415 15.20 28 GP-447 17.48

11 GP-424 11.26 29 GP-461 12.65

12 GP-427 12.18 30 GP-462 17.08

13 GP-430 13.90 31 GP-463 16.09

14 GP-425 16.30 32 GP-466 15.38

15 GP-428 12.42 33 GP-467 15.02

16 GP-429 13.20 34 GP-471 17.93

17 GP-422 19.35 35 GP-473 12.44

18 GP-423 11.23 36 GP-476 15.56

26

Objectives: To estimate different toxic constituents in cake of various castor genotypes and its

detoxification .

Techniques used: H.L.Craig et.al., 1952 Preparation of toxic Ricin filed July 3,

Results and discussion:

Thirty seven castor cake samples were analysed for crude ricin. The toxic constituents content was in

the range of 1.03-1.92 % in the different DOC samples. GP-420 (1.03 %) showed lowest toxic

constituents and GP-460 (1.92%) had the highest toxic constituents (Table 5.1.15). After the series of

treatments for detoxification, namely soaking 3 hours in 0.5 M NaOH ,and 0.5 M Ca(OH)2,, heated in

water bath and autoclaving, resulted in traces or undetectable levels of toxic constituents were

observed.

Table 5.1.15: Crude ricin content before and after detoxification

Sample Name Before Detoxification Crude Ricin

content

After treatment

Ricin content%

DOC-1 1.09 Trace

DOC-2 1.44 Trace

DOC-3 1.65 Trace

DOC-4 1.04 Trace

DOC-5 1.14 Trace

DOC-6 1.58 Trace

DOC-7 1.29 Trace

DOC-8 1.30 Trace

GP-401 1.64 Trace

GP-402 1.40 Trace

GP-407 1.64 Trace

GP-408 1.07 Trace

GP-409 1.80 Trace

GP-415 1.57 Trace

GP-417 1.67 Trace

GP-419 1.71 Trace

GP-416 1.85 Trace

GP-420 1.03 Trace

GP-421 1.60 Trace

GP-422 1.69 Trace

GP-424 1.72 Trace

GP-425 1.66 Trace

GP-427 1.03 Trace

GP-428 1.37 Trace

GP-429 1.39 Trace

GP-430 1.69 Trace

27

GP-434 1.72 Trace

GP-435 1.27 Trace

GP-437 1.48 Trace

GP-440 1.42 Trace

GP-441 1.06 Trace

GP-442 1.01 Trace

GP-444 1.17 Trace

GP-445 1.08 Trace

GP-447 1.68 Trace

GP-460 1.92 Trace

GP-461 1.48 Trace

Objectives: To determine Lignin and Cellulose content of castor stem from different castor

genotypes

Techniques used: Official Methods of Analysis of the AOAC Lignin (35)-Official Final Action

Direct Method

Results and discussion

Eighteen castor genotypes were analyzed for lignin and cellulose content of stem by chemical

method. The lignin and cellulose content was noted in the range of 14.1 to18.8 and 34.9 to 45.7%

respectively (Table 5.1.16).

Table 5.1.16: Determination of lignin and cellulose by chemical method

Genotypes % Lignin % Cellulose Genotypes % Lignin % Cellulose

Geeta 18.8 39.1 GCH-4 14.6 38.2

GAUCH-1 16.3 40.7 VP-1 16.6 40.3

VI-9 17.0 40.8 GCH-2 19.2 36.8

SKP-84 14.4 40.1 JI-96 15.7 35.0

GCH-2 17.7 44.3 GC-3 16.8 34.9

48-1 15.9 41.8 SH-72 17.3 38.4

SKI-215 15.7 37.1 GC-2 16.5 41.7

GCH-7 17.2 45.7 JP-65 17.3 42.2

GCH-5 14.1 41.2 JI-35 18.7 44.1

28

Summary

Field demonstration: Total 465 farmers’ field demonstrations were conducted. The yield level of

selected villages viz. Gangudara, Chodungari, Kamali, Matpur, and Garamadi (rainfed) was 19-

21, 23-25, 31-33, 33-34 and 6-8 q/ha, respectively. Through the agro technological

demonstration, the results indicated that the range of increase in seed yield of castor in different

selected villages was 15.7 to 23.9 percent. On an average, the magnitude of increase in yield over

present level was 34 percent which was 11.8 per cent more than targeted yield. During 2011-12

total 672 demonstrations were conducted. The yield level of selected villages viz. Gangudara,

Chodungari, Kamali, Matpur, and Kasalpura was 19-21, 23-25, 31-33, 33-34 and 35-40 q/ha,

respectively. On an average, the magnitude of increase in yield over present level and targeted

yield was 37.6 per cent, respectively.

Value addition in castor cake: Among, Fifty one castor genotypes analysed, the protein content

varied from 19.93 to 30.81%. Maximum protein content was noted in GP-415 (30.81%)

genotype. Thirty six castor genotypes were analysed for protein isolation from cake. The protein

isolated from different genotype varied from 11.05to 19.35%. Among all the genotypes, GP-422

(19.35 %) recorded maximum isolated protein content. Thirty seven castor cake samples were

analysed for crude ricin ranging from 1.03-1.92 % in the different DOC samples. GP-420 (1.03

%) showed lowest toxic constituents and GP-460 (1.92%) had the highest toxic constituents.

After the series of treatments for detoxification, resulted in traces or undetectable levels of toxic

constituents were observed. Eighteen castor genotypes were analyzed for lignin and cellulose

content of stem by chemical method. The lignin and cellulose content was noted in the range of

14.1 to18.8 and 34.9 to 45.7% respectively.

29

5.2. POST HARVEST TECHNOLOGIES

Objectives: Development of post harvest processing improving oil recovery in extraction of oil

from castor seed and in-plant study of castor oil extraction industry for energy efficiency.

Activity 1:

Improved sickles, hand operated cutting tool will be evaluated for efficient harvesting the

castor spikes. The losses occurs at different stage will be measured and technology

developed / suggested to reduce losses. The harvested castor spikes will be dried under

different drying methods viz., natural drying, solar drying and mechanical drying.

The economically efficient drying methods will be suggested to the growers

Activity 2:

The different available hand and power operated castor decorticators will be studied.

Efficient castor decorticator will be standardized for the uniform size of castor seed for

prominent castor genotypes of North Gujarat.

Activity 3:

The different secondary processing equipments like pre seed cleaner cum aspirator,

cleaner cum grader and destroyer will be used to improve the quality of raw material.

The cleaned and graded produce will be packed in different size / quality of packaging

material.

Activity 4:

Existing oil extraction plants (two each of small and medium capacity) of the region will

be evaluated for time -motion operation and energy audit.

The energy audit study will identify the aspects of where and how energy is used and

converted from one form to another, opportunities for reduction in energy loss ;

evaluation of the technical and economic viability of the energy conservation measures

proposed

Recommendations will be generated on above aspects.

After completion of experimental part in each activities, the analysis of data will be

carried out.

30

Study on different harvesting tools for higher cutting efficiency & minimum losses

Achievements:

The local sickle, improved sickle and secator were evaluated for efficient harvesting of castor

crop (variety: GCH-7) and minimum losses. The average harvesting capacity of castor spike was

found 65.90 kg/hr for secator followed 52.99 and 51.24 kg/hr for improved sickle and local

sickle respectively (Table 5.2.1). The higher percent losses were observed for improved and local

sickles as compared to secator.

Table 5.2.1 Harvesting of castor spikes (Area: 1 ha)

Sr.

No

Types of

harvesting

devices

Times

(Hours)

Weight of

Harvested

spike (kg)

Harvesting

Capacity

(Kg/hr)

Average

capacity

(Kg/hr)

Losses

during

harvesting

(kg)

Percentage

of losses

1 Local

sickle

25.25 1570.70 62.21 51.24 63.62 4.05

23.14 1325.75 57.30 62.34 3.94

21.04 941.91 44.76 54.35 5.77

26.38 939.39 35.60 41.69 4.43

22.44 1264.31 56.34 59.09 4.67

2 Improved

Sickle

27.35 1578.28 57.70 52.99 63.31 4.01

25.25 1110.10 43.97 35.67 3.21

23.14 1045.95 45.20 48.91 4.67

16.83 1111.11 66.02 41.35 3.72 19.64 1022.72 52.07 44.10 4.31

3 Secator 21.04 1598.48 75.97 65.90 52.22 3.27

18.93 1146.46 60.56 31.65 2.76

23.14 1116.16 48.23 32.11 2.88

14.73 1098.48 74.57 23.88 2.17

18.23 1279.48 70.18 28.60 2.23

Study on tractor drawn castor planter

31

Title of experiment: Performance-evaluation of tractor drawn castor planter

Achievements:

A) Castor seed sowing by tractor drawn castor planter

Plot size: 10.60 m (width) X 51 m (length) Plot area: 540.6m2

Diesel consumption: 3.01 lit / ha. (0.1622 lit for 540.6 m2 area)

Germination, %: 4 plants / sqm. ; 76 plants / 100 sqm

B) Manually sowing method:

Nos. of labours required: 5 labours for 1 hectare sowing (in 8 hours).

Cost for manual sowing: Rs. 500 / ha. (Rs.100/lab our)

Economic benefit with mechanized sowing:

(i) Fuel consumption: 3.01 lit / ha Cost of fuel: 3.0 x 42.00=126.00

(ii) Operating cost including tractor driver & skilled labour charges

For 1 hectare sowing using tractor drawn planter 2.77 hrs (3 hrs) is required the expenditure for

labours is Rs. 150/- considering Rs.200/- day per skill lab our

Benefit by mechanized sowing: Rs. (500-276) = Rs. 224.00 per hectare

The castor planter was tested for single, double and triple groove rollers (pvc) for sowing

of castor seeds (variety: GCH7). Single groove roller (pvc) was found more suitable to

maintain row to row and plant to plant distance.

The purchased tractor drawn castor planter is also found satisfactory to maintain the

depth of sowing.

Single groove roller is found satisfactory to maintain the depth of sowing and plant to

plant distance.

Expenditure under mechanized sowing per hectare Expenditure under manual sowing

Per hectare

Cost of fuel: 3.0 x 42.00 = Rs. 126.00 Cost for manual sowing: Rs. 500

Labour cost = Rs. 150.00 (Rs. 100 / labour)

--------------------------------------------------------

Total Rs. 276.00 (excluding seed saving cost)

In manually sowing method double seeds are sown at crossed marked point. Therefore, the

seeds require in double quantity which also increase the cost of sowing.

32

Study on to standardize the hand and power operated castor decorticators for the uniform

size of castor seed for prominent castor genotypes of North Gujarat.

The performance testing of power operated castor decorticator was done. The uncleaned castor

capsules were found slightly higher. Therefore the upper sieve size was replaced with suitable

size of hole. The castor decorticator was tested in field condition. The cleaning efficiency and

broken percentage was found 82 to 89% and 1.2 to 4.2% respectively (Table 5.2.2).

Table-5.2.2: Performance of purchased modern castor decorticator

Sr.

no

Total weight

of sample,

kg

Unthresh

ed seed,

kg

Unthreshe

d seed, %

Cleaned

seeds, kg

Cleaned

seed. %

Breakage

seeds, kg

Breakage

seed, %

1 1.437 0.092 6.41 1.284 89.35 0.059 4.17

2 1.230 0.151 12.27 1.035 84.14 0.043 3.51

3 1.610 0.148 9.19 1.426 88.57 0.035 2.17

4 1.362 0.238 17.47 1.115 81.86 0.054 3.96

5 1.105 0.128 11.58 0.967 87.51 0.026 2.35

6 1.395 0.138 9.89 1.241 88.96 0.016 1.15

Average 1.143 0.149 10.98 1.178 86.73 0.039 3.41

33

Study on solar drying of castor spikes under low cost poly solar dryer

Low cost poly solar dryer: Low cost poly solar dryer for drying the castor spikes was installed.

The dryer was tested for temperature and humidity controlled under no load condition. The

performance data are as per under (Table 5.2.3). The experiment was conducted in first week of

December-2010, to dry the freshly harvested castor spikes in low cost poly solar dryer and open

space sun drying. The material was dried earlier 5 to 6 days in low cost ploy solar dryer at 30%

humidity and 36 to 37O C whereas the outside ambient temperature was 22 to 25

O C. Using low

cost poly solar dryer, the farmers can dry their harvested crops earlier and get benefit of

immediate market price. Traditional drying of castor spike in open space on pakka floor.

Table 5.2.3 Performance evaluation of low cost poly solar dryer under no load condition

Date & Time Humidity Temp. inside

the dryer (oc)

Outside Temp

(ambient), (oc)

Outside Humidity

(%)

14-07-2010

8:30 (A.M.) 20 49 32 64

11:30 (A.M.) 20 55 35 50

15:00 (P.M.) 20 53 41 27

17:30 (P.M.) 20 51 36 55

15-07-2010

8:30 (A.M.) 30 47 31 58

11:30 (A.M.) 30 52 36 47

15:00 (P.M.) 30 55 41 32

17:30 (P.M.) 30 57 39 33

16-07-2010

8:30 (A.M.) 40 39 33 68

11:30 (A.M.) 40 45 37 32

15:00 (P.M.) 40 48 39 44

17:30 (P.M.) 40 51 38 34

17-07-2010

8:30 (A.M.) 50 41 31 80

11:30 (A.M.) 50 44 37 44

15:00 (P.M.) 50 52 39 42

17:30 (P.M.) 50 50 38 47

19-07-2010

8:30 (A.M.) 60 39 32 70

11:30 (A.M.) 60 42 34 61

15:00 (P.M.) 60 55 40 41

17:30 (P.M.) 60 52 38 49

20-07-2010

8:30 (A.M.) 70 36 35 51

11:30 (A.M.) 70 39 37 46

15:00 (P.M.) 70 45 40 41

17:30 (P.M.) 70 41 36 45

by Tractor drawn castor planter

34

21-07-2010

8:30 (A.M.) 80 34 32 62

11:30 (A.M.) 80 36 38 48

15:00 (P.M.) 80 40 39 36

17:30 (P.M.) 80 39 37 41

Summary

After base line survey of six districts of north Gujarat, in three years time two thousand

four hundred demonstrations comprising about 2000 under irrigated and 400 under

rainfed conditions demonstrating different agro-techniques were conducted on farmers’

field during 2009-2012.

Visited farmer's field & gave suggestion for plant protection measures for insect-pests

and disease management and adoption of new latest high resistant variety.

Farmer’s field days in villages till 2009 to 2012 in Kuttch and Banskantha, Patan district

villages and provided the castor production technology.

Solar dryer is more suitable for drying of crops drying was found 6 to 7 days earlier as

compared to traditional drying method.

On the basis of demonstration of farmer's field single groove planter was found most

suitable for sowing castor crop sown at fixed crop geometry.

Fifty one castor genotypes were analyzed for protein content in castor cake which ranges

from 19.93 (GP 495) to 30.81% (GP 415).

Thirty seven genotypes analyzed for ricin content in castor cake which ranged from 1.03

(GP 420) to 1.92 % (GP 460). After detoxification only trace ricin content was found.

Eighteen genotypes were analyzed for cellulose and lignin content. The cellulose ranged

from 39.4-45.7% and lignin between 14.1 -19.2% with lowest in GCH 5 & GC 3 and

highest in GCH 2 & GCH 7, respectively.

35

5.3 Research Achievement of RCPL, Sidhapur

Objective: To make various ester based on castor oil

12 H.S.A. was starting molecule having following properties

ACID VALUE : 180.06

HYDROXYL VALUE: 158.00

IODINE VALUE : 2.86

COLOUR : 5 (Gardner)

Esterification of 12 H.S.A. with Higher alcohol (Octanol)

Experimental set up:

1. 5 liter round bottom flask was attached with condenser and dean and stark assembly and

agitator.

2. The reaction mass was heated by heating metal.

Reaction condition and Inputs:

1. 1 Kg 12-H.S.A.

2. 780 gm octanol

3. 0.2 %catalyst

4. Temperature 120˚C

5. Time 4 hr

The 2-EH esters are not good in color which were prepared by H2SO4 or other acid catalyst.

Also they have lower viscosity, so they are not also useful as lubricants or hydraulic fluids. The

hydroxyl group also neutralize by some acid molecule. The acidity of the esters also become as

near by1.0 and the H.V. of the esters also nil. If the acidity of the sample is more then it becomes

rancid and the odor of the sample is bad. The acid catalyst is also difficult to neutralize. If the

neutralize materials with strong base then there may be the possibility of the saponification of the

2-eh esters and soap formation.

Trial for various catalysts for Esterification

1. Technique Used : Few Esterification Catalyst procured from the market :

2. Maharastra Organo metallic catalyst Pvt Ltd ( OM – 06 )

3. Navdup Chemicals Pvt Ltd. (NC – 07 )

4. Amrit Chemicals ( AC – 08 )

Preparation of the different esters with other catalyst

(1) 12 H.S.A + OCTANOL + OM – 06

(2) 12 H.S.A + OCTANOL + NC – 07

(3) 12 H.S.A + OCTANOL + AC – 08

36

1ST

STAGE ESTERIFICATION REACTION

Analysis of the Data: 1st Stage Reaction

12 H.S.A. + OCATANOL + OM – 06

SR NO. A.V. H.V. I.V. COLOR VISCOSITY@ 40

1 0.5 101.6 2.4 2.8 35.88

2 1.0 99.2 2.10 2.9 34.66

3 0.98 98.9 2.6 2.8 35.11

12 H.S.A + OCTANOL + NC – 07

SR NO. A.V. H.V. I.V. COLOR VSICOSITY@40

1 1.8 95.6 2.9 2.9 33.70

2 1.0 96.2 1.8 2.9 34.15

3 0.6 95.7 2.2 2.8 33.12

12 H.S.A + OCTANOL + AC – 08

SR NO. A.V. H.V. I.V. COLOR VISCOSITY@40

1 1.5 93.2 2.6 2.8 32.10

2 1.2 94.6 2.8 2.75 33.02

3 0.99 94.7 2.4 2.8 33.69

37

RESULTS AND DISCUSSION:

1st Stage Reaction

Catalyst seems to be effective and acid value is considerably reduced.

Color of the product is approximately 3G meaning acceptable

Viscosity is bit on lower side

Hydroxyl Value is higher side which has to be reduce

Reduction in the HV may result in the reduction of Viscosity.

2nd

Stage Reaction

2nd Stage Reaction: Comments:

All the Catalyst are effective for the esterification

The final products seems clear and transparent

Viscosity of the products has reduced

Hydroxyl value is reduced as desired.

38

Hydroxyl Value of the reaction product reduces the hydrolitical properties of the products. The

reaction product react these hydroxyl Value with Acetic Acid as.

ETHYL ESTER (WITH –OH) + ACETIC ACID

ETHYL ESTER (WITHOUT –OH) + H2O

SR NO. A.V. H.V. I.V. COLOR VISCOSITY@ 40

1 1.6 2.6 2.4 3.8 30.92

2 1.97 3.2 2.10 3.9 29.66

3 2.3 3.9 2.6 3.8 31.11

4 3.0 3.6 3.00 4.0 31.00

5 2.6 2.9 2.79 3.6 30.88

6 2.88 3.4 2.88 3.9 29.66

Further Viscosity Enhancement : -

Products can be trans-estrified to make bigger molecule , Various experiments have been

planned.

Using some higher Acids for Esterification to eliminate the HV

Reacting the hydroxyl value with higher molecular weight fatty acids.

Addition of Viscosity improver in additive package.

Reaction of Octyl 12 – H.S.A ( with hydroxyl value ) with Butyric acid

2nd Stage Reaction after Reaction of Octyl 12 – H.S.A (with hydroxyl value ) with Butyric acid

SR NO. A.V. H.V. I.V. COLOR VISCOSITY@ 40

1 0.41 NIL 2.4 3.0 33.91

2 0.38 NIL 2.8 2.9 33.10

3 0.35 NIL 2.6 3.0 33.05

4 0.45 NIL 2.5 3.0 33.20

Addition of one more reaction step to enhance the viscosity:

Target to achieve higher viscosity to the level of above 42 cst @ 40 Degree C / above 8 cst

@100 Degree C.

Mechanism :- To improve viscosity we have modified the reaction steps as follow :-

After 1stage reactions we have added condensation reaction as given below :-

39

Now the reaction steps can be as given below :-

1st Stage Reaction

12 H.S.A. + OCATANOL + CATALYST

↓

Octyl 12-HSA

2nd

Stage reaction :-

Condensation reaction :-

12-OHS +12-OHS -- Mixture of 12-OHS + Dimer + 2EH

3rd

Stage reaction :-

Reduction of Hydroxyl value :-

Mixture of 12-OHS + Acetic Acid - Final product ( with nil –OH value)

Detailing of second stage reaction :-

Second stage reaction was controlled by way of recovery of the product 2EH

Final results of the products is as given below:-43.8-48.6 @40 degree C and 8.4 to 9.6 @1000C

Tentitive Specification

TYPICAL PHYSICO – CHEMICAL PROPERTIES

SR. NO. PROPERTIES LIMITS

1. VISCOSITY@40ºC 42 MIN

2. VISCOSITY@100ºC 8 MIN

3. VI 162 MIN

4. CLOUD POINT ºC - 20 MIN

5. POUR POINT ºC - 25 MIN

6. FLASH POINT ºC 200 MIN

7. ACID VALUE (MAX.) 0.5 MAX

8. COLOR 3.0 – 3.5 MAX

9 BIODEGRADABILITY HIGHLY BIODEGRADABLE

40

5.4. Research Achievement: Indian Institute of Chemical Technology, Hyderabad

OBJECTIVES

Process development for the enriched methyl ricinoleates from castor oil methyl esters

Comparison of properties of the derivatives manufactured through enriched methyl

ricinoleates and castor methyl esters.

Preparation of first generation products/advanced derivatives utilizing enriched methyl

ricinoleates

Use of undecenoic acid for high value derivatives (wax esters, surfactants and lubricants)

development

METHODOLOGIES OF RESEARCH

Enrichment of methyl ricinoleate from castor oil fatty acids: Methyl ricinoleate was

enriched from crude castor oil fatty acid methyl esters by employing liquid-liquid

extraction concept using aqueous methanol and refined non-hydroxy vegetable oils like

sunflower oil. In addition, liquid paraffin was also explored as a medium in place of

refined vegetable oils for the enrichment.

Preparation of UDA-based Surfactants: Preparation of undecenoic acid-based mono

and diethanolamides were conducted in a solvent-free medium during this period.

Different reaction conditions like molar ratios of substrates, temperature and reaction

time were optimized for the preparation mono and diethanolamide.

OH

O

+ H2NOH 1300C, 1700C1500C,

1:2

UDA ETHANOLAMINE

n NH

O

nOH +

O

nOH

O

N

n

Looking at the insolubility of diethanolamide, it was decided to phosphorylate the hydroxyl

functionality.

41

N

O

O

OH( )7

( )7N

O

O

( )7

( )7

O P

O

ONa

ONa

1. (H3PO4

2. NaOH in ethanol

)n,CHCl3 /H2O

Another undecenoic acid-based surfactant, N-methyldiethanolamide diundecenoate were also

carried out and evaluated for their surfactant properties.

UDA N-methyl Di ethanolamine

Ester

OH

O

8+

OHN

OHNaHSO

4.H

2O

120 °C NO

O

O

O

8

85%

O

O

N

O

O

DMS,DCM

Room tmep

O

O

N

O

O

MeSO4

+-

Direct and indirect phosphorylation of UDA was also carried out to synthesize two new

surfactants.

Upscaling studies for the Enrichment of Methyl Ricinoleate from Castor Oil Methyl Esters

using Refined Sunflower Oil as a Medium

In continuation of the earlier work, efforts are mad to minimize the vegetable oil contamination

by increasing the residence time for the separation of the extract and raffinate. The vegetable oil

contamination in the enriched methyl esters were evaluated as follows.

Castor oil methyl esters (1.5 kg) and refined sunflower oil (3 kg) are thoroughly

mixed in a 20 lit plastic container. Castor oil methyl esters were cooled to 20oC and 10% aq.

methanol (9 lit) was added and mixed vigorously. Then the mixture was taken in to the jacketed

glass tubular separator (20 lit) and the temperature (20oC) was maintained by using Julabo

circulator. The mixture was allowed to stand for 30 min till the two layers were separated. The

upper layer (aq. methanol) was removed and concentrated by distilling out the solvent in to 10

lit glass rota evaporator at 80 to 90oC under reduced pressure. The raffinate was again treated

with another 9 lit aq. methanol and the extract was dried as above (extract-1). Finally the

42

raffinate was extracted with anhydrous methanol at 50oC (extract-2). The samples 1 and 2

obtained are analyzed by GC. Extract was found to contain 96.2% of Ricinoleic acid with 85%

yields. The weights of the samples are given in Table 5.4.1.

Table 5.4.1: Weight of the Extracts and Raffinate

Sample Name Weight (kg)

Extract-1 (Aq.Methanol) 1.16

Extract-2 (Hot Methanol) 0.24

Raffinate 3.02

Determination of Purity of Enriched Methyl Ricinoleate Fraction Employing Column

Chromatography: The enriched methyl ricinoleate may contain small amounts of sunflower oil in

addition to non-hydroxy fatty acids. Hence the purity of enriched methyl ricinoleate (1.9 g) was

determined employing silica gel column chromatographic method using gradient elution of

hexane and ethyl acetate solvent system. The composition of the sample is given in Table 5.4.2,

which reveals that the purity of methyl ricinoleate is up to 97.8% and traces of sunflower oil is

associated with methyl ricinoleate

Table 5.4.2: Column Chromatographic Separation of Enriched Methyl Ricinoleate

Fraction Composition (wt%)

Refined Sunflower Oil (TG) 0.9%

Non Hydroxy Methyl Esters 1.3%

Methyl Ricinoleate 97.8%

Studies for the Enrichment of Methyl Ricinoleate by LLE using Liquid Paraffin as

Medium

The following experiments were conducted and evaluated for the enrichment of methyl

ricinoleate from castor oil methyl esters by LLE using liquid paraffin as medium instead of

sunflower oil. Significant number of experiments were carried out for with heavy paraffin oil as

the medium using aqueous methanol as the extractant. The extraction conditions like extraction

time, temperature and speed of agitation were optimized at lab scale for maximum enrichment

of methyl ricinoleate from castor oil methyl esters and the experimental data is presented in

Table 5.4.3

43

Table 5.4.3: Optimization of Process Parameters for the Enrichment of Methyl Ricinoleate

from Castor Oil Methyl Esters by Liquid-Liquid Extraction

*2nd

LLE 98.7%; 3rd

LLE 99.6%

Experimental procedure : A synthetic mixture was prepared by mixing known quantities of

castor oil methyl esters (CME) and heavy paraffin oil. Required amount of aqueous methanol

was added to this mixture and the contents were mildly stirred for a certain period at a particular

temperature. Then the mixture was allowed to settle for phase separation. The extractant phase

was separated and passed through a celite bed to adsorb the finely dispersed droplets of paraffin.

Further methanol and water from the enriched extractant phase was separated by simple

distillation. Finally the extractant was thoroughly dried under reduced pressure. The enriched

CME was analyzed by GC for its purity

Conclusions:

1. Based on the above data, it can be inferred that good results were obtained when the

stirring period increased from 30 min to 60 min.

2. When the volume of the extracting agent (methanol) increased, consequently yields and

conversions increased

The following experimental protocols were employed to avoid/minimize the contamination of

liquid paraffin in extractant and the results of these experiments resulted with good result.

Adsorption method: Extract was passed through a bed of celite to effectively remove the

vegetable oil/liquid paraffin contamination in the enriched methyl ricinoleate (lab scale).

Centrifugal separation: Extract was centrifuged in a batch type centrifuge at 7,000-10,000 rpm

at 15-20oC for 15-20 min. Vegetable oil/liquid paraffin fine globules coalesce at the bottom and

the upper extract is free of contamination.

Feed Process conditions Analytical results Remarks

CME

(g)

Paraffi

n

(g)

MeO

H

(g)

H2

O

(g)

Tim

e

(min

)

Tem

p

(°C)

Stirrin

g

(rpm)

Recovere

d MeoH

(g)

Yield

(%)

Purity

(%)

147 295 2160 300 420 20 0 1340

88.77 97.3 1:16

CME:aq.

MeOH(1

0%)

25 50 360 50 30 10 155 387.57 86.01 96.9 “

25 50 360 40 30 20 50 383.65 92.13 95.99* 1:16

25 50 360 40 30 RT 50 394.42 87.64 95.69 1:16

25 50 360 40 60 RT 150 363.25 92.7 94.7 1:16

25 50 180 20 30 10 50 - 69 97.54 1:8

25 50 180 20 60 10 50 - 82.2 97.47 1:8

44

Employing the above optimized conditions upscaling experiments were conducted as per the

given process flow diagram

Equilibrium Studies for the Extraction of Castor Oil Methyl Esters by LLE

Castor oil methyl esters (different concentrations, 0.5 to 5 g) were accurately weighed and taken

in the 250 ml conical flask. Paraffin (5 g) and 10% aq. methanol (16 g) were added to castor oil

methyl esters. The contents were stirred on orbital shaker for 12 hr at room temperature at 100

rpm. After 12 hr, the mixture was transferred into a separating funnel and allowed to settle for 15

min to separate out the two layers. The lower layer (paraffin) was collected in to the sample

bottle and upper layer (aq. methanol extract, cA alc) was collected and dried over sodium sulphate

and analyzed by GC for determination of composition of castor oil methyl esters in both the

phases . KD is the distribution coefficient for the extraction system. The paraffin phase (cA org)

was treated with hot methanol and the extract was also analyzed by gas chromatography for

determination of retained castor oil methyl esters along with paraffin. The results are tabulated as

shown below (Table 5.4.4, 5.4.5. and 5.4.6) and presented in Fig 5.4.1.

Super

CCentrifuge Rectification

column

Raffinate

Hot Methanol

Treatment

Product

Extraction

vessel

Separator

FEED

45

Table 5.4.4: Analysis of castor oil methyl esters in the aq. methanol extract

S. No. Weight (g) % Purity

10% aq MeOH 5% aq MeOH

1 0.5 99.45 -

2 1.0 99.36 96.26

3 2.0 97.82 94.76

4 3.0 97.15 93.27

5 4.0 96.39 91.88

6 5.0 95.72 90.29

Table 5.4.5: Distribution of castor oil methyl esters in the organic and aqueous phase

S. No. Weight (g) 10% aq MeOH 5% aq MeOH

cA alc cA org KD cA alc cA org KD

1 0.5 0.49725 0.00275 - -

2 1.0 0.9936 0.0064 0.9626 0.0374

3 2.0 1.9564 0.0436 1.8952 0.1048

4 3.0 2.9145 0.0855 2.7981 0.2019

5 4.0 3.8556 0.1444 3.6752 0.3248

6 5.0 4.786 0.214 22.36 4.5145 0.4855 9.30

Table 5.4.6: Analysis of castor oil methyl esters retained in paraffin (hot methanol extract)

0

1

2

3

4

5

6

0 0.1 0.2 0.3 0.4 0.5 0.6

c A org, g/cc

c A

alc

, g/c

c

10% aq MeOH

5% ag MeOH

Fig 5.4.1: Equilibrium data for the LLE system CME in paraffin and aqueous methanol

S. No. Weight (g) % Purity

10% aq MeOH 5% aq MeOH

1 0.5 87.83 -

2 1.0 86.11 87.67

3 2.0 85.72 82.34

4 3.0 82.90 79.52

5 4.0 80.55 77.28

6 5.0 81.43 78.59

46

Conclusions

1. It is inferred from the above equilibrium data that better distribution was obtained in the case of

extraction of CME with 10% aq methanol

2. The distribution coefficient was also high for extraction of CME with 10% aq methanol

compared to extraction of CME with 5% aq methanol

3. Knowledge of the equilibrium data and distribution coefficients are essential for designing a good

extraction system

Upscaling Studies on the Enrichment of Methyl Ricinoleate

The enriched methyl ricinoleate was evaluated by column chromatography for the paraffin oil

contamination and it was observed that the contamination of paraffin oil is to the extent of only 0.5%.

Efforts are on to further minimize the paraffin oil contamination by modifying the speed of centrifugation

for the separation of the extract and raffinate (Table 5.4.7).

Table 5.4.7: Column Chromatographic Separation of Enriched CME fractions

CME: aq. MeOH Sample name % Purity %Yield

1:16 Enriched CME(after extraction) 97.3 80

Enriched CME (after centrifuge) 97.5 -

1:8 Enriched CME (after extraction) 97.4 60

Enriched CME (after centrifuge) 97.8 -

Conclusions

1. Using adsorbents like celite can reduce liquid paraffin contamination in the enriched methyl

ricinoleate (but limited to small scale)

2. Passing the extract in a Pennwalts’ super centrifuge at 15000 G is effectively reducing the liquid

paraffin contamination in the enriched methyl ricinoleate.

3. Using higher amounts of solvent (aqueous methanol) during LLE (1:16) the yield of enriched

methyl ricinoleate is higher to the extent of 85-90% with GC purity of 96-97%.

4. Using lower amounts of solvent (aqueous methanol) during LLE (1:6.5) the yields of enriched

methyl ricinoleate are lower to the extent of 50% with a GC purity of 99%.

Preparation of Ricinoleic-based Derivatives Employing Enriched Methyl Ricinoleate:

1. Hydrogenation of Enriched Methyl Ricinoleate (MR) and Castor oil Methyl Ester (CME): A

number of experiments were carried out (250 g batch) to standardize the experimental conditions for the

preparation of hydrogenated castor oil methyl esters and hydrogenated enriched methyl ricinoleate.

Hydrogenation of CME or MR (250 g scale) was carried out in a 500 ml autoclave using Ni as catalyst.

Optimized conditions were found to be: Temperature, 150oC; Ni catalyst, 0.5%; pressure, 3-4 kg/cm

2 for

obtaining hydrogenated products. The iodine value was reduced to aproximately 5-8 units. The analysis

of hydrogenation products is given in Table 5.4.8.

47

Table 5.4.8: Iodine and Hydroxyl Values of Castor Oil Methyl Esters, Enriched Methyl Esters and

their Hydrogenated Products

Sample Name Iodine value Hydroxyl value

CME 76.2 162.6

Hydrogenated CME 7.5 162

Enriched MR 84.5 172.1

Hydrogenated MR 7.0 169.8

2. Preparation of Dehydrated Castor Oil Methyl Esters: A number of experiments were carried out

(300 g batch) to standardize the experimental conditions for the preparation of dehydrated castor oil

methyl esters and dehydrated enriched methyl ricinoleate. CME or MR (300 g) was taken in a 500 ml RB

flask and to this 5% Korvi (acidic) earth was added. The reaction mixture was subjected for heating at

160 to 180oC in oil bath for a period of 3 hr. The mixture was stirred by using mechanical stirrer and the

water generated during the reaction was removed under reduced pressure. The product was filtered by

passing through the celite bed to remove the earth. The samples were analyzed by GC and TLC and the

analytical data is given in Table 5.4.9.

Table 5.4.9: Analysis of Dehydrated Castor Oil Samples

Sample Name % of MR Iodine value Conditions

CME 87.6 76.17 -

Dehydrated-CME 15 113.2 3% Earth+3 hrs, 160oC

Dehydrated-CME 10 118.5 5% Earth+3 hrs, 180oC

Dehydrated-CME <1 128.3 5% Earth+2 ml 1% H2SO4, 3 hr, 180oC

Conclusions:

1. Using 1-2 ml of 1% H2SO4 along with 3% korvi bleaching earth at 180oC for a period of 2 hr is

effective in dehydration of enriched CME having minimum hydroxyl value and maximum iodine value.

2. Experiments using sodium bisulphate and sodium sulphite as a catalyst for the dehydration of enriched

methyl ricinoleate under the similar conditions did not result in good conversions.

3. The extent of conjugation was determined by UV-spectroscopy and it was found between 18-20%.

4. Work is in progress to increase the extent of conjugation in the dehydration products.

5. Efforts are on to separate and identification of the conjugated and non-conjugated fatty acid by HPLC

and silver ion chromatography

PREPARATION OF UDA-BASED SURFACTANTS

1 Preparation of Mono and Diundecenyl Ethanolamides: Preparation of undecenyl ethanolamide was

conducted by taking different ratios of undecenoic acid (UDA) & ethanolamine at 170°C in a solvent-free

medium. Results obtained are outlined in Table 5.4.10.

48

OH

O

H2NOH

UDA

NH

O

OH

O

OH

O

N

+170

0C,

2:1,ETHANOLAMINE

n n+

n

n

1:1, 3:1

Table 5.4.10: Optimization of molar ratio of substrate for the formation of undecenyl

monoethanolamide and diethanolamide.

Reaction

conditions

Time

(hrs)

UDA Monomer Dimer

UDA-

Ethanolamine

1:1,170 °C

1 16.46 81.79 1.74

2 7.79 91.11 1.09

3 5.36 84.89 9.74

UDA-

Ethanolamine

2:1,170 °C

1 16.50 32.84 50.65

2 11.08 25.33 63.57

3 9.06 25.88 65.04

UDA-

Ethanolamine

3:1,170 °C

1 77.36 0.0 22.63

2 73.91 1.58 24.50

3 30.31 0.62 69.05

Results obtained indicate that unimolar ratio of substrate is required for the preferential

formation of monoethanolamide, whereas a 3:1 molar ratio of UDA:ethanolamine for

diundecenyl ethanolamide.

1. Condensation of unimolar Ratio of UDA and Ethanolamine: UDA (3 g, 0.0162 m) and

ethanolamine (0.98 g, 0.0162 m) was taken in 100 mL R.B flask stirring at 170 °C for 3

hrs. The progress of the reaction was monitored by TLC and also by injecting in GC after

silylation. After the completion of reaction, reaction mixture was extracted with ethyl

acetate, washed with water and 5% NaHCO3 solution and dried over anhydrous sodium

sulphate and concentrated. The product was solubilized in hexane and the monomer

precipitates out, which was separated by filtration. Hexane soluble part contains

unreacted UDA, dimer and traces of monomer. The isolated yield of monomer is 95%.

Though monomer formation is predominant within 2 hrs, but as the reaction progresses,

there is slow conversion of monomer to dimer.

49

2. Condensation of 2:1 molar ratio of UDA and ethanolamine: UDA (3 g, 0.0162 m) and

ethanolamine (0.494 g, 0.0081 m) was taken in 100 mL R.B flask stirring at 170 °C for 3

hrs. The reaction was monitored every 1 hr using TLC and GC after silylation. Reaction

mixture was extracted with ethyl acetate and washed with water and 5% NaHCO3

solution and dried over anhydrous sodium sulphate and concentrated. The product was

soluble in hexane partially and the monomer (solid part) was separated by filtration.

Hexane soluble part contains UDA, dimer and traces of monomer. In this case, both

monomer and dimer are formed in equal amount.

3. Condensation of 3:1 molar ratio of UDA and ethanolamine: UDA (3 g, 0.0162 m) and

ethanolamine (0.32 g, 0.0054 m) was taken in 100 mL R.B flask stirring at 170 °C for 3

hrs. The reaction was monitored every 1 hr using TLC and GC after silylation. The

reaction mixture was passed through the basic alumina to get a pure dimer compound.

Isolated yield of dimer is 85%.

4. Optimization of conditions for the preparation of undecenyl ethanolamide: Based on

these results, optimization of different reaction conditions such as temperature, time and

molar ratio of substrates for the predominant formation of undecenyl monoethanolamide

were conducted. Initially, condensation of stoichiometric amounts of UDA and

ethanolamine were conducted at different temperature under stirred conditions.

UDA (3 g, 0.0612 m) and Ethanolamine (0.98 g, 0.0162 m) was taken in 100 mL R.B flask and

stirred at different temperature (90, 110, 130, 150 and 170 0C) for 10 hrs. The progress of

reaction was monitored by TLC and also by GC after silylation. After 10 hrs, the reaction

mixture was extracted with ethyl acetate and washed with 5% NaHCO3 solution and also using

water, dried over anhydrous sodium sulphate and concentrated in the rotavap.

Monoethanolamide of UDA is insoluble in hexane, whereas the diethanolamide has partial

solubility in hexane. The crude product was solubilized in hexane and the monomer separates

out. Hexane soluble part contains unreacted UDA, diethanolamides and traces of

monoethanolamides of UDA. GC results obtained during the progress of reaction are outlined in

Table 5.4.11.

50

Table 5.4.11: Percentage of conversion of undecenyl mono and diethanolamides during the reaction

between UDA and ethanol amine (1:1, mol/mol) at different period of time.

Reaction conditions Time

(hrs)

Ethanolamine

(%)

UDA

(%)

Monomer

(%)

Dimer

(%)

1:1, 90 °C 10 28.19 66.68 5.11 -

1:1, 110 °C 10 15.37 50.09 34.53 -

1:1, 130 °C 2 21.77 51.01 27.20 -

4 17.54 45.37 37.08 -

6 11.62 36.98 51.39 -

8 6.77 31.08 60.73 1.4

10 1.42 26.20 69.29 3.07

UDA-Ethanolamine

1:1, 150 °C

2 7.72 29.10 62.77 0.79

4 5.33 20.03 73.87 0.87

6 0.69 10.26 87.14 1.89

8 - 6.93 84.99 8.07

10 - 6.39 80.93 12.66

UDA-Ethanolamine

1:1, 170 °C

1 - 16.46 81.79 1.74

2 - 7.79 91.11 1.09

3 - 5.36 84.89 9.74

Results obtained indicate that the optimum conditions for the exclusive formation of

undecenylethanolamide are: Equimolar ratio of UDA and ethanolamine, 170 °C of temperature and a

reaction time of 2 hrs. The product was characterized by NMR, IR and ESI-MS. Whereas Table 1 shows

that the optimum conditions for the exclusive formation of diundecenylethanolamide are: 3:1 molar ratio

of UDA:ethanolamine, 170 °C of temperature and a reaction time of 2 hrs. Both the products are

characterized by NMR, IR and ESI-MS.

Spectral data of Undecenylethanolamide: IR (neat; cm-1

): 3294, 3092, 1643, 1561; 1H NMR (in CDCl3;

ppm): δ 1.15-1.3 (m; 9H), 1.5-1.6 (m, 2H), 1.9 (m, 2H), 2.1 (t, 2H), 3.3 (m, 2H), 3.6 (m, 2H), 4.8-4.9 (dd,

2H), 5.7 (m, 1H), 5.9 (Br.s, 1H); ESI-MS: 228 (M++1), 250 (M

++ Na).

Spectral data of N, N-diundecenylethanolamide: IR (neat; cm-1

): 3299, 1737, 1641, 1553; 1H NMR (in

CDCl3; ppm): δ 1.2-1.4 (m; 20H), 1.5-1.7 (m, 4H), 2.0 (dd, 4H), 2.15 (t, 2H), 2.3 (t, 2H), 3.5 (dd, 2H),

4.18 (m, 2H), 4.2-4.3 (m, 2H), 4.85-5.0 (dd, 2H), 5.65-5.85 (m, 1H); EI-MS: 393 (M+)..

Both the compounds were taken for the determination of surface properties. However, N, N-

diundecenylethanolamide is found to be insoluble in water. Aqueous solutions of the monoethanolamide

of UDA were prepared by dissolving appropriate amounts in Milli-Q water and surface tension and cmc

were measured using Kruss K100 tensiometer. Variation of surface tension as a function of logarithm of

surfactant concentration is shown in Fig. 1, depicting the effectiveness of the monoethanolamide in

reducing the surface tension of water. The cmc value was found to be 3.08 × 10 -4

mM and surface tension

at cmc, is 30.7 mN/m.

51

-12 -11 -10 -9 -8 -7

30

35

40

45

50

55

60

65

70

75

Su

rface t

en

sio

n, m

N/m

ln C

Monoethanolamide of UDA

1. Preparation of Mono and Diundecanoylethanolamides: The above optimized conditions were taken

up for the preparation of mono and diundecanoylethanolamide, the saturated analog of UDA.

OH

O

H2NOH

NH

O

OH

O

OH

O

N

+170

0C,

ETHANOLAMINE

n n+

n

n

1:1, 3:1

Undecanoic acid

Equimolar mixture of UDA (6 g, 0.032 m) and ethanolamine (1.97 g, 0.032 m) was taken in 100 mL R..B

flask and stirred at 170 °C for 2 hrs. The progress of reaction was monitored by TLC as well as by GC

after silylation. The reaction mixture was extracted with ethyl acetate and washed with water followed by

5% NaHCO3 solution, dried over anhydrous sodium sulphate and concentrated in the rotavap. The product

was soluble in hexane partially. Monomer was separated out by filtration. The isolated yield of

monoethanolamide is 96 %.

Spectral data of Undecanoylethanolamide: IR (neat; cm-1

): 3300, , 1643, 1456; 1H NMR (in CDCl3; ppm):

δ 0.9 (t, 3H) 1.15-1.3 (m; 12H), 1.5-1.6 (m, 2H), 2.2 (m, 4H), 3.4 (t, 2H), 3.7 (t, 2H), 2.2 (s, 1H), 6.1(s,

1H) ; ESI-MS: 230 (M++1),231(M

++2) 252 (M

++ Na).

52

For the preparation of diethanolamide of undecanoic acid, 3:1 molar ratio of UDA (6 g, 0.032 m) and

ethanolamine (0.64 g, 0.01 m) was taken in 100 mL R.B flask and stirred at 170 °C for 3 hrs. After

completion of reaction in 3 hrs, the reaction mixture was passed through the Basic alumina to get a pure

dimer compound. Isolated yield of dimer is 87%.

Spectral data of N, N-diundecanoylethanolamide: IR (neat; cm-1

): 3350, 1737, 1641, 1453; 1H NMR (in

CDCl3; ppm): δ 0.9 (t, 6H) 1.2-1.4 (m; 24H), 1.5-1.7 (m, 4H), 2.2-2.5 (dd, 4H), 3.5 (t, 4H), 4.18 (t, 4H),

5.65-5.85 (s, 1H); EI-MS: 398 (M+

+1)..

Both the compounds were taken for the determination of surface properties. However, N, N-

diundecanylethanolamide is found to be insoluble in water. Aqueous solutions of the monoethanolamide

of undecanoic ethanolamide were prepared by dissolving appropriate amounts in Milli-Q water and

surface tension and cmc were measured using Kruss K100 tensiometer. Variation of surface tension as a

function of logarithm of surfactant concentration is shown in below, depicting the effectiveness of the

monoethanolamide in reducing the surface tension of water. The cmc value was found to be 2.71 × 10 -4

mM and surface tension at cmc, is 37.4 mN/m.

-7 -6 -5 -4 -3 -2 -1

35

40

45

50

55

60

65

70

75

undecanioc-ethanolamide(mono-0.6mMol)

0.271 Mol/l

Avg

.Su

rf.t

en

sio

n m

N/M

lnC

2. Preparation of UDA-based Ester Quats: Esterification of N-Methyl diethanolamine with UDA was

carried out in presence of 5% sodium bisulphate monohydrate at 120 °C temperature under stirred

conditions. The esterified product was then quaternized to get the desired product.

53

UDA N-methyl Di ethanolamine

Ester

OH

O

8+

OHN

OHNaHSO

4.H

2O

120 °C NO

O

O

O

8

85%

UDA (6.19 g, 0.336 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken in 100 mL R.B flask

followed by the addition of 5% Sodium bisulphate monohydrate. The reaction mixture was stirred at 120

°C for 4 hrs. The progress of reaction was monitored by TLC. After completion of reaction, the reaction

mixture was extracted with ethyl acetate, washed with 5% NaHCO3 and also with water, dried over

anhydrous sodium sulfate and finally concentrated in the rotavap to get the crude product. The compound

was passed through basic alumina and the structural confirmation of the compound was confirmed by IR,

GC, GC-MS, NMR and ESI-Mass. The isolated yield of diester is 85% based on N-methyl

diethanolamine.

Spectral data of N-Me diethanolamine diundecenate diester: IR (neat; cm-1

):3010, 2960,1760,1615,1560,

1456; 1H NMR (in CDCl3; ppm): δ 1.15-1.3 (m; 20H), 1.5-1.6 (m, 4H),2.0 (m, 4H), 2.2 (t, 4H),2.4 (s,3H),

2.7 (t, 4H) 4.2 (t, 4H), 4.9-5.1 (d, 4H), 5.7-5.9 (dd, 2H); ESI-MS: 452(M++1),453(M

++2).

O

O

N

O

O

DMS,DCM

Room tmep

O

O

N

O

O

MeSO4

+-

N-methyl diethanolamine diundecenoate of was taken in dry DCM followed by the addition of 2 molar

equivalent of anhydrous dimethyl sulphate (DMS). The reaction mixture was kept stirred for 4 hrs at

room temperature using calcium chloride guard tube. After completion of reaction, the organic solvent

was evaporated. The reaction mixture was kept in an ice bath followed by the slow addition of dry diethyl

ether. The solid obtained was separated by filtration. The filtrate was kept further for crystallization. The

combined precipitate was dried and weighed. The quaternized product was characterized by ESI-Mass.

Isolated yield of quats ester is 86%.

Aqueous solutions of the quaternized salt was prepared by dissolving appropriate amounts in Milli-Q

water and surface tension and cmc were measured using Kruss K100 tensiometer. Variation of surface

tension as a function of logarithm of surfactant concentration is shown below, depicting the effectiveness

of the compound in reducing the surface tension of water. The cmc value was found to be 3.0 × 10-2

mM

and surface tension at cmc, is 25.46 mN/m.

54

-6 -5 -4 -3 -2 -1

20

25

30

35

40

45

50UDA_DMS_DIESTER(1mm)-2

Avg

.Su

rf.t

en

sio

n m

N/M

lnC

Accordingly, the saturated analog of the above ester quat, N-Methyl diethanolamine diundecanoate was

also synthesized. Esterification of N-Methyl diethanolamine with undecanoic acid was carried out in

presence of 5% sodium bisulphate monohydrate at 120 °C temperature under stirred conditions. The

esterified product was then quaternized to get the desired product.

N-methyl Di ethanolamine

Ester

OH

O

8+

OHN

OHNaHSO

4.H

2O

120 °C NO

O

O

O

8

85%

Undecanoic acid

Undecanoic acid (4.7 g, 0.025 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken in 100 mL R.B

flask followed by the addition of 5% sodium bisulphate monohydrate. The reaction mixture was stirred at

120 °C for 4 hrs. The progress of reaction was monitored by TLC. After completion of reaction, the

reaction mixture was extracted with ethyl acetate, washed with 5% NaHCO3 and also with water, dried

over anhydrous sodium sulfate and finally concentrated in the rotavap to get the crude product. The

compound was passed through basic alumina and the structural confirmation of the compound was

confirmed by IR, GC,GC-MS,NMR, ESI-Mass. The isolated yield of diester is 87% based on N-methyl

diethanolamine.

55

Spectral data of N-Me DiEthanolamine diundecanoate: IR (neat; cm-1

): 2960,1760, 1560, 1456;

1H NMR (in CDCl3; ppm): δ 0.9 (t, 6H) 1.15-1.3 (m; 24H), 1.5-1.6 (m, 4H), 2.2 (m, 4H),2.4 (t,4H), 2.8 (t,

4H) 3.6 (s, 3H), 4.2 (t, 4H); ESI-MS: 456(M++1),457(M

++2).

O

O

N

O

O

DMS,DCM

Room tmep

O

O

N

O

O

MeSO4

+-

N-methyl diethanolamine diundecanoate was taken in dry DCM followed by the addition of 2 molar

equivalent of anhydrous dimethyl sulphate (DMS). The reaction mixture was kept stirred for 4 hrs at

room temperature using calcium chloride guard tube. After completion of reaction, the organic solvent

was evaporated. The reaction mixture was kept in an ice bath followed by the slow addition of dry diethyl

ether. The solid obtained was separated by filtration. The filtrate was kept further for crystallization. The

combined precipitate was dried and weighed. The quaternized product was characterized by ESI-Mass.

Isolated yield of ester quats is 91%.

Aqueous solutions of the N, N-dimethyl Diethanolamine diundecanoate were prepared by dissolving

appropriate amounts in Milli-Q water and surface tension and cmc were measured using Kruss K100

tensiometer. Variation of surface tension as a function of logarithm of surfactant concentration is shown

in Fig 5.4.2, depicting the effectiveness of the monoethanolamide in reducing the surface tension of

water. The cmc value was found to be 0.42× 10 -2

mM and surface temsion at cmc is 22.52 mN/m.

-9 -8 -7 -6 -5 -4 -3

20

30

40

50

60

70

80N-Me_DMS_Undeca-diester(0.1 mMol)

Avg

.Su

rf.t

en

sio

n m

N/M

lnC

56

In the previous quarter, UDA-based ester quats such as N-methyl diethanolamine diundecenoate

dimethylsulphate and also its saturated counterparts, N-methyl diethanolamine diundecanoate

dimethylsulphate were synthesized and evaluated. To study the effect of double bond and also its

position on the alkyl chain on their surface properties, two more compounds, N-methyl

diethanolamine distearate dimethylsulphate and N-methyl diethanolamine dioleate

dimethylsulphate were synthesized and evaluated during this period. Initially, N-methyl

diethanolamine distearate was prepared by taking stoichiometric amounts of stearic acid and

N-methyl diethanolamine and 5% sodium bisulphate monohydrate and heating the mixture at

120°C temperature under stirred conditions. The product was quaternized with dimethyl sulphate

to get N-methyl diethanolamine distearate dimethyl sulphate.

Briefly, stearic acid (7.163 g, 0.025 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken

in 100 mL R.B. flask followed by the addition of 5% Sodium bisulphate monohydrate and the

reaction mixture was stirred at 120 °C for 4 hrs. The progress of reaction was monitored by TLC.

After completion of reaction, the reaction mixture was extracted with Ethyl acetate, washed with

5% NaHCO3 and also with water, dried over anhydrous sodium sulfate and concentrated in the

rotavap to get the crude product. The crude mixture was passed through the basic alumina

column to get the pure product (isolated yield is 85%). The structure of the product was

confirmed by IR, GC, GC-MS, NMR and ESI-Mass.

N-methyl Di ethanolamine

Ester

OH

O

+OH

N

OHNaHSO

4.H

2O

120 °C NO

O

O

O

Stearic

15

15

15

Quaternization of N-methyl diethanolamine distearate was conducted in a R.B flask in Dry DCM

in presence of anhydrous dimethyl sulphate (DMS). The reaction mixture was stirred for 5 hrs at

room temperature using calcium chloride guard tube. After completion of reaction, the organic

phase was evaporated. The reaction mixture was taken in dry diethyl ether and kept in an ice-

bath. A solid product separates out, which was separated and further solubilized in dry ether and

cooled in an ice-bath. This operation was repeated thrice to get pure quaternized product. The

structure of the final quaternized product was confirmed by using TLC and ESI-Mass.

57

DMS,DCM

Room tmep

MeSO4

+

-

Ester

NO

O

O

O

15

15

NO

O

O

O

15

15

Aqueous solutions of the compound were prepared by dissolving appropriate amounts in Milli-Q

water and surface tension and cmc was measured using Kruss K100 tensiometer. Variation of

surface tension as a function of logarithm of surfactant concentration is shown in Figure 1. Three

measurements were taken in total for three different solutions of surfactants. The average cmc

and surface tension at cmc of this compound was found to be 14.95 × 10-2

moles/L and 56.59

mN/m respectively.

-6 -5 -4 -3 -2 -1 0 1

52

54

56

58

60

62

64

66

68

70

72

AV

g S

.F.T

mN

/M

ln C

Di Stearic N-Me-Diethanolamine Ester(1 mM)3rd

CMC= 0.212 ST at cmc 55.3

Figure 5.4.2. Variation of surface tension as a function of logarithm of surfactant concentration of N-

methyl diethanolamine distearate dimethylsulphate.

Similarly, N-methyl diethanolamine dioleate was prepared by taking stoichiometric amounts of

oleic acid and N-methyl diethanolamine and 5% sodium bisulphate monohydrate and heating the

58

mixture at 120 °C temperature under stirred conditions. The product was quaternized with

dimethyl sulphate to get N-methyl diethanolamine dioleate dimethyl sulphate.

Briefly, Oleic acid (7.118 g, 0.025 m) and N-methyl diethanolamine (1 g, 0.0084 m) was taken in 100 mL

R.B. flask followed by the addition of 5% Sodium bisulphate monohydrate and the reaction mixture was

stirred at 120 °C for 4 hrs. The progress of reaction was monitored by TLC. After completion of reaction,

the reaction mixture was extracted with Ethyl acetate, washed with 5% NaHCO3 and also with water,

dried over anhydrous sodium sulfate and concentrated in the rotavap to get the crude product. The crude

mixture was passed through the basic alumina column to get the pure product (isolated yield is 80%). The

structure of the product was confirmed by IR, GC, GC-MS, NMR and ESI-Mass.

N-methyl Di ethanolamineEster

OH

O

a

a +

OHN

OHNaHSO

4.H

2O

120 °C

NO

O

O

OOleic acid

a

a

a

a

Quaternization of N-methyl diethanolamine dioleate was conducted in a R.B flask in Dry DCM in

presence of anhydrous dimethyl sulphate (DMS). The reaction mixture was stirred for 5 hrs at room

temperature using calcium chloride guard tube. After completion of reaction, the organic phase was

evaporated. The reaction mixture was taken in hexane and the hexane-insoluble part was separated.

Hexane was removed from the hexane soluble part to get the crude product. The reaction mixture was

taken in dry diethyl ether and kept in an ice-bath. A solid product separates out, which was separated and

further solubilized in dry ether and cooled in an ice-bath. This operation was repeated thrice to get pure

quaternized product. The structure of the final quaternized product was confirmed by using TLC and ESI-

Mass.

DMS,DCM

Room tmep

MeSO4

+

-

Ester

a

a

a

a

NO

O

O

Oa

a

a

a

NO

O

O

O

Aqueous solutions of the compound were prepared by dissolving appropriate amounts in Milli-Q

water and surface tension and cmc was measured using Kruss K100 tensiometer. Variation of

surface tension as a function of logarithm of surfactant concentration is shown in Figure 5.4.3.

Three measurements were taken in total for three different solutions of surfactants. The average

59

cmc and surface tension at cmc of this compound was found to be 59.6 × 10-2

moles/L and 45.55

mN/m respectively.

-5 -4 -3 -2 -1 0 1

45

50

55

60

65

70A

Vg

S.F

.T m

N/M

ln C

Di Oliec N-Me-Diethanolamine ester(2 mM)

CMC=0.5596, ST at cmc 45.94

Figure 5.4.3. Variation of surface tension as a function of logarithm of surfactant concentration of N-

methyl diethanolamine dioleate dimethylsulphate.

Surface properties of all the four ester quats surfactants, namely N-methyl diethanolamine

diundecenoate dimethylsulphate, N-methyl diethanolamine diundecanoate dimethylsulphate, N-

methyl diethanolamine distearate dimethylsulphate and N-methyl diethanolamine dioleate

dimethylsulphate were also determined using fluorescence spectrophotometer using pyrene as

fluorophore.

60

Figure 5.4.4. Plot of I1/I3 of pyrene against the logarithm of concentration of surfactants.

For fluorescence measurements, the pyrene concentration was held constant at 5.0 μM, and the

surfactant concentration varied over a wide range. Then 3 mL of each solution was placed in a

10-mm rectangular quartz cell, and the spectra were run on a Fluorescence Spectrophotometer

(M/s Varian, Model: Cary Eclipse). Py was excited at 337 nm, and emissions was recorded over

the range of 350 to 500 nm at a scan rate of 120 nm/min. The excitation slit width was set at 20

nm and emission at 2.5 nm. The first and third vibronic peaks of pyrene was measured at 373 and

383 nm. In all cases, the CMC was determined from the inflection point of the plot I1/I3 vs.

concentration of the surfactant. All solutions were aged for 24 h before measurement. The cmc

of the four ester quats was determined and are shown in Table 5.4.12.

A comparative study of surface properties of four ester quats surfactants, namely N,N-dimethyl

diethanolamine diundecenoate dimethylsulphate, N,N-dimethyl diethanolamine diundecanoate

61

dimethylsulphate, N,N-dimethyl diethanolamine distearate dimethylsulphate and N,N-dimethyl

diethanolamine dioleate dimethylsulphate was made.

Table 5.4.12. Comparative surface properties of the four ester quats.

Compound Name cmc

(×10-2

mM/L)

By Fluorescence

cmc

(×10-2

mM/L)

By Surface

Tensiometer

Surface tension

at cmc

(mN/m)

N,N-Dimethyl diethanolamine

diundecenoate dimethylsulphate

9.67 3.0 25.46

N,N-Dimethyl diethanolamine

diundecanoate dimethylsulphate

1.57 0.42 22.52

N,N-Dimethyl diethanolamine

dioleate dimethylsulphate

-- 59.6 45.55

N,N-Dimethyl diethanolamine

distearate dimethylsulphate

9.42 14.95 56.59

3. Phosphorylation of Diundecenyl ethanolamide: N, N-diundecenylethanolamide was

found to be insoluble in water. The hydroxyl group of this compound was derivatized by

phosphorylation using polyphosphoric acid, followed by making sodium salts.

N

O

O

OH( )7

( )7N

O

O

( )7

( )7

O P

O

ONa

ONa

1. (H3PO4

2. NaOH in ethanol

)n,CHCl3 /H2O

Procedure: Diundecenylethanolamide (3.7 g, 0.0095 mol) was dissolved in chloroform and poly

phosphoric acid (1.81 ml, 0.011 mol) was added slowly into it. The reaction mixture was

refluxed at 70 °C for 10 min followed by the addition of water (5 ml). The total reaction mixture

was refluxed for 4 hr and the progress of reaction was monitored by TLC. After completion of

the reaction, chloroform was evaporated and the reaction mixture was extracted with ethyl

acetate (EA) and washed with water thoroughly. The organic layer was dried over anhydrous

sodium sulphate and concentrated to get the 3.5 g (78.6%) of phosphate product. The product

was finally converted to its Na-salts by the quantitative addition of ethanolic NaOH (22.18 mL of

0.0148 M of NaOH in ethanol). The ethanol was evaporated from the final product and

62

crystallized from ether to get 2.8 g (74.6%) of disodium salt of diundecenylethanolamide

phosphate.

The purified compound was taken for the measurement of surface tension using Kruss

Tensiometer. The compound was found to have CMC 3.68 mM and surface tension at CMC 25.6

mN/M.

-4 -3 -2 -1 0 1 2

20

30

40

50

60

70CMC=3.68 mM

SFT=25.6 mN/M

Su

rfa

ce t

en

sio

n (

dyn

es/c

m)

ln C

Figure 5.4.5. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salt of diundecenylethanolamide phosphate.

In a similar fashion, the hydroxyl group of undecenylethanolamide was also phosphorylated

using polyphosphoric acid, followed by conversion to its sodium salts.

NH

O

OH( )7 N

H

O

( )7

O P

O

ONa

ONa

1. (H3PO4

2. NaOH in ethanol

)n /H2ODCM,

63

Procedure: Undecenylethanolamide (2 g, 0.0088 mol) was dissolved in DCM and poly

phosphoric acid (1.71 ml, 0.001 mol) was added slowly into it. The reaction mixture was stirred

at R.T for 10 min followed by the addition of water (5 ml). The total reaction mixture was stirred

for 4 hr and the progress of reaction was monitored by TLC. After completion of the reaction,

DCM was evaporated and the reaction mixture was extracted with ethyl acetate (EA) and washed

with water thoroughly. The organic layer was dried over anhydrous sodium sulphate and

concentrated to get the 1.45 g (53.7%) of phosphate product. The product was finally converted

to its Na-salts by the quantitative addition of ethanolic NaOH (14.2 mL of 0.0094 M of NaOH in

ethanol). The ethanol was evaporated from the final product and crystallized from ether to get

1.2 g (72.7%) of disodium salt of undecenylethanolamide phosphate.

The purified compound was taken for the measurement of surface tension using Kruss

Tensiometer. The compound was found to have CMC 0.552 mM and surface tension at CMC

33.54 mN/M.

-5 -4 -3 -2 -1 0 1

20

30

40

50

60

70

UDA Ethanolamide Phospho sodiumsalts(4mmol)2nd

CMC=0.5528 mmolSFT=33.549

Avg

,S.F

.T m

N/M

ln C

Figure 5.4.6. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salt of Undecenylethanolamide phosphate.

64

4. Preparation of Undecenyl Phospho Di Sodium Salts: Direct phosphorylation of

undecenoic acid was also carried out using polyphosphoric acid. Initially UDA was converted to

its methyl ester by the treatment of 2% H2SO4 in methanol. The resulting methyl undecenoate

was reduced to undecenyl alcohol by the treatment of NaBH4, which was finally phosphorylated

and converted to its di-sodium salts.

OH

O2%H2SO4 MeOH

O

OMe

NaBH4 t-BuOH-MeOH

OH

(H3PO4)n

DCM/H2OO

POH

OHO

OP

O-Na+

O-Na+O

NaOH/EtOH

UDA

Undecenyl AlcoholUndecenyl Phosphate

Di sodiumsalts of Undecenyl Phosphate

Procedure: Undecenyl Alcohol (5 g, 0.029 mol) was dissolved in DCM and polyphosphoric

acid (5.68 ml, 0.035 mol) was added slowly into it. The reaction mixture was stirred at R.T for

10 min followed by the addition of water (5 ml). The total reaction mixture was stirred for 4 hrs

and the progress of reaction was monitored by TLC. After completion of the reaction, DCM was

evaporated and the reaction mixture was extracted with ethyl acetate (EA) and washed with

water thoroughly. The organic layer was dried over anhydrous sodium sulphate and concentrated

to get the 6.12 g (83.6%) of phosphate product. The product was finally converted to its Na-salts

by the quantitative addition of ethanolic NaOH (29.78 mL of 0.049 M of NaOH in ethanol). The

ethanol was evaporated from the final product and crystallized from ether to get 3.8 g (52.4%) of

disodium salt of Undecenyl phosphate. The purified compound was taken for the measurement

of surface tension using Kruss Tensiometer. The compound was found to have CMC 1.005 mM

and surface tension at CMC 32.4 mN/M.

65

-4 -3 -2 -1 0 1 2

20

30

40

50

60

70

Sodium salts of Undecenyl Phosphate(8mmol)1st

CMC=1.005 mmol SFT=32.401A

vg.S

.F.T

mN

/M

ln C

Figure 5.4.7. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salt of Undecenyl phosphate.

5. Preparation of Di Sodium Salts of 11-Phospho-10-hydroxy Methyl Undecanoate: In

an alternate approach, the side chain double bond of methyl undecenoate was functionalized. The

pathway involves epoxidation of double bond followed by the ring opening by orthophosphoric

acid as outlined in the scheme given below.

66

UDA

10,11-epoxy methyl Undecanoate

O

OMeOH

O

2%H2SO4/MeOH

OMe

O

O

Reflux

mCPBA/DCM

R.T

H3PO4

Toluene, R.T

OMe

O

OH

OP

OH

OH

O

Ethanol/NaOH(1 M)

OMe

O

OH

OP

NaO

ONa

O

_+

+ _

11-phospho,10-hydroxy methyl Undecanoate

Di sodium salts of 11-phospho,10-hydroxy methyl Undecanoate

Methyl Undecenoate

Procedure: 10,11-epoxy methyl Undecanoate l (10 g, 0.046 mol) was dissolved in Toluene and

orthophosphoric acid (2.61 ml, 0.046 mol) was added slowly into it. The reaction mixture was

stirred at R.T for 2 hr and the progress of reaction was monitored by TLC. After completion of

the reaction, toluene was evaporated and the reaction mixture was extracted with ethyl acetate

(EA) and washed with water thoroughly. The organic layer was dried over anhydrous sodium

sulphate and concentrated to get the 12.28 g (84.28%) of phosphate product. The product was

finally converted to its Na-salts by the quantitative addition of ethanolic NaOH (42.54 mL of

0.0708 M of NaOH in ethanol). The ethanol was evaporated from the final product and

crystallized from ether to get 12.1 g (96.0%) of disodium salt of 11-phospho-10-hydroxy methyl

undecanoate.

The purified compound was taken for the measurement of surface tension using Kruss

Tensiometer. The plot of ln C vs surfactant concentration showed continuous decrease in surface

tension with the increasing concentration of surfactants till 200 mM. This unusual phenomenon

of this surfactant will be looked into by both surface tension and fluorescence probing

techniques.

67

-2 -1 0 1 2 3 4

40

45

50

55

60

65

70

11-Phospho,10-Hydroxy methylUndecanoate sodium salts(100mM)A

vg

.S.F

.T m

N/M

ln C

Figure 5.4.8. Variation of surface tension as a function of logarithm of surfactant concentration of

disodium salts of 11-phospho-10-hydroxy methyl undecanoate.

SUMMARY

Enrichment of Methyl Ricinoleate from Castor Oil Methyl Esters:

Using liquid paraffin as a medium, the selectivity in enrichment of methyl ricinoleate from castor

oil methyl esters is good but due to the closer densities of liquid paraffin and aqueous methanol

the contamination of liquid paraffin with the solute was to the extent of 2.5-3.5% which was

determined by TLC and column chromatography. Therefore, the experiments using liquid

paraffin as medium in enrichment of methyl ricinoleate by LLE is not satisfactory.

The method of using refined vegetable oil as medium in enrichment of methyl ricinoleate by

LLE, the selectivity is good and the contamination of oil with solute is less than 0.8% as

determined by TLC and column chromatography. Efforts are on at further minimizing the

contamination. Standardization of up-scaling experimental conditions are in progress. Efforts are

on to explore the possibilities of separation of solute from extract using solvent resistant thin film

composite reverse osmosis membranes. Using the enriched methyl ricinoleate various derivatives

68

are planned to prepare and compare the properties with respect to the CME. Experiments are in

progress to standardize the experimental conditions.

Further upscaling experiments are being conducted for the enrichment of methyl ricinoleate from

castor oil methyl esters. Adsorbents like celite will be tried in reducing the vegetable oil

contamination in the extract. Centrifugation is another option to be explored in minimizing the

vegetable oil contamination. Thin film composite RO membranes will be explored in separation

of the solute from the solvent of the extract in liquid-liquid extraction process. Efforts are on in

increasing the conjugation in the dehydrated products and methodology for evaluation of

conjugated fatty acid esters in the products by HPLC and Silver ion Thin layer chromatography.

Design and fabrication of Liquid-liquid extraction set-up is under progress.

Preparation of UDA-based Surfactants: Optimized conditions for exclusive preparation of N-

undecenylethanolamine and N, N-diundecenylethanolamine. N-undecenylethanolamine was

prepared by taking 1:1 molar ratio of UDA and ethanolamine and heating the reaction mixture at

170 °C for 2 hrs. The structure of the compound was confirmed by NMR, IR and mass. The cmc

and surface tension at cmc was determined following Kruss Tensiometer. The cmc value was

found to be 3.08×10-4

mM and surface temsion at cmc, is 30.7 mN/m. N,N-

diundecenylethanolamine was prepared by taking 3:1 molar ratio of UDA and ethanolamine and

heating the reaction mixture at 170 °C for 2 hrs. Attempts to determine the micellar properties of

this compound failed as the compound is almost insoluble in water.

UDA-based ester quats, N, N-dimethyl diethanolamine diundecenoate dimethylsulphate was

prepared by esterification in presence of 5% sodium bisulphate monohydrate at 120 °C under

stirred conditions. The cmc value of the ester quat was found to be 3.0 × 10-2

mM/L and surface

tension at cmc, is 25.46 mN/m. Four UDA-based surfactants are synthesized and evaluated for

their surface properties using surface tension and fluorescence probing techniques. Influence of

the presence of unsaturation and also its location in the hydrophobic chain on surface properties

of four different ester quats are also studied.

69

5.5 Research Achievement: Jayant Agro Organic Limited, Mumbai

The ultimate goal of the project is to develop value added products from deoiled castor cake and

2-octanol based on the techno-commercial processes. The intended value added products from

the deoiled castor cake-high protein and 2-octanol are as under:

Deoiled castor cake based value added products:

Extraction of the protein from the deoiled castor cake and /or deoiled castor cake-high

protein by using an alkaline solution of the sodium hydroxide

o Optimization of the pH of alkaline solution for the maximum protein extractability

from said raw materials.

o Optimization of the solid to liquid ratios for the maximum protein extractability

Isolation of the protein from the alkaline extract by precipitation process

o Optimization of the iso-electric point (pH) for maximum protein precipitation and

the yield.

Preparation of the bio-film and the adhesives based on the CPI, SPI and a combination of

CPI and SPI.

o The comparative studies of bio-film and adhesives.

Scale up of the processes for commercialization.

2-Octanol based value added products

To carry out the esterification reactions using anhydrides like phthalic, maleic, etc. and

carboxylic acids such adipic, benzoic, etc. to develop products, which will add the value.

Also, compare the properties & performance of such developed products with existing

commercial products based on 2-ethyl hexanol.

To carry out an etherification reactions to from symmetrical and asymmetrical ethers

using 2-octanol and epichlorohydrin respectively.

To optimize the reaction parameters like temperature, mole ratios, and catalyst

concentration.

To purify both symmetric and asymmetric ethers by distillation and these will be tested

for their applications, and/or will be evaluated their performance by outside parties.

Scale up the processes for commercialization.

70

5.5.1 Deoiled castor cake based value added products:

The aim was to obtain protein isolate from deoiled castor cake after extraction and isolation as it is

described in the objective of the research work and prepare the adhesive and bio-film. The research work

observation and results as under:

The protein extraction process was developed for deoiled castor cake by using alkaline solution of

sodium hydroxide. Experimentally, the effect of ratio of cake to liquid such as 1:10,

1:15,1:20,1:25 and 1:30 wt/v, and effect of pH of solution like 7,9,11, and 13 on protein

extraction were evaluated for process optimization. 1:10 wt/v, a ratio of cake to liquid and pH 13

of solution were optimized for protein extraction.

Maximum extractability of protein found more than 97 % based on the total protein present in

castor cake.

Attempts have been made to obtain the castor protein isolate (CPI) from alkaline extract of

protein using iso-electric point. For castor protein isolation, experimentally tested protein

precipitation at 3, 3.5, 4.0, 4.5 and 5.0, and 4.5 pH gave maximum precipitation of protein from

its alkaline extract.

Low recovery of protein from alkaline extract followed by precipitation using iso-electric point

(pH-4.5) was obtained. This is due to lack of specific filtration medium. In this studies we used

Whatman filter paper number 42.

When iso-electric point (pH) precipitation process used for main extract and washing separately,

the recovery of protein increased by 8-9 %. However, dark colour CPI was found

Efforts have been made to obtain protein by neutralization of the alkaline extract using both

phosphoric acid and citric acid, separately and subsequently sun-dried in tray at ambient

temperature. The colour of protein isolate was improved.

Efforts are being made to prepare bio-film & adhesive based on CPI, SPI, and a mixture of CPI

and SPI. The comparison study will be carried out for such bio-films & adhesives.

Efforts will be made to increase the recovery castor protein isolate.

5.5.2 Octanol based value added products

2-octanol is a secondary alcohol and has different chemical properties in relation to 2-ethyl hexanol and

1-octanol. It undergoes similar chemical reactions as other alcohols follow such as esterification,

dehydration, etherification, ethoxylation, sulfation, etc. Hence, the derivatives, which are being

industrially manufactured based on the 2-ethyl hexanol, and the similar derivatives can be produced using

2-octanol. The production of 2-octanol is entirely dependent on the demand of sebacic acid and price of

the raw material (castor oil). By adding value to the 2-octanol by converting it to value added products

will improve the economics of the sebacic acid production and thus increase the usage & thus indirectly

benefit the castor plant growing farmers by increasing demand for the castor seeds & oil.

71

Aim was to prepare 2-octanol based esters and ether, optimize process parameters, and study comparison

between existing 2-ethyl hexanol and/or isononanol esters and ethers. The following ester and ether were

prepared using 2-octanol.

5.5.3 Esters based on 2-octanol

Dicapryl Phthalate (DCP):

Phthalic esters based on 2-octanol could be prepared by esterification using p-TSA, organo-

metallic catalysts, TBM, etc and also by trans-esterification using dimethyl phthalate and sodium

methoxide and a mixture of sodium methoxide and calcium hydroxide.

The synthesis of DCP using Insocat-TBM resulted in poor conversion, and dark colour ester was

obtained. When the esterification of PAN was carried out for six hours in the presence of solvent

(toluene) using same catalyst and 2-octanol only 80% conversion of PAN was found with dark

coloured ester product.

Synthesis of DCP based on 2-octanol by trans-esterification using DMP, sodium methoxide and a

mixture of sodium methoxide and calcium hydroxide also resulted in poor conversion and dark

colour of ester.

Both organo-metallic catalysts, namely SV CAT 100 and FASCAT 2001 were superior to other

catalysts and were used in the synthesis of DCP as described in earlier reports. Henceforth, in the

synthesis of DCP for scale up study and further industrial utilization, these two catalysts can be

employed. Mole ratio of 2-octanol to PAN was 2.42 and reaction temperature 220 deg C were

optimized. When organo-metallic catalysts were used > 99 % conversion of PAN was obtained

with light colored ester appearance. The loading of catalyst was increased by five fold (0.1 % to

0.5% based on weight of PAN) and the reaction time significantly decreased.

Remarkable and appreciable results were observed when the bleached DCP was tested for both

compact and foam layers evaluations against DEHP and DINP in PVC formulations. The results

were incorporated in earlier report.

Dicapryl sebacate (DCS):

Based on the synthesis of DCP and its reaction parameters, the synthesis of DCS was carried out

using sebacic acid (SA), 2-octanol and, organo-metallic catalyst (FASCAT-2001) at 220 deg C.

The loading of catalyst was 0.5 % based on the weight of SA. > 99 % conversion of SA was

found with light appearance of the ester.

Remarkable and appreciable results were observed when the bleached DCS was tested for both

compact and foam layers evaluations against DEHP and DINP in PVC formulation. The results

were incorporated in earlier report.

72

Dicapryl maleate (DCM):

Synthesis of DCM was carried out using maleic anhydride (MAN), 2-octanol and

catalysts such as p-TSA and FASCAT 2001. When p-TSA was used as catalyst at 120

deg under vacuum, a poor conversion of MAN was found with dark colour of ester.

When FASCAT-2001 was used as catalyst and the reaction carried out 220 deg C, > 99

% conversion of MAN was found. The synthesized DCM can be used as anionic

surfactant after sulfonation with sodium bisulfite. The synthesized sulfonated ester can be

used in place of sodium dioctyl sulfosuccinate. Efforts are being made to prepare sodium

dicapryl sulfo succinate.

5.5.4 Synthesis of Dicapryl adipate (DCA) and capryl benzoate (CB)

Syntheses of DCA and CB were carried out using the same parameters as optimized in

case of DCP and DCS syntheses. >99 % conversion of the adipic acid was obtained when

the reaction was carried out using 2-octanol and FASCAT-2001 at 220 deg C.

>98 % conversion of benzoic acid was found when the reaction was carried out using the

same reaction parameters as described earlier.

5.5.6 Ethers based on 2-octanol

Capryl glycidyl ether (CGE):

Synthesis of CGE was carried out using 2-octanol, sodium hydroxide, epichlorohydrin

and TBAB (Tetra butyl ammonium bromide) as a phase transfer catalyst at 40-42 deg C.

In the synthesis of asymmetrical ethers maximum conversion was obtained about 87 %.

The un-reacted reactants such 2-octanol and epichlorohydrin need to be distilled off and

reused in another batch for synthesis. The maximum conversion could be expected using

sodium caproxide instead of 2-octanol and sodium hydroxide.

Dicapryl ether (DCE)

Synthesis of symmetrical ethers based on 2-octanol alone could be possible in the

presence of acid catalysts at lower temperature (130- 140 deg C), and / or using 2-octanol

and 2-octene in the presence of acidic resin at lower temperature.

The products were developed under NAIP-JAOL Project are shown in Fig 5.5.1, Fig 5.5.2 and

Fig 5.5.3.

73

NAIP

2-OCTANOL BASED DERIVATIVES

2-octanol Esterification

Plasticizer: Flooring, cable,

wire, film and sheetPAN & Cat.

SA & Cat.

Adipic acid &

Cat.

MAN & Cat.

BA & Cat.

PAN, 2EH &

Cat.

DCP

DCS

DCM /

DCF

DCA

CB

COP

Plasticizer: Medical

applications

Plasticizer: Flooring,

cable, cling and film

Plasticizer and

emollient

Plasticizer and

surfactants

(on further rxn.)

Plasticizer: Flooring,

cable, wire, film and sheet

Etherification

Acid cat.

Dehydration

2-octene

ECH &PTC

CGE

Plasticizer and surfactants

(on further rxn.)

DCE

Solvent

Other derivatives

Ethoxylation /Sulfation

CE/SCS/SCES

Surfactants

(Anionic and non ionic)

Fig 5.5.1: Products developed based on 2-octanol under NAIP-JAOL Project

NAIP

Property DCS DCP DINP DEHP

Rheology at

low shear rate-- -- 0 0

Rheology at

higher shear

rate

+ 0 0 0

Paste ageing 0/- - 0 0

Air Release + 0/+ 0 0

Efficiency ++ 0/+ 0 +

Gloss - 0 0 0

Transparency - + 0 0

Yellow Index - 0/- 0 0

Exudation -- 0 0 0

Odour 0 0 0 0

Weight Loss at

70° C- 0 0 0/-

Thermal

Stability0 0 0 0

Water pick up 0/+ + 0 0

COMPACT LAYERS – SUMMARY OF

RESULTS

+: Better 0: Good -: Less desired

Property DCS DCP DINP DEHP

Rheology + 0 0 0

Paste ageing 0 0 0 0

Yellow Index - 0/- 0 0

Cell Quality - 0 0 0

Surface Quality - - 0 0

Cell Density + 0 0 0

Expansion rate + + 0 0

FOAM LAYERS – SUMMARY OF

RESULTS

Fig 5.5.2: Castor protein isolate (CPI) (spray dried), CPI based adhesive and curing effect at

different time at 120 deg C

74

NAIP

DCC

CPI

Ricin Testing

JAOL

Before loading

Note: Detection limits 5 nano gram/ ml

IMPACT & COMPARISON:

PHOTOGRAPHS OF NAIP-JAOL UNDER DEVELOPED PRODUCTS BASED ON

DEOILED CASTOR CAKE

Fig 5.5.3: Comparison study for ricin testing for deoiled castor cake and castor protein isolate

75

Summary:

Under this project developed value added products based on the 2-octanol like phthalate,

maleate, fumarate, sebacate, adipate, benzoate and these can be used as plasticizers in PVC and

resins for various applications. 2-octanol is co-product of the castor industry and based on its

such value added products will earn good returns to the stakeholders

Based on the estimation, the 2-octanol based esters as plasticizers will be cheaper than the

existing products based on 2-ethyl hexanol and isononanol.

Developed process technologies for esters based on 2-octanol will be able to replace petroleum

derived products thus increasing the value of the castor plant & indirectly benefit the farmers due

to increased demand

Deoiled castor cake is also a co-product of castor industry and it has rich content of protein.

Apart from this it also comprises of other constituents. One of the constituents of castor cake is

found very toxic. Due to this the deoiled castor is not used as foodstuff for live stock in spite of

rich amount of protein. The developed process of extraction and isolation shows the protein from

castor deoiled cake is free from toxic component i.e. ricin. Hence such isolated protein can be

used for industrial applications like adhesive and bio-film and can be partially or fully replaced

by soy protein isolate as this is being used in the food products. Also could be considered for

feed purpose after satisfactory trials

76

4. Innovations

Esterification process developed without formation of byproducts & of high

purity based on agro-based raw-material replacing petrochemicals.

Castor based esters evaluated as plasticizers for PVC in place of petrochemical

based esters & results found encouraging.

New source of protein from castor seeds identified and developed process for its

extraction & isolation.

Identified and demonstrated on laboratory scale development of adhesive based

on the castor protein.

Identified and demonstrated on laboratory scale development of biofilm based on

the castor protein.

7. Process/ Product/Technology Developed

S. No. (Process/Product/Technology

Developed

Adoption/ Validation/

Commercialization, etc.

Responsible

Partner

1 Developed products based on 2-

octanol such as Dicapryl

phthalate, Dicapryl sebacate,

Dicapryl maleate, Dicapryl

fumarate, Dicapryl adipate,

Dicapryl ether, Capryl glycidyl

ether, 2-octene, etc.

Some the products were validated and

others have been sent for validation.

Approached local manufacturers of

plasticizers for commercialization of

the process technologies based on the

research carried out under NAIP-

project

JAOL, Mumbai

2 Developed process technology for

extraction and isolation of the

protein from deoiled castor cake

Bench scale process developed and the

scale up operation is essentially to be

done for either adoption or

commercialization by interested protein

and protein based products

manufacturers

JAOL, Mumbai

3 Developed adhesive formulation

for industrial applications (wood)

using castor protein

Developed castor protein based

adhesive and has given to local

adhesive manufacture for performance

evaluation in applications against the

existing soy protein based adhesive.

The valuable feed back from them yet

to be received.

JAOL, Mumbai

77

Patents (Filed/Granted)

Title of Patent Inventor(s) (Name & Address) Filed / Published

/ Granted

(No./Date)

Responsible

Partner

“Preparation of Esters

from 2-octanol”

Dr. Subhash V. Udeshi.

M/s. Jayant Agro-Organics Ltd.

38 Marol Co-op. Ind. Estate Off M.

V. Rd, Sakinaka, Andheri(E),

Mumbai-400059 India.

Dr. Kishor D. Ambawade

M/s. Jayant Agro-Organics Ltd.

38 Marol Co-op. Ind. Estate Off M.

V. Rd, Sakinaka, Andheri (E),

Mumbai-400059 India.

Under process JAOL,

Mumbai

8. Linkages and Collaborations

S. No. Linkages developed

(Name & Address of

Organization)

Date/Period From-To Responsible Partner

Nil

9. Status on Environmental and Social Safeguard Framework

India is major producer of castor and castor related products such as castor oil, castor oil based

oleochemicals and deoiled castor cake. Products developed under this project, are agro-based

materials which replace petroleum derived products. The petroleum products emit carbon

dioxide during their manufacturing and thus increase the global warming. Also lead to fossil

reserves depletion. Our products being agro-based are from renewable resource and thus non-

depleting. Further there is balancing of the carbon dioxide as the castor plant absorbs CO2 from

the atmosphere. The farming also creates rural employment and leads to social harmony. Further

the technology is based on energy saving principles. All in all there is improvement in Health,

Environment and Economy for all sections of society.

10. Constraints, if any and Remedial Measures Taken

It was realized that coordination was poor among the partners.

78

11. Publications (As per format of citation in Indian Journal of Agricultural Sciences)

A. Research papers in peer reviewed journals-Not Applicable as under patenting

S.

No.

Authors, Title of the paper,

Name of Journal, Year, Vol. & Page No.

NAAS

Ratings

Responsible

Partner

1. Patel, R.M. Prajapati, T.R. and Patel, P.S. (2010).

Yield advances in castor through adaptation of

recommended package of practices on farmer’s field.

Journal of Oilseeds Research. 27 (sp. issue): 312-315

2.9 SDAU

2. M.K. Patel, Jignasa V. Modh, Jignesh P. Patel and

P. S. Patel (2010) Journal of Oil Seed Research 155N

0970-2776 Vol. 27 (Special issue) P. 302-303

2.9 SDAU

B. Books/ Book chapters/ Abstracts/ Popular articles, Brochures, etc.

S. No. Authors, Title of the papers

Name of Book/ Seminar/ Proceedings/Journal, Publisher, Year, Page No.

1. Papers presented: “A simple method for the enrichment of methyl ricinoleate from

castor oil methyl esters by LLE, K.V.S.A. Rao, P. Vijayalakshmi, D. Pramod Reddy

and R.B.N. Prasad presented at National Symposium on “Research and development

in castor: present status and future strategies” during October 22-23, 2010,

Hyderabad

12. Media Products Developed/Disseminated

S.

No.

CD, Bulletins, Brochures,

etc. (Year wise)

No. of Copies Distribution Responsible

Partner

Nil

79

13. Meetings/Seminars/Trainings/Kisan Mela, etc. organized-Not Applicable

S.

No.

Details of

Meetings/Seminars/

Trainings, etc.

Duration

(From-To)

No. of

Personnel

Trained

Budget

(`)

Organizer

(Name & Address)

1. Training of 100

farmers of

Shankhalpur and

Matpur villages

4 days 100 20000/- Main Castor

Mustard Research

station SDAU SK

Nagar

2. Castor production

technology and its

derivatives

3 Days 150 20000/- Main Castor

Mustard Research

station SDAU SK

Nagar

3. Castor production

technology and its

derivatives

2days 60 5000/- Main Castor

Mustard Research

station SDAU SK

Nagar

14. Participation in Conference/ Meetings/Trainings/ Radio talks, etc.

S.

No.

Details of

Meetings/Seminars/

Trainings/Radio talk,

etc.(Name &Address)

Duration

(From-To)

Budget

(`)

Participant

(Name & Address)

Nil

15. Foreign Trainings/Visits:

S.

No.

Name,

Designation,

Address of

the Person

Visit/Training/Seminar

its Place, Organization

and Duration (From-

To)

Dates of

Seminar

Delivered and

Report

Submitted on

Return

Follow up

Action

Total Cost

(`)

Nil

80

16. Performance Indicators

S.

No. Indicator Total No.

1 No. of production technologies released and/or adopted 5

2 No. of processing technologies released and/or adopted 4

3 Number of technologies/products commercialized based on NAIP

research Nil

4 No. of new rural industries/entreprises established/ upgraded Nil

5 No. of product groups for which quality grades developed and agreed 1

6 Total no. of private sector organizations (including NGOs) participating

in consortium 2

7 No. of farmers involved in consortia activities Approx. 2200

8 Total number of farmers’ group developed for marketing and processing Nil

9 Number of patent/intellectual property protection applications filed

based on NAIP research 1

10 Number of patents/intellectual property protections granted/published

based on NAIP research Nil

11 Number of scientists trained overseas in the frontier areas of science Nil

12 Number of scientists trained overseas in consortium-based subject areas Nil

13 No. of scientists participated in conference/seminar etc. abroad Nil

14 Success stories Nil

15 Incremental employment generated (person days/year/HH) Baseline Final

Nil

16 Increase in income of participating households (` per annum) Baseline Final

Nil

17 Number of novel tools/protocols/methodologies developed 2

18 Publications

Articles in NAAS rated journals -

Articles in other journals 2

Book(s) Nil

Book chapter(s) Nil

Thesis Nil

Popular article(s) (English) Nil

Newspaper article(s) Nil

Seminar/Symposium/Conference/Workshop Proceedings 1

Technical bulletin(s) 2

Manual(s) Nil

CDs/Videos Nil

Popular article(s) in other language -

Folder/Leaflet/Handout Nil

Report(s)

8 Quarterly

reports were

submitted

Success stories Nil

81

17. Employment Generation (man-days/year)

S. No. Type of Employment Generation Employment

Generation

up to End of

Sub-project

Responsible

Partner

No direct employment generated

18. Assets Generated

(i) Equipment

Sr.

No.

Name of the equipments with manufacturers

name, model

Date of

purchase

Quantit

y (Nos.)

Cost (`)

1 Centro fix vertical autoclave 23.03.2010 One 84375/-

2 Tractor Drawn Castor

planter

Umiya 26.03.2010 One 29925/-

3 Power Operator Castor

Decorator

Umiya 26.03.2010 One 35438/-

4 Farm track Tractor 45 DB (42HP) 27.03.2010 One 467000/-

5. Field Crop Solar Dryer 23.03.2010 One 166375/-

6 Gel Documentation System 27.03.2010 One 742000/-

7 Vertical Electrophoresis 27.03.2010 One 171260/-

8 BD instrument make

hybridation incubator

BDI 54 A 29.03.2010 One 105000/-

9 Ultra filtration membrane 8200 UF 29.03.2010 One 226966/-

10 Horizontal Electrophorosis BMH 8 5.06.2010 One 79985/-

11 Electrical digital AX-200 15.11.2010 One 66700/-

12 Electrical digital Balance AX-200 15.11.2010 One 66700/-

13 Thermogravimetric analyzer TG/DTA/6300

Exstar

3.12.2010 One 1359064/

-

14 Digital Camera DSCH-1S 31.12.2010 13950/-

15 Tissue Homogenizer PRO 250 31.12.2010

159600/-

16 Ricin Estimation kit LCC USA Make

Cat. No.P-12

6.01.2011 One 1694925/

-

SRS optimalt USA

Mo. MPA 100

One 57750/-

17 Electroquip vacuum oven POE 7071 6.01.2011 One

18 Digital melting point

apparatus

EIE Make 6.01.2011 One 174000/-

19 Pessurize oil extractor - 7.01.2011 One 1511096/

-

82

20 Universal testing machine - 7.01.2011 One 264600/-

21 Computers HP-8000 & 7000

series

31.12.2010 Three 108150/-

22 21. Laser printer HP(L)CP 1215 24.02.2011 one 20909/-

23 Air screen seed pre-cleaner

with aspirator/ Air screen

cleaner cum grader/ Destoner/

Specific Gravity Separator

- 24.3.2011 One 797850/-

24 Fluorescence

Spectrophotometer (IICT,

Hyderabad)

- 40392 One 987000/-

25 Differential Scanning

Calorimeter (IICT, Hyderabad)

- 29-03-2010 One 1200000/-

(ii) Works

S. No. Particulars of the Work,

Name and Address of

Agency Awarded the

Work

Year of

Work Done

Quantity

(Nos.)

Total

Cost

(`)

Responsible

Partner

Nil

(iii) Revenue Generated

(Details may be given on revenue generated in the sub-project viz., sale of seeds, farm produce,

products, patents, commercialization, training, etc.)

S. No. Source of Revenue Year Total amount

(`)

Responsible

Partner

Nil

(iv) Livestock

(Details of livestock procured/produced in the sub-project)

S. No. Details of

Livestock

(Breed, etc.)

Year of

Procurement/Production

Nos. Total

Cost (`)

Responsible

Partner

Nil

83

19. Awards and Recognitions

S. No. Name,

Designation,

Address of

the Person

Award/

Recognition

(with Date)

Institution/ Society

Facilitating (Name

& Address)

Responsible Partner

Nil

20. Steps Undertaken for Post NAIP Sustainability

Under NAIP-II project provided high yielding Castor seed for production and get

maximum return to the farmers in irrigated as well as rainfed areas. Therefore, the field

demonstration of improved farm technologies should be continued.

The technologies developed are of much use and will be considered as a base for further

research and scaling up of technology.

More than 2000 farmers were trained through the interventions of NAIP-II for improved agro-

technologies and post harvest practices developed by university. Regular interaction between

farmers and scientists will be made under different programs conducted by university. For

ensuring smooth supply of quality seed to the farmer’s the centre is producing breeder seed as

per the indent of state agencies and national agencies. All the seed production sites are regularly

monitored by castor scientist for maintaining good crop vis-à-vis quality seed production. The

industry is working on value addition of castor cake and development of derivatives from castor

oil. Due to integrated intervention castor cake is included in Fertilizer Control Order.

21. Possible Future Line of Work

If castor growing areas provide high yielding varieties than easily increases castor

production in rainfed as well as irrigated condition.

In undeveloped areas gives the farmers training programme for new technology adoption.

Provide knowledge about new innovation in production technology.

Large scale manufacturing of the esters and the protein is likely to be taken by

commercial organizations, which will indirectly benefit the farmers due to increase in

demand for the castor seeds.

84

22. Personnel

(Staff of Lead Centre & Partner-wise, their Name, Designation, Discipline and Duration)

Research Management (CL) From – To (DD/MM/YYYY)

1.

2.

3.

Scientific (CPI, CCPI, others)

5. Dr. P. S. Patel, CPI & Research Scientist, Plant

Breeding and Genetics

March 1, 2009 to June 30, 2012

6. Dr. R. M. Patel, CCPI, Agronomy (Agriculture) March 1, 2009 to June 30, 2012

7. Dr M.K. Patel, CCPI, Bio-chemistry

8. Dr. S. Shah, CCPI, Bio-chemistry Jan, 11, 2012 to June 30, 2012

9. Dr. S. H. Suthar, CCPI, (Post Harvest

Technology )

March 1, 2009 to June 30, 2012

10. Dr. S. R. Vyas, CCPI, (Bio-Chemistry) March 1, 2009 to June 30, 2012

11. Dr. Subhash V. Udeshi, (Director) CCPI March 1, 2009 to June 30, 2012

12. Dr. RBN, Prasad, CCPI March 1, 2009 to June 30, 2012

13.

Technical

14. NIL

15.

Contractual

16. Mr. Mukesh Kumar Man, Senior Research

Fellow

May 28, 2010 to June 30, 2012

17. Mr. Bedse Ramchandra, Senior Research Fellow July 15, 2011 to June 30, 2012

18. Mr. Chirag Patel, Senior Research Fellow September 11, 2011 to June 30,

2012

19. Dr. Kishor D. Ambawade, Research Associate July 6, 2009 to June 30, 2012

85

23. Governance, Management, Implementation and Coordination

A. Composition of the various committees (CIC, CAC, CMU, etc.)

S. No. Committee Name Chairman

(From-To)

Members

(From-To)

1. CIC

2. CAC

3. CMU

B. List of Meetings organized (CIC, CAC, CMU, etc.)

S. No. Details of the meeting Date Place & Address

1. CIC

2. CAC

Ist CAC

IInd

CAC

IIIrd

CAC Dec 23, 2009 2, Arti society,

Near atma jyoti ashram,

Baroda- 390 011, Gujarat.

IVth CAC May 5, 2010 Jayant Agro Organics Ltd

Akhandanad , 34, Marol, Coop

Industrial Estate, OFF M VRoad

Skainaka, Andheri, `Mumbai

Vth CAC Oct 10, 2010 Lipid Sciences and Technology,

Indian Institute of Chemical Technology,

Hyderabad 500 007

VIth CAC Jun 7, 2011 Royal Castor Products Ltd., Industrial Area,

Khali Char rasta

Sidhpur, District: Banaskantha, Gujarat.

VIIth

CAC Jan 5, 2012 Jayant Agro Organics Ltd

Akhandanad , 34, Marol, Coop

Industrial Estate, OFF M VRoad

Skainaka, Andheri, Mumbai

1

Part III : Budget and its Utilization (SDAU: S. K. Nagar )

Sanction Letter No. _F. No. (5) 2007-NAIP

Total Sub-project Cost : 387.0685/-

Sanctioned/Revised Sub-project cost (if applicable): 393.7593/-

Date of Commencement of Sub-project :July 2009

Duration: From: July 2009_to June 30, 2012

Funds Received in each year

I Year : 1,4411560/- II Year : 37,66154/- III Year : 26,97402/- Total fund received 29872616/-Total expenditure 14307207/-

Expenditure Head-wise:

Sanctioned Heads Funds

Allocated

(*)

Funds Released Expenditure Incurred Total

Expenditure

Balance as

on date

Requirement of

additional

funds

Remarks

1st Year 2

nd Year 3

rd Year 1

st Year 2

nd Year 3

rd Year

A. Recurring

Contingencies

(1) TA 41901 74252 24847 141000

(2) Workshops 45461 48214 5000 98675

(3) Contractual

Services/RA/SRF

212080 810878 618024 1640982

(4) Operational costs 818644 1366629 730102 2915375

Sub-Total of A (1-4) 14411560 3766154 2667610 1118086 2299973 1377973 4796032

B. HRD Component

(5) Training - 7500 46915 54415

(6) Consultancy - - - -

Sub-Total of B (5-6) - 7500 46915 54415

C. Non-Recurring

(7) Equipment 2121624 6153336 - 2173145 6261486 - 8434631

(8) Furniture 498000 - - 49800 - - 49800

(9) Works (new

renovation)

500000 - - - 494962 494962

(10) Others (Animals,

Books, etc.)

51521 156049 494962 - 47899 - 47899

Sub-Total of C (7-10) 12280000 6309385 494962 2222945 6309385 494962 9027292

D. Institutional

Charges*

43488 385980 - 429468

Grand Total

(A+B+C+D)

16634505 10075539 3162572 3384519 9002838 1919850 14307207 6538117

* Institutional charges will be 10% of the recurring contingencies for the Lead Consortium and 5% for Consortia Partners.

2

Part III : Budget and its Utilization (IICT, Hyderabad)

Sanction Letter No. _F. No. (5) 2007-NAIP

Total Sub-project Cost : 387.0685/-

Sanctioned/Revised Sub-project cost (if applicable): 393.7593/-

Date of Commencement of Sub-project :1st March, 2009

Duration: From: March 01, 2009 to June 30, 2012

Funds Received in each year

I Year : 3522060/- II Year : 462012/- III Year 1131516/- Total fund received 4669758/-

Expenditure Head-wise: Sanctioned Heads Funds

Allocated (*) Funds Released Expenditure Incurred Total

Expenditure Balance as on date

Requirement of additional funds

1st Year 2

nd Year 3

rd Year 1

st Year 2

nd Year 3

rd Year 4th Year

A. Recurring Contingencies

(1) TA 35000 25000 40155 44283 15155 44580 0 104018 -3863

(2) Workshops 0 0 0 2000 0 0 0 2000 -2000

(3) Contractual Services/RA/SRF

187200 218400 600000 210658 319200 271200 134400 935458 70142

(4) Operational costs 2.75 2.07751 4.37479 2.07751 4.12479 1.22159 1.74992 9.17381 2849

Sub-Total of A (1-4) 4.972 4.51151 10.77634 4.64692 7.46834 4.37939 3.09392 19.58857 67128

B. HRD Component

(5) Training

(6) Consultancy

Sub-Total of B (5-6)

C. Non-Recurring

(7) Equipment 3000000 0 0 2000000 191563 0 24000 2167563 832437

(8) Furniture -

(9) Works (new renovation)

(10) Others (Animals, Books, etc.)

Sub-Total of C (7-10) 3000000 0 0 2000000 191563 0 24000 2167563 832437

D. Institutional Charges* 24860 10861 0 9801 37342 18254 0 65397 24206

Grand Total (A+B+C+D) 3522060 462012 0 2474490 975739 456193 285392 4191817 923771

* Institutional charges will be 10% of the recurring contingencies for the Lead Consortium and 5% for Consortia Partners.

3

Budget and its Utilization (JAOL: Mumbai)

STATEMENT OF EXPENDITURE (Final) Sanction Letter No.: F. No. 1(5)/2007-NAIP

Total Sub-project Cost

Sanctioned/Revised Sub-project cost (if applicable)

Date of Commencement of Sub-project July 6, 2009

Duration: From March 1, 2009 to June 30, 2012

Funds Received in each year

I Year: 6.48795/- II Year: 10.54048/- III Year: 6.70681/- Total amount received: 23.73524 Total expenditure:

Expenditure Head-wise:

Sanctioned Heads

Funds

Allocated

(*)

Funds Released Expenditure Incurred Total

Expenditure

Balance as

on date

Requirement

of additional

funds

Remarks 1st Year 2nd Year 3rd Year 1st Year 2nd Year 3rd Year

A. Recurring Contingency

1. T.A. 1.75 0.03288 0.29014 0.43055 0.75357

2. Workshops 0.00

3. Contractual Services 9.594 2.05291 2.77768 4.66989 9.50048

4. Operational Costs 26.00 1.42320 4.23413 3.03012 8.68745

Sub-Total of A (1-4) 37.344 3.50899 7.30195 8.13056 18.9415

B. HRD Component

5 (a) National Training 0.00 0.00 0.00 0.00 0.00

5 (b) International Training 0.00 0.00 0.00 0.00 0.00

6. Consultancy 0.00 0.00 0.00 0.00 0.00

Sub-Total of B (5-6) 0.00 0.00 0.00 0.00 0.00

C. Non-Recurring Contingency

7. Equipments 0.00 0.00 0.00 0.00 0.00

8. Furniture (Work Tables, etc.) 0.00 0.00 0.00 0.00 0.00

9. Works (New/Renovations) 0.00 0.00 0.00 0.00 0.00

10. Others (Animals, Books, etc.) 0.00 0.00 0.00 0.00 0.00

Sub-Total of C (7-10) 0.00 0.00 0.00 0.00 0.00

Total (A+B+C) 37.344 3.50899 7.30195 8.13056 18.9415

D. Institutional charges 1.8672 0.61540 0.61540 0.61540 1.8462

Grand Total (A+B+C+D) 39.2112 6.48795 10.54048 6.70681 4.12439 7.91735 8.74596 20.7877 2.94754

during 01.04.2012 to 30.06.2012 the expenditure as consultancy: Rs 93600 and other operating maintenance charges: Rs 154417 and Closing balance

Rs 23141

3rd

year figures are till March 31st 2012.

4

SDAU: S. K. Nagar (Budget and its Utilization) STATEMENT OF EXPENDITURE (Final) (Period from July 2009 to June 2012)

Sanction Letter No. _F. No. (5) 2007-NAIP Funds Received in each year: Total Sub-project Cost : Rs. 387.0685/-__ I Year : Rs. 1,4411560/- Sanctioned/Revised Sub-project cost (if applicable) `__393.7593/-___ II Year: Rs. 37,66154/- Date of Commencement of Sub-project ___July 2009___ III Year: Rs. 26,97402/- Duration: From _July 2009_to __June 30, 2012__ (DD/MM/YYYY) Total expenditure: Rs. 14644232/- Expenditure Head-wise: Sanctioned Heads Funds

Allocated (*)

Funds Released Expenditure Incurred

Total Expenditure

Balance as on

date

Requirement of additional

funds

Remarks

1st

Year 2nd

Year 3rd

Year 4th

Year 1st

Year 2nd

Year 3rd

Year 4th

Year

2009-10 2010-11 2011-12 2012-13 2009-10 2010-11 2011-12 2012-13

A. Recurring Contingencies

(1) TA 42500 75000 42500 - 41901 74252 24847 2289 143289 - - -

(2) Workshops 50000 50000 50000 - 45461 48214 5000 3000 101675 - - -

(3) Contractual Services/RA/SRF

435600 976800 1267200 - 212080 810878 618024 197694 1838676 - - -

(4) Operational costs 1341500 2758000 1229000 - 818644 1366629 730102 94157 3009532 - - -

Sub-Total of A (1-4) 1869600 3859800 3850200 - 1118086 2299973 1377973 297140 5093172 - - -

B. HRD Component

(5) Training 75000 150000 100000 - - 7500 46915 - 54415 - - -

(6) Consultancy - - - - - - - - - -

Sub-Total of B (5-6) 75000 150000 100000 - - 7500 46915 - 54415 - - -

C. Non-Recurring

(7) Equipment 11680000 - - - 2173145 6261486 - 8434631 - - -

(8) Furniture 50000 - - - 49800 - - 49800 - - -

(9) Works (new renovation)

500000 - - - - - 494962 - 494962 - - -

(10) Others (Animals, Books, etc.)

50000 50000 50000 - 47899 - 94157 47899 - - -

Sub-Total of C (7-10) 12280000 50000 50000 - 2222945 6309385 494962 295340 9027292 - - -

D. Institutional Charges* 186960 385980 385020 - 43488 385980 - 39885 469353 - - -

Grand Total (A+B+C+D) 14411560 4445780 4385220 - 3384519 9002838 1919850 337025 14644232 - - -

* Institutional charges will be 10% of the recurring contingencies for the Lead Consortium and 5% for Consortia Partners.

5