Download - Biodiesel- An outline
What?
An oxygenated, sulfur-free, biodegradable, non-toxic, and eco-friendly alternative diesel oil.
Chemically - a fuel composed of mono-alkyl esters of long chain fatty acids derived from renewable sources, such as vegetable oil, animal fat, and used cooking oil designated as B100.*
Remember!! ASTM and European standards.
*Source: ASTM D6571
Rudolf Diesel, Pioneer of Age of the Power
“The diesel engine can be fed with vegetable oils and would help considerably in the development of agriculture of the countries which use it” and that “The use of vegetable oils for engine fuels may seem insignificant today. But such oils may become in course of time as important as petroleum and the coal tar products of the present time.”
Source: dieselnews.wordpress.com
Made From..
Vegetable Oils
Animal fats
(Waste
Yellow Grease
High ₹Low FFA
Low ₹High FFA
Different sources same property!!Ed
ible
Oil • Castor Oil
• Coconut Oil• Soyabean Oil• Peanut Oil• Palm Oil• Mustard Oil• Sunflower Oil• Rapeseed Oil
Non
-Edi
ble • Jatropha Oil
• Jojoba Oil• Pongamia Oil• Copaiba Oil• Paradise Oil
Anim
al F
at • Tallow • Lard• Chicken Fat• Animal Fat
Mix
Lipids
Yellow grease
Animal Fat
Vegetable Oil
Esters of glycerol and fatty acids
Lipids
Fatty acids and alcohol
Simple
Unsaturated/saturated fatty acid + glycerol
Fats and Oils
Fatty acids + mono or dihydric alcohol
Waxes
Simple + Phosphoric acid, sugars,
sphingosine etc.Compound
Phosphoric acid+ Nitrogenoeus Base
Phospholipids
Hydrolytic products of simple and compound
lipidsDerived
Free long chain fatty acids
Fatty acids
Glycerol and other sterol
Alcohol
Based on Products of Hydrolysis
Lipids..
Fatty acid
s.. Fatty Acids
Saturated Unsaturated
Polyunsaturated
Omega3Soybean
Rapeseed
Omega6Corn oil
Sunflower oil
Monounsaturated
Omega9Olive oilPeanuts
Fatty acid contentFatty acid Chemical Formula
Lauric (12:0) CH3 (CH2)10 COOH
Palmitic (16:0) CH3 (CH2)14 COOH
Estearic (18:0) CH3 (CH2)16 COOH
Oleic (18:1) CH3 (CH2)7 CH = CH (CH2)7 COOH
Linoleic(18:2) CH3 (CH2)4 CH = CH CH2 CH = CH (CH2)7 COOH
Linolenic(18:3) CH3 CH2 (CH = CH CH2)3 (CH2)6 COOH
Ricinoleic (18:1) CH3 (CH2)5 CHOH CH2 CH = CH (CH2)7 COOH
Oil/Fat SFA (% w/w) NSFA ( % w/w)
Soybean 14 86
Palm 49 51
Peanut 17 83
Yellow Grease 33 67
Beef tallow 48 52
Triglycerides
• Ester• 3 fatty acids bond to a glycerol
Oil Type Palmitic acid Myristic acid Stearic acid Oleic acid Linoleic acid
Soybean
Palm
Peanut
Jatropha
Source: http://www.chempro.in/fattyacid.htm
Biodiesel Vs Petroleum diesel
Petrodiesel: 95 percent saturated hydrocarbons and 5 percent aromatic compounds
Biodiesel: Fatty acid methyl esters (FAME)
Source: Energy fact sheet, Penn State University
Biodiesel Vs Petroleum Diesel
Higher lubricity (Reduce Engine Wear)Much less toxicPractically no sulphurHigher oxygen content (10-12%)
More likely to oxidize (react with oxygen) toform a semisolid gel-like massTends to thicken and “gel up” at low temperaturesmore readilyMore chemically active as a solvent
Source: Energy fact sheet, Penn State University
Vegetable Oil to Biodiesel
Treatment of Raw material Transesterification Separation Purification
Upstream
DownstreamSource: Springer books, Introduction to Biodiesel Production
Treatment of raw materials
Extraction
Refining
Rendering
Mechanical Pressing
Volatile Solvents
DegummingPhosphotides
NeutralizingDi/Mono Glycerides,
Protein matter, Resins, FFA
BleachingColouring matter
Source:http://www.chempro.in/processes.htm
WHY TREATMENT?Highest glycerin quality
and yield
Higher economy
of the plant
Optimum cold
stability
Output: Straight vegetable oil
What makes it bio-”Diesel”?
Transesterification!!
FAME
Raw materials Required
Alcohol-to-oil Volume Ratio, 1:4 (R = 0.25)
Catalyst
Basic: Sodium hydroxide (NaOH), potassium hydroxide (KOH), carbonates.
Acid: Sulfuric acid, sulfonic acids and hydrochloric acid
Enzymatic: Lipases
Alcohol
Most widely used: Methanol (CH3OH) and Ethanol (C2H5OH).
Methanol: Most widely used. Petrochemical origin.
Ethanol: Less used, more complex production technology. Biomass origin.
Source: Springer books, Introduction to Biodiesel Production
Conversion of an ester(vegetable oil or animal fat)
into a mixture of esters of the fatty acids that makes
up the oil (or fat).
Transesterification
Catalyst should be completely mixed with the alcohol to
form alkoxide.
Alcohol-Catalyst Mixing
Oil is mixed with alkoxide, Carried out a higher
temperature(50-60oC) and under continuous stirring.
Chemical Reaction
Alcohols and oils do not mix at room temperature
Source: Springer books, Introduction to Biodiesel Production
Separation• What? From glycerol (1.28) and unused reactants
such as methanol (0.79) and catalyst (0.97), and any solids that may have formed.• How? Liquid-liquid separations- phase separation
Separation
Centrifugation
Physical separation
Source: Springer books, Introduction to Biodiesel Productionhttp://www.biodieselmagazine.com/
0.88
Purification
• Removal of remains of methanol, catalyst and glycerin – water soluble. • Avoid the formation of emulsions
during the washing steps.• After drying, the purified product is
ready for characterization as biodiesel according to international standards
Wash with water
Neutralize the esters- with
acidified water
Dried to eliminate traces
of water
Source: Springer books, Introduction to Biodiesel Production
Terminology
• Cloud Point: Temperature at which dissolved solids are no longer completely soluble, precipitating as a second phase giving the fluid a cloudy appearance. • Pour Point: Temperature at which it becomes semi solid and loses its flow
characteristics• Flash Point: Lowest temperature at which it can vaporize to form an ignitable
mixture in air• Cetane Number: An indicator of the combustion speed of diesel fuel.
StandardsSpecifications American
ASTM D6571EuropeanEN14214
Petroleum DieselEN 590:1999
Flash Point 93 0C 120 0C 55 0C
Cetane Number 47 51 51
Sulfur Content 15 mg/kg 10 mg/kg 350 mg/kg
Water Content 500 mg/kg 500 mg/kg 200 mg/kg
Total Glycerine 0.24 % mass 0.25% mass
Density 0.86-0.90 g/cm3 0.82-0.845 g/cm3
Viscosity 1.9-6.0 mm2/s 3.5-5.0 mm2/s 2.0-4.5 mm2/s
Industrial Process
Engineering Aspects
Planning
Process plant size
Plant site selection
Location
Feedstock sourcing
Biodiesel Marketing
Glycerine Outlet
Critical parameters
Operating/ Capital Costs
Safety
Quality
Uptime/Downtime
Environmental Issues
NOx Emission
Movement of agrichemicals
Economics
Economic Assessment
Resource Availability
Financial Analysis
Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
Resource Availability
Land Requirement• Wasteland (32.2 millon ha)• 20 million ha = 20 million tons of
oil (biodiesel)
Water Requirement• Minimum rainfall of
600 millimeters (mm)
Wasteland Selection CriteriaAnnual rainfall > 600 millimeters.pH of the soil < 9.Temperature > 0°C and frost
conditions should not prevail.The slope of land < 30°.The land should not be
waterlogged.The land should not be barren or
rocky.
Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
Financial analysis
Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
Biodiesel Supply Chain- Critical Bottlenecks Supply- Chain Segment Critical Bottlenecks
Nursery Lack of high-yielding varieties and, good-quality planting material; and high variation in yields
Plantation andharvesting
• Limited land availability and allocation• Agronomic and management practices that are not fully developed• Absence of minimum procurement price of seed• Long gestation period; no revenue in first few years• High labor cost of harvesting• Uncertainty about the future of the industry
Oil extraction • Higher cost of extraction due to low capacity utilization• Inadequate supply of seeds• Dispersed feedstock production, limiting economies of scale
Trans-esterification • Higher cost of trans-esterification due to low capacity utilization• Shortage of feed stocks• Dispersed feedstock production, limiting economies of scale• Uncertainty in the biodiesel industry
Blending andretailing
• Non-remunerative prices set by OMCs, which are not revised regularly• Opposition of OMCs to direct retailing of biodiesel by other
Source: Financial and Economic Assessment of Biodiesel Production and Use in India, Asian Development Bank.
Safety Procedures
• Biodiesel plants use a considerable quantity of highly flammable liquid (methanol) & corrosive material (sodium methoxide).• Process plant: Designed as a
hazardous area environment- defined by NFPA-497 (NFPA-National Fire Protection Association).• Methanol and sodium methoxide
storage tanks must be designed in accordance with NFPA 30.
• NFPA 497- • Criteria to determine ignitability
hazards in chemical process areas using flammable liquids, gases, or vapors to assist in the selection of electrical systems and equipment for safe use in classified locations.
• NFPA 30- • Safeguards to reduce the hazards
associated with the storage, handling, and use of flammable and combustible liquids.
Source: www.nfpa.org
Policies and RegulationsPolicy :
1. Central role for Biodiesel2. Accelerated development and promotion -
cultivation, production and use of 3. Substituting petrol and diesel with bio-
diesel for transport.4. Creating new employment opportunities
and leading to environmentally sustainable development.
Approach: 1. Target of 20% blending of biofuels by 2017.2. Focus to utilize waste and degraded forest
and non-forest lands and non-edible oil seeds for production of bio-diesel.
3. Cultivators, farmers, landless laborers etc were encouraged to undertake plantations that provide the feedstock for bio-diesel.
4. Corporates were also enabled to undertake plantations through contract farming by involving farmers, cooperatives and Self Help Groups etc.
Distribution & Marketing1. Responsibility (Storage, transport and
distribution) - OMCs. 2. The entire value chain- determining the bio-
diesel purchase price.Source: National Policy on Bio-fuels,2009
Advantages
Pros
EnvironmentFriendly- No sulfur dioxide production
Rural employment generation
High Cetane
Number
Emission Control
Extends the life of diesel engines
90% reduction in risk of cancer and neonatal defects
Bio-degradable (within 28 days in water)
Disadvantages
Cons
1.5 times expensive
than normal diesel
Higher fuel consumption
Higher freezing point
May degrade plastic and
rubber hoses
May lead to fuel filter clogging
Distribution infrastructure
needs improvement
Biodiesel can be used in blends with diesel fuel
Biodiesel Blends
Blend % Biodiesel Engine Modification Application
B100 100 Yes Diesel Engines
B20 20
No Rail EnginesB5 5
B2 2
Hot Research on..
Why Jatropha?Non-edible OilDrought ResistantCheaper feedstockNon-forest area for cultivationHigh Oil Yield:
Soybeans- 280 gallons per acreRapeseed - 740 gallons per acreJatropha - 2,226 gallons per acre
Source: www.jatrophabiodiesel.org/
Comparison of Base and Enzyme Catalysis
Catalyst Base Enzyme
Reaction temperature 60-70°C 30-4OoC
Free fatty acids in raw materials
Saponified products (soap formation) Methyl esters
Water in raw materials Interference with the reaction No influence
Yield of Methyl esters Normal Higher
Recovery of glycerol Difficult
Purification of methyl esters Repeated washing None
Catalyst cost Cheap Relatively expensive
Current Research in India
Source: http://www.eai.in/
Phycological Society of India
Central Salt & Marine Chemicals
Research InstituteDBT‐ICT Centre for Energy Biosciences, Institute of Chemical Technology
Indian Council of Agricultural research
The Energy and Resource Institute
The International Crops Research Institute for the Semi-Arid Tropics (ICRISAT)
Biodiesel Related Companies in India
Source: http://dbtjatropha.gov.in/companies.php
Biodiesel in India• Shatabadi Express ran on 5% bio-
diesel from Delhi to Amritsar on 31st December 2002.
• Five hundred government buses in Mysore are proposed to be run on biodiesel as per proposals cleared by Karnataka Cabinet.
• The Indian Railways has put forward plans to set up four biodiesel plants costing about Rs 1.2 billion.
• A research project in India has fuelled a Chevrolet diesel Tavera on a 20% biodiesel blend made from marine micro algae.
• The project was part of the New Millennium India Technology Leadership Initiative (NMITLI) with researchers from the Ministry of Earth Sciences (MoES) and Council of Scientific and Industrial Research (CSIR).
On the Spotlight!
ConclusionEconomically viableCan generate sizable employment
opportunitiesProduction is limited to wasteland,
the food sector will not be adversely affected.
Significant potential to reduce carbon emissions and generate carbon revenues.
Government interventions :Research on the agronomy of
oilseed plants Allocation of wastelandEstablishment of a dedicated
agency for biodieselProvision of an incentive package
for private investors & small-scale producers