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


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


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.


Financial analysis


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


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

Education

Biodiesel- An outline