BIODIESEL PRODUCTION TECHNOLOGY & FEEDSTOCKS FOR

INDIA

PROF. NAVEEN KUMARCOORDINATOR, BIODIESEL RESEARCH

DELHI COLLEGE OF ENGINEERINGDELHI, INDIA

Email: naveenkumardce@rediffmail.comPhone : 27871248, 32924637 Mobile : 9891963530, 9810363530

UNIVERSITY OF MINNESOTA, OCTOBER 24,2006Organized by

Moving Toward Sustainable Energy Systems: Exploring Global Pathways to a Common

Destination

Expert Lecture at Workshop on

What is

Biodiesel?

Biodiesel, a fuel composed of mono-alkyl esters of long chain fatty acids derived from variety of vegetable oils or animal fats, designated as B100, and confirming to different quality standards e.g. ASTM D 6751, EN14214 or IS 15607.

Glycerol

O O OMe Me Me

O = O =O =

HO

HO

HO

Biodiesel(Methyl Ester Alcohol)

3 ester alcohol + 1 glycerine

O =O O

O =O

O =

Triglyceride

1 triglyceride + 3 alcohol

3 MeOH

KOHCatalyst

catalyst

Transesterification Reaction

Fats and oils have quite big molecules with a spinal of glycerol on which are bond three fatty acid rests.

By the transesterification, the fatty acid rests are removed from the glycerol and each is bond with methanol.

The products are one mole glycerol and three mole of fatty acid methyl ester.

Molecular Structure

Issues Related to Base Catalyzed Transesterification Process

Feedstock IssuesFFAWater

Process IssuesType of AlcoholMolar RatioCatalystReaction time & temperatureAgitation

Feedstock Issues

1. Free Fatty Acids (FFA)Free Fatty acids in the oils react with alkaline catalyst to form soaps.

R-OH + KOH K-OR + H2O Acid + KOH Soap + water

It results in loss of catalyst and reduction in yield

2. Water Water deactivates the catalysts. Drying of oil is required. Water hydrolyses fats to form free fatty acids. Free fatty acids react with alkali catalysts forms soaps Soaps semi solid mixture glycerol separation

Feedstock Issues

Process Issues

• Methanol, Ethanol, Butanol etc• Methanol –commercially used• In methanolysis, emulsion forms and separated into

lower glycerol portion and upper ester portion. Reaction time is small

• In ethanolysis, emulsions are stable and requires more complicated separation and purification process. Reaction time is large

• Typical alcohol: TG ratio is 6:1 for base catalyzed reactions.

Type of Alcohol

Catalyst?

“Chemical marriage brokers”The presence of a catalyst facilitates reactions that would be kinetically impossible or very slow without a catalyst

Homogeneous versus Heterogeneous

Homogenous

The catalyst, reactants and products are all in one phase, normally the liquid phase. The reactions proceed over a intermediate complex and are often highly selective, but separation of the products and the catalyst is difficult.

Hetrogenous

The catalyst is in one phase, normally solid, while the reactants and products are in another phase. Separation of catalyst and products is easy, but the reaction is often less selective, because the catalyst material is not homogeneous

Various Catalysts used in Biodiesel Production

• Base Catalysts: NaOH, KOH, NaMeO• Acid Catalysts: H2SO4, PTSA, MSA, H3PO4, CaCO3 Typical base concentrations are :

NaOH/KOH – 0.3 to 1.5 %Na MeO – 0.5 % or less

• Sulfated Zeolites & Clays• Hetro-poly acids• Metal Oxides, Sulfates• Composite materials

Homogenous

Heterogeneous

Reaction time , Temperature & Agitation

Transesterification reaction will proceed at ambient (30°C) temperatures but needs 4-8 hours to reach completion.

Reaction time can be shortened to 2-4 hours at 40°C and 1-2 hours at 60°C.

Higher temperatures will decrease reaction times but require pressure vessels because methanol boils at 65°C.

Better agitation should be adopted to accelerate reaction.

Batch, Base Catalyzed Process

TG

Alcohol

Catalyst

Batch Reactor

Ester

Crude Glycerol

Alcohol

Alcohol

Wat

er

Water

Neutralized Glycerol

Wash Water

Dryer

Biodiesel

Water

Acid

Reaction Vessel

Heating Element

Water Cooled Condenser

Cooling Water

10 Liters Biodiesel UnitStirrer

Development Cost : US $ 1300

600 LITERS/DAY BIODIESEL UNIT

Vacuum DrierSeparating VesselReaction Vessel

Washing Vessel

Control Panel

Oil Tank

Methaoxide Vessel

Skid

Motor & Gear Box

Motor& Gear PumpDevelopment Cost : US $ 7000

High FFA Feed Stocks

Biodiesel feed stocks are classified by the amount of free fatty acids they contain:

• Refined vegetable oils < 0.05%• Crude vegetable oil 0.5-5%• Used Cooking Oil 2-7%• Animal fat 10-30%

Price decreases as FFAs increase but processing cost also increase

Base Catalyzed Reaction not suitable for high FFA feeds because of soap formation.

Most of the non-edible oils available in India contains high FFA (2-12%) & to decrease the cost of biodiesel, it is imperative to utilize high FFA oil or fatty acids

Acid Catalyzed Processes

Acid catalyzed processes are used for direct esterification of free fatty acids in a high FFA feedstock

Limitations: Water formation by

FFA + methanol ==> methyl ester + water High alcohol: FFA ratio required – about 40:1 Large amounts (5 to 25 %) catalyst may be

required

1. Use acid catalysis for conversion of FFAs tomethyl esters, until FFA < 0.5%.

Acid esterification of FFA is fast (1 hour) but acid catalyzed transesterification is slow (2 days at 60°C).

2. Then, add additional methanol and base catalyst to transesterify the triglycerides.

Preferred method for High FFA feeds: Acid Preferred method for High FFA feeds: Acid Catalysis followed by base catalysisCatalysis followed by base catalysis

Methanol+

KOH

Vegetable OilStorage

Tank1500 Kg

Methanol +

H2SO4

Motor

Storage Tank

500 Ltrs.

Motor

BiodieselStorage

Tank1000 Ltrs.

P2

SV2

Rea

cto

r 6

00 L

trs.

SV2

AirSVO

P1

SV3

P3

Set

tling

T

ank

100

0 L

trs. Vaccum

Drier

Separating Column500 Ltrs./ Charge

Washing Column500 Ltrs./ Charge

Vaccum

Drier

Glycerol Storage Tank 500 Ltrs.

Transesterification Reactor, 500Lts./Charge

P4

P5

P6P7P8

Biodiesel Unit1tpd Capacity

Design byDCE

Barriers to Homogeneous Catalyst

Sensitivity to FFA & water content of the feedstocks

Removal of catalyst Formation of soap with high FFA feedstock Large quantity of effluent water as a result of

removal of catalyst Necessities pre-treatment of oil in case FFA

content are higher No scope for regeneration or re-utilization

Heterogeneous Catalyst

Benefits - Heterogeneous Catalyst

Catalyst Regeneration – Decrease of Catalyst Cost

Utilization of lower quality feed stocks for biodiesel production

Simplification of separation process – Decrease of production cost

Decrease of wastewater – Development of environmental friendly process

Product Quality

Product quality is important – modern diesel engines are very sensitive to fuel.

It is not biodiesel until it meets Quality Standards. Reaction must be >98% complete. Acid number – for degrading, oxidized fuel Flashpoint – for residual methanol Water & sediment – fuel fouling, deposits Sulfated ash – for residual catalyst Total glycerin – for incomplete conversion, detects

residual mono, di and tri glycerides Free glycerin – inadequate fuel washing

Feed Stocks for India

Feedstock Countries

Rape seed , Sunflower EU

Soya bean U.S.A.

Palm Oil Malaysia

Coconut Philippines

Linseed & Olive oil Spain

Cotton Seed Oil Greece

Jatropha Curcas Oil Nicaragua

Used Cooking Oil Japan

Beef Tallow Ireland , USA

Used frying Oil Australia

Feed stocks used in different Countries

WHY JATROPHA THE SUITABLE CHOICE ? Thrives on any type of soil Needs minimal inputs or management Has no insect pests Not browsed by cattle or sheep Can survive long periods of drought Propagation by seed/cutting is easy Rapid growth Yield from the 2nd year onwards Yield from established plantations 5 tonne per ha. 30% oil from seeds by expelling Seed meal excellent organic manure

Target Output per HectareEstimated Biodiesel productionper Hectare = 3,000 litres/700Gal

Potential yields of 12 tonnes per hectare and 55% oil Extraction are also attainable

2500 trees per hectare produces Seed 6.9 tonnes Seedcake 4.2 tonnes Vegetable Oil 2.7 tonnes Glycerol 0.27 tonnes

Anti-Erosive Properties

Reduces wind and water erosion of soilImproved absorption of water by soil

Properties of press cake as fertilizer

Quality seedling preparation

10 x 20 cm bag

Germination -3 days

3-6 months old seedlings

VIEW OF JATROPHA PLANT NURSERY

Intercropping with Jatropha

Indian Biodiesel Program Name of Biodiesel started making appearance at Indian

Conferences, Workshops & Seminars in 1999 ‘Report of the Committee on Development of Biofuel’ – Planning

Commission, GOI in 2003 Stage I ‘Demonstration Project’ use Jatropha curcas on 400,000

ha (0.5 MMT BD) Nation-wide investment $ 300mn Stage II – 11 mill ha (13 MMT biodiesel) for 20% blend. Demonstration project started with initial grant of $11mn for

nursery raising rest is expected to be sanctioned late this year First 10,000 TPA plant in Hyderabad about to start production Garware100,000 TPA DMT plant modified for biodiesel

production A 250,000 TPA plant is being setup in Vishakhapatnam , A.P. A 100,000 TPA plant is coming up in Kakinada , A.P.

India’s target of bio-diesel production

5 % mixing of Biodiesel in HSD by 2007 20 % mixing of Biodiesel in HSD by 2012

Diesel & Biodiesel Demand, Area Required under Jatropha For Different Blending Rates

Year Diesel Demand(MT)

Biodiesel requirement for blending (MMT)

Area Requirement for Blending

(Mha)

@5%

@ 10%

@ 20%

@5%

@ 10%

@ 20%

2006-07 52.33 2.62 5.24 10.48 2.19 4.38 8.76

2011-12 66.90 3.35 6.69 13.38 3.35 5.58 11.19

Land requirement for different blending percentages

Summary

Biodiesel is an renewable fuel for diesel engines that can be made from virtually any oil or fat feedstock.

Biodiesel with a potential consumption of 15000 million litres can have a retail turnover of more than US$ 9000 mn per year

It can provide huge rural employment potential of 40 to 50 million families and transform the rural economy

Remote village electrification and power for agriculture application – Energy grown & used by village.

The technology choice is a function of desired capacity, feedstock type and quality, alcohol recovery, and catalyst recovery.

Summary

The dominant factor in biodiesel production is the feedstock cost which around 70%, with capital cost contributing only about 7 % of the product cost. Therefore high FFA, lower quality feedstock should be promoted for biodiesel production in India.

For meeting energy security and electricity for all, it is necessary to develop and commission small to medium capacity biodiesel unit at village & community level..

Maintaining product quality is also essential for the growth of the biodiesel industry in India.

Thank You all for your precious time