Biodiesel Production Technology

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BIODIESEL PRODUCTION TECHNOLOGY FEEDSTOCKS FOR
INDIA
Expert Lecture at Workshop on
Moving Toward Sustainable Energy Systems
Exploring Global Pathways to a Common
Destination
Organized by
UNIVERSITY OF MINNESOTA, OCTOBER 24,2006
PROF. NAVEEN KUMAR COORDINATOR, BIODIESEL
RESEARCH DELHI COLLEGE OF ENGINEERING DELHI,
INDIA Email naveenkumardce_at_rediffmail.com Phone
27871248, 32924637 Mobile [phone],
9810363530
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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.

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• Transesterification Reaction

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Molecular Structure
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.
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Issues Related to Base Catalyzed
Transesterification Process

• Feedstock Issues
• FFA
• Water
• Process Issues
• Type of Alcohol
• Molar Ratio
• Catalyst
• Reaction time temperature
• Agitation

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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

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Feedstock Issues
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
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Process Issues
Type of Alcohol

• 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 61 for base
  catalyzed reactions.

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Catalyst?
Chemical marriage brokers The presence of a
catalyst facilitates reactions that would be
kinetically impossible or very slow without a
catalyst
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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
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Various Catalysts used in Biodiesel Production
Homogenous

• 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

Heterogeneous

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

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Reaction time , Temperature Agitation

• Transesterification reaction will proceed at
  ambient (30C) temperatures but needs 4-8 hours
  to reach completion.
• Reaction time can be shortened to 2-4 hours at
  40C and 1-2 hours at 60C.
• Higher temperatures will decrease reaction times
  but require pressure vessels because methanol
  boils at 65C.
• Better agitation should be adopted to accelerate
  reaction.

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Batch, Base Catalyzed Process
Alcohol
Water
Water
TG
Ester
Biodiesel
Alcohol Catalyst
Dryer
Alcohol
Wash Water
Water
Acid
Batch Reactor
Crude Glycerol
Neutralized Glycerol
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10 Liters Biodiesel Unit
Stirrer
Water Cooled Condenser
Cooling Water
Reaction Vessel
Heating Element
Development Cost US 1300
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600 LITERS/DAY BIODIESEL UNIT
Control Panel
Motor Gear Box
Skid
Oil Tank
Methaoxide Vessel
Washing Vessel
Vacuum Drier
Separating Vessel
Reaction Vessel
Development Cost US 7000
Motor Gear Pump
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High FFA Feed Stocks

• Biodiesel feed stocks are classified by the
  amount of free fatty acids they contain
• Refined vegetable oils lt 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
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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 gt methyl ester water
• High alcohol FFA ratio required about 401
• Large amounts (5 to 25 ) catalyst may be required

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

• Use acid catalysis for conversion of FFAs to
• methyl esters, until FFA lt 0.5.
• Acid esterification of FFA is fast (1 hour) but
  acid catalyzed transesterification is slow (2
  days at 60C).
• 2. Then, add additional methanol and base
  catalyst to transesterify the triglycerides.

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Air
SVO
Design by DCE
SV2
Biodiesel Unit 1tpd Capacity
P1
Motor
Methanol H2SO4
Vegetable Oil Storage Tank 1500 Kg
Reactor 600 Ltrs.
Settling Tank 1000 Ltrs.
Vaccum Drier
SV2
P3
P2
Motor
Methanol KOH
SV3
Storage Tank 500 Ltrs.
Biodiesel Storage Tank 1000 Ltrs.
P6
P8
Vaccum Drier
P7
P5
Transesterification Reactor, 500Lts./Charge
P4
Washing Column 500 Ltrs./ Charge
Glycerol Storage Tank 500 Ltrs.
Separating Column 500 Ltrs./ Charge
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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

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Heterogeneous Catalyst
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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

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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 gt98 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

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Feed Stocks for India
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Feed stocks used in different Countries
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
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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

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Target Output per Hectare
Estimated Biodiesel production per 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
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Anti-Erosive Properties
Reduces wind and water erosion of soil Improved
absorption of water by soil
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Properties of press cake as fertilizer
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Quality seedling preparation
10 x 20 cm bag Germination -3 days 3-6 months
old seedlings
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VIEW OF JATROPHA PLANT NURSERY
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Intercropping with Jatropha
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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.

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Indias 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) Biodiesel requirement for blending (MMT) Biodiesel requirement for blending (MMT) Area Requirement for Blending (Mha) Area Requirement for Blending (Mha) Area Requirement for Blending (Mha)
Year Diesel Demand (MT) _at_ 5 _at_ 10 _at_ 20 _at_ 5 _at_ 10 _at_ 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
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Land requirement for different blending
percentages
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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.

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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.

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Thank You all for your precious time