Research Activities on Biodiesel at INDIAN INSTITUTE OF PETROLEUM DEHRADUN INDIA

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Research Activities on Biodiesel at INDIAN
INSTITUTE OF PETROLEUMDEHRADUN - INDIA

• Biodiesel conclave
• November 5, 2005
• INDIA HABITAT CENTER, NEW DELHI

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• Activities on Biodiesel Technology Development

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• Research activities on process development for
  Biodiesel (methyl esters) carried out under a
  sponsored project by Department of Biotechnology,
  New Delhi
• RD preparation of ethyl esters of Jatropha
  curcas oil and its field trials on diesel
  vehicles is being pursued under a collaborative
  project with MNES, New Delhi.
• Studies on bio-diesel from waste cooking oils and
  greases being carried under a sponsored project
  by PCRA, New Delhi

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Feedstocks for Biodiesel

• Biodiesel is prepared from oils and fats.
• Oils and fats are composed of molecules called
  triglycerides.
• USA Soya Oil is predominant
• Europe Canola, rapeseed oil largely used
• Other feedstock Tallow, lard, yellow grease,
  palm oil Include etc.

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Feedstocks in Indian Context

• For India non-edible oils obtained from plants
  which can be grown on waste/ semi arid lands are
  more suitable. Species can be selected based on
  the regional climatic conditions
• Most of the non-edible oils available in India
  contains high FFA (2-12)

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Non Edible Vegetable Oils Available in India
Possible raw materials for biodiesel Ratanjyot
Jatropha curcas Karanja Pongamia
glabra Mahua Madhuca indica Pilu Salvadora
oleoides Sal Shorea robusta Nahor Mesua
ferra linn Kamala Mallotus phillipines Kokam G
arcinia indica Rubber Seed Hevea Brasilensis
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Feedstocks Tested at IIP for Biodiesel Production

• Jatropha curcas
• Pongamia glabra
• Madhuca Indica
• Salvadora Oleoides
• Hevea Brasileusis (Rubber seed oil)
• Palm stearin
• Waste Palm oil

• Prinspia Utilis
• Sapindus Mukorossi
• Soya oil
• Rape seed oil
• Mixed vegetable oils
• Waste grease / oil from restaurants

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Commercial Biodiesel Technologies

• Currently used technologies for producing
  biodiesel can be classified into three
  categories
• Base catalyzed transesterification with refined
  oils
• Base catalyzed transesterification with low fatty
  acid greases and fats
• Acid esterification followed by
  transesterification of lower or high free fatty
  acid fats and oils.
• Other process under development include
  biocatalyzed transesterification, pyrolysis of
  vegetable oil/ seeds and transesterification in
  supercritical methanol.

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• The goal of all technologies is to produce fuel
  grade esters meeting standard specifications
  (e.g. ASTM/ European/BIS).
• The key quality control issues involve
• complete (or nearly complete) removal of alcohol,
  catalyst, water, soaps, glycerine and unreacted
  or partially reacted triglycerides and free fatty
  acids (FFA).
• Failure to remove these contaminants causes the
  biodiesel to fail one or more fuel standards.

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Basic Process

• The basic process involves transesterification
  of vegetable oil/fats in presence of a catalyst
  in batch or continuous mode. Continuous process
  may not be suitable, if the variation in quality
  of feedstocks are wide.

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• There are numerous variations of basic
  technology
• Different catalysts e.g. NaOH, KOH, MeONa, Non
  alkaline catalysts, acids, metal complexes and
  bio catalysts etc. can be used.
• Anhydrous ethanol, isopropanol or butanol can be
  substituted for methanol.
• Alcohols other than methanol may require
  additional process steps and quality control.
• Basic transesterification is carried out at
  atmospheric pressure and temperature around
  60-70C.
• Some technologies use higher temperatures and
  elevated pressure, typically in super critical
  range of methanol.
• For high FFA feedstocks acid catalysed
  esterification followed by base catalysed
  transesterification is used or FFA can be removed
  first and the purified oil is transesterified.

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Problems of Biodiesel Production

• Both base and acid catalyzed processes are
  associated with several inherent problems
• Free fatty acids interfere with
  transesterification deactivate the basic
  catalysts loss of catalyst and biodiesel yield.
• Water deactivates both basic and acidic
  catalysts. Drying of oil may be required.
• Soaps formed with basic catalyst form emulsion
  and foam and difficult to remove.
• When processing feed stocks with high free fatty
  acids additional steps must be taken.
• After basic transesterification, the purification
  and adequate testing during processing is
  required to produce fuel grade esters.

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Appropriate Technology

• The selection of appropriate technology for
  production of biodiesel requires careful
  selection of processing steps, catalyst and
  downstream process integration. The quality of
  feed vegetable oil particularly FFA content plays
  and important role in identifying the suitable
  technology.

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• The important factors to be considered include
• Must be able to process variety of vegetable oils
  without or minimum modifications.
• Must be able to process high free fatty
  containing oils/ feed stocks.
• Must be able to process raw both expelled and
  refined oil.
• Process should be environment friendly almost
  zero effluents.
• Able to produce marketable by products glycerin,
  fatty acids, soap if any.
• Must be able to produce fuel grade esters
  Biodiesel produced should meet the standard
  specifications.
• The process should be adaptable over a large
  range of production capacities.

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IIP Processes for Biodiesel

• India Institute of Petroleum has developed three
  processes for biodiesel from non-edible oils and
  under exploited oils including Jatropha curcas,
  Pongamia, Salvadora, Madhuca Indica and Mixed
  Oils.

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Process I

• Base catalysed process
• This process is suitable for feed stocks having
  FFA content gt1 to about 20.
• The oil is pretreated before transesterification
  at moderate temperature (60-80C) in presence of
  a base catalyst.
• FFA are also converted to biodiesel resulting in
  higher yield of biodiesel.

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IIP Processes for Biodiesel Process I
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Main Features of IIP Process I

• Flexibility for processing variety of vegetable
  oils separately or mixed without any
  modification.
• Tolerance of higher levels of free fatty acids
• Conversion of free fatty acids present in feed
  oils to biodiesel or alternatively free fatty
  acids can be recovered as byproduct or soap.
• Biodiesel produced meets the standard
  specification (ASTM, European or proposed BIS).
• Glycerin produced is 99 pure.
• Process can be adapted to wide range of
  production capacities.

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Process II

• Solid catalyst process
• This process is suited to feed stocks containing
  wide range of FFA or 100 FFA.
• In this process esterification of FFA and
  transesterification of triglycerides is carried
  out in a single step over a heterogeneous
  catalyst at moderate temperature and pressure.

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Fresh Vegetable Oil
Esterification Transesterfication
Fresh Methanol
Methanol Recovery
Recycle Methanol
BIODIESEL
Biodiesel Purification
Phase Separation
Glycerine Phase
Glycerine Refining
Glycerine
IIP Processes for Biodiesel Process II
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Main Features of IIP Process II

• Flexibility for processing variety of vegetable
  oils separately or mixed.
• Tolerance of higher levels of free fatty acids.
  Requires no pretreatment or removal of FFA.
• Conversion of free fatty acids present in feed
  oils to biodiesel.
• Tolerance of water in alcohol (aqueous ethanol
  can be used)

Continued...
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IIP Process II

• No emulsion or soap formation
• Catalyst is recycled and is not deactivated
  either with water or FFA.
• Biodiesel produced meets the standard
  specification (ASTM, European or proposed BIS).
• Glycerine produced is 99 pure.
• Process can be adapted to wide range of
  production capacities.
• The process is ecofriendly with almost zero
  effluents.

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Heterogeneous catalyst Process.Technological
and economic benefits
IIP Process II

• Use of heterogeneous catalyst has direct impact
  on the economics of biodiesel production.
• Several neutralisation and washing steps needed
  for processes using homogeneous catalysts such as
  NaOH, KOH, MeONa etc. are eliminated.
• Associated waste streams are eliminated.

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Process III

• Base catalyst-solvent process
• This process is suitable for feedstocks having
  upto about 6 FFA .
• Transesterification is carried out at ambient
  conditions in presence of a base catalyst. After
  separation of glycerin biodiesel is purified by
  distillation.
• Oil containing higher FFA can also be processed,
  if a pretreatment step is included.
• From technical point of view this process is
  especially suitable for small scale operations.

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MeOH Catalyst
IIP Processes for Biodiesel Process III
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Comparison of Biodiesel (IIP Processes) With
National International Specifications
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• Any of these processes can be selected to
  produce biodiesel depending upon the
  characteristics of feed oil stock. Biodiesel
  produced meets standard specifications (ASTM /
  European / BIS proposed) by all three processes.

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Economics

• The cost analysis indicates that the cost of oil
  is major component (about 75-80 ) of total cost
  of biodiesel.
• Use of lower cost feed stocks would have
  tremendous impact on biodiesel economics.
• Another approach which leads to reduction in
  operating cost is improvement in technology

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Effect of by-products on economics

• Market value of glycerol produced as a by-product
  is an important factor in biodiesel economics.
• Glycerol market is limited, any major increase in
  biodiesel capacity would undoubtedly lead to
  glycerol prices to decline, thereby affecting the
  over all economics of biodiesel.
• Value addition to oil cake would have greater
  impact on economics

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Economics of Biodiesel productionEffect of
Technology improvements -
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Activities on Quality and Performance Evaluation
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Corrosion Behaviour of Biodiesel on Diesel
Engine Parts

• Corrosion behavior of biodiesel produced from
  various non-edible oils was estimated during long
  duration static immersion test.
• Biodiesel from Mohua Karanj shows no corrosion
  on piston metal piston liner where as salvadora
  biodiesel has a marked corrosion effect on both
  the metals indicating that this oil is not
  suitable for biodiesel production especially when
  Bharat III Bharat IV norms will be implemented.
  
• Higher corrosion with salvadora biodiesel is
  probably due to its high sulfur content, 1600
  ppm.
• Jatropha curcas has slight corrosive effect on
  piston liner possibly due to the presence of
  linoleic acid 182 fatty acids.

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Corrosion Behavior of Biodiesels on Diesel
Engine Parts Using Static Immersion Test for 300
Days
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Lubricity of LCO/Diesel - Biodiesel Blends

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• The lubricity behavior of base fuel, Light cycle
  oil LCO/Diesel and biodiesel blends of Jatropha
  curcas and Pogamia glabra in LCO were assessed by
  HFRR test (ISO 12156 method).

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Base Fuel Properties (LCO)
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Base Fuel Properties (Diesel)
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HFRR Lubricity Evaluation for Biodiesel in LCO
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LUBRICITY OF BIODIESEL DIESEL BLENDS
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Studies on Lubricity Behaviour of
Biodiesel-Diesel Blends

• Addition of Bio-diesel to diesel / LCO Biodiesel
  improved the lubricity of diesel and LCO.

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Thermoxidative Stability of Biodiesel-Diesel
Blends

• Thermo-oxidative stability of Biodiesel-diesel
  blends determined by UOP-413 method.
• Biodiesel reduced the sediments thereby
  suppressed the aging of fuel.

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Thermo Oxidative Stability of Biodiesel-diesel
Blends (Test Method UOP-413)
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Detrioration of Vegetable oils during storage

• Effect of aging on the physico-chemical
  characteristics of various non-edible vegetable
  oils were studied over a period of 30 months
• Similar studies on Bio-diesel are in progress

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Variation in Acid Value of Vegetable Oils with
Time
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Current R D Programmes on Bio-diesel

• Continuous Pilot Plant testing of Heterogeneous
  Trans-esterification Process
• Studies to evaluate various vegetable oils for
  bio-diesel production
• Performance evaluation of Bio-diesel-Diesel
  blends in engines and field trials on Indigo cars
• Effect of bio-diesel on spray characteristics in
  diesel engines using CFD.
• Development of additives for Bio-diesel-Diesel
  blends

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Status of Technology

• Currently IIP is operating batch pilot plants
  (5-20 lit/ batch) producing biodiesel using base
  catalyst.
• Heterogeneous catalyst is being tested in
  continuous pilot plant.
• Engine testing of biodiesel and field trials on
  diesel car is in progress.
• Developed Sulfur free Multifunctional additives
  (MFA)for diesel and bio-diesel Diesel blends.

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Thank you