BIODIESEL

Production

and Issues
XI Programme on ³Advances in Petroleum Refining Technology and Related Aspects´
Programme Theme ´Alternative Fuels : Challenges & Opportunitiesµ
Dr A K Gupta

INDIAN INSTITUTE OF PETROLEUM DEHRADUN

Can Vegetable Oils be used as diesel? In long run not suitable

LIMITATION OF VEGETABLE OILS AS DIESEL FUEL
High viscosity Poor atomization Poor volatility Thermal cracking in diesel engines. Poor oxidation stability. Polymerisation in combustion chamber leading to deposits. ‡ Injection fouling by deposits ‡ Fuel line and filter clogging ‡ Polymerisation of triglycerides in the lube oil ‡ ‡ ‡ ‡ ‡ ‡ Hence modification of vegetable oils is necessary for efficient & trouble free engine operation.

WHAT IS BIODIESEL?
Biodiesel is a renewable fuel. Technically biodiesel is vegetable oil methyl / ethyl ester. The biodiesel molecules are very simple hydrocarbons containing no sulfur, ring molecules or aromatics associated with fossil fuels.

TECHNICAL ADVANTAGES
‡ Very low sulphur content. ‡ No Aromatics ‡ No net carbon dioxide addition to environment. ‡ 99.6% bio-degradability within 21 days ‡ Renewable Source.

SOCIO-ECONOMIC ADVANTAGES
Energy security Economic and social cohesion Healthy environment Upliftment of Rural Communities Employment generation Rejuvenation of Wasteland

DISADVANTAGES
Modification in FI Lower energy content (5-7%less than distillate system for more/optimized fuel air fuel) mixture More deposit on engine components(olefins, traces of glycerides) Engine oil degradation Marginal NOx increase (1-6%) Use of additives

Use of improved engine oil Use of after treatment devices

BIODIESEL·S PHYSICAL CHARACTERISTICS
Specific Gravity Kinematic viscosity @40°C Cetane Number Higher heating value (btu/lb) Sulfur, wt% Cloud point °C Pour point °C Iodine number Lower heating value (btu/lb) Flash point 0.87 to 0.89 3.7 to 5.8 46 to 70 16,928 to 17,996 0.0 to 0.0024 -11 to 16 -15 to 13 60 to 135 15,700 to 16,735 ~ 130 C

MOTIVATION FACTORS FOR BIODIESEL
‡ Biodiesel is non-toxic, biodegradable and exhibits high flash point- handling and storage are therefore safer than petroleum diesel. ‡ Biodiesel can be used in existing engines and fuel injection equipment without negative impact to operating performance. Virtually the same MPG rating as conventional diesel. ‡ Biodiesel can extend engine life because of its superior lubricating properties. Can be used as lubricity improver additive in petro diesel. ‡ It operates well in a conventional diesel engine with very few or no engine modifications. ‡ It can be used neat and as blend with conventional diesel ‡ Biodiesel reduces tailpipe emissions, visible smoke and noxious odors.

LUBRICITY BENEFITS Number 1 &2 diesel (500 ppm max. sulfur)
Percent Biodiesel 0.0 0.4 1.0 2.0 20.0 100.0 HFRR, WSD microns Number 2 536 481 321 322 314 314 Number 1 671 649 500 355 318 314

For No. 2 diesel 1% biodiesel was sufficient. For No. 1 diesel 2% biodiesel was sufficient. For still low sulfur diesel bodiesel dozes can be increased to meet lubricity requirement.

IIP has developed an additive which improves the lubricity and stability of both diesel and biodiesel. Dozes levels of 50-150 ppm are sufficient to meet lubricity requirements.

ECONOMIC FACTORS
‡ Biodiesel is 1.5-2 times costlier than petro-diesel, depending upon the price of feed vegetable oil. Cost of vegetable oil accounts for about 75% cost of biodiesel. ‡ Biodiesel and biodiesel blends have not penetrated the market due to its higher cost. ‡ To have a greater impact on the Indian Farm/Rural sector biodiesel may have to compete with petrodiesel. ‡ Use of alternative low cost vegetable oils/feedstocks may reduce the cost of biodiesel. ‡ One possible solution to this problem is to market biodiesel as a fuel additive that would be blended in the range of 1-3% by volume with petro-diesel to enhance fuel performance with respect to lubricity, cetane no., emissions and biodegradability ‡ Biodiesel may be more competitive as diesel fuel additive.

Transesterification is a suitable way to convert oils and fats into biodiesel ‡ Lowering of - Viscosity - Boiling point - Flash point ‡ Increase of cetane number (10 to 20 units). ‡ Cleaner combustion / lower engine deposits.

TRANSESTERIFICATION OF VEGETABLE OIL
Vegetable Oil (Triglyceride) CH2 ± OCOR CH ± OCOR CH2 ± OCOR + 3CH3OH 3RCOOCH3 + Methanol / ethanol Esters + Glycerine

CH2OH CH OH CH2OH

µR¶ REPRESENTS HYDROCARBON CHAINS OTHER REACTIONS Fatty Acids RCOOH Methanol CH3OH Ester RCOOCH3 + Water H2O

+

COMMERCIAL BIODIESEL TECHNOLOGIES
‡ Base catalysed transesterification with refined oils. ‡ Base catalysed transesterification with low fatty acid greases and fats. ‡ Acid esterification followed by transesterification of low or high free fatty acid fats and oils. Others under development include: ‡ Biocatalysed transesterification. ‡ Pyrolysis of vegetable oils/seed. Transesterification is simple and easily adaptable at commercial scale. .

TECHNOLOGY GOAL
‡ The goal of all technologies is to produce fuel grade biodiesel whose proportion meet standard specifications [ASTM / European / Proposed 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 FFA. ‡ Failure to remove these contaminates causes the biodiesel to fail one or more fuel standards.

Technologies can be run as
‡ Batch ‡ Continuous

Continuous processes may not be suitable if the variation in quality of feedstocks are wide.

GENERAL PROCESS STEPS
Vegetable Oil Methanol Mixing Catalyst (KOH/NaOH) Transesterification 1-3 stages

Glycerine Separation Crude Glycerine

Methanol Recovery

Biodiesel Purification Bio diesel

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°-70°C. ‡ Some technologies use higher temperatures and elevated pressure, typically in super critical range of methanol. ‡ For high FFA feedstocks ² acid catalysed esterification followed by base catalysed transesterification is used or FFA can be removed first and the purified oil is tranesterified.

Majority of commercial processes use base catalysed reaction because it is most economic for several reasons:
‡ Low reaction temperature upto 100°C and pressure up to 10 bar. ‡ High conversion (~98%) and minimal side reactions and reaction time. ‡ Direct conversion to methyl esters with no intermediates. ‡ Exotic material of construction are not necessary.

BIODIESEL PRODUCTION TECHNOLOGIES
Reaction conditions Company P (atm) 1 1 1 1 1 1 3.5 50 T (°C) Ambient Ambient >Ambient 60-70 60-70 50-130 95 200 Catalyst Mode of operation

Transesterification Comprimo/Vogel and Noot Idaho University Novamont / Technimont Conneman/Field and Hahn Lurgi IFP/sofiproteal Gratech Desmet Others: Olefina, Procter & Gamble, ME KFT Hydrogenation Cammit Abrokern

KOH KOH Organic NaOH Alkaline Alkaline/acid ? Nonalkaline

Batch Batch Batch Continuous Continuous Batch Continuous Continuous

40-100

360-380

Cobalt / molybdenum

Continuous

ENERGY INPUTS AND OUTPUTS PER GALLON OF SOYADIESEL PRODUCED
Electricity 7,308 Btus Diesel Other 14,522 Btus 6,235 Btus Steam 24,155 Btus Transport 456 Btus Electricity Methanol 2,666 Btus 7,320 Btus solvent Steam 1,575 Btus 18,225 Btus Catalyst 902 Btus Transport 228 Btus

Nitrogen 1,893 Btus Phosphorous 1,079 Btus

AGRICULTURE
Potash 1,482 Btus Peticides 3,739 Btus

EXTRACTION AND REFINING

ESTERIFICATION Soydiesel
132,902 Btus (1 gallon)

Soy Meal 81,229 Btus

Glycerin 17,010 Btus

Based on the energy used on the average soya bean farm and in oil extraction, refining and esterification facilities for every 1 Btu of energy input into the production system an average 2.51 Btus of energy output is realised i.e 151% energy gain.

MASS FLOW BALANCE IN THE PRODUCTION OF A GALLON OF SOYADIESEL
Fertilizers 0.62 lbs Diesel Fuel 0.10 gal AGRICULTURE Biomass -20 lbs

SOYABEAN SEED (41 pounds) Steam 11.53 lbs Electricity 0.46 KWh Solvent 0.005 gal

OIL EXTRACTION

Soy Meal 33.3 lbs

SOYABEAN OIL (7.7 pounds) Steam 16.6 lbs Electricity 0.25 KWh Methanol 0.26 gal SOYADIESEL (7.36 pounds of 1 gallon) Glycerine 0.80 lbs

ESTERIFICATION

PROBLEMS OF BIODIESEL PRODUCTION
‡ Free fatty acids interfere with transesterification deactivate the basic catalysts ² 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 feedstocks 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.

FEEDSTOCKS FOR BIODIESEL
‡ Biodiesel is prepared from oils and fats. ‡ Oils and fats are composed of molecules called triglycerides. ‡ Each triglyceride is composed of fatty acid three long-chains fatty acids of 8-22 carbons attached to a glyceride backbone.

TYPICAL FATTY ACID COMPOSITIONCOMMON OIL SOURCE ( ref. Kincs, 1985)
Fatty acid Lauric Myristic Palmitic Stearic Oleic Linoleic Linolenic Soyabean Cottonseed Palm Lard Tallow Coconut

0.1 0.1 10.2 3.7 22.8 53.7 8.6

0.1 0.7 20.1 2.6 19.2 55.2 0.6

0.1 1.0 42.8 4.5 40.5 10.1 0.5

0.1 1.4 23.6 14.2 44.2 10.7 0.4

0.1 2.8 23.3 19.4 42.4 2.9 0.9

46.5 19.2 9.8 3.0 6.9 2.2 0.0

Biodiesel feedstocks are classified based on free fatty acid content.
‡ Refined oils such as soya bean or canola oil (FFA <1.5%). ‡ Low FFA oils yellow greases and animal fats (FFA<4%) ‡ High FFA oils greases, spent frying oils and animal fats (FFA 5 to u20%).

Other feed stocks sewage greases and high FFA greases (FFA > 50)

COMMON FEEDSTOCKS FOR BIODIESEL
Vegetable Oil Rape seed Sunflower Soyabean Palm Linseed, Olive Cotton Jatropha curcas Used Frying Oils Other Waste oils & fats. Country France, US Italy, Southern France USA Malaysia Spain Greece Nicaragua, India Australia USA

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%)

NON EDIBLE VEGETABLE OILS
Possible raw materials for biodiesel Ratanjyot Karanja Mahua Pilu Sal Nahor Kamala Kokam Rubber Seed Jatropha curcas Pongamia glabra Madhuca indica Salvadora oleoides Shorea robusta Mesua ferra linn Mallotus phillipines Garcinia indica Hevea Brasilensis

APPROPRIATE TECHNOLOGY
‡ Must be able to process variety of vegetable oils without or minimum modifications. ‡ Must be able to process high free fatty containing oils/ feedstocks. ‡ Must be able to process raw both expelled and refined oils. ‡ Process should be environment friendly almost zero effluents. ‡ Able to produce marketable by products glycerine, 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.

Research Activities on Biodiesel Production and Performance Evaluation at Indian Institute of Petroleum, Dehradun

OBJECTIVES
‡ Development of a processes for biodiesel from various feedstocks. ‡ To evaluate biodiesel as an admixture with regular diesel for performance and emissions in diesel vehicles including field trials.

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.

PROCESS - I
This process is suitable for feed stocks having FFA content >1% to about 20%. The oil is pretreated before transesterification at moderate temperature (60-80°C) in presence of a base catalyst. FFA are also converted to biodiesel thus higher yield of biodiesel.

IIP PROCESS - I
Vegetable oil Oil Pretreatment

Methanol + catalyst

Transesterification

Crude glycerine Methanol recovery Glycerine refining

Crude Biodiesel

Refining

Biodiesel Glycerine

MAIN FEATURES OF IIP PROCESS-I
‡ Flexibility for processing variety of vegetable oils separately or mixed. ‡ 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). ‡ Glycerine produced is ~ 99% pure. ‡ Process can be adapted to wide range of production capacities.

PROCESS - II
‡ This process is suited to feedstocks containing wide range of FFA or 100% FFA. In this process esterification of FFA and transesterificagtion o triglycerides is carried out in a single step over a proprietary catalyst at moderate temperature and pressure. The catalyst is recycled and glycerine is obtained as by product. ‡ The catalyst is not deactivated either with water or FFA.

MAIN FEATURES OF IIP PROCESS-II
‡ Flexibility for processing variety of vegetable oils separately or mixed. ‡ Tolerance of higher levels of free fatty acids ‡ Conversion of free fatty acids present in feed oils to biodiesel ‡ Tolerance of water in alcohol aqueous ethanol can be used. ‡ No emulsion or soap formation ‡ Catalyst is recycled ‡ 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.

IIP PROCESS - II
Vegetable Oil

Alc + Cat.

Esterification & Transesterification

Crude glycerine Alcohol recovery Glycerine refining

Crude Biodiesel

Refining

Catalyst

Biodiesel Glycerine

PROCESS - III
This process is suitable for feedstocks having FFA<1%. Transesterification is carried out at ambient conditions in presence of a base catalyst. After separation of glycerine biodiesel is purified by distillation / water washings. This process is especially suitable for small scale operations.

IIP PROCESS - III
Oil Feed

Removal of FFA (Optional) Solvent MeOH + Catalyst

Transesterification

Glycerine separation

Glycerine

Biodiesel purification

Solvent

Biodiesel

‡ 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).

Comparison of Biodiesel (IIP process) with National & International Specifications
Characteristics Density, 15°C Viscosity @ 40°C Flash Point, °C Pour Point, °C Mol. Wt. Sulfated Ash content max., % max Sulphur max. % mass Cu corrosion 3 hr/50°C, max Neutral No. mgKOH/g Carbon residue % max Cetane Number 0.05 0.02 0.01 ASTM D6751 1.9-6.0 u130 India Proposed BIS 0.87-0.90 3.5-5.0 u100 -Draft EU 0.86-0.90 3.5-5.0 >100 JCO 0.8887 4.55 135 0 320 0.05 Karanja Oil 0.8944 5.07 174 -358.9 0.002 Mahua Oil 0.8808 5.13 120 +15 294.4 0.002 Salvadora Oil 0.8790 3.34 130 +6 258.1 0.01

0.05 No. 4 e0.8 0.5 --

0.05 1 e0.8 > 51

0.01 1

0.001 1 0.8 0.13

4.5 ppm 1 1.1 0.45 --

4.3 ppm 4 1.1 0.14 --

0.16% 3 0.5 0.16 --

--

56.6

STATUS OF TECHNOLOGY
‡ Currently IIP is operating batch pilot plants (5-20 lit/ batch) producing biodiesel. ‡ Studies to scale up and performance evaluation of bio-diesel on commercial engines are in progress. ‡ IIP has already run a bus on Bio-diesel blend ‡ IIP has already filed 1-Indian & 1-PCT patent ‡ IIP is in the process of filling 2-Indian and 2-PCT patents

THANK YOU

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