Alternative Automotive Fuels - Biodiesel

Technical presentation to VW India Alternative Automotive Fuels - Biodiesel Fredrick A Bosch Ltd., Research & Development Date : 15 th July 2010 Venue : University of Agricultural Sciences, GKVK Campus, Hebbal, Bangalore 1 Internal RBIN/EP 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Content What is Biodiesel? Standardisation, comparison with European standards Understanding the Bx notations Significant characteristics Key issues Pictorial representation Conclusions BIODIESEL IS 15603 3

What is Biodiesel? Biodiesel is a fatty acid alkyl ( Methyl or Ethyl ) ester for use as an automotive fuel in diesel engines How is Biodiesel manufactured? NaOH or KOH 4 Internal DS/EAC1 - IN 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Vegetable oil + Methanol or Ethanol Catalyst NaOH or KOH Heat, 60 C Biodiesel B100 Methyl Ester or Ethyl Ester As per European / Indian Biodiesel Standard + Glycerine as per Diesel Fuel Spec. Diesel Fuel + 5-7% ester B5, B7 10% ester B10 100% ester B100 Future targets! 5 Internal DS/EAC1 - IN 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

FAME Fatty Acid Methyl Ester SOME Soya Methyl Ester RME Rapeseed Methyl ester Jatropha Methyl Ester USA Europe India Soyabean Edible Rapeseed Edible Honge, Jatropha Non - edible Type of Biofuel depends upon geography, abundance,. 6 Internal DS/EAC1-IN 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Indian standard for Biofuel, B100, IS 15607 : 2005, released by BIS Specification is a blend of American & European Current feedstock for Biodiesel in India : Jatropha, Honge Jatropha plant Honge plant BIS - Bureau of Indian Standards 7 Internal DS/EAC1-IN 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Extract - Indian Diesel Fuel standard 8

Extract - Indian Biodiesel, B100 standard 5 5 9

Extract - European Diesel Fuel standard 10

Extract - European Biodiesel, B100 standard 11

Biodiesel : Overview Diesel Fuel 100 90 Volume in ml 80 12 Biodiesel Blend B5 100 Biodiesel Blend B10 100 Biodiesel B100 100 90 90 90 80 80 80 70 70 70 70 60 60 60 60 50 50 50 50 40 40 40 40 30 30 30 30 20 20 20 20 10 10 10 10 0 0 B0 5 B5 0 B10 0 B100

Summary : Available National Standards Region Biodiesel, neat Diesel fuel, neat Biodiesel blends B100 B0 B5 B6 - B20 > B20 India IS 15607 IS 1460 IS 1460 Not available Not available Europe EN 14214 EN 590 EN 590 ( B7 ) Not available Not available USA ASTM D 6751 ASTM D 975 ASTM D 975 ASTM D 7467 Not available 13

Significant characteristics : B0, B100, B6 - B20 Major Regions India India Europe USA Biodiesel blend B0 B100 B100 B100 B6 - B20 Interpretation Diesel Biodiesel Biodiesel Biodiesel Blend Oxidation stability, 110 C ( Rancimat ) Bosch Recommendation ~ 48h ( evaluated, not spec. ) 6 h 6 h 3 h 6 h - 6 h > 20 h Oxidation stability, 95 C/16 h, g/m 3 25 Not specified Acid value, mg KOH/g - 0.5 0.5 0.5 0.3 14

Significant characteristics : B0.... B7 Major Regions India Europe USA USA Biodiesel blend B0 & B5 B0 & B7 B0 & B5 B6 - B20 Description of bulk Diesel Diesel Diesel Diesel Official Standard IS 1460 EN 590 ASTM D 975 ASTM D 7467 Oxidation stability, 110 C Rancimat Not specified 20 h ( upto B7 ) Not specified 6 h Oxidation stability, 95 C/16 h, g/m 3 25 25 Not specified Not specified Acid value, mg KOH/g Not specified Not specified Not specified 0.30 B0 implies neat conventional diesel fuel B5, B7 blends is covered in the respective Diesel fuel standard itself 15

Acidity_ Stability_ Interpretation Good Acid value in mg KOH/g Bad Diesel Fuel High Low Diesel Fuel Bad Oxidation stability in hours Good 16

Key Issues 1. Fuel ageing An intrinsic characteristics of Biodiesel Perfectly suitable as far as the ageing reserve has not depleted Ageing results in formation of organic acids, polymers Acids results in corrosion Polymers results in deposit formation, leading to malfunction 17

Induction period for B100 ( EN 14112 ) 18

Induction period for B7 ( EN 15751 ) Rancimat EN 14112 & EN 15751 EN ISO 12205 & modifications Good Induction period (ageing reserve) of good quality biodiesel is necessary Conductivity [µs/cm] 600 500 400 300 200 100 Ageing reserve Fuel fit for use B7 Fuel ageing has started Usability expired 0 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 Time [hrs] Induction period 19

Reasons for approving IP > 20 hours for EN 590 Positive field validation of B5 with IP > 20 hours (2005). Lower IP are not validated Very few FAME related failures reported in Germany until after 2006 Failures occur most frequently for vehicles on forecourts after standing for 2 months or more Customer protection required action Limit was set to 20 hours minimum but does not seem to include a big safety margin!! ( India being tropical! ) Any lower limit value is not acceptable. A higher value would be desirable but was not approved in order to avoid additional expenditure and costs for (bio)fuel producers 20

2. Engine oil dilution Increase in Engine oil level Deposit generation on piston rings Deterioration in tribological characteristics of oil Catalyst failures 3. Ash generation Increased ash generation in Exhaust Effect on particulate filter 21

Fuel aging Definition of fuel ageing Ageing products Effects on the fuel system Change of fuel composition and properties during storage and/or usage effected by: Oxygen (aeration) Temperature Light Fuel quality Blend stocks Additives Impurities Insoluble polymers (gum, sludge) Soluble polymers Ageing acids Clogging, e.g. filters Deposit build-up, entire system Restricted moving parts Strong injector coking Resin formation Restricted guidance clearances Corrosion of metallic surfaces Deposits formation by soaps with metal ions (e.g. from wear or corrosion) Peroxides Embrittlement of elastomers 22

Nozzle coking from RME operation Glycerides, Sodium carbonate are present Na 2 CO 3 is formed from Na-ions And CO 2 from combustion chamber atmosphere Deposit formation in the slots of the VE pump plunger 23

High Pressure axial piston Distributor pump, Distributor Head with FAME polymer coating High Pressure Axial piston Distributor pump, Distributor head with seized / cracked plunger 24

General guidelines for use of Biodiesel & its blends ( 1 ) Neat Biodiesel, B100 must have sufficient stability Fuel ageing risks to be considered as follows, High risk for low use vehicles eg Gensets High risk at high ambient temperatures, eg Tropics Low risk for high usage vehicles eg Fleet Stability of diesel fuel itself ( used for blending ) varies as follows High sulphur diesels are more stable than Low Sulphur diesels S1000 > S500 > S350 > S50 [ Sx S = Fuel Sulphur, x = ppm Sulphur ] Worldwide migration towards Low Sulphur diesels, Euro 1... 5! Current Bosch experience in Europe for biodiesel blends upto 7% biodiesel An oxidation stability of min. 20 hours has been satisfactory! Fuel blends having adequate ageing reserve are suitable (B100 = 6h, B0 =>48h) Interchanging fuels in vehicles, Diesel >< Biodiesel / blends - not recommended Enhances risk of pre-existing deposits to clog filters (high solvency) 25

General guidelines for use of Biodiesel & its Blends ( 2 ) Elastomers in contact Biodiesel, to be necessarily changed over to Fluorocarbon base ( Viton ) Bench Endurance tests do not necessarily reflect biodiesel specific problems High fuel throughput Continuous operating cycle Fuel changed at regular fixed intervals at Bosch Adequate field testing ( with positive results ) is recommended To reflect actual conditions ( both vehicle & environment ) Above tests enable a possible Risk Assessment of a specific blend used All Bosch FIE are suitable for operation with Biodiesel blends as far as the ageing reserve is not depleted! 26

Summary & Conclusion ( 1 ) The experience with diesel blends B5 and B7 in the European market is positive and the number of incidents being reported continues to be low This is achieved through high quality standards for both the marketed fuel (B7, EN 590) and the bio-component (B100, EN 14214) A safe approach of introducing biofuel blends is highly recommended for other markets because certain risks with FAME blends exist that need to be minimised by defining the appropriate fuel quality India is going the right way by following the European standardisation India is now faced with the task of taking the next step and introducing the additional stability requirement Induction period into IS 1460 in due time before desulphurisation and 5 % blending of FAME is put into force Special attention also needs to be paid to fuel contamination, additive interactions, oil dilution and material selection 27

Summary & conclusion ( 2 ) Bosch supports the use of biodiesel blends upto max. 7% v/v Worldwide FIE manufacturers Position statement, max 7% blend Quality of Biodiesel should meet the requirement Availability of good quality Biodiesel on a continuous basis to be ensured Food vs Fuel crisis? 28

Thank You 29

Backup 30

Oxidation stability : Diesel Fuel vs Biodiesel Fuel Test method Unit India Europe USA Diesel Fuel, B0 ISO 12205 or ASTM D 2274 Measures sludge /Ageing behaviour g/m 3 max 25 25 not specified IS 1460 EN 590 ASTM D 975 Biodiesel, B100 EN 14112 Measures change in conductivity / Induction period hours min 6 6 3 IS 15607 EN 14214 ASTM D 6751 B5 ( Diesel fuel with 5% biofuel ) ISO 12205 or ASTM D 2274 Measures sludge / induction period g/m 3 max 25 25 not specified IS - Indian standard, EN - European norm, ASTM - American standard 31 Internal DS/EAC1 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Oxidation stability : Comparison of test methods ISO 12205 EN 14112 Spec : max. 25 g/m 3 ( Sludge ) ( for Diesel fuel, B0 ) Fuel sample is aged as follows : Fuel Temp. = 95 ºC Time period = 16 hours Passing Oxygen Sample is cooled, filtered for insolubles Adherent insolubles are removed by using suitable solvents Indirect measure of Induction period ( ageing reserve ), start of ageing Report : Total insolubles in g/m 3 Spec. : no change in conductivity, upto 6 hours ( for Biodiesel, B100 ) Fuel sample is aged as follows : Fuel Temp. = 110 ºC Time period = 6 hours Stream of purified air is passed is passed thru the sample Vapours released above is passed thru distilled water The above set-up is equipped with an electrode for measuring conductivity. The end of the induction period is indicated by a rapid change in conductivity of sample. Accelerated increase is caused by the dissociation of volatile carboxylic acids produced during the oxidation process & absorbed in water. 32 Internal DS/EAC1 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Sl. No. Characteristics Unit IS 15607 India EN 14214 Europe ASTM D 6751 USA ASTM D 7467 USA 1 Ester content % m/m 96.5 96.5 ( FAME ) - - 2 Density @ 15 C Kg/m 3 860-900 800-900 - - 3 Kin Visc. @ 40 C mm 2 /s 2.5-6.0 3.5-5 1.9-6.0 1.9-4.1 4 Flash Point C min 120 101 93 52 5 Sulphur content mg/kg ( ppm) 50 10 15, 500 15 % m/m, max 0.005-0.0015, 0.05 0.0015 6 Carbon residue on 10% % m/m, max 0.05 ( on 100% sample ) 0.3 0.05 0.35 7 Cetane no. min # 51 51 47 40 8 Sulphated ash % m/m, max 0.02 0.02 0.02 0.01 9 Water content mg./kg, max 500 500 500 (water + sedi.) 500 34 Internal DS/EAC1 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Sl. No. Characteristics Unit IS 15607 EN 14214 ASTM D 6751 ASTM D 7467 India Europe USA 10 Total contamination mg/kg, max 24 24 - - 11 Copper strip corrosion Rating, max Class 1 Class 1 No. 3 No.3 12 Oxidation stability, 110 C Hours, minim 6 6 3 6 13 Acid value mg KOH/g 0.5 0.5 0.5 0.3 14 Iodine value gi 2./100g max To report 120 - - 15 Linolenic acid methyl ester % m/m, max - 12 - - 16 Polyunsat. methyl esters % m/m, max - 1 - - 17 Methanol content % m/m, max 0.2 0.2 0.2 - Flash point min C - - - - Ethanol content % m/m, max 0.2 - - - 35 Internal DS/EAC1 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,

Sl. No. Characteristics Unit IS 15607 EN 14214 ASTM D 6751 ASTM D 7467 India Europe USA 18 Monoglyceride content % m/m, max - 0.8 - - Diglyceride content % m/m, max - 0.2 - - Triglyceride content % m/m, max - 0.2 - - 20 Free glycerol ( glycerin ) % m/m, max 0.02 0.02 0.02 - Total glycerol % m/m, max 0.25 0.25 0.24-21 Group I metals ( Na + K ) mg/kg, max 5 5 5 - Group I metals ( Ca + Mg ) mg/kg, max 5 5 5-22 Phosphorus content mg/kg, max 10 4 10-23 Distillation temp. C - - max 360 max 343 24 Cold soak Filterability - - max 360-25 Lubricity, HFRR µm, max - - - 520 36 Internal DS/EAC1 15/07/2010 Bosch Limited 2010. All rights reserved, also regarding any disposal, exploitation, reproduction, editing,