SIAM
Bio-Diesel as Fuel for Diesel Vehicles
– OEM’s Viewpoint of Requirements &
Issues
Dr. Mathew Abraham
Mahindra & Mahindra Ltd.
&
SIAM
Petroleum Federation of India
National Seminar on Bio-Fuels – Needs of the
Hour, New Delhi
13 Oct. 2008
1
Bio Fuels for Automotive Use
Process
Vegetable Oil
TransEsterification
Product
AUTO F U E L
BIO RAW
MATERIALS
Feed Stock
SIAM
Bio-Diesel
2
What is Biodiesel ?
SIAM
Biodiesel is monoalkyl ester of
long chain fatty acids produced
from the Trans-esterification
reaction of vegetable oil with
alcohol in the presence of
catalyst & can be used as fuel
3
What is Biodiesel ? Contd….. SIAM
 Bio-Diesel may be in the form of :
Fatty Acid Methyl Ester or Fatty Acid Ethyl Ester
 Main Characteristics:
• Better lubricity
• High Flash Point
• Comparable Heating Value content
• Readily mixes with diesel
• Ready to use in diesel run engines
4
Raw materials for Biodiesel SIAM
Soyabean oil
USA, Canada
Rape seed oil
Europe
Palm oil
South East Asian Countries
Waste Cooking oil
USA, Canada
Jatropha oil
India, China,
Karanje oil
India
Sunflower oil
Europe
Cotton Seed oil
Greece
Beef Tallow oil
Ireland
5
Status of Biodiesel in Automotives SIAM
 B2 (2% Biodiesel) : being used at
some places as a fuel additive /
lubricity enhancer
 B5 (5% Biodiesel) :Already
approved by FIE manufacturers &
running very successfully in some
parts of world without any problems.
 B10-B20 (10-20% Biodiesel)
under assessment
 100 (100% Biodiesel) : future
option
2nd Generation biofuels (BtL/GtL):
techno-economic studies being done
world-wide. Cost effective process still a
Challenge.
 USA uses B20 blends
popularly
 EU – 5-15%
 Blending Targets of EU is
5.75% by 2010 and 20%
by 2020
 India planning 5%
blending mandatory.
6
SIAM
Trans-esterification Process
CH2OCOR’
|
CHOCOR” + 3ROH
|
CH2OCOR
”’
Jatropha Oil
Alcohol
Catalyst
+
CHOH
NaOH
ROCOR
CH2OH
CH2OH
Glycerine
+
ROCOR
+
ROCOR
Bio-Diesel
7
SIAM
Bio Diesel Process & Product Quality
•Bio-Diesel Quality Depends on :
*Rawmaterial or Source of oil
*Trans-esterification Process
Process Factors
•Alcohol Selection
•Alcohol to Oil Ratio
•Catalyst Used
•Process Control
Impact on Product
•Product Quality
•Cost
•Yield
•Process Speed
Optimum
& Stable
BioDiesel
8
Fuel Quality Aspects
SIAM
• Several Countries have developed national specifications for
Biodiesel
• Bio-diesel Specs worldwide:
Country /Area
Specifications
EU
US
EN 14214
ASTM D 6751
Germany
DIN E 51601
India
Brazil
IS 15607:2005
ANP42
Japan
JASO M360
9
SIAM
Comparison of EU, BIS & ASTM Standards
Unit
EN
14214:2003
IS
15607:2005
ASTM D6751-02
% m/m,min
96.50
96.50
NA
Kg/m3
860-900
860-900
NA
mm2 /sec
3.5-5.0
2.5-6.0
1.9-6.0
C ,min
120
120
130
mg/kg,max
10
50
51 min
51 min
47 min
mg/kg,max
500
500
0.05 %vol (water
& Sediments
Rating
Class 1
Class 1
No. 3 max
hours ,min
(at 110oC)
6.00
6.00
NA
Property
Ester content
Density at 15oC
Kin. Viscosity at 40oC
Flash Point
Sulpher Content
o
Cetane No.
Water Content
Copper Strip Corrosion
3 h at 500C
Oxidation Stability
15 max
10
SIAM
Comparison of EU, BIS & ASTM Standards
Unit
EN
14214:2003
IS
15607:2005
ASTM
D6751:02
mg KOH /g
0.50
0.50
0.80
g Iodine/ 100g
max
120
to report
NA
Methanol or Ethanol
% m/m,max
0.20
0.20
NA
Free Glycerol
% m/m,max
0.02
0.02
0.02
Total Glycerol
% m/m,max
0.25
0.25
0.25
Group I Metal (Na+K)
mg/Kg,max
5
5*
5
Group II Metal (Ca+Mg)
mg/Kg,max
5
5*
NA
Phosphorus Content
mg/Kg,max
10
10
0.001 %mass
C ,max
NA
NA
360
Property
Acid Value
Iodine Value
Distillation Temp. (90%
recovery ,T90) oC ,max
o
11
* Amended in the 2007 revision which is under release
Impact of Process Quality on Bio-diesel
SIAM
Property
Effectiveness of Trans Est. process
Free Methyl Ester
Completeness of Trans Est. process
Free Glycerin
Unsaturated Fatty Acid
Oxidation Stability
Effective Catalyst Removal
Gr. I & II Metals
Effective Methanol Removal
Free Methanol
Feedstock Property
Acid, Oxidation Stab.
Contamination on process
Sulphur level
Insufficient Water Removal
Water Content
12
Comparison of Bio-Diesel Data
SIAM
sl no
Parameters
K-1
K -2
K-3
J-1
J-2
Specification as
per IS:156072005
1.
Density @ 150C, Kg / m3
898
893.5
0.899
880
882
860 - 900
2.
Kinematic Viscosity @ 400, cst
5.08
6.71
5.56
4.4
4.5
2.5 - 6.0
3.
Flash Point,(PMCC) 0C
188
178
184
174
176
120 (min)
4.
6
7
9
0
0
50.0 (max)
0.22
0.045
0.50
0.057
0.14
0.05 (max)
6.
Sulphur, mg/kg
Ramsbotaon Carbon Residue, % by
wt.,
Sulphated ash, % by wt.,
0.01
0.008
0.004
0.01
0.01
0.02 (max)
7.
Water Content, mg/kg.,
350
452
602
822
622
500 (max)
8.
Total Contamination, mg/kg.,
34
50
82
22
24
24 (max)
1a
1a
1a
1a
1a
1 (max)
5.
9. Copper Strip Corrosion 3hrs at 500 C
11.
Acid Value, mgKOH/g
0.15
0.16
0.48
0.16
0.15
0.50 (max)
12.
Methanol, % by wt.,
NIL
0.03
0.015
Nil
Nil
0.20 (max)
13.
Ethanol, % by wt.,
NIL
0.001
Nil
Nil
Nil
0.20 (max)
14.
Ester Content, % by wt.,
99.71
99.89
99.64
99.5
99.7
96.5 (min)
15.
Free Glycerol, % by wt.,
Nil
NIL
Nil
Nil
Nil
0.02 (max)
16.
Total Glycerol, % by wt.,
Nil
NIL
Nil
Nil
Nil
0.25 (max)
17
Iodine Value
152
76.91
96
97
95
18
Oxidation Stability at 1100 C,Hrs
4
1hr 45min
20 min
3.5
5
13
6 (min)
Effect of Oxidation Stability Additives
SIAM
KARANJA B 100 (T) OXIDATION STABILITY WITH DIFFERENT
ADDITIVES
JATROPHA B 100 OXIDATION STABILITY WITH DIFFERENT
ADDITIVES
7
16
12
13.21
8
8.09
4
9.19
5.53
STABILITY, hrs
STABILITY, hrs
6
14.24
6.37
5
4
4.15
3
2
4.52
3.55
1
2.26
0
0
J
J+L
J+B
J+T
TK
J+V
TK+L
TK+T
TK+B
TK+V
M &M , P -2, J UNE 08 RRP
SOYBEAN B 100 OXIDATION STABILITY WITH DIFFERENT
ADDITIVES
KARANJA B 100 (FES) OXIDATION STABILITY WITH DIFFERENT
ADDITIVES
7
8
5
6.1
4
3
2
1
4
4.08
4.11
4.26
TS + B
TS + T
4.34
3.23
0.14
0.4
1.05
1.31
BK
BK + T
BK + L
BK + B
0
M &M , P -2, J UNE 08 RRP
STABILITY, hrs
STABILITY, hrs
6
0
BK + V
TS
M &M , P -2, J UNE 08 RRP
TS + L
TS + V
14
Storage Stability of Bio-Diesel
SIAM
• Biodiesel ages more quickly than fossil diesel fuel
due to the chemical structure of fatty acids and
methyl esters present in biodiesel.
• Typically up to 14 types of fatty acid methyl esters
in the biodiesel.
• Saturated fatty acid methyl esters (C14:0, C16:0)
increase cloud point, cetane number & improve
stability whereas more poly-unsaturates (C18:2,
C18:3) reduce cloud point, cetane number and
stability.
15
Cold Flow Properties of Bio-Diesel
SIAM
At low operating temperature, fuel thickens & affect
flow to fuel lines, fuel pumps & injectors –
Deteriorates Performance.
Cold filter plugging point of biodiesel is very poor
CFPP depends on Raw material used for Bio-Diesel –
Karanje, Palm etc has poor CFPP. Jatropha has good
CFPP
Need to include CFPP in Bio-Diesel Specs
16
Potential FIE /Engine Problems
Fuel
Characteristics
•Fatty acid methyl
esters
•Free Methanol in
Biodiesel
•Biodiesel process
chemicals
•Dissolved water in
Biodiesel
•Free water in
mixtures
•Free glycerin,
mono- & diGlyceride
Effect
SIAM
Failure Mode
•Causes some Elastomers including
nitrile rubbers to soften, Swell
•Fuel Leakage
•Corrodes Aluminums & Zinc
•Low Flash point
•Corrosion of FIE
•Potassium & Sodium compounds ,
Solid particles
•Blocked nozzles
•Reversion of Biodiesel to fatty acid •Filter plugging
•Corrosion, sustains bacteria
•Increase conductivity of fuel
•Corrosion of FIE
• Sludging
•Corrodes non ferrous metals,
•Soaks cellulose filters,Sediments
on moving parts & lacquering
•Filter clogging
•Injector coking
17
Potential FIE /Engine Problems
SIAM
Free fatty acid
•Provides an electrolyte &
hastens corrosion of Zinc
•Salts of Organic acids
compounds formed
•Corrosion of FIE
•Filter plugging
•Sediments on parts
High Viscosity at low
Temperature
•Generates excessive heat
locally in rotary pumps
•higher stress on
components
•Pump seizures
•Early life failures
•Peer nozzle spray
Solid Impurities
•Potential lubricity
Problems
•Corrodes metallic parts
•Reduced service life
Acids (Formic,acetic)
Higher molecular
org. acids
•Similar to fatty acid
Polymerization
products
•Deposits especially from
fuel mixes
•Corrosion of FIE
•Filter plugging
•Lacquering formation in
hot areas
18
SIAM
Emission Advantage with Bio-Diesel
Pollutants
(g / km)
Percentage Improvement for each
Fuel
B10
B20
B100
HC
18
24
40
NOx
0.0
-2.6
-4
CO
0
0
0
CO2
0.4
-0.3
-1.6
PM
12
20
36
19
Emission Test results on SUV with CRDi meeting Euro III emission
Performance Study - Some Highlights
Test Description
SIAM
Effect Bio-diesel over Diesel
B10
B20
B100*
Fuel Economy (kmpl)
No change
No change
No change
Power @ Wheel (kw)
No change
1-2%
10-12%
Accn
speedwise
No change
No change
10%
distancewise
No change
No change
2%
Max Speed (kmph)
No change
No change
5%
Gradability (angle deg.)
No change
No change
-----
Engine Noise (db)
No change
No change
5%
* Engine tested as it is without modification over normal Diesel settings
20
Finding of Engine Durability studies
SIAM
If the Acid value, Moisture content & Oxidation Stability parameters of the fuel
exceeds the prescribed limits, ageing starts & Bio Diesel degrades to the point
where it is out of specifications
The Effects of fuel ageing on the Engine and FIP :
Ageing Product
Consequences for the FIE
Polymers, Insoluble
(gum, sludge)
•Filter clogging
•Deposit formation inside the entire FIE
•Sticking moving parts
•Injector coking
Polymers, Soluble
•Resin forming inside the entire FIE
Ageing acids
•Corrosion of metal parts
•Soap formation with metal ions deriving from
wear or corrosion (deposits)
Peroxides
•Embitterment of elastomers
21
Material Compatibility Results
Components /
Test Desc.
SIAM
Observations / Results
Fuel tank
Same as diesel till B10
Fuel Line / Hoses
Natural Rubber needs to be changed to Polymer
Fuel Filter
OK for B5 & B10
Material review required beyond B10
FIP
Natural rubber O-Rings, Seals and Gaskets to be
replaced with Viton Material
22
Engine Durability Aspects
SIAM
Ensuring Fuel Quality: OEMs are concerned that
Biodiesel which is not of adequate purity & quality affects
engine & fuel system component durability.
Ensuring Fuel Stability: Biodiesel may undergo oxidation
during storage, handling & use, causing fuel system
deposits. These deposits could cause plugging & damage
engine fuel system components.
23
Key Benefits Reported from Studies
SIAM
Benefits:
• Reduction in HC, PM, CO emission – % gain depends on Blend
ratio, vehicle type, Emission level etc
• No deterioration in performance of the vehicle in terms of Fuel
economy, Drivability up to B10 blends
• The cold temperature Startability & Performance good
• No Adverse effect on the engine durability
• Engine & FIP Wear within the prescribed limits
• Lube oil analysis results shows satisfactory results
• Fuel Filter life with B10 comparable to Neat Diesel
24
SIAM
Issues for Bio-Diesel Implementation
•OEMs recognize environmental & sustainability benefit of
Bio-Diesel & encourage its implementation in phases
•Sufficient Infra structure Facilities Should be Ensured for
Continuous Supply of Bio-diesel to Oil Companies for a
Sustained Mixing of Blends
•Govt policies & tax structure to encourage the rural
sector farmers to grow Jatropha or Kranje plantations.
Encourage private-public partnerships to work out viable
model for Bio-plant farming. Farmers need incentives to
get over the gestation period- 3 years for Jatropha & 5
years for Karanje
•B5 can be implemented in India in the near future.
Beyond that has to be proceeded after proper studies
25
SIAM
Issues for Bio-Diesel Implementation
•Ensure Fuel Quality is big Challenge & needs Specific
Attention. Moisture, Oxi. stability & Acid value require
Control.
•Ensure Bio-diesel Meets the specification IS 15607 & Be
Mandatory for Any Supplier of Bio-Diesel in India. Need
for Quality Bio-diesel is Still not Appreciated by Bio-diesel
manufacturers in India
•Durability issues with higher Blends have to sorted out
before considering it. Increase Deposit Forming
Tendencies on FIE Parts May Hamper Blends Above B10.
•Sufficient Lead Time Must be There Before Bio-Diesel
Implementation for Pilot Field Studies. FIE suppliers need
approve OEMs to go ahead with higher blends
26
SIAM
27