Combustion and Emissions

Characteristics of Biodiesel Fuel

Alan C. Hansen
Department of Agricultural and Biological Engineering
University of Illinois
CABER Seminar May 5, 2008

Outline of Presentation

Introduction
What is biodiesel?
What are its advantages and disadvantages?
How is biodiesel produced?
How much is being used at present?
How does it compare to other fuels?
Some fundamentals of combustion and emissions
Combustion and emissions comparisons between
biodiesel and diesel fuel using engine measurements
and models
Final comments

What is Biodiesel?
Technical Definition for Biodiesel
(ASTM D 6751):
Biodiesel, na fuel comprising mono-alkyl esters of long chain
fatty acids derived from vegetable oils or animal fats, designated
B100, and meeting the requirements of ASTM D 6751.

Conversion to ester reduces viscosity

to same level as diesel fuel and potentially
increases cetane number to be the same or
even higher than diesel fuel

What are the advantages of biodiesel fuel?

Renewable
carbon neutral

Biodegradable
benefits environment

Domestically grown
reducing imported oils

Low emissions
except maybe NOx

No engine modifications required

except replacing some fuel lines for older engines

Safer
less flammable

Non-toxic

Advantages of Biodiesel (cont.)

Very favorable energy balance, 3.2 to 1

Can be blended in any proportion with petroleum
diesel fuel
High cetane number and excellent lubricity
Very high flashpoint (>300F)
Can be made from waste restaurant oils and
animal fats

What are the disadvantages of biodiesel fuel?

Lower energy content

6-9% less energy per unit volume for B100
Effect of B2 B10 on power less than 1%

Soybean oil-based biodiesel will start to crystallize at

around 0C. This can be mitigated by blending with
diesel fuel or with additives.
Biodiesel is less oxidatively stable than petroleum diesel
fuel. Old fuel can become acidic and form sediments
and varnish. Additives can prevent this.
There is limited supply. Soybean oil is widely available
but expensive. Inedible animal fats are less expensive
but have limited supply.

Disadvantages of biodiesel

Cost is high and is feedstock sensitive

Government subsidies allow biodiesel to compete
with petroleum-based diesel fuel
3%

2%

7%

1%
12%

75%
Oil Feedstock
Energy
General Overhead

Chemical Feedstocks
Direct Labor
Depreciation
(Source: Van Gerpen, J., 2004)

How is biodiesel produced?

A simplified representation of biodiesel production:

Transesterification
Chemical reaction between methanol or ethanol and a vegetable
oil or animal fat
Requires a catalyst, such as caustic soda (NaOH) or KOH
Removal of glycerin reduces viscosity

Biodiesel Production: Soybeans

One Bushel
Soybeans

~1.5 gallons
Soybean oil

~1.5 gallons
Biodiesel

~10 litres
Soybean oil

~10 litres
Biodiesel

OR
100 kg
Soybeans

Why not use straight vegetable oil?

Viscosity too high (x 10 that of biodiesel)

Cetane number too low (below ASTM limit of 40)
Poor atomization causes coking and deposits in
combustion chamber
Reacts with lubricating oil to create sludge and
compromise lubrication

U.S. Biodiesel Production

450
400
350
300
Million
250
Gallons
200
Biodiesel
150
100
50
0
1999 2000 2001 2002 2003 2004 2005 2006 2007*
est.
(Source: National Biodiesel Board - www.biodiesel.org)
NBB goal: Replace equivalent of 5 % of nations on-road diesel
fuel with biodiesel by 2015

EU Biodiesel Cons.
(millions gallons)

Biodiesel Production in EU
1600
1400
1200
1000
800
600
400
200
0

EU Production
Capacity:
3 billion
gallons

1998 2000 2002 2003 2004 2005 2006 2007

Source: European Biodiesel Board (www.ebb-eu.org)

US and EU Biodiesel Production Comparison

3
2.5
2
Billion
1.5
Gallons/Year

1
0.5
0

US
US
EU
EU
Production Production Production Production
2007
Capacity
2006
Capacity
2007
2006

Diesel versus biodiesel consumption

US Gasoline Consumption: 146 Billion Gallons/year
60
50
40
Billion
30
Gallons/Year

20
10
0

US
US Diesel
Consumption Production
2007
2007

US
Production
Capacity
2007

EU
Production
2006

EU
Production
Capacity
2006

Biodiesel Usage at Present (U.S.)

as a low-level blend (B2 B5, B11)

for lubricity purposes non-sulfur formula
US EPA requirement for sulfur

15 ppm Oct 2006 for on-road vehicles

as a medium-level blend (B20-B50)

Energy Policy Act credit; federal incentive

as a neat fuel (B100)

6000
5000
4000

SL-BOCLE ASTM D 6078

Lubricity test
3400

3000
2000

5450

Increasing lubricity
with increasing
biodiesel %

3500

2600
2100

1000
(Source: Schumacher, L.G., 2004)

0
#2 Diesel

1/2% BD

1% BD

2% BD

100% BD

Source: McCormick (2006)

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@
36
26

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et
ha
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an
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LN
G
Et
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5

an
o

Pr
op
an

se
l

ol
in
e

Bu
t

G
as

Bi
od
i

D
ie

Energy Content (kJ/Litre)

Energy Density of Fuels

45000

40000

35000

30000

25000

20000

15000

10000

5000

Fossil Energy Ratio

Source: McCormick (2006)

Do we have enough land for oil crops from which to

produce biodiesel?
6,000-36,000 lbs
oil/acre

4500
4000
3500
3000
2000
1500
1000
500

Crop

ae
A
lg

Pa
lm

0
So
yb
e
Su an
nf
lo
w
er
Pe
an
ut
C
an
ol
a
O
liv
e
C
as
to
r
Ja
tr
op
ha
C
oc
on
ut

lbs oil/acre

2500

Source: Wikipedia

Soybean Fatty Acid Composition

90

Percentage Content

80
70
60
50
40
30
20
10
0
Palmitic Acid Stearic Acid
(C16:0)
(C18:0)
Min-Graboski
Max-NSRL2000

Oleic Acid
(C18:1)

Linoleic Acid Linolenic Acid

(C18:2)
(C18:3)

Max-Graboski
High Oleic Acid

Min-NSRL2000

Graboski, M.S. and R.L. McCormick, 1998. Combustion of fat and vegetable oil derived fuels in diesel engines.
Prog. Energy Combust. Sci. 24:125-164
NSRL, 2000. Illinois variety trials (2000), Varietal Information Program for Soybeans, NSRL

Range of Fatty Acid Composition

100

Percentage in Oil or Fat

90
80
70
60
50

Soybean
Rapeseed
Beef Tallow
Peanut
Canola
Olive
Coconut
Corn
Palm
Safflower

Sunflower
Sunola
Butterfat
Lard
Cottonseed
Crambe
Linseed
H.O. Safflower
Sesame

40
30
20

Upper
Lower
Average

10
0
C8:0 C10:0 C12:0 C14:0 C16:0 C18:0 C20:0 C22:0 C24:0 C18:1 C22:1 C18:2 C18.3

Fatty Acids

Cetane Number and Fatty Acids

(Source: Graboski and McCormick, 1998)

90
80
Cetane Number

70
60
50
40
30
20
10
0
Palmitic
(C16:0)

Stearic
(C18:0)

Oleic
(C18:1)

Linoleic
(C18:2)

Linolenic
(C18:3)

Methyl Esters

CN increase with increasing saturation and with increasing chain length

How a Four-Stroke Engine Works

Comparison of Conventional Engines and HCCI/LTC

Making gasoline engines run more like diesels and diesel engines more like gasoline

Some Combustion Chemistry:

Lean vs Rich Mixtures
Diesel fuel molecule represented as C16H34
Chemically correct air-fuel ratio assumes all fuel burnt
to CO2 and H2O
C16H34 + 24.5O2 + 92N2 92N2 + 16CO2 + 17H2O

1 kg

14.9 kg

3.1 kg

Chemically correct air to fuel ratio: 14.9: 1

Soybean biodiesel fuel molecule: C19H36O2
1 kg fuel and 12.5 kg air 2.8 kg CO2

Chemically correct air to fuel ratio: 12.5: 1

Requires less air
than diesel

Note the
Oxygen in
the fuel
molecule

Air-Fuel Mixing in Diesel Engines

Impossible to obtain uniform mixing of air & fuel in diesel

engine

Single spray plume

from injector
Rich Spray
Core
Correct
A/F Ratio
Lean A/F
Mixture

Very Lean
In betweencombustible
A/F ratio
Very
Rich

How is energy released in diesel combustion?

Premixed combustion
Fuel that evaporates and mixes with
air during ignition delay burns
simultaneously, producing sharp
peak in energy release

Diffusion (mixing-controlled)
combustion
Air and fuel vapor diffuse toward
each other to continue combustion
Slower process than premixed phase

Ignition delay controls proportions

of energy released in premixed &
diffusion combustion phases
IGNITION
DELAY

START
INJECTION

START
COMBUSTION

HDC

NOx/Soot Trade-Off and LTC Combustion

Fuel-Air Mixture
Leaner Richer

Increased
Soot Formation

LTC
Target

al
n
tio t
n
e oo
v
n /S ff
C o O x e- o
N ad
Tr

Increased
NOx Formation
Low

Combustion Temperature

LTC Low Temperature Combustion

High

Nonroad EPA Emission Standards

0.6

Tier I (1996)

PM (g/kWh)

0.5

EPA Emission Standards: Nonroad Diesel Engines

130kW Power 560 kW

0.4
0.3

Tier 3 (2006)

0.2

Tier 2 (2001-2003)*

Tier 4 (2011-2014)**

0.1
0

*Dependent on power range

**PM full compliance by 2011
NOx 50% compliance 2011-2013

10

NOx (g/kWh)
Source: www.dieselnet.com

Nonroad EU Emission Standards

0.6

Stage I (1999)

PM (g/kWh)

0.5

Europe Emission Standards: Nonroad Diesel Engines

130kW Power 560 kW

0.4
0.3

Stage IIIA (2006)

0.2

Stage II (2002)

Stage IV (2014)

0.1

Stage IIIB (2011)

NOx (g/kWh)

10

Source: www.dieselnet.com

Impact of Biodiesel on Emissions

0.25

0.12

1.60
1.40

0.20

-17%

1.00
0.80

0.10

0.05

-11%

5.00

-41%

4.80

-38%

0.06

4.60

0.04

4.50
0.02

0.20

B20

D2

4.40

0.00

0.00

B100

3%

4.70

0.40

0.00

10%

4.90
0.08

0.60

-84%

NOx emission (g/hp-hr)

5.10

0.10

-15%

1.20

0.15

PM emission (g/hp-hr)

CO emission (g/hp-hr)

HC emission (g/hp-hr)

B100

B20

D2

4.30
B100

B20

D2

B100

B20

D2

Key regulated emissions for compression-ignition (diesel)

engines are particulate matter (PM) and Oxides of Nitrogen
(NOx)
PM created from incomplete combustion
NOx caused by high temperatures in combustion chamber
oxidizing nitrogen

(Sharp et al., 2000)

U.S. EPA Emissions Regulations

0.7

Tier 1

0.6

C16:0
C18:0

PM (g/kWh)

0.5

C18:1
C18:2

0.4

C18:3

0.3

Diesel

Tier 2

Soydiesel
Tier 1

0.2

Tier 3

Tier 4

0.1

Tier 2
Tier 3
Tier 4

0
0

NOx (g/kWh)

Saturated fatty acid esters produce lower emissions

(Data Source: Graboski and McCormick, 1998)

10

MechSE Optical Engine Facility

Quartz Piston
Side Window

3-D Imaging

Piston Extension

Hydraulic System

Implement high speed camera and laser

techniques
Analyze combustion products and
exhaust gases
Investigate effect of multiple injection
strategies for Low Temperature
Combustion (LTC)

Soot Diagnostics: Back Illumination Light Extinction

Fiber from
Copper vapor laser

Light
Diffuser

Band pass
Filter

Narrow band pass filters (~ 5nm) to reduce combustion noise,

Frame rate: 12000 fps
Measurement area denoted by the black rectangle
Due to the curvature of two side-windows only part of soot is
measured

Single versus Split Injection

Single

Split

Effect of Split Injection

Up to 5 independent fuel injections per cycle are now achievable

at the prototype level from the major Fuel Injection Equipment
suppliers
SAE 940897

Effect of Split Injection (cont.)

SAE 940897

Flame Development Comparison: B0 and B100

B0: -20, 0

B100: -20, 0

-7.00

3.50

5.75

8.00

14.00

20.00

26.00

38.00

18.50

20.00

26.00

38.00

B100: - 30, 10

Biodiesel fuel results in faster late

cycle burning of soot than European
low sulfur diesel fuel

Increasing gap between first injection and main injection helps reduce soot
emissions

(Lee et al. 2006)

Soot Images Comparison: B0 and B100

B0: -20, 0
Crank angles: 41, 47, 53, 65, 77, 89,
128 CAD ATDC

B100: -20, 0
Crank angles: 41, 47, 53, 65, 77, 89,
128 CAD ATDC

Bio-diesel leads to weaker soot signal

than European low sulfur diesel fuel

(Lee et al. 2006)

Biofuel Combustion and Emissions Modeling

KIVA combustion model modified for

biodiesel and LTC
KIVA-3V: 3-D chemically reacting CFD model
developed by Los Alamos National Laboratory to
simulate work of internal combustion engines
Sub-models for wall heat transfer, evaporation,
turbulence, spray breakup, ignition, combustion
and emissions formation
Both biodiesel and biodiesel-diesel blend
combustion modeled

Biodiesel Property Measurement and

Computation for Combustion Modeling
Fatty Acid Profiles for Five Biodiesel Types
70
60
50
Percentage

Soybean
Rapeseed

40

Coconut
30

Palm
Beef Lard

20
10

Measured properties of biodiesel

produced from source materials with a
broad range of fatty acid compositions
Updated computational models for
estimating viscosity, surface tension,
density, thermal conductivity for engine
combustion modeling

0
C12:0

C14:0

C16:0

C18:0

C18:1

C18:2

C18:3

Fatty Acid

Kinematic
Viscosity of
Biodiesel
from five
different
source
materials

Kinematic Viscosity,mm^2/s

Soybean

Rapeseed

Coconut

Palm

Beef Lard

#2 Diesel

7
6
5
Max. limit ASTM D975 @ 40C

4
3
2
1
0
20

30

40

50

60

70

Temperature, C

80

90

100

BDProp
Program for
computing
biodiesel fuel
properties

KIVA Combustion Model results

Biodiesel

Diesel

Fuel injections at 330 and 370

(Lee et al. 2008)

NOx Emissions from Biodiesel (Lee et al. 2008)

Retarding main injection effectively reduces the emission

Biodiesel may or may not increase NOx emission

NOx Emissions from Biodiesel

National Renewable Energy Lab reports no consistent effect

Lab tests tend to show increase
Chassis tests not conclusive
Emissions affected by test cycle and engine technology

Metal Engine Experiments

6.0

John Deere 4045HF475 4-cylinder

4.5L engine (Tier II)
Effect of Exhaust Gas Recirculation on
NOx emissions from biodiesel and
blends

1400 rpm, 500 Nm

5.0
BSNOX (g/kw-h)

4.0
3.0
2.0
D2

1.0
Particulate filter

10

B2
15

EGR (%)

Heat exchanger

EGR Valve

Low Pressure
EGR System

B20
20

B100
25

Graduate Automotive Technology Education

Center of Excellence
for
Advanced Automotive Bio-Fuel Combustion Engines
Mechanical Science
and Engineering

Agricultural and
Biological Engineering
Comprehensive GATE
syllabus (M.S./Ph.D)

DOE support
(GATE fellowships)

Industrial advisory
board

Highly skilled UIUC graduates who can lead

industrial application of bio-fuel engine technology

Final Comments

Biodiesel fuel as an alternative to petroleumbased diesel fuel has many advantages

Fuel cost still plays a major role
Source material can affect biodiesel fuel
properties substantially
While CO, HC and PM emissions are
reduced, NOx emissions may increase in
some engines
Optical engine tests and combustion
modeling provide insight into combustion
and emissions processes
Biodiesel shows some advantages over diesel
fuel when Low Temperature Combustion
strategies are applied

Thank you!

achansen@uiuc.edu