Rudy Smaling

November 3, 2006

Biodiesel and Air Quality

HARC Brownbag Presentation

"The use of vegetable oils for engine fuels may seem insignificant today.
But such oils may become in the course of time as important as the
petroleum and coal tar products of the present time"

Rudolph Diesel, 1912

1
Biodiesel and Air Quality - Overview
• Fundamentals

• Production

• Fuel Properties

• Engine Exhaust Emissions

• Life Cycle Analysis

• Local Policy Issues

2
What is Biodiesel?

• Mono-alkyl esters of fatty acids (i.e. methyl or ethyl esters)

Oleic Acid Linoleic Acid Linolenic Acid

• Must meet the quality requirements of ASTM D6751

• Biodiesel is not unrefined vegetable oil or used cooking oil
• Typically used as a blend with petroleum diesel

3
What is Biodiesel Often Claimed to be?
Biodiesel is a non-toxic* fully renewable* fuel produced
from new or used vegetable or animal oil or fat that can
be run in any* diesel engine without any* modification
and is virtually sulfur free*
• Not quite non-toxic (biocides, antioxidants, process leftovers)
• Not fully renewable (methanol input, energy required to grow
feedstock and process seeds and oils)
• Not in any diesel engine (only up to up to B5 – B20)
• Not without modifications (fuel injection system and controls,
no natural rubbers, different maintenance schedule)
• Biodiesel lifecycle SO2 emissions are comparable to petroleum
diesel lifecycle SO2 emissions

4
Biodiesel is a Renewable Fuel, Although…

• Many lifecycle analyses (LCA) show that biodiesel is a

largely renewable fuel
• NREL studies found that it takes 0.31MJ of fossil energy
to generate 1 MJ of biodiesel energy, similar figures have
been reported from other sources
• A more recent LCA1 suggests that it takes 1.08-1.32 MJ
of fossil energy input for every 1MJ of biodiesel energy
• Higher energy inputs into Soy agriculture
• Electricity, herbicides, machinery, fuel, fertilizers, lime,…
• Still considered far more energy efficient than ethanol
1
Pimentel, D., T.W. Patzek, 2005
5
Biodiesel Delivery Infrastructure

6
Typical Oil Crop Yields
litres US
Crop kg oil/ha lbs oil/acre
oil/ha gal/acre
corn (maize) 145 172 129 18
cotton 273 325 244 35
hemp 305 363 272 39
soybean 375 446 335 48
linseed (flax) 402 478 359 51
pumpkin seed 449 534 401 57
mustard seed 481 572 430 61
camelina 490 583 438 62
sesame 585 696 522 74
safflower 655 779 585 83
rice 696 828 622 88
sunflowers 800 952 714 102
cocoa (cacao) 863 1026 771 110
peanuts 890 1059 795 113
opium poppy 978 1163 873 124
rapeseed 1000 1190 893 127
olives 1019 1212 910 129
castor beans 1188 1413 1061 151
pecan nuts 1505 1791 1344 191
jojoba 1528 1818 1365 194
jatropha 1590 1892 1420 202
macadamia nuts 1887 2246 1685 240
brazil nuts 2010 2392 1795 255
avocado 2217 2638 1980 282
coconut 2260 2689 2018 287
oil palm 5000 5950 4465 635

http://www.Journeytoforever.org
7
Some of the (Texas) Air Quality Concerns
• An additional 5 million acres of land is required to grow
feedstock to feed Texas biodiesel production plants
• 200,000,000 gallon current and planned production capacity
• Average Soy crop yield of 48 gallons/acre
• Resulting agricultural emissions? Water Use? Fertilizer? Etc…

• Most of the Texas production facilities are located (or locating)

in non-attainment areas
• Significant emissions added to non-attainment areas?

• In-use emissions of most pollutants will decrease with biodiesel

• Significant reductions of PM, HC, and CO
• Considerable uncertainty regarding NOx
• Little (relevant) data compared to TxLED baseline fuel

8
Biodiesel and Air Quality - Overview
• Fundamentals

• Production

• Fuel Properties

• Engine Exhaust Emissions

• Life Cycle Analysis

• Local Policy Issues

9
Basic Biodiesel Production Process

Vegetable Oils Recycled Greases

Dilute Acid Sulfuric Acid

Esterification + Methanol

Methanol + KOH Transesterification

Methanol Recovery Crude Glycerin Crude Biodiesel

Glycerin Refining Refining

Glycerin Biodiesel

10
Rapeseed Oil to Rapeseed Methyl Ester (RME)

11
Making Biodiesel is Easy…Too Easy?

• Biodiesel is extremely easy to make:

• Obtain clean oil (any vegetable or animal oil)
• Add Methanol and Lye (KOH)
• Stir and wait for glycerin to settle
• Pour off “biodiesel”

• Many small-batch biodiesel producers

around that give biodiesel a bad name
• Poor quality, consistency, etc…

• This has led to the BQ9000 certification

BiodieselProject.gvp

12
Biodiesel Processing Mass Balance

Input Output
• Virgin oil 1000 kg • Biodiesel 942.4 kg
• Potassium Hydroxide 9.3 kg • Glycerin + Impurities 206.9 kg
• Methanol 140 kg

• Total Input 1149.3 kg • Total output 1149.3 kg

13
Annual Biodiesel Production
• 2006 annual biodiesel production
is estimated at 250M gallons
• 2006 annual biodiesel production
capacity is 580M gallons
• 2007 annual biodiesel production
capacity is planned to be 1.4B
gallons
• 2005 annual petroleum diesel production was 49B gallons
• Biodiesel share of total diesel production is 0.15%
• Projected to grow to 0.5% in 2006
• Assuming representative crop yields (50 gal/acre):
• 2006 biodiesel production requires 7,812 sq miles of crop land (~NJ)
• 2006 biodiesel capacity requires 18,125 sq miles of crop land (~WV)
• 2007 estimated capacity requires 43,750 sq miles of crop land (~OH)
• Complete displacement of petroleum diesel requires 1.54M sq miles (~6X TX)

14
Current Biodiesel Production Plants September 13, 2006

• US total 2006 biodiesel production capacity is ~580,000,000 gallons/year

• Texas: 13 plants with a combined capacity of ~100,000,000 gallons/year

National Biodiesel Board

15
Biodiesel Plants Under Construction September 12, 2006

• 2007 US biodiesel production capacity estimated to be ~ 1.4B gallons/year

• Texas: 9 plants with a combined capacity of ~100,000,000 gallons/year
National Biodiesel Board
16
 Texas Ozone Non-Attainment Areas

17
An alternative Biodiesel?

• Nestle Oil has developed a

“next generation” biodiesel
• Hydrogenation the fatty
acid feedstock resulting in a
HC biodiesel they call
NExBTL (next generation
biomas to liquids)
• The 100% paraffin fuel has superior properties compared to either
ultra low sulfur diesel or biodiesel (ULSD)
• Emissions testing by Scania shows significant decreases in both PM
(~25%) and NOx (~18%) compared to European ULSD
• 60,000,000 gpy plant being built in Porvoo, Finland at a cost of
$125M. Fuel cost?
Nestle Oil

18
Biodiesel and Air Quality - Overview
• Fundamentals

• Production

• Fuel Properties

• Engine Exhaust Emissions

• Life Cycle Analysis

• Local Policy Issues

19
Definitions

• Cloud Point: Temperature at which fine crystals are first

visually observed as the fuel is cooled
• Cold Filter Plug Point: Temperature at which enough
crystals have agglomerated to plug the fuel filter
• Cetane number: A measure of a fuel's willingness to
ignite when it's compressed. Higher Cetane number
indicates a greater willingness to ignite
• Iodine Value: A measure of the level of saturation of
the oil (m)ethyl-ester. Low Iodine Number indicates
high saturation

20
Oils, melting points and Iodine Values
• Iodine Value (IV) is a measure of the Approx.
number of double bonds (indicating Oil
melting Iodine
the level of saturation) in the methyl- point Value

ester molecule Coconut oil

(deg C)
25 10
• The IV is an indication of the Palm kernel oil
Mutton tallow
24
42
37
40
oxidative stability of both the oil and Beef tallow - 50
methyl-ester of that oil Palm oil 35 54
Olive oil -6 81
• Oxidation initially results in Castor oil -18 85
hydroperoxides, but can also lead to Peanut oil 3 93
polymerization Rapeseed oil
Cotton seed oil
-10
-1
98
105
• Iodine Value is also an indication of
Sunflower oil -17 125
Soybean oil -16 130
the melting point (or cloud point) of Tung oil -2.5 168
the oil and oil methyl-ester Linseed oil -24 178
Sardine oil - 185
• EN 14214 calls for a max. IV of 120 http://www.Journeytoforever.org

21
Various Methyl Esters Cetane Number

DOE/GO-102006-2288
22
Composition of Various Biodiesel Feedstocks

DOE/GO-102006-2288
23
Cetane Number of Various Biodiesels

TxLED requires a minimum Cetane number of 48

DOE/GO-102006-2288
24
In Summary
• Good cold flow properties require a highly unsaturated
biodiesel fuel
• Combustion performance, fuel oxidation and polimerization are problems

• Fuel stability and good combustion require a highly

saturated biodiesel fuel
• Viscous or solid at low temperatures

• However, local Biodiesel properties are driven by

regionally available feedstocks
• Reality results in a compromise fuel
• Fuel additives may be a solution, but Cetane enhancers
have shown little effect on newer engines

25
NExBTL Holds Promise…But at What Cost?

Nestle Oil

26
National Standards for Biodiesel
Czech
- Europe Austria Republic France Germany Italy Sweden USA Australia
Standard/ Journal ASTM D- Fuel Std.
specification EN 14214 ON C1191 CSN 65 6507 Officiel DIN V 51606 UNI 10635 SS 155436 6751 (Biodiesel)
Date 2003 Jul-97 Sep-98 Sep-97 Sep-97 Apr-97 Nov-96 Jan-02 Sep-03
Application FAME FAME RME VOME FAME VOME VOME FAMAE -
860 to 890
Density 15°C g/cm 0.86 -0.90 0.85 - 0.89 0.87 - 0.89 0.87 - 0.90 0.875 - 0.90 0.86 -0.90 0.87 - 0.90 - kg/m3
Viscos. 40°C mm2/s 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 3.5-5.0 1.9-6.0 3.5-5.0
90% @
Distillat. 95%°C - - - <360 - <360 - 360°C <360
Flashpoint °C >120 >100 >110 >100 >110 >100 >100 >130 >120
CFPP °C *country
(cold filter plug specific 0/-15 -5 - 0/-10/-20 - -5 - -
Sulfur % mass <10 mg/kg <0.02 <0.02 - <0.01 <0.01 <0.001 <0.05 <10 mg/kg
Water mg/kg <500 - <500 <200 <300 <700 <300 <0.05% vol. <0.05% vol
Total contam. mg/kg <24 - <24 - <20 - <20 - <24
hrs;110°C 6 hours min - - - - - - - 6 hours min
Cetane No. >51 >49 >48 >49 >49 - >48 >47 >51
Methanol % mass <0.20 <0.20 - <0.1 <0.3 <0.2 <0.2 - <0.2
Ester cont. % mass >96.5 - - >96.5 - >98 >98 - >96.5
Free glycerol
% mass <0.02 <0.02 <0.02 <0.02 <0.02 <0.05 <0.02 <0.02 <0.02
Iodine No. <120 <120 - <115 <115 - <125 - -
<0.001%
Phosphor mg/kg <10 <20 <20 <10 <10 <10 <10 mass <10
http://www.Journeytoforever.org

27
US Fuel Quality Specifications
• ASTM D6751 Specification for B100 for Blending currently being
modified to:
• Generally tighten the specification and improve quality
• Address stability concerns of OEMs
• Ensure compatibility with 2007/2010 diesel technology

• B20 finished fuel specification in progress

• Users, OEMs want B20 specification ASAP
• Recently balloted at ASTM -failed on lack of oxidation stability spec. for B20

• Additional research is required to define test methods and

specification limits
• Limiting factor is lack of data relating fuel stability, fuel stability test
results, and deposit formation in engines
• Limits added recently for calcium and magnesium (ASTM D-6751-06a)

28
Potential Fuel Injection Equipment Failures
Fuel Characteristic
Fatty acid methyl esters (general)
Free methanol in biodiesel
Biodiesel process chemicals
Dissolved water in biodiesel
Free water in mixtures
Free glycerin, mono- & di-glyceride
Free fatty acid
Higher modulus of elasticity
High viscosity at low temperature
Solid impurities
Corrosive acids (formic & acetic)
Higher molecular organic acids
Polymerization products
29
Effect Failure Mode
Causes some elastomers including nitrile
rubbers to soften, swell, or harden and Fuel leakage
Corrodes aluminum & zinc
Low flash point Corrosion of FIE
Potassium and sodium compounds
Solid particles Blocked nozzles
Reversion of biodiesel to fatty acid Filter plugging
Corrosion Corrosion of FIE
Sustains bacteria Sludging
Increases the electrical conductivity of
fuel
Corrodes non ferrous metals Filter clogging
Soaks cellulose filters
Sediments on moving parts and
lacquering Injector coking
Provides an electrolyte and hastens the
corrosion of zinc Corrosion of FIE
Salts of organic acids Filter plugging
Organic compounds formed Sediments on parts
Increases injection pressure Potential of reduced service life
Generates excessive heat locally in
rotary distributor pumps Pump seizures
Higher stressed components Early life failures
Poor nozzle spray atomization
Potential lubricity problems Reduced service life
Aging products
Corrodes all metallic parts Corrosion of FIE
Similar to fatty acid
Filter plugging
Deposits especially from fuel mixes Lacquering formation in hot areas
Biodiesel and Air Quality - Overview
• Fundamentals

• Production

• Fuel Properties

• Engine Exhaust Emissions

• Life Cycle Analysis

• Local Policy Issues

30
Criteria Pollutant Emissions Effects

EPA
31
Particulate Matter PM Emissions
• Testing performed with a CCRT
paticulate filter
• Balance Point Temperature (BPT)
significantly lower for B100
• Cert fuel: ~360 C
• B20: ~320 C
• B100: ~250 C

• The lower BPT is thought to be

responsible for higher DPF
regeneration rates
• This explains the additional PM
reductions in a CCRT + B20
combination
NREL Milestone report: NREL/TP-540-39606

32
Potential for Future PM Reductions
• Increased fuel consumption for biodiesel lies around 2-3%
for a B20 blend, commensurate with the lower energy
content of the biodiesel
• Total fuel penalty for a DPF + B20 combination ~ 5%
• However, many HD truck have mild duty cycles resulting in
low exhaust temperatures requiring active PM regeneration,
with fuel penalties approaching 10%
• A biodiesel fuel (B20-B100) may allow the use of passive PM
filter systems where active systems would otherwise be
required
• Additional savings can be obtained from optimized filter
designs for dedicated biodiesel applications
NREL Milestone report: NREL/TP-540-39606

33
Comparison of Data to Basic NOx Correlation

• EPA compiled and

studied a large dataset
of biodiesel tests
• Study published in 2002
covered only older
engines
• All testing was engine
dynamometer based
• The data shows significant scatter in the NOx results
• Unsure whether averaging the data was appropriate given that
the feedstock, test engines, and test protocols were not
representative

34
Composition of Various Biodiesel Feedstocks

DOE/GO-102006-2288
35
NOx From Single Types of Methyl Esters

DOE/GO-102006-2288
36
NOx Emissions From Various B100 Fuels

DOE/GO-102006-2288
37
Biodiesel Composition effects on NOx

• Reiterates previous slides: higher

un-saturation results in higher NOx
emissions
• For a B20 blend, a NOx neutral
Iodine Value lies around 95 (based
on the EPA biodiesel database)
• This suggests that higher and lower
I.V. fuels may be a strategy to
eliminate the NOx increase in older
engines

NREL
38
Biodiesel NOx Engine Effect

• It is speculated that the higher bulk modulus for biodiesel fuel causes more rapid
needle lift in the fuel injector, advancing fuel injection timing, this effect is larger
in newer (higher pressure) fuel injection systems

39
Biodiesel Bus Chassis Dynamometer Testing
• B20 vs. conventional diesel fuel
• In-use buses tested (40,000 lb
GVWR)
• City Suburban Heavy Vehicle Cycle
(CSHVC) at 35,000 lb inertia
• Cummins ISM 2000 Engine –No
EGR
• Expected reductions (g/mile basis)
• PM ≈18%
• HC ≈29%
• CO ≈24%
• Fuel Economy ≈3%
• Unexpected reductions in NOx
• 4% reduction
• statistical confidence > 99%

40
Comparison of engine and Vehicle Emissions

• EPA predictive model based

on engine dynamometer data
• Model results compared here
to vehicle (chassis
dynamometer) test results
• On average NOx is reduced in
vehicle testing
• The bottom line on biodiesel and NOx:
• There are insufficient data, and insufficiently representative data,
to draw any conclusions regarding the average effect of biodiesel
on NOx emissions, even directionally

41
NExBTL Shows Significant NOx and PM Reductions

All testing on Scania Euro 4 engines

Scania

42
Aggregate Toxics Effect of Biodiesel

From a USEPA study:

• Formaldehyde and
acetaldehyde emissions from
biodiesel are 30% lower than
from petroleum diesel
• PAH and NPAH emissions are
reduced by more than 85%

From a European study (Institute of Biosystems Engineering):

• Formaldehyde emissions can be anywhere from -10% to +50%
compared to petroleum diesel (seems test method dependent)
• Shows far smaller decreases in PAH emissions (5-50%)
USEPA Institute of Biosystems Engineering, Federal Agricultural
Research Centre, Braunschweig, Germany
43
More Detailed Toxics Data
• Available toxics data evaluating Correlation of % change in toxics with % biodiesel
effects of biodiesel provides few % change in toxics = c × (% biodiesel) × 100%

answers
• Quantitative effects are
inconclusive as are directional
effects

Institute of Biosystems Engineering, Federal Agricultural

Research Centre, Braunschweig, Germany EPA420-P-02-001

44
Effects on Emissions Control Systems

• Effect on Diesel Particulate Filter (DPF) performance is

very positive
• Data shows that biodiesel soot is more reactive, contains oxygen, is less
carbonaceous with a higher soluble organic fraction
• Filter regenerates at lower temperatures at greater rates

• Some concern exists regarding process chemicals

Calcium, Potassium, Sodium, and Magnesium
• These chemicals can negatively affect ceramic substrate durability

• No data is available at all for biodiesel fuel effects on

NOx emissions control technologies such as Selective
Catalytic Reduction, Lean NOx Catalysts, or NOx traps

45
Biodiesel and Air Quality - Overview
• Fundamentals

• Production

• Fuel Properties

• Engine Exhaust Emissions

• Life Cycle Analysis

• Local Policy Issues

46
 Lifecycle Air Emissions for Biodiesel
(gr/bhp.hr)

47
Lifecycle Air Emissions for Petroleum Diesel
(gr/bhp.hr)

48
Lifecycle Air Emissions comparison (gr/bhp.hr)
Lifecycle Air Emissions
Production Cycle Air Emissions
Excluding Foreign Emissions
0.9

N2O Petroleum
0.8
Biodiesel

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

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SO
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N

N
NM

xP
0x
de

10

10
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or
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00
10

49
Ecological Effects of RME Substitution

IFEU – Institut für Energie- und Umweltforschung Heidelberg, Germany

50
Biodiesel Lifecycle Emissions Summary
• On a lifecycle basis:
• CH4, SOx, HF, PM, and CO are
positively affected
• NOx, HCL, HC, and NH3 are negatively
affected

• Analyzing data can be difficult

• National averages assumed
• Specific case study for Chicago was
presented showing additional
advantages from the national average

• Studying the Texas case would be

of value
• Texas is the largest biodiesel producer
• Mostly using imported feedstocks
• Unique electric grid

51
Net CO2 Life Cycle Emissions

• This analysis is for biodiesel

derived from Soybeans
• B100 emits 10% more CO2
at the tailpipe compared to
petroleum diesel
• B100 emits 78% less CO2
based on non-renewable
sources only
• These numbers depend on
many assumptions!

52
Various Tax and Other Credits

• Biodiesel or ethanol blended with taxable diesel, that is

identified when sold or used as a biodiesel or ethanol
fuel blend, is exempt from the diesel fuel tax.
(Reference Texas Statutes, Tax Code, Sections 162.001
and 162.204)
• Blender credit of $0.01 per percent biodiesel blended
into petroleum diesel
• Some concerns: reports that some fleets are blending their own B99 fuel to
get the maximum credit without regard for engine durability effects
• Another reported loophole: some companies import cheap palm oil, blend in
some petroleum and sell off to foreign markets…

53
Biodiesel and Air Quality - Overview
• Fundamentals

• Production

• Fuel Properties

• Engine Exhaust Emissions

• Life Cycle Analysis

• Local Policy Issues

54
Texas Fuel Specification Rule
• Texas implemented requirements for a Texas Low
Emissions Diesel fuel formulation (TxLED)
• Must contain less than 10% aromatics and have a
cetane number of at least 48 (compared to 40 for EPA
#2 diesel and 50 for CARB spec low sulfur diesel)
• Impacts only the non- and near-non-attainment areas
in Texas
• Any biodiesel or biodiesel blend must meet these same
specs or cannot be sold or used in the affected counties
• In fact, biodiesel (blends) must not emit more NOx than
TxLED certified fuels

55
So What’s the Issue?
• Texas is the largest biodiesel producer in the nation with
production facilities near HGA and DFW
• AG and Energy industries and petroleum independence
advocates all want biodiesel for various reasons
• TCEQ is responsible for meeting air quality targets and is
putting on the brakes…
• Old data suggests NOx increases
• Old data based on engine based testing which is still both a TCEQ, EPA, and
CARB requirement
• New data from vehicle based testing shows decreases in NOx, however there
are no vehicle based test protocols (yet)

• TCEQ (Mr. Shanbacher) on record saying “proper science and

supporting data is lacking to make a decision for biodiesel”

56
What can/should HARC do?
• Data, data, data
• Impact of biodiesel production in the (near) non-
attainment areas?
• What if a B5 or B20 would be allowed in all of Texas?
• What feedstocks? Additional fuel specs?
• NOx emissions? Ozone forming potential?
• Vehicle based test protocols (same issue with Hybrids, any synergies?)

• Planning a biodiesel workshop to develop a scope of work

that may allow us to answer these questions through
modeling
• The question is: what model inputs are required and how
do we obtain that required data?

57
 Questions?

58