National Renewable Energy Laboratory Biodiesel: Emissions & Health Effects K. Shaine Tyson Treasure Valley Air Quality Workshop October 1, 2003 Operated for the U.S. Department of Energy by Midwest Research Institute • Battelle • Bechtel
National Renewable Energy Laboratory
Biodiesel:Emissions & Health Effects
K. Shaine Tyson
Treasure Valley Air Quality WorkshopOctober 1, 2003
Operated for the U.S. Department of Energy by Midwest Research Institute • Battelle • Bechtel
DOE Office and Program StructureOffice of Energy Efficiency and Renewable Energy
David Garman
National Renewable Energy LaboratoryShaine Tyson
Bob McCormick
Office of Technology DevelopmentRichard Moorer
PROGRAMSSolar
Wind & HydropowerGeothermal
Distributed Energy, Electric Infrastructure & Reliability
BiomassIndustrial Technology
Freedom Car & Vehicle TechnologyHydrogen & Infrastructure
Building TechnologiesWeatherization & Intergovernment Grants
FEMP
Office of The Biomass ProgramDouglas Kaempf
What is BiodieselDefined by ASTM, EPA and DOE and byeach State’s Weights and MeasuresAgency or State Regulations
“A fuel consisting of long-chain fatty acid alkylesters made from renewable vegetable oils,recycled cooking greases, or animal fats “ thatmeets ASTM standardsASTM D 6751 - 02
Biodiesel Terminology
Pure biodiesel or 100% Biodiesel (B100)Also called NEAT Biodiesel
Biodiesel BlendBXX for XX% biodieselB20 is 20% biodiesel and 80% petro diesel fuelB50 is 50% biodiesel and 50% petro diesel fuel
Avoid calling blends “biodiesel” because itcan lead to a lot of confusion!
What is true for B100 may not be true for B20And visa versa
Biodiesel Manufacturing
Glycerinmolecule
Biodieselmolecules
Triglyceride:Fat or Oilmolecule
Pictures provided by
Campa® als Kraftstoff
0
5
10
15
20
25
30
1998 1999 2000 2001 2002 2003
Mil
gal
00.511.522.533.54
$/ga
l
Sales Price
Sales Volume and Price Trends
estimated
2001-2003 Prices incorporate effect of USDA subsidy for soybiodiesel ranging between $0.85 and $1.30/gal B100. Assumedextended through 2003.
2001-2003 Prices incorporate effect of USDA subsidy for soybiodiesel ranging between $0.85 and $1.30/gal B100. Assumedextended through 2003.
Benefits of BiodieselUse just like No. 2 diesel fuel in existingequipment with no modifications in mostcasesOn-road and off-road transportation
B20 is a drop in technology, no changes toequipment or infrastructureB100 requires careful management, but fewchanges to equipment
Electric generators similar to transport issuesHeating oils
Blends up to 20% with heating oil No. 2
Benefits of BiodieselBTU Content (121,000 BTU/gal)
Diesel No. 2 averages 131,000Diesel No. 1 averages 126,000
High Lubricity (Over 6000 g SLBOCLE)1% or less can improve a poor lubricity diesel fuel by 40%
BiodegradableUsed as a clean up technology with oil spills
Non Toxic in small quantitiesFatty acid methyl esters listed as a food additive with FDADO NOT DRINK!
Safer to use than dieselVery high flash point
EPA Emission Analysis
B20 NOx Emissions are Within Legal LimitsD2 and B20 Emissions Improving over Time
Increase is Consistent Across Time & Engine Types
02468
101214
6V-7
1N-7
7M
UI
DD
C-6
V-
92T
A-8
7
6V-9
2TA
-81
/89
MU
I
6V-7
1N-7
7M
UI
6V-9
2TA
-88
DD
EC
II
Cu
mm
ins
N14
198
7
Cu
mm
ins
L10
198
7
DD
C 6
019
89
DD
C60
1991
DD
C 6
019
91
Cu
mm
ins
B5.
9 R
ME
Cu
mm
ins
B5.
9 R
EE
g N
Ox/
bhp-
hr
D2 B20
All Data EPA HD FTP Composite & Replicated Hot Starts
Biodiesel (B100) NOx Emissions
0%
2%
4%
6%
8%
10%
12%
14%
16%
Perc
enta
ge c
hang
e in N
Ox
g/bh
p-hr
EPAHighwayDiesel
Lard EdibleTallow
InedibleTallow
YellowGrease 1
YellowGrease 2
Canola Soy
O2 content = 0% 11.82% 11.74% 11.08% 11.10% 11.28% 11.04% 11.16%
B100 - CO, HC, PM Emissions
-80
-70
-60
-50
-40
-30
-20
-10
0
Perc
enta
ge c
hang
e in
Emission
s
Lard EdibleTallow
InedibleTallow
YellowGrease
1
YellowGrease
2
Canola Soy
THC CO PM
NOx Emissions of BiodieselComponents
-10%-5%0%5%
10%15%20%25%
Perc
enta
ge c
hang
e in
NOx
g/bh
p-hr
Diese
l
C12:
0
C16:
0
C18:
0
C18:
1
C18:
2
C18:
3
Types of Fatty acids methyl esters
Feedstock Composition
≤C12 C14:0 C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 ≥C20
Soy 0 0 12 0 4 23 55 7 1Corn 0 1 9 1 3 40 45 0 1
Yel Grease 0 1 23 1 10 50 15 0 0Rape 0 0 4 0 1 10 15 10 60Mustard 0 0 3 0 2 39 15 9 30Sunflower 0 0 6 0 4 19 69 0 2Lard 0 1 25 2 14 46 10 0 3Tallow 0 2 27 2 25 40 2 0 2
Fatty Acids: C# carbons: # C=C bonds
saturated monounsaturated polyunsaturatedSaturated &monounsaturated
Fuel Iodine No. and NOx
3.5
4
4.5
5
5.5
6
0 50 100 150 200
Iodine N um ber
NOx g/bh
p-h
Soy
YellowGrease
Fuel Cetane and NOx
3.5
4
4.5
5
5.5
6
30 40 50 60 70 80 90
C etan e N u m b er
NOx g/bhp-h
Soy
YellowGrease
NOx Solutions for B20
4.14.24.34.44.54.64.74.84.9
5
B20 with EPA Cert B20 with 1% DTBP C20 with "CARB" C20 with 1% DTBP
YG Soy EPA cert fuel "CARB"
4.723
4.478
5.0 g NOx/bhp-hr is the legal limit for 1991/1994DDC Series 60
“CARB” is a fuel with 10% aromatics purchased to represent atypical low aromatic CARB test fuel.
NOx Solutions for B20
4
4.2
4.4
4.6
4.8
5
N o E H N 0.5% E H N 1% E H N
NOx g/bh
p-hr
S o y B 20 E P A cert fuel
4.821
5.0 g NOx/bhp-hr is the legal limit for 1991/1994DDC Series 60
TO CC1 12 SPECIATIONTOTAL MASS AND OZONE POTENTIAL
0.0
0.2
0.4
0.6
0.8
1.0
1.2
SUM
MED
CO
MPO
SITE
MA
SS/O
ZON
E (G
/HP-
HR
)
B100 B20 2D B100 B20 2D B100 B20 2D
MASS OZONE POTENTIAL
Cummins N14 DDC Series 50 Cummins B5.9
Tier I Health EffectsData supplied by SWRI
to NBB, 1997-8
FORMALDEHYDE EMISSIONS
0.0
10.0
20.0
30.0
40.0
50.0
B100 B20 2D B100 B20 2D B100 B20 2DCummins N14 DDC Series 50 Cummins B5.9
FORMALDEHYDE EMISSIONS
FOR
MA
LDEH
YDE (M
G/H
P-HR
)
Nocatalyst catalyst
Tier I Health EffectsData supplied by SWRI
to NBB, 1997-8
0 2 4 6 8 10
tetramethyl butaneethyl benzene
xylene (dimethyl benzene)C9 n-nonane
ethyl methyl benzeneHeptanol
C10 n-decaneHeptenoic acid, methyl ester
ethyl hexanoldiethyl benzene
methyl propyl benzeneC4-Benzene or C2-benzene
phenyl ethanonemethylisopropylbenzene
C11 n-undecanebenzoic acid
ethyl dimethyl benzeneoctanoic acid (caprylic acid)
nonanolbutoxyethoxy ethanol
1-dodeceneC12 n-dodecane
dimethyl undecanehexyl cyclohexane
nonanoic acidmethyl tridecane
tetrahydro dimethyl naphthaleneC13 n-tridecane
methyl naphthaleneundecanol
trimethyl dodecaneC14 n-tetradecane
ethyl naphthalenedimethyl naphthalene
hexanedioic acid, bis methylethyltetramethyl hexadecane
2,5-cyclohexadiene-1,4-dioneC15 n-pentadecane
1,1'-ethylidenebis-benzene1.1'-biphenyl, 3-methyl-
methyl ethyl naphthalenetrimethyl naphthalene
C16 n-hexadecanetrimethyl pentadecane
diphenyl methanoneC17 n-heptadecane
C18 n-octadecanehexadecanoic acid methyl ester
octadecadienoic acid methyl esteroctadecenoic acid methyl ester
0 0 2 4 6 8 10
RELATIVE EMISSION RATE (MG/HP-HR)
B100 B20
0 2 4 6 8 10
2D
HEAVY HC SPECIATION - CUMMINS N14 ENGINE
Tier I Health Effects Datasupplied by SWRI, 1997-8
PAH EMISSIONS SUMMARYALL ENGINES
0
2
4
6
8
10
12
14
16
B100 B20 2D B100 B20 2D B100 B20 2DCummins N14 DDC Series 50 Cummins B5.9
PAH EMISSIONS SUMMARYALL ENGINES
SUM
MED
CO
MPO
SITE PAH
(µG/H
P-HR
)
CatalystNo CatalystTier I Health Effects Datasupplied by SWRI, 1997-8
NPAH EMISSIONS SUMMARYALL ENGINES
0.0
0.5
1.0
1.5
2.0
2.5
3.0
B100 B20 2D B100 B20 2D B100 B20 2DCummins N14 DDC Series 50 Cummins B5.9
SUM
MED
CO
MPO
SITE nPAH
(µG/H
P-HR
)
CatalystNo CatalystTier I Health Effects Datasupplied by SWRI, 1997-8
PAH Air Toxics on Semi Volatiles
0
1
2
3
4
5
6
nano
gram
s/bh
p-h
2-m
ethy
l nap
htha
lene
1-m
ethy
lnap
htha
lene
biph
enyl
2,6-
dim
ethy
l nap
htha
lene
acen
apht
hyle
ne
acen
apht
hene
2.3.
5-tri
met
hyln
apht
hale
ne fl
uore
ne
fluor
ene
1-m
ethy
l phe
nant
hren
e
phen
athr
ene
anth
race
ne
fluor
anth
ene
pyre
ne
chry
sene
benz
o(b)
fluor
anth
ene
benz
o(k)
fluor
anth
ene
benz
o(e)
pyre
ne
benz
o(a)
pyre
ne
pery
lene
inde
no(1
,2,3
-cd)
pyre
ne
dibe
nz(a
h)an
thra
cene
benz
o(gh
i)per
ylen
e
DieselBiodiesel
Mutagenicity Testing
0
2
4
6
8
10
12
Rev
erta
nts/
bhp-
hr x
10^
5
Cold +S9 Hot +S9 Cold -S9 Hot -S9
Diesel
Biodiesel
Tier II Health Effects
Testing at Lovelace Respitory ResearchInstitute, 1999Exposed 10 wk old F & M F344 rats
6 hrs/day, 5 days/wk for 13 weeksWhole diluted emissions, 1998 Cummins B5.9100 % biodiesel produced from soybean oil3 levels (H, M, L) plus negative control
LRRI Health EvaluationsGeneral Toxicity:
Body Weight & Feed Consumption, Clinical Observation,Mortality, Hematology (cell counts), Clinical Chemistry (liver& kidney function)
Pathology (gross and histopathology, all organs)OphthalmologyNeuropathology
Histopathology of brain, spinal cord, nervesBrain glial fibrillary acidic protein
ReproductionDNA Damage:
Micronucleus in bone marrow red blood cellsSister chromatid exchange in lymphocytes
Tier II ResultsNo Significant Exposure-Related Effects On:
Feed Consumption, Clinical Condition, Mortality,Ophthalmology, DNA (Micro-nucleus, Sister Chromatid),Neural Parameters, Reproduction (Fertility, Teratology)
Minor Exposure Effects Deemed Not BiologicallySignificant
Body and Organ Weights:Lower liver weight, Higher relative lung weight in F,Higher relative testis weight in M
Clinical Chemistry:4 Liver-related parameters decreased, Glucoseincreased
Tier II Results cont.Minor Exposure Effects:
Lung Histopathology:Dose-related increase in macrophages containing particulate matterMinor alveolar cell changes in 4/30 females in the high level groupCaused by particles, but not toxic effectEffect diminished after 28 days non-exposure
Only Biologically Significant Biodiesel Exhaust ExposureEffect was a Small Effect in Lungs at the High ExposureLevel:
Increased macrophages in M & FSlight increase in F lung weightCellular changes in a few F
Based on this, the No Observable AdverseEffects Level (NOAEL) was the Medium Level
ConclusionsB20 is a drop in technologyB100 can be used in existing infrastructure with somecautionsB20 increases NOx by 0-4%B100 by 1.5% to 16% depending on fuel composition
NOx solutions are evolving and likely to make an impact in the nearfuture
B100 reduce CO, PM, NMHC an average of 43%, 55%, and56% respectivelyB20 reduction of CO, PM, NMHC linear with blend levelBiodiesel offers significant reductions in Air Toxics
For More Info
National Biodiesel Boardwww.biodiesel.org1-800-841-5849
K. Shaine Tyson and Robert McCormickwww.ott.doe.gov/biofuels303-384-6284 Tyson - Feedstocks & Processing202-275-4432 McCormick - End Use R&D