biodiesel: emissions & health effects

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


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


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

biodiesel: emissions & health effects

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