Biodiesel: Emissions & Health Effects

Transcription

1 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

2 DOE Office and Program Structure Office of Energy Efficiency and Renewable Energy David Garman Office of Technology Development Richard Moorer PROGRAMS Solar Wind & Hydropower Geothermal Distributed Energy, Electric Infrastructure & Reliability Biomass Industrial Technology Freedom Car & Vehicle Technology Hydrogen & Infrastructure Building Technologies Weatherization & Intergovernment Grants FEMP Office of The Biomass Program Douglas Kaempf National Renewable Energy Laboratory Shaine Tyson Bob McCormick

3 What is Biodiesel Defined by ASTM, EPA and DOE and by each State s Weights and Measures Agency or State Regulations A fuel consisting of long-chain fatty acid alkyl esters made from renewable vegetable oils, recycled cooking greases, or animal fats that meets ASTM standards ASTM D

4 Biodiesel Terminology Pure biodiesel or 100% Biodiesel (B100) Also called NEAT Biodiesel Biodiesel Blend BXX for XX% biodiesel B20 is 20% biodiesel and 80% petro diesel fuel B50 is 50% biodiesel and 50% petro diesel fuel Avoid calling blends biodiesel because it can lead to a lot of confusion! What is true for B100 may not be true for B20 And visa versa

5 Biodiesel Manufacturing Triglyceride: Fat or Oil molecule Biodiesel molecules Glycerin molecule Pictures provided by Campa als Kraftstoff

6 Sales Volume and Price Trends Mil gal estimated $/gal Sales Price Prices Prices incorporate incorporate effect effect of of USDA USDA subsidy subsidy for for soy soy biodiesel biodiesel ranging ranging between between $0.85 $0.85 and and $1.30/gal $1.30/gal B100. B100. Assumed Assumed extended extended through through

7 Benefits of Biodiesel Use just like No. 2 diesel fuel in existing equipment with no modifications in most cases On-road and off-road transportation B20 is a drop in technology, no changes to equipment or infrastructure B100 requires careful management, but few changes to equipment Electric generators similar to transport issues Heating oils Blends up to 20% with heating oil No. 2

8 Benefits of Biodiesel BTU Content (121,000 BTU/gal) Diesel No. 2 averages 131,000 Diesel No. 1 averages 126,000 High Lubricity (Over 6000 g SLBOCLE) 1% or less can improve a poor lubricity diesel fuel by 40% Biodegradable Used as a clean up technology with oil spills Non Toxic in small quantities Fatty acid methyl esters listed as a food additive with FDA DO NOT DRINK! Safer to use than diesel Very high flash point

9 EPA Emission Analysis

10 B20 NOx Emissions are Within Legal Limits D2 and B20 Emissions Improving over Time Increase is Consistent Across Time & Engine Types g NOx/bhp-hr 6V-71N-77 MUI DDC-6V- 92TA-87 6V-92TA- 81/89 MUI 6V-71N-77 MUI 6V-92TA- 88 DDECII Cummins N Cummins L DDC DDC DDC Cummins B5.9 RME Cummins B5.9 REE D2 B20 All Data EPA HD FTP Composite & Replicated Hot Starts

11 Biodiesel (B100) NOx Emissions Percentage change in NOx g/bhphr 16% 14% 12% 10% 8% 6% 4% 2% 0% EPA Lard Edible Inedible Yellow Yellow Canola Soy Highway Tallow Tallow Grease 1 Grease 2 Diesel O 2 content = 0% 11.82% 11.74% 11.08% 11.10% 11.28% 11.04% 11.16%

12 B100 - CO, HC, PM Emissions 0 Percentage change in Emissions Lard Edible Inedible Yellow Yellow Canola Soy Tallow Tallow Grease Grease 1 2 THC CO PM

13 NOx Emissions of Biodiesel Components 25% 20% 15% 10% 5% 0% -5% -10% Percentage change in Diesel C12:0 C16:0 C18:0 C18:1 C18:2 C18:3 NOx g/bhp-hr Types of Fatty acids methyl esters

14 Feedstock Composition Fatty Acids: C# carbons: # C=C bonds C12 C14:0 C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 C20 Soy Corn Yel Grease Rape Mustard Sunflower Lard Tallow saturated monounsaturated polyunsaturated Saturated & monounsaturated

15 Fuel Iodine No. and NOx NOx g/bhp-h Yellow Grease Soy Iodine Num ber

16 Fuel Cetane and NOx N O x g/bhp-h Soy Yellow Grease Cetane Num ber

17 NOx Solutions for B g NOx/bhp-hr is the legal limit for 1991/1994DDC Series B20 with EPA Cert B20 with 1% DTBP C20 with "CARB" C20 with 1% DTBP YG Soy EPA cert fuel "CARB" CARB is a fuel with 10% aromatics purchased to represent a typical low aromatic CARB test fuel.

18 NOx Solutions for B20 NO x g/bhp-hr g NOx/bhp-hr is the legal limit for 1991/1994DDC Series No EHN 0.5% EHN 1% EHN Soy B20 EPA cert fuel

19 C 1 TO C12 SPECIATION TOTAL MASS AND OZONE POTENTIAL SUMMED COMPOSITE MASS/OZONE (G/HP-HR) B100 B20 2D B100 B20 2D B100 B20 2D Cummins N14 DDC Series 50 Cummins B5.9 Tier I Health Effects Data supplied by SWRI to NBB, MASS OZONE POTENTIAL

20 FORMALDEHYDE EMISSIONS 50.0 FORMALDEHYDE (MG/HP-HR) B100 B20 2D B100 B20 2D B100 B20 2D Cummins N14 DDC Series 50 Cummins B5.9 Tier I Health Effects Data supplied by SWRI to NBB, No catalyst catalyst

21 HEAVY HC SPECIATION - CUMMINS N14 ENGINE B100 B20 2D octadecenoic acid methyl ester octadecadienoic acid methyl ester hexadecanoic acid methyl ester C18 n-octadecane C17 n-heptadecane diphenyl methanone trimethyl pentadecane C16 n-hexadecane trimethyl naphthalene methyl ethyl naphthalene 1.1'-biphenyl, 3-methyl- 1,1'-ethylidenebis-benzene C15 n-pentadecane 2,5-cyclohexadiene-1,4-dione tetramethyl hexadecane hexanedioic acid, bis methylethyl dimethyl naphthalene ethyl naphthalene C14 n-tetradecane trimethyl dodecane undecanol methyl naphthalene C13 n-tridecane tetrahydro dimethyl naphthalene methyl tridecane nonanoic acid hexyl cyclohexane dimethyl undecane C12 n-dodecane 1-dodecene butoxyethoxy ethanol nonanol octanoic acid (caprylic acid) ethyl dimethyl benzene benzoic acid C11 n-undecane methylisopropylbenzene phenyl ethanone C4-Benzene or C2-benzene methyl propyl benzene diethyl benzene ethyl hexanol Heptenoic acid, methyl ester C10 n-decane Heptanol ethyl methyl benzene C9 n-nonane xylene (dimethyl benzene) ethyl benzene tetramethyl butane Tier I Health Effects Data supplied by SWRI, RELATIVE EMISSION RATE (MG/HP-HR)

22 PAH EMISSIONS SUMMARY ALL ENGINES SUMMED COMPOSITE PAH (µg/hp-hr) B100 B20 2D B100 B20 2D B100 B20 2D Cummins N14 DDC Series 50 Cummins B5.9 Tier I Health Effects Data supplied by SWRI, No Catalyst Catalyst

23 NPAH EMISSIONS SUMMARY ALL ENGINES SUMMED COMPOSITE npah (µg/hp-hr) B100 B20 2D B100 B20 2D B100 B20 2D Cummins N14 DDC Series 50 Cummins B5.9 Tier I Health Effects Data supplied by SWRI, No Catalyst Catalyst

24 PAH Air Toxics on Semi Volatiles Diesel Biodiesel nanograms/bhp-h methyl naphthalene 1-methylnaphthalene biphenyl 2,6-dimethyl naphthalene acenaphthylene acenaphthene trimethylnaphthalene fluorene fluorene 1-methyl phenanthrene phenathrene anthracene fluoranthene pyrene chrysene benzo(b)fluoranthene benzo(k)fluoranthene benzo(e)pyrene benzo(a)pyrene perylene indeno(1,2,3-cd)pyrene dibenz(ah)anthracene benzo(ghi)perylene

25 Mutagenicity Testing 12 Revertants/bhp-hr x 10^ Cold +S9 Hot +S9 Cold -S9 Hot -S9 Diesel Biodiesel

26 Tier II Health Effects Testing at Lovelace Respitory Research Institute, 1999 Exposed 10 wk old F & M F344 rats 6 hrs/day, 5 days/wk for 13 weeks Whole diluted emissions, 1998 Cummins B % biodiesel produced from soybean oil 3 levels (H, M, L) plus negative control

27 LRRI Health Evaluations General Toxicity: Body Weight & Feed Consumption, Clinical Observation, Mortality, Hematology (cell counts), Clinical Chemistry (liver & kidney function) Pathology (gross and histopathology, all organs) Ophthalmology Neuropathology Histopathology of brain, spinal cord, nerves Brain glial fibrillary acidic protein Reproduction DNA Damage: Micronucleus in bone marrow red blood cells Sister chromatid exchange in lymphocytes

28 Tier II Results No 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 Biologically Significant 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, Glucose increased

29 Tier II Results cont. Minor Exposure Effects: Lung Histopathology: Dose-related increase in macrophages containing particulate matter Minor alveolar cell changes in 4/30 females in the high level group Caused by particles, but not toxic effect Effect diminished after 28 days non-exposure Only Biologically Significant Biodiesel Exhaust Exposure Effect was a Small Effect in Lungs at the High Exposure Level: Increased macrophages in M & F Slight increase in F lung weight Cellular changes in a few F Based on this, the No Observable Adverse Effects Level (NOAEL) was the Medium Level

30 Conclusions B20 is a drop in technology B100 can be used in existing infrastructure with some cautions B20 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 near future B100 reduce CO, PM, NMHC an average of 43%, 55%, and 56% respectively B20 reduction of CO, PM, NMHC linear with blend level Biodiesel offers significant reductions in Air Toxics

31 For More Info National Biodiesel Board K. Shaine Tyson and Robert McCormick Tyson - Feedstocks & Processing McCormick - End Use R&D