UNIVERSITY OF CINCINNATI

Date: 26-Nov-2007 I, Aisha Tzillah hereby submit this original work as part of the requirements for the degree of: ,

Master of Science
in

Environmental Engineering

It is entitled:

The Emissions of Criteria Air Pollutants from Biodiesel Fuel Usage

Student Signature:

Aisha Tzillah

This work and its defense approved by: Committee Chair:

Mingming Lu, PhD
Mingming Lu, PhD

Edwin Corporan
Edwin Corporan

Sumana Udom Keener, PhD

Sumana Udom Keener, PhD

11/17/2009

258

The Emissions of Selected Air Pollutants from Biodiesel Fuel Usage

A thesis submitted to the

Division of Research and Advanced Studies of the University of Cincinnati

In partial fulfillment of the requirement for the degree of

MASTER OF SCIENCE
In the Department of Civil and Environmental Engineering of the College of Engineering 2008

By: Aisha Tzillah Bachelors of Science in Chemical Engineering, University of Cincinnati 1998 Committee: Dr. Mingming Lu (Chair) Dr. Sumana Keener Edwin Corporan, P.E.

Abstract Diesel-powered compression ignited engines contribute large amounts of sub-micron particulate matter to the environment and have been shown to contribute to atmospheric greenhouse gases and deleterious health effects. Biodiesel is a proposed alternative biofuel produced through transesterification, a process in which organically derived oils combine with a methyl or ethyl alcohol in the presence of a catalyst, typically potassium or sodium hydroxide, to form ethyl or methyl ester. This biomass derived ethyl or methyl ester is non-toxic, less odorous, biodegradable, renewable, and safer to handle than petroleum diesel. Biodiesel can mix with conventional petroleum diesel fuel or used as a neat fuel in compression ignited engines. The main objectives of the research are to compare selected emissions of petroleum diesel fuel with biodiesel fuel and fuel blends, soybean as the source oil, under different engine conditions in order to determine its impact on air quality. A non-road diesel engine generator allowed for the characterization of the emissions from operating on petroleum diesel fuel, B50, and B100. The particulate matter and gaseous emissions were collected with a high-volume single dilution sampler and the exhaust stream was evaluated with a gas analyzer. The filters utilized for particulate matter collection and the adsorbents employed for gaseous pollutant collection were extracted for organic analysis with GC/MS instrument. The organic composition of the fuels and the emitted particulate matter and gaseous pollutants were compared at various engine loads. The use of biodiesel in compression ignition engines has shown to be a viable alternative to petroleum diesel. Biodiesel is an environmentally sustainable fuel that does not contain sulfur or aromatics and may decrease the overall detrimental effects of diesel-powered engines.

Table of Contents Outline..i List of Tables.......ii List of Figures......ii List of Tables in Appendix A....vii List of Tables in Appendix B...viii List of Tables in Appendix C...viii Outline 1. Introduction1 1.1. Petroleum Diesel Fuel.1 1.2. Biodiesel Fuel.3 1.3. Research Objective.8 2. Experimental Design and Method.9 2.1. Sampling Method..13 2.2. Extraction Method20 2.3. Analytical Method21 3. Results and Discussion23 3.1. Sampling Analysis23 3.1.1. Temperature Stability of the Diesel Engine Generator..23 3.1.2. Sampling Parameters.25 3.1.3. PM Mass Collected Under Actual Experimental Conditions....25 3.1.4. Fuel and Energy Consumption..26 3.2. Particulate Analysis..29 3.2.1. Diesel Particulate Matter (PM)......29 3.3. Exhaust Gas Analysis...37 3.3.1. Temperature...38 3.3.2. Carbon Monoxide..39 3.3.3. Carbon Dioxide..40 3.3.4. Oxides of Nitrogen (NOx)..40 3.3.5. Percent Oxygen..41 3.4. Chemical Composition Analysis..43 3.4.1. Soluble Fractions of PM........43 3.4.2. n-Alkanes...44 3.4.3. Polycyclic Aromatic Hydrocarbons...60 3.4.4. Methyl Esters.70 3.4.5. Compound Percentages in Total Identified Organics80 4. Conclusion and Recommendations......82 5. References86 Appendix A: n-Alkane Amount in Particulate and Gaseous Phase of Exhaust for B0, B50, and B100 Fuels..89 Appendix B: Polycyclic Aromatic Hydrocarbon (PAH) Amount in Particulate and Gaseous Phase of Exhaust for B0 and B50 Fuels..97 Appendix C: Methyl Ester Amount in Particulate and Gaseous Phase of Exhaust for B50 and B100 Fuels105

List of Tables Table 2-1: ASTM Fuel properties of Peter Cremer Nexsol Biodiesel.......12 Table 2-2: Soybean Methyl Ester Formula, from National Biodiesel Board....13 Table 3-1: Real over rated power output percentage for B0, B50, and B100....24 Table 3-2: Performance characteristics of dilution sampler......25 Table 3-3: Actual Experimental Conditions for B0, B50, and B100 over the loads.26 Table 3-4: Average Fuel Consumption for B0, B50, and B100 (gal/hr)...27 Table 3-5: Average Energy Consumption (kJ/hr) for B0, B50, and B10028 Table 3-6: Average PM Emissions for B0, B50, and B100 over all loadings...35 Table 3-7: Average Gaseous Emissions for B0, B50, and B100 over all loadings...42 Table 3-8: Percent Organics Extracted for GC/MS analysis of B0, B50, and B100 at each sampling load (kW)44 Table 3-9: Total amount of mass collected (mg) for GC/MS analysis of B0, B50, and B100 at each sampling load (kW)......44 Table 3-10: n-Alkane standard elution order and chemical properties..45 Table 3-11: U.S. EPA 16-priority PAH standard elution order and chemical property..60 Table 3-12: Methyl Ester Rapeseed Oil standard, elution order and chemical property...70 List of Figures Figure 2-1: B0, B100, and B50 fuel (left to right in image) with pieces of rubber tubing and sampling lines, aged 6 months....10 Figure 2-2: Schematic of dilution sampling equipment.16 Figure 2-3: Calibration Line of the Dilution Sampler...............18 Figure 3-1: Generator engine exhaust temperature stability over the loadings, Time (minutes) vs. Temperature (C)....25 Figure 3-2: Fuel Consumption (gal/hr) for B0, B50, B100, and Manual Reference.28 Figure 3-3: Energy Consumption (kJ/hr) for B0, B50, and B100.28 Figure 3-4: Quartz fiber filters after dilution sampling with B0 at 0 kW (A), 25 kW (B), and 50 kW (C) for 30 minutes and at 75 kW for 15 minutes (clockwise).30 Figure 3-5: Quartz fiber filters after dilution sampling with B100 at 0 kW (A), 25 kW (B), 50 kW (C), and 75 kW (D) for 30 minutes.....30

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Figure 3-6: PM Concentration (mg/std m3) in Total Sampling Volume for B0, B50, and B100 over sampling loads (kW)....31 Figure 3-7: PM Emission Rate (g/hr) for B0, B50, and B100 over sampling loads (kW)...32 Figure 3-8: PM Emission Rate (g/kW-hr) for B0, B50, and B100 over sampling loads 25, 50, and 75 kW....32 Figure 3-9: PM Emission Rate (mg emitted mass/kg of fuel consumed) for B0, B50, and B100 over sampling loads (kW)34 Figure 3-10: PM Emission Rate (g emitted mass/kJ of fuel consumed) for B0, B50, and B100 over sampling loads (kW)....34 Figure 3-11: Temperature Profile of exhaust stream (C) for B0, B50, and B100 over sampling loads (kW)..38 Figure 3-12: Carbon Monoxide (ppm) in the exhaust stream for B0, B50, and B100 over sampling loads (kW)..39 Figure 3-13: Carbon Dioxide (%) in exhaust stream for B0, B50, and B100 over sampling loads (kW)......40 Figure 3-14: Oxides of Nitrogen (ppm) in exhaust stream for B0, B50, and B100 over sampling loads (kW)..41 Figure 3-15: Percent Oxygen in exhaust stream for B0, B50, and B100 over sampling loads (kW)..42 Figure 3-16: Percent Organics Extracted for B0, B50, and B100 over sampling loads (kW)...43 Figure 3-17: n-Alkanes Concentration (%) in B0 and B50 Fuel...46 Figure 3-18: n-Alkane PM Concentration (g/std m3) for B0 over sampling loads (kW).......................................................................................................................48 Figure 3-19: n-Alkane PM Emission Rate (mg/hr) for B0 over sampling loads (kW)...48 Figure 3-20: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)49 Figure 3-21: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)....49

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Figure 3-22: n-Alkane Concentration in Gaseous Phase (g/std m3) for B0 over sampling loads (kW)......50 Figure 3-23: n-Alkane Gaseous Emission Rate (mg/hr) for B0 over sampling loads (kW).......................................................................................................................50 Figure 3-24: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)...................51 Figure 3-25: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)...............51 Figure 3-26: n-Alkane PM Concentration (g/std m3) for B50 over sampling loads (kW).......................................................................................................................52 Figure 3-27: n-Alkane PM Emission Rate (mg/hr) for B50 over sampling loads (kW)....52 Figure 3-28: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)..53 Figure 3-29: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)..53 Figure 3-30: n-Alkane Concentration in Gaseous Phase (g/std m3) for B50 over sampling loads (kW)......54 Figure 3-31: n-Alkane Gaseous Emission Rate (mg/hr) for B50 over sampling loads (kW)...................................................................................................................54 Figure 3-32: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW).55 Figure 3-33: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW).55 Figure 3-34: n-Alkane PM Concentration (g/std m3) for B100 over sampling loads (kW)...................................................................................................................56 Figure 3-35: n-Alkane PM Emission Rate (mg/hr) for B100 over sampling loads (kW)...56 Figure 3-36: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)....57 Figure 3-37: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW)....57

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Figure 3-38: n-Alkane Concentration in Gaseous Phase (g/std m3) for B100 over sampling loads (kW)..58 Figure 3-39: n-Alkane Gaseous Emission Rate (mg/hr) for B100 over sampling loads (kW).......................................................................................................................58 Figure 3-40: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)...............59 Figure 3-41: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW).......59 Figure 3-42: PAH Concentration (%) in B0 and B50 Fuel....61 Figure 3-43: PAH PM Concentration (g/std m3) for B0 over sampling loads (kW)...62 Figure 3-44: PAH PM Emission Rate (mg/hr) for B0 over sampling loads (kW)62 Figure 3-45: PAH PM Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)..63 Figure 3-46: PAH PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)..63 Figure 3-47: PAH Concentration in Gaseous Phase (g/std m3) for B0 over sampling loads (kW)......64 Figure 3-48: PAH Gaseous Emission Rate (mg/hr) for B0 over sampling loads (kW).64 Figure 3-49: PAH Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)65 Figure 3-50: PAH Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)65 Figure 3-51: PAH PM Concentration (g/std m3) for B50 over sampling loads (kW)...66 Figure 3-52: PAH PM Emission Rate (mg/hr) for B50 over sampling loads (kW)..66 Figure 3-53: PAH PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)..67 Figure 3-54: PAH PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)..67 Figure 3-55: PAH Concentration in Gaseous Phase (g/std m3) for B50 over sampling loads (kW)......68

Figure 3-56: PAH Gaseous Emission Rate (mg/hr) for B50 over sampling loads (kW)...68 Figure 3-57: PAH Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)..69 Figure 3-58: PAH Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)..69 Figure 3-59: Methyl Ester Concentration (%) in B50 and B100 Biodiesel Fuel...71 Figure 3-60: Methyl Ester PM Concentration (g/std m3) for B50 over sampling loads (kW).......................................................................................................................72 Figure 3-61: Methyl Ester PM Emission Rate (mg/hr) for B50 over sampling loads (kW)...72 Figure 3-62: Methyl Ester PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW).73 Figure 3-63: Methyl Ester PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW).73 Figure 3-64: Methyl Ester Concentration in Gaseous Phase (g/std m3) for B50 over sampling loads (kW)..74 Figure 3-65: Methyl Ester Gaseous Emission Rate (mg/hr) for B50 over sampling loads (kW)...74 Figure 3-66: Methyl Ester Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)..75 Figure 3-67: Methyl Ester Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)..75 Figure 3-68: Methyl Ester PM Concentration (g/std m3) for B100 over sampling loads (kW)...76 Figure 3-69: Methyl Ester PM Emission Rate (mg/hr) for B100 over sampling loads (kW)...................................................................................................................76 Figure 3-70: Methyl Ester PM Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)...............77 Figure 3-71: Methyl Ester PM Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW)...............77

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Figure 3-72: Methyl Ester Concentration in Gaseous Phase (g/std m3) for B100 over sampling loads (kW)..78 Figure 3-73: Methyl Ester Gaseous Emission Rate (mg/hr) for B100 over sampling loads (kW)...78 Figure 3-74: Methyl Ester Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)79 Figure 3-75: Methyl Ester Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW)79 Figure 3-76: Percentage of identified n-Alkanes PM and Gaseous Phase for B0 and B50.80 Figure 3-77: Percentage of identified PAHs in PM and Gaseous Phase for B0 and B50.81 Figure 3-78: Percentage of identified Methyl Esters in PM and Gaseous Phase for B50 and B100........81 List of Tables in Appendix A Table A-1: n-Alkane PM Concentration (g/std m3) for B0, B50, and B100 over sampling loads (kW)..89 Table A-2: n-Alkane PM Emission Rate (mg/hr) for B0, B50, and B100 over sampling loads (kW)..90 Table A-3: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B0, B50, and B100 over sampling loads (kW)..91 Table A-4: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0, B50, and B100 over sampling loads (kW)..92 Table A-5: n-Alkane Concentration in Gaseous Phase (g/std m3) for B0, B50, and B100 over sampling loads (kW)..93 Table A-6: n-Alkane Gaseous Emission Rate (mg/hr) for B0, B50, and B100 over sampling loads (kW)..94 Table A-7: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0, B50, and B100 over sampling loads (kW)95

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Table A-8: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0, B50, and B100 over sampling loads (kW)96 List of Tables in Appendix B Table B-1: PAH PM Concentration (g/std m3) for B0 and B50 over sampling loads (kW)...97 Table B-2: PAH PM Emission Rate (mg/hr) for B0 and B50 over sampling loads (kW)...98 Table B-3: PAH PM Emission Rate (mg emitted compound/kg fuel consumed) for B0 and B50 over sampling loads (kW)...99 Table B-4: PAH PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0 And B50 over sampling loads (kW)100 Table B-5: PAH Concentration in Gaseous Phase (g/std m3) for B0 and B50 over sampling loads (kW)101 Table B-6: PAH Gaseous Emission Rate (mg/hr) for B0 and B50 over sampling loads (kW)102 Table B-7: PAH Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0 and B50 over sampling loads (kW)103 Table B-8: PAH Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0 and B50 over sampling loads (kW)104 List of Tables in Appendix C Table C-1: Methyl Ester PM Concentration (g/std m3) for B50 and B100 over sampling loads (kW)105 Table C-2: Methyl Ester PM Emission Rate (mg/hr) for B50 and B100 over sampling loads (kW)105 Table C-3: Methyl Ester PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 and B100 over sampling loads (kW)..106 Table C-4: Methyl Ester PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 and B100 over sampling loads (kW)106 Table C-5: Methyl Ester Concentration in Gaseous Phase (g/std m3) for B50 and B100 over sampling loads (kW)107

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Table C-6: Methyl Ester Gaseous Emission Rate (mg/hr) for B50 and B100 over sampling loads (kW)107 Table C-7: Methyl Ester Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 and B100 over sampling loads (kW)108 Table C-8: Methyl Ester Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 and B100 over sampling loads (kW)108

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1. Introduction There are two major types of engines utilized currently compression ignited engines operating on diesel fuel and spark ignited engines operating on gasoline fuel. Compression ignition engines are widely used in on-road and non-road applications with high power output and great fuel economy. Although compression ignited engines emit lesser amounts of carbon monoxide and total hydrocarbon compounds than spark ignited engines, they form large quantities of fine particulate matter.1 From the United States Environmental Protection Agency (U.S. EPA) National-Scale Air Toxics Assessment, diesel emissions are among the substances that pose the greatest relative risk.2 According to the 1996 U.S. EPA National Air Toxics Inventory, approximately 5.24 x 105 tons per year of diesel particulate matter was emitted nationwide.

1.1. Petroleum Diesel Fuel Petroleum diesel fuel consists mainly of saturated and aromatic hydrocarbons. Paraffins, cycloparaffins, monoaromatics, diaromatics, polynuclear aromatics, and sulfur

compounds are the major compound types typically found in petroleum diesel fuel.3 According to the World Health Organization (WHO), C10 to C28 n-alkanes are the dominant saturated hydrocarbons for general diesel fuel. Branched alkanes also comprise a large percentage of the fuel. Aromatic compounds constitute 10 to 30% and the total concentration of the polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, phenanthrene, acenaphthene, acenaphthylene, fluorine, fluoranthene, chrysenes, pyrenes, benzanthracenes, and perylenesin, is typically <5% by volume.3 For on-road diesel fuel application, fuel sulfur content was reduced from 500 ppm (low-sulfur diesel) to 15 ppm

(ultra-low sulfur diesel) on June 1, 2006. For non-road applications, current U.S. EPA regulation on sulfur content is 500 ppm, which was reduced from 3400 ppm in 2007 and will be reduced even further to 15 ppm in 2010.

The National Institute of Occupational Safety and Health (NIOSH) and U.S. EPA classify diesel particulate matter (PM) as a probable human carcinogen.2 Diesel exhaust particles are essentially sub-micrometer. Due to their median aerodynamic diameter of 0.1 to 0.3 m, with 90% less than 1.0 m, the particles are readily inhaled, and about 10% are deposited in the alveolar region of the lung. The carcinogenic effect of diesel exhaust exposure is mainly ascribed to the inhalation of soot particles. According to the U.S. EPA, emissions from non-road diesel machines are significantly higher than on-road diesel engines because of lower fuel quality, inadequate engine maintenance, older engine ages, and less public supervision.4

Diesel emissions contain hundreds of chemical compounds, partitioned in the gaseous and in the particulate phase.1 Both phases in diesel exhaust contain known or suspected mutagens and carcinogens, such as PAHs.2 Diesel PM is a complex mixture of organic and inorganic compounds that exist in particle phase. Organic compounds, which

constitute 20 to 60% of diesel PM, appear as the soluble organic fraction. The organic carbon fraction is a complex mixture of unburned fuel and hundreds of organic compounds, including PAHs and nitro-PAHs, which can either be formed directly or through secondary processes such as condensation and adsorption.3 Carbonaceous materials account for about 70 to 80 % of diesel PM, and are classified as elemental

carbon and organic carbon.1 Elemental carbon, the diesel soot particles core, is a product of incomplete combustion. It consists of carbon layers that are structurally similar to graphite.

1.2. Biodiesel Fuel Biodiesel is a compression ignition diesel equivalent fuel made from transesterified fatty acids. Biodiesel is a biodegradable, renewable, nonflammable fuel that may replace conventional petroleum diesel fuel. The fuel may be used neat (100%) or in blends with petroleum diesel, as biodiesel is completely miscible in petroleum diesel.5 Biodiesel was standardized by the American Society for Testing and Materials (ASTM) in 1999 as provisional standard PS 121-99 and became a full standard, ASTM D6751 in 2002. In 1994 Europe created the biodiesel standard DIN V 51506. Commercial use of biodiesel as an alternative fuel has occurred since the late 1980s in most countries.4

Biodiesel has been researched as a fuel extender or supplement in various transportation fuels. According to the United States Department of Energy, Energy Information

Administration, approximately 4,243 thousand barrels of distillate fuel were consumed per day in 2007. The use of diesel fuel blends containing even relatively small amounts (5%) of biodiesel could equate to substantial petroleum fuel savings daily.6 Number 2 petroleum diesel fuels are the transportation fuels to which biodiesel is typically compared.7

The chemical process to make biodiesel is known as transesterification and consists of treating animal fats and vegetable oils, such as soybean, sunflower, and rapeseed, with reactants methanol or ethanol in the presence of the catalyst, typically sodium or potassium hydroxide, to obtain a methyl or ethyl ester and glycerin.8 There are more than 350 oil-bearing crops identified; among which sunflower, safflower, soybean, cottonseed, rapeseed, and peanut oils are considered as potential alternative fuels for diesel engines.9 Fats and vegetable oils are primarily composed of glycerol esters of fatty acids (triglycerides). In the process of transesterification, the glycerol components of the triglyceride molecules exchange for a lighter methanol (or ethanol). The product is composed of fatty acid methyl or ethyl esters, consisting of straight saturated and unsaturated alkyl groups with C15 to C17 hydrocarbon chains and C14 to C22 alcohol esters that exhibit varying degrees of un-saturation, depending on source.10 The most widely used product, soyate methyl ester, is made through a reaction of soybean oil and methanol.11 Methanol is most commonly used for making biodiesel because of its low cost.12

Biodiesel is considered nontoxic, and has a higher biodegradability and is less polluting to water and soil than fossil diesel. According to the United States Department of Energy, Office of Energy Efficiency and renewable Energy, biodiesel is as biodegradable as sugar, ten times less toxic than table salt, and degrades about four times faster than petroleum-based diesel fuel upon accidental release into the environment. Emissions from biodiesel engines show reduced values of carcinogenic and mutagenic substances. Because biodiesel does not contain sulfur, which is known to contribute to acid

deposition and poison catalytic converters in vehicles, the use of an oxidation catalyst engine has a high potential of reducing exhaust-gas components while burning biodiesel fuel.13

Biodiesel fuels have similar composition whether produced from animal fats or vegetable oils. The primary difference between the source oils is that the animal fat-based biodiesel contains more saturated fatty esters. Soybean oil is typically about 12 to 15 % saturated, while tallow is typically about 50% saturated. This greater saturation raises the cloud point, or the temperature at which waxy crystals in an oil or fuel form a cloudy appearance, of animal-fat based biodiesel and has shown to have questionable effects on the overall combustion and exhaust emissions characteristics of the biodiesel fuel.5

Biodiesel fuels have a kinematic viscosity range 1.9 to 6.0 centistokes (mm2/s) versus 1.3 to 5.8 centistokes for petroleum diesel. The higher viscosity of biodiesel compared to petroleum diesel makes it an excellent lubricity additive and provides lubricating properties that may reduce engine wear and extend engine life.14 Replacing diesel fuel with biodiesel reduces the wear of aluminum, iron, chromium, and lead components in a diesel engine.15 However, the injection droplet size from the higher viscosity can impact emissions due to poor distribution of the fuel and increased burning times. The viscosity of a fuel is important because it affects the atomization of the fuel being injected into the engine combustion chamber. A small droplet is desired for complete combustion to occur. A high viscosity fuel will produce larger fuel droplets, which may not burn as completely as smaller droplets. Unburned oxidized fuel will build up in the engine

around valves, injector tips, and on piston sidewalls and rings.14 Biodiesel is less compressible than diesel fuel. The pressure in the fuel injection system can develop faster and with the increased viscosity of biodiesel, this leads to reduced fuel losses during the injection processes.16

All Number 2 petroleum diesel fuels have relatively high flash points, which measures the tendency of a fuel to form a flammability mixture with air, typically at 71C (160F); the flash point of neat biodiesel is even higher, greater than 90C (194F), typically around 150C (302F). A material with a 90C or greater flash point is considered by ASTM standards as non-hazardous from storage and fire-hazard point of view.5 The relatively high flash point of biodiesel makes it less volatile and safer to transport or handle than petroleum diesel.

Biodiesel fuels may contain residual alcohol from the transesterification process, which can remove deposits from fuel tanks and lines causing filter plugging during initial use. Biodiesel has poor oxidation stability, which can result in long-term storage problems. Biodiesel fuel is an excellent medium for microbial growth.5 Microbes cause fuel system corrosion and premature filter plugging. Any amount of water contaminating the fuel will accelerate the microbial growth.16

Biodiesel fuels have lower heat content, about 89% of Number 2 diesel fuel, and are therefore less energy efficient fuels. The addition of biodiesel to petroleum diesel will decrease the overall heating value. Fuel consumption is proportional to the volumetric

energy density of the fuel based upon the lower or net heating value.5 Diesel fuel is pumped to the engine on a volumetric basis, and the density of the biodiesel blend is higher than that of diesel so that a larger mass flow rate for the same fuel volume is pumped to the engine, resulting in increase in torque and power. However, as the biodiesel percentage in the fuel increases, the power will decrease below that of diesel fuel due to the lower heating value and higher viscosity of the biodiesel, possibly resulting in poorer atomization and incomplete combustion.17

Biodiesel fuel is free from aromatic compounds and contains fuel bound oxygen. It has an oxygen content of 10 to 11% and this has an effect on particulate matter (PM) and NOx emissions.18 The oxygen in biodiesel can be used in combustion, especially in the fuel rich flame zone, for a more complete combustion which can result in increasing the torque and power and reducing exhaust emissions such as hydrocarbons (HC), smoke, and carbon monoxide (CO).17 Oxygenated fuel combustion products that minimize soot formation are those where the oxygen atom from the fuel is bonded to a different carbon atom in the products. This prevents the carbon atom in the product from forming unsaturated species that lead to soot or elemental carbon.16 Higher temperatures of combustion resulting from biodiesel fuel usage results in higher NOx emissions.17

Some fuel system modifications are recommended when operating both on-road and nonroad engines on biodiesel fuel. Fuel systems should be optimized for biodiesel fuels because of their higher density and subsequent gumming problems as a result of poor storage and oxidative stability. Biodiesel has shown to dissolve rubber materials and

cause swelling and hardening or cracking of some elastomer seals within the fuel system and engine. Pure biodiesel fuel is not stable, and its acid content increases over time, which can damage powder metal components. Other areas of concern when operating with biodiesel fuels include fuel gelation and filter plugging at low temperatures. Because of biodiesel fuels poor storage and thermal stability, filter plugging, injector deposits, and blockage of the fuel nozzles and passages can occur.8

1.3. Research Objective The U.S. EPA conducted a compilation study where publicly available data were utilized to determine the emission characteristics of biodiesel usage. The majority of the

available data were collected on heavy-duty on-road engines, which demonstrated that biodiesel use results in a decrease in particulate matter, carbon monoxide, and hydrocarbon emission with an increase in NOx. It also concluded that non-road engines and on-road diesel engines respond differently, since non-road engines mainly operate in transient modes and additional data are required on non-road engines response to biodiesel.19

As detailed emissions data from biodiesel combustion in non-road engines are limited, the overall goal of this research is to characterize the emissions of selected air pollutants from biodiesel fuel blends compared with petroleum diesel fuel while operating a nonroad compression ignited engine. To consider the combustion profile, regulated

emissions such as PM, CO, and NOx as well as organic compounds are evaluated. Organic compound analysis focused on n-alkanes, the 16 U.S. EPA priority PAHs, and

major methyl ester concentrations in the petroleum and biodiesel blend fuel and exhaust. Fuel consumption, soluble fraction of the particulate matter, the exhaust stream oxygen, carbon dioxide, and temperature are also measured and compared between biodiesel fuel blends and petroleum diesel fuel.

2. Experimental Design and Method For this study, a non-road diesel engine generator was utilized to evaluate compression ignition emissions while operating on petroleum diesel and biodiesel fuels. The

generator is located at University of Cincinnati Center Hill Research Facilities in Cincinnati, Ohio. It is a 1992 compression-ignition Generac Power Systems, Inc. liquid cooled diesel engine generator Model SD080, 5.0 Direct-injection, turbo-charging, 4 cylinders, rated output at 80 kW, 60 Hz, with a 0.8 power factor, 122 hp at rated output, with a normal engine speed of 1800 rpm, and compression ratio 17.5:1. According to the diesel engine generator reference manual, the exhaust flow at rated output 60 Hz is 24 m3/min (848 ft3/min) with exhaust temperature at rated output 509C (950F). The generator is specified to operate on Number 2 diesel fuel with a minimum Cetane number of 40. The generator had approximately 750 hours of operation prior to usage.

According to the Code of Federal regulations (CFR) Title 40 Part 89.104, Control of Emissions from New and In-use Non-road Compression Ignition Engines, the useful life of a non-road engine rated over 37 kW is 8,000 hours or 10 years, whichever comes first.

Since the solvent properties of biodiesel can dissolve elastomers5, all rubber tubing fuel lines located in the engine were replaced with polyurethane tubing. Figure 2-1 depicts

the fuels utilized for this study with pieces of rubber tubing and sampling lines aged for six months. The 100% biodiesel (B100) deteriorated all the rubber tubing as evidenced by the dark color in the sampling jar. The 50/50 mixture of petroleum and biodiesel (B50) deteriorated the rubber lining to a much lesser extent.

Figure 2-1: B0, B100, and B50 fuel (left to right in image) with pieces of rubber tubing and sampling lines, aged 6 months

The diesel engine generator was equipped with a 254 mm (10 in.) inner diameter metal exhaust pipe fashioned after the diesel muffler. This pipe extends across the top of the generator 1.8 m horizontally, 1.9 m vertically down the side and 2.3 m across, for a wellmixed exhaust gas with relatively high residence time. The schematic of the dilution sampling system is depicted in Figure 2-2. The same sampling points were employed consistently for each method of sampling.

A positive load bank simulator, Merlin 100 manufactured by SIMPLX 160 k, airflow 4,000 cfm, 3-wire connection, maximum power output at 100 kW, high voltage up to

10

240/480 V, 60 Hz simulated various load conditions from 0 (idle) to 75 kW (maximum load on the diesel engine generator is 80 kW) by applying steady-state banks of heaters to the generator with 25 kW increments. To determine the energy output, the voltage and amperage were recorded. The generator voltage was set at 480 volts and kept constant with the rated output for all trials at nearly 100%. For all trials, the fuel by-pass apparatus was employed for fuel addition and fuel consumption data.

The petroleum diesel was On Road Diesel Supreme Ultra-Low Sulfur (ULS) fuel from Steve Krebs Oil Company supplied by BP Oil Company, labeled with a sulfur content of <15 ppm. According to the Material Safety Data Sheet (MSDS), the physical properties include a flash point at 51.7 C (125F) with an approximate density of 0.80 g/cm3, and the initial boiling point is 160C (320F). The dynamic viscosity is 2.4 to 3.96

centipoises (0.0024 to 0.00396 kg/m-s or mPa-s) at 38C (100F) and the pour point is 23.3C (-10F). The fuel was stored outside the test facility in a metal drum.

Peter Cremer North America, product Nexsol BD-0100 Biodiesel with soybean oil as the source oil, supplied the biodiesel utilized. The biodiesel was stored in a metal drum inside at room temperature. Soy methyl ester (SME) synonyms include rapeseed methyl ester (RME), methyl tallowate, and palm methyl ester. The MSDS product description of the fuel is a methyl ester from lipid sources. The fuel is recommended to be stored in airtight, closed containers between 10C (50F) and 48C (120F). Physical and chemical properties from the MSDS include the initial boiling point of 200C (392F), fuel is <2% volatiles by volume, the flash point is over 150C min (300F min), and the average

11

molecular weight of soybean oil methyl ester is 292.2 g/gmol with an average density of 0.88 g/cm3.

Table 2-1 lists the ASTM D 6752 fuel standard specifications and results from Peter Cremer North America analysis. Table 2-2 lists the biodiesel fuel composition in terms of the methyl ester content determined from the National Biodiesel Board for a typical soybean oil methyl ester, calculated using the average fatty acid distribution for soybean methyl esters. Table 2-1: ASTM Fuel properties of Peter Cremer Nexsol Biodiesel Property ASTM Method Limits Results Flash Point D93 130C min <180C Water & Sediment D2709 0.050% vol. max <0.025 Kinematic viscosity, 40C D445 1.9 to 6.0 mm2/sec 4.1 Sulfated Ash D874 0.020% mass max <0.001 Sulfur D5453 15 ppm max 1 Copper Strip Corrosion D130 No. 3 max 1A Cetane D613 47 min 50 Cloud Point D2500 Report to customer -1C Carbon Residue, D4530 0.050% mass max <0.050 100% sample Acid Number D664 0.5 mg KOH/gm max 0.37 Free Glycerine D6584 0.020% mass max 0.011 Total Glycerine D6584 0.240% mass max 0.018 Phosphorus Content D4951 0.001% mass max <0.001 Distillation temp, atm equiv D1160 360C max 352C temp, 90% recovered Sodium & Potassium Metals VOP391-91 5 ppm max combined 1.4

12

Table 2-2: Soybean Methyl Ester Formula, from National Biodiesel Board Methyl Ester Formula Molecular Weight Boiling Melting Density Percent Point Point (g/cm3) Weight (C) (C) (g/gmol) Methyl Palmitate C17H34O2 270.45 12.0 185 34 0.852 Methyl Stearate C19H38O2 298.52 5.0 181 37 41 N/A* Methyl Oleate C19H36O2 296.5 25.0 218 N/A 0.874 Methyl Linoleate C19H34O2 294.48 52.0 192 -35 0.889 Methyl C19H32O2 292.46 6.0 182 N/A 0.895 Linolenate *N/A = Data not available

2.1. Sampling Method A common method for measuring the mass of organic aerosol involves filter collection and subsequent thermal analysis. Dilution sampling techniques are generally

recommended for studying diesel exhaust emissions. Dilution sampling rapidly cools the exhaust and mixes it with filtered ambient air. This method simulates the particulate matter behavior in the environment since the diesel exhaust leaving the pipe is immediately cooled and diluted with atmospheric air.2

Engine testing procedures for non-road diesel engine is outlined in Federal Test Procedure 40 CFR Part 89, Control of Emissions from New and In-Use Non-Road Compression Ignition Engines. In 40 CFR 89.419, Dilute gaseous exhaust sampling and analytical system description, the dilution sampling system utilizes the CVS concept as described in 40 CFR Part 1065 Test Procedure and Equipment. The constant volume sampling (CVS) system is designed to measure the true mass of gaseous and particulate emissions of diesel engines. CVS maintains a constant total flow volume of the system by altering the dilution airflow as the exhaust flow varies. With a CVS

13

system, as exhaust flow increases, such as during increased load, the dilution air is decreased and the sampling source is representative of exhaust variations. Because some compounds present in the exhaust are soluble in water, the flow capacity of the CVS must be large enough to keep water from condensing in the system.

According to 40 CFR 1065.140, Dilution for gaseous and PM constituents, the sampling system should maintain sample temperature less than 455C, primary dilution air at 25C 5C, utilize a HEPA filter to remove any background PM in the dilution air, a Reynolds number greater than 4,000 in the dilution tunnel, and sufficient length to cause complete mixing of the exhaust and dilution air, generally recommending at least 10 pipe diameters in length.

Figure 2-2 schematic of the sampling system illustrates the simplified arrangement employed in the tests for particulate and gaseous sampling. The single dilution system follows the temperature requirements for CFR Federal Test Procedure for non-road dilution sampling and basic design parameters, such as inert sampling materials which are stable at high temperatures, the filter situated 10 tunnel diameters downstream from where the exhaust enters dilution tunnel, with lengths no more than 50 outside diameters, gradual bends in the system, with enough residence time for condensation to occur and turbulent mixing in the dilution tunnel. Constant total flow volume sampling was not employed in this study because of the inability for flow compensation, which may have been maintained by adjusting the dilution air. However, constant sampling times and a

14

low dilution ratio minimized this discrepancy. Sampling time for all loads was 30 minutes. At least three runs at each load per fuel combination were analyzed.

The dilution system was equipped with a high volume blower, General Metal Works Model 2000, Serial Number 10696, 115 volt, 60 cycles, one phase, with a total flow rate of approximately 300 L/min, used to draw air through the system. The total diluted sample flow rate was determined with a Magnehelic Gauge, range of 0 to 100 inches of H2O. The exhaust was diluted with ambient air filtered using a high efficiency

particulate filter (HEPA) with 99.97% removal efficiency and was measured by a Dwyer Ratemaster Flow Meter, range of 0 to 20 standard cubic feet per minute (scfm) of air. The PM was collected on quartz fiber filters (Millipore) at temperatures <455C, filter diameter of 90 mm, positioned with Teflon o-rings situated in the Tisch Environmental filter holder assembly equipped with temperature sampling ports. Following the quartz filter, exhaust passed through Amberlite XAD-2 adsorbent and clean Supelco highvolume polyurethane foam (PUF) plugs 0.6 cm outer diameter situated in a glass cartridge, which adsorbed the organic compounds in the gaseous stream. Approximately 10 grams of adsorbent was sandwiched between two PUFs. Adsorbent cartridges are typically employed for monitoring semivolatiles.

15

Figure 2-2: Schematic of dilution sampling equipment

18 m

Non-Road Diesel Engine Generator

1.9 m 2.3 m

Exhaust Stream
Inlet Metal Probe, 1.2 m, 10 mm I.D.

10 in. I.D. Sampling Port

Dwyer Flow Meter (Qd) 19.1 mm I.D.,

1.3 m

19.1 mm I.D., 1.3 m

Teflon Connection, 0.4 m Dilution Tunnel, 38.1 mm I.D., 2.2 m

HEPA Filter

Ambient Air
PUF/XAD/PUF

Quartz Fiber Filter, 90 mm

Magnehelic Gauge (Qt)

Blower

The primary metal inlet probe was insulated with Virginia Foam insulation tape, catalogue number K-501, in order to maintain the temperature of the exhaust gas before mixing with the dilution air. The metal inlet probe had a 10 mm inner diameter, 12.7 mm outer diameter, 1.2 m in length attached with a Teflon connection 0.4 m in length to the dilution air tunnel. The dilution tunnel was PVC Braided Teflon tubing with a 38.1 mm inner diameter, 2.2 m in length to the filter holder. The HEPA filter was connected to a 19.1 mm Fisherbrand inner diameter Teflon tubing, 1.3 m to the flow meter and 1.3 m to the flue gas inlet. The sampling system was installed on a cart for easy mobility. The

16

dilution sampler probe was inserted 1.9 m on the traverse of the exhaust stream pipe. The tubing was rinsed with acetone between runs.

The pressure drop as measured by the Magnehelic gauge (in. of H2O) was calibrated to the volumetric flow rate with use of a standard Pitot tube. The Pitot tube was used to measure total dilution stream flow rate at a range of pressure drops before sampling the engine generator exhaust. To correlate the pressure drop to the flow, the velocity of the stream was first determined. For a standard pitot tube from Apex Instruments, the air

T p velocity, Vs, is determined by the following relation: Vs = 85.49 s M P s s

1/ 2

, where,

85.49 is the units factor to yield a Vs in units of ft/s, Ms is the stack gas molecular weight, taken as 29 lb./lb.-mol, Ps is the absolute exhaust stream pressure taken as ambient barometric pressure (in. of Hg), Ts is the exhaust stream temperature in Rankine, and p is the velocity head of the exhaust stream gas (pressure drop) measured from a manometer attached to the Pitot tube in inches of H2O.

Figure 2-3 shows the calibration results and verifies the strong linear correlation of the pressure drop relating to the volumetric flow rate of the dilution stream. The square root of the pressure drop measured with the Magnehelic gauge (in. of H2O) was plotted against the volumetric flow rate, Qs, calculated from the Pitot tube results (standard liter per minute). This calibration line is specific to the high-volume blower and Magnehelic gauge employed in the sampling system. As the blower life increases, the calibration line may shift. Results repeated at the conclusion of the experiments verified the stability of the system flow meter.
17

Figure 2-3: Calibration Line of the Dilution Sampler

500 450
Qs (slpm)

400 350 300 250 200 3.5 4.5 5.5 6.5

1/2

y = 56.695x R = 0.9981
2

7.5

8.5

Magnehelic Gauge (P, in. of water)

The dilution ratio was determined by the following equation (ratio of the dilution air flow to the exhaust gas flow): q =
Qd where, Qd is the dilution flow rate and Qt is the Qt Qd

total flow rate (exhaust gas flow plus dilution gas flow). There is no set guideline for the dilution ratio in the Federal Test Procedure 40 CFR Part 1065.

In 40 CFR 89.331, Test Conditions, all volumes and volumetric flow rates are corrected to the temperature and pressure of 0C (273.15 K) and 101.3 kPa (1 atm). The total sampling volume was corrected to standard conditions by filter temperature, Tm, and ambient pressure, Pm, with the following relation: Vstd = Vm
PmTstd . Pstd Tm

An Omega HHM31 thermocouple was used to measure the filter temperature through a probe opening in the filter holder and the ambient percent relative humidity and ambient

18

temperature was measured with use of the Fisher Scientific Traceable Hygrometer. The particulate mass concentration was determined from the total flow over the test period.

The quartz fiber filters were baked at 550C (1,022F) prior to sampling for a minimum of 12 hours, to reduce residual carbon levels associated with new filters, and weighed with Sartorius CP225D Electronic Semi-micro and Analytical Precision Balance 0.1 mg, with 0.02 mg standard deviation. After sampling, the filters were stored in a

desiccator for 24 hours at 20C5.6C and ambient pressure, weighed, and then extracted. After extraction described in section 2.2, the filters were dried and weighed again. Quartz fiber filters were selected because they are suitable for thermal analysis and extraction. However, these filters have large surface areas upon which adsorption of gases can be considerable. Adsorption of organic vapors onto filter during or after sample collection can overestimate the organic aerosol concentration.3 Significant pressure drops over the filter can generate underestimation.3 The filters were contained in covered glass Petri dishes for transportation and storage.

The Testo Gas Analyzer measured the emissions of carbon monoxide (CO), carbon dioxide (CO2), oxides of nitrogen (NOx), percent oxygen (O2), and exhaust temperature. Multiple measurements were taken at each load. The Testo Gas Analyzer is not as accurate as an U.S. EPA standard method; however, it is utilized for a general assessment of the combustion processes. The instrument employs sensors that measure the emissions on a dry weight basis. The CO sensor has a measuring range of 0 to 10,000 ppm with an accuracy of 10 ppm, a resolution of 1 ppm CO, and a 40-second reaction time. The

19

temperature measuring range is -40 to 1,200C (-40 to 2,192F). The CO2 sensor has a resolution of 0.01% volume with a 20-second reaction time. The O2 sensor has a

measuring range of 0 to 25 % volume with an accuracy of 0.8% volume, a resolution of 0.1% volume, and a 20-second reaction time. The NOx sensor has a range of 0 to 3,000 ppm with an accuracy of 5 ppm and a 30-second reaction time. The Testo Gas Analyzer was inserted 1.5 m on the horizontal pipe. In 40 CFR 89.309, the analyzers required for gaseous emissions include non-dispersive infrared absorption type, on a dry basis for carbon monoxide and carbon dioxide analysis and a chemiluminescent detector for measuring oxides of nitrogen.

2.2. Extraction Method To analyze the particulate matter for organic composition, the quartz filters underwent Ultrasonic assisted extraction with the solvent HPLC grade dichloromethane (DCM, Fisher Scientific). The filters were analyzed individually for the extractions and analysis for organic composition was performed with a GC/MS (gas chromatography/mass spectrometry) instrument.

After gravimetric analysis, the filter was rinsed with 100 mL DCM in a volumetric flask, sealed with aluminum foil and Parafilm and placed in a Branson 1510 sonicator water bath for 1 hour. Slow vacuum filtration through a 25 mm Alltech Polytetrafluoroethylene filter membrane (pore size 0.2 m) was performed to remove the insoluble fractions (such as soot) and for the sensitivity of the GC/MS.

20

After filtration, the 100 mL solution was evaporated to approximately 10 mL under a gentle stream of nitrogen or evaporated in ambient air. The extraction concentration amount was chosen based on previous studies3 and appropriate component amounts for GC/MS analysis. The solution was transferred to a vial, stored in the freezer, and analyzed directly with the GC/MS.

All filters were weighed before and after extractions. The dissolved fraction or percent soluble is defined as
M2 M3 * 100 , where M1 is the mass of the filter after baking and M 2 M1

before sampling, M2 is the mass after sampling and desiccation, and M3 is the mass dried extracted filter.

To analyze the gas phase for organic composition, the XAD and PUF were weighed, washed repeatedly with DCM, the solution vacuum filtered to 0.2 m, concentrated under a nitrogen stream, and analyzed with the GC/MS.

2.3. Analytical Method Most of the organic compounds typically present in PM extract, such as alkanes, PAHs, alkylated PAHs, oxygenated PAHs, alkyl benzenes, fatty acids, and esters, can be analyzed with a GC/MS instrument. A Varian GC/MS system (CP-3800 GC, Saturn 2200 Ion Trap MS) equipped with a CP-8400 automatic sampler with the column CP-Sil 8 CB Low Bleed/MS (30 m x 0.25 mm ID coating x 0.25 mm, equivalent of DB-5ms) was employed for the organic compositional analysis.

21

The chromatographic procedure followed column temperature set at 30C for 2 minutes, raised to 200C at 10C/min, raised 5C/min to 270C, then at 10C/min to 300C, held at 300C for 10 minutes for a total analysis time of 45 minutes. The injector was in splitless mode at a temperature of 280C. Helium was used as the carrier gas with a flow rate of 1.2 mL/min, and the MS was set as ion trap with a 2.8-minute solvent delay. Compound identification in total ion chromatogram (TIC) was performed with the assistance of the National Institute of Standards and Technology (NIST) standard library. Standards reference compounds acquired from Restek Corporation were utilized for peak and retention time comparison and mass fragmentation patterns. Eight Peak Index mass to charge ratio was utilized to confirm the NIST results.

From the chromatogram of intensity (abundance) versus retention time from the GC/MS analysis, the peaks were compared against three external standards for n-alkanes, PAHs, and methyl ester content. To obtain the concentration of the particular compound in the sample, the response factor was first determined as the area of the peak divided by the concentration within the standard. Compositional analysis with the GC/MS requires accurate response factors for compound quantification based on external standards. Response factors were validated by injection of the standard compounds with multilevel concentrations using the same analytical method. Calibration curves were obtained with the R2 value greater than 0.96. The peak area divided by the response factor at each component yielded the concentration within the extract in ppm. To determine the

concentration within the flue gas in g/m3, the concentration of the extract (ppm) is

22

multiplied to the final extraction volume (mL) over the total sampling volume (m3) corrected to the standard temperature and pressure.

Before sample analysis, pure DCM was injected into the column to ensure stable status of the instrument and identify possible laboratory contaminants in the samples. All sample and standard solutions were sealed in vials and stored in the freezer; sample containers, sampling equipment, and laboratory glassware was cleaned and stored to minimize contamination from external sources.

3. Results and Discussion

The fuels tested included 100% ultra-low sulfur (ULS) petroleum diesel, 50/50 mixture of biodiesel and ULS diesel, and 100% biodiesel fuel. The petroleum diesel was On Road Diesel Supreme ULS petroleum fuel, referred to as B0 (0% biodiesel). The

biodiesel utilized was Peter Cremer North America Soy Methyl Ester Biodiesel. A 50/50 mixture of biodiesel and petroleum diesel fuel is referred to as B50 and 100% biodiesel is referred to as B100.

3.1. Sampling Analysis 3.1.1. Temperature Stability of the Diesel Engine Generator Power output for the engine generator was determined from the voltage of the generator and the amperage of the simulator. It was observed that on average the rated power output was lower for the 100% biodiesel.

23

Table 3-1: Real over rated power output percentage for B0, B50, and B100 Load Real/Rated Power Output (%) (kW) B0 B50 B100 25 99.70.05 96.21.04 95.5 50 960.52 99.53.98 93.4 75 92.31.01 92.41.01 84.2

The diesel engine generator operated at least 15 minutes at each load for temperature stabilization and steady state conditions before the start of the dilution sampling. According to 40 CFR 1065.530, Emission Test Sequence, for testing that involves hot stabilizing environment measurements, the test should start within 10 minutes of achieving temperature stability. The exhaust temperature was monitored from the initial start at each load. Figure 3-1 illustrates temperature variation for B0 (100% ULS

petroleum diesel fuel) as increasing loads are applied to the engine generator from time zero and that at 15 minutes when steady state was achieved. For most trials, more than 15 minutes for stability were allotted before the initiation of the dilution monitoring. The results at 15 minutes represent the initial sampling temperatures and are the approximate values found at each respective load for the petroleum diesel fuel.

24

Figure 3-1: Generator engine exhaust temperature stability over the loadings, Time (minutes) vs. Temperature (C)
325 275
Temperature (C)

225 175 125 75 0 5 10 Time (min) 15 20

0 kW 25 kW 50 kW 75 kW

3.1.2. Sampling Parameters Table 3-2 refers to the sampling system parameters employed during the experiments. The dilution ratio is low (~2), sufficient to maintain the filter temperature at an average of 20C (68F). During this high-volume dilution sampling, the filter temperature increased with the load increasing under similar dilution ratio.
Table 3-2: Performance characteristics of dilution sampler Parameter Range Exhaust flow 80 100 L/min Dilution air flow, Qd 120 200 L/min Total flow, Qt 200 300 L/min Dilution Ratio ~2 Reynolds Number, flow through mixing duct >10,000, turbulent

3.1.3. PM Mass Collected Under Actual Experimental Conditions Table 3-3 lists the average mass collected, ambient conditions, and sampling volumes corrected to standard temperature and pressure of 0C (273.15 K) and 101.3 kPa (1 atm)

25

for each fuel at the varying loads. Although constant total flow volume sampling, collecting the same total volume for each trial as outline in 40 CR 89 and 40 CFR 1065, was not performed, the low dilution ratio allowed total sampling volume and dilution volumes for all fuel types at all loads to be within 8% of all trials. All volumes decreased with load. As volumes decreased during the trial, an integrated average of the volume was used in determining the volume amounts. Constant total volume generally occurred at all loads except at the 75 kW loading. At 75 kW, a filter change was required with the B0 and B50 due to an increased pressure drop across the filter.

Table 3-3: Actual Experimental Conditions for B0, B50, and B100 over the loads Load Mass of Total Dilution Ambient % Filter Setting PM Volume Volume Temp. Relative Temp. (kW) collected, std m3 std m3 C Humidity C mg 0 0 43.43.1 7.250.55 4.430.64 23.63.9 30.45.4 15.6 25 46.35.7 7.330.23 4.740.22 22.73.2 31.61.4 18.3 50 38.77.9 7.010.24 4.530.17 25.81.8 28.85.5 21.1 75 55.94.8 5.900.38 3.890.37 28.65.0 30.72.5 23.9 B50 0 58.89.6 7.540.18 4.710.20 30.22.4 31.71.6 10.0 25 115.721.2 7.290.11 4.690.15 27.45.0 32.23.5 12.8 50 65.18.4 7.270.20 4.780.15 25.71.4 31.96.6 15.6 75 59.77.6 6.751.08 4.400.81 26.52.2 28.03.0 18.3 B100 0 72.611.1 6.970.06 3.970.32 33.31.1 23.82.3 21.1 25 186.61.7 6.530.19 3.960.05 36.50.7 16.42.4 23.9 50 105.61.4 6.300.21 4.070.02 35.30.3 14.21.2 26.7 75 74.40.5 6.190.35 4.110.26 35.60.0 12.00.0 29.4

3.1.4. Fuel and Energy Consumption Figure 3-2 illustrates fuel consumption in gallons per hour measured with the gravimetric burette of the fuel by-pass apparatus. Fuel consumption increased linearly with

increasing load. There is higher fuel consumption for B50 when compared to B0. Fuel consumption is proportional to the volumetric energy density of the fuel based upon the

26

lower or net heating value.5 This is consistent with petroleum diesel having a higher heat of combustion. The average energy content for biodiesel as analyzed for OKI Analytical Laboratory is 124,513 BTU/gal. The average energy content for petroleum diesel fuel is 129,500 BTU/gal. The reference data for fuel consumption is obtained from the Generac Power Systems, Inc. operating data manual for 25, 50, 75, and 100% load at 60 Hz. The rated output for these loads corresponds to 20, 40, 60, and 80 kW at 2.3, 3.2, 4.3, and 6 gallons per hour, respectively.

On average, the B50 had approximately 35% higher volumetric fuel consumption than the petroleum diesel. The fuel consumption for 100% biodiesel was about 25% higher than that of the petroleum diesel. At the lower loadings, B100 and B50 have similar fuel consumptions; however, at the higher loadings B100 operates with about 10% lower fuel consumption. Table 3-4 outlines the average fuel consumption results in gallons per hour. Table 3-5 outlines the average energy consumption in kilojoules per hour. Figure 3-5 illustrates the energy consumption per hour for B0, B50, and B100 over the sampling loads.
Table 3-4: Average Fuel Consumption for B0, B50, and B100 (gal/hr) Load Setting Fuel Consumption (gallons/hour) (kW) B0 B50 B100 0 1.05 1.33 1.38 25 1.98 2.64 2.65 50 3.17 4.38 3.81 75 4.32 5.95 5.02

27

Figure 3-2: Fuel Consumption (gal/hr) for B0, B50, B100, and Manual Reference
6
Fuel Consumption (gal/hr)

5 4 3 2 1 0 0 20 40 Load (kW) 60 80 B0 B50 B100 Ref

Table 3-5: Average Energy Consumption (kJ/hr) for B0, B50, and B100 Load Setting Energy Consumption (kJ x 105/hour) (kW) B0 B50 B100 0 1.45 1.85 1.81 25 2.71 3.55 3.29 50 4.34 5.11 5.01 75 5.91 7.10 6.60 Figure 3-3: Energy Consumption (kJ/hr) for B0, B50, and B100
7.00E+05 6.00E+05 5.00E+05 4.00E+05 3.00E+05 2.00E+05 1.00E+05 0 20 40 Load (kW) 60 80 B0 B50 B100

Energy Consumption (kJ/hr)

28

On average, the B50 energy consumption was 24% higher than B0 and B100 had on average only 20% higher energy consumption than the B0 fuel, even though the B100 has lower energy content than B50. The higher fuel consumption of the biodiesel is not only due to the lower fuel energy but may also be from a reduction in combustion efficiency.

3.2. Particulate Analysis The particulate matter, NOx, and carbon monoxide diesel engine emission rates for an engine rated between 56 kW to 130 kW are outlined in 40 CFR Part 1039, Control of Emissions from New and In-Use Non-Road Compression Ignition Engines. The

emissions rates of 0.02 g/kW-hr PM, CO 5.0 g/kW-hr, and 0.40 g/kW-hr NOx are required by 2014.

3.2.1. Diesel Particulate Matter (PM) The total PM mass concentration (soluble and insoluble) was determined by gravimetric method prior to the soluble extraction, with the total mass collected on the filter being divided by the total sampling volume, corrected to standard temperature and pressure 0C (273.15 K) and 101.3 kPa (1 atm). Sampling time for all loads was 30 minutes; B0 and B50 required three filter changes at 75 kW because of increased pressure drop across the filter. B100 did not require any filter changes in order to sample for the 30 minutes at any load. At minimum three runs at each load per fuel combination were analyzed. Figure 3-4 illustrates the filters for B0 at 0, 25, 50, and 75 kW. Figure 3-5 shows the filters after sampling with B100. The B0 filters are noticeably darker.

29

Figure 3-4: Quartz fiber filters after dilution sampling with B0 at 0 kW (A), 25 kW (B), and 50 kW (C) for 30 minutes and at 75 kW (D) for 15 minutes

Figure 3-5: Quartz fiber filters after dilution sampling with B100 at 0 kW (A), 25 kW (B), 50 kW (C), and 75 kW (D) for 30 minutes

Figure 3-6 compares the total diesel particulate matter (PM) concentration (mg/std m3) for the ultra low-sulfur petroleum diesel (B0) with the B50 blend and B100 fuel. Overall, the results indicate a much higher total particulate emission concentration for the biodiesel and biodiesel blend due to increased soluble compounds on the filter; however, the PM concentration for B50 is lower than B0 at 75 kW. At 25 and 50 kW, B50 emits about twice as much PM as B0 and B100 emits about three times as much PM as B0.
30

The total PM exhaust concentration for the B100 is higher at all loadings. The highest concentration for B50 and B100 occurs at 25 kW with the lowest at 0 kW. The lowest concentration for B0 occurs at 50 kW with the highest at 75 kW with similar concentrations at 0 and 25 kW loadings.

Figure 3-6: PM Concentration (mg/std m3) in Total Sampling Volume for B0, B50, and B100 over sampling loads (kW)
30 PM Concentration (mg/std m)
3

25 20 15 10 5 0 0 20 40 Load (kW) 60 80 B0 B50 B100

To determine the emission rate of total PM, the PM concentration over the total sampling volume by the exhaust gas flow rate yields the emission rate in terms of grams of emission per hour over each load. Figure 3-7 illustrates the PM emission rate (g/hr) for B0, B50, and B100 over each load. Figure 3-8 illustrates the emission rate (g/kW-hr) for B0, B50, and B100 over the sampling loads 25, 50, and 75 kW.

31

Figure 3-7: PM Emission Rate (g/hr) for B0, B50, and B100 over sampling loads (kW)
8 Emission Rate (g/hr) 7 6 5 4 3 2 1 0 0 20 40 Load (kW) 60 80 B0 B50 B100

Figure 3-8: PM Emission Rate (g/kW-hr) for B0, B50, and B100 over sampling loads 25, 50, and 75 kW
0.35 Emission Rate (g/kW-hr) 0.30 0.25 0.20 0.15 0.10 0.05 0.00 20 30 40 50 Load (kW) 60 70 80 B0 B50 B100

The PM emission rate (g/hr) generally decreased with load with a spike at 25 kW load for the biodiesel fuels. B100 emits the most grams of PM per hour than B50 or B0. B50 emitted the lowest by about 10% at 75 kW loading; however, it was within the uncertainty range of the B0 results and the B50 was much higher at 25 and 50 kW. B100
32

produced the highest emission rate (g/hr) at 25 kW, in excess of three times as much as B0. It is important to note that white smoke was continually evident during all trials at 25 kW for B100. White smoke was not apparent during any other runs. White smoke is generally an indication of the exhaust of water vapor or partially combusted biodiesel due to the relatively high fuel flow and low combustion temperatures at that power setting. During the engine start-up, all fuels produced a cloud of black smoke. The black smoke was darker for the petroleum fuel than was for the biodiesel fuel. The PM emission rate in g/kW-hr decreased as load increased for B50 and B100. B0 increased in PM emission rate (g/kW-hr) at the high loading. All fuels exceeded the PM limit of 0.02 g/kW-hr.

In order to further quantify the results, the PM concentration in the exhaust gas, along with the exhaust gas flow rate, fuel consumption, and the approximate density of the fuel was utilized to determine the milligram of PM emission per kilogram of fuel consumed. Figure 3-9 illustrates this emission rate (mg PM/kg fuel consumed) for B0, B50, and B100 over the loads. At the 0 and 75 kW loading, B50 produces the lowest emission rate by 6 and 50%, with an increase of 50% at the 25 kW loading. Although it is lower than B0 at 75 kW by 10%, the B100 produced much higher emission rates for mass of PM emitted per mass of fuel consumed at the other loadings, with a spike occurring at the 25 kW load. Figure 3-10 shows the emission rate in terms of micrograms of PM emitted per kilojoules of fuel consumed. Table 3-6 outlines the overall averages for the PM mass concentration and emission rates for each fuel tested over all loadings.

33

Figure 3-9: PM Emission Rate (mg emitted mass/kg of fuel consumed) for B0, B50, and B100 over sampling loads (kW)
1000 900 800 700 600 500 400 300 200 100 0 0 20 40 Load (kW) 60 80

mg PM / kg fuel consumed

B0 B50 B100

Figure 3-10: PM Emission Rate (g emitted mass/kJ of fuel consumed) for B0, B50, and B100 over sampling loads (kW)
30
Emission Rate (g/kJ)

25 20 15 10 5 0 0 20 40 Load (kW) 60 80 B0 B50 B100

34

Table 3-6: Average PM Emissions for B0, B50, and B100 over all loadings Emission Emission Emission Rate, Emission Load PM Conc., Rate, g/hr Rate, mg PM Rate, Setting mg/std m3 g/kW-hr emitted/kg fuel (kW) g/kJ burned B0 0 6.00 0.59 1.58 0.16 492.3 48.8 10.89 1.08 25 6.33 1.01 1.81 0.28 0.072 0.012 301.5 46.3 6.67 1.06 50 5.52 1.27 1.88 0.43 0.039 0.009 195.8 45.2 4.33 1.00 75 10.21 2.37 3.88 0.90 0.056 0.014 297.6 68.9 6.55 1.53 B50 0 7.78 2.13 2.05 0.56 481.7 131.8 11.40 3.12 25 15.85 2.80 4.53 0.80 0.189 0.034 539.3 94.9 12.77 2.25 50 8.96 2.97 3.06 1.01 0.060 0.018 220.1 72.9 5.21 0.77 75 9.11 1.19 3.48 0.45 0.050 0.007 183.9 21.2 4.33 0.57 B100 0 10.40 1.50 2.74 0.39 595.6 85.9 15.07 2.17 25 28.56 0.56 8.17 0.16 0.342 0.007 924.2 18.1 23.38 0.46 50 16.77 0.78 5.72 0.26 0.122 0.006 450.1 20.8 11.39 0.53 75 12.04 0.61 4.60 0.23 0.073 0.004 274.8 13.9 6.95 0.35

While operating the 1992 non-road diesel test engine generator with single dilution sampling, results indicated that the biodiesel blends produce more PM (prior to soluble extraction) than the petroleum diesel and that PM concentration (mg/std m3) increases with increasing biodiesel concentration at the same loading. Results also indicate that the biodiesel and biodiesel blend operates the least efficient at the 25 kW loading. The emission rate (g/kW-hr) decreased as loading increased.

Several studies have also found an increase in PM for biodiesel fuel in comparison to petroleum diesel fuel.4, 6, 20, 21 A possible explanation may be due to the higher density of the biodiesel fuel, as the density of fuel is correlated with particulate emissions. An increase in density correlates to an increase the particulate matter emissions.22 The increase in PM may also be attributed to the poor atomization and vaporization of the fuel due to its higher viscosity and lower vapor pressure. It is possible that biodiesel produces more unburned hydrocarbons due to its decreased combustion efficiency.

35

Related studies with similar emission rates on comparable engines and sampling methods may indicate the age of the engine and the absence of control technology may also contribute to higher PM concentrations. In a related study, an increase in PM and NOx with a decrease in insoluble PM, hydrocarbon emissions, and PAH emissions was determined from operating a direct-injection, 52 kW four-cylinder engine on rapeseed and soybean methyl esters in comparison to petroleum diesel. The sampling method employed was a double isokinetic dilution tunnel. Particulate matter concentration

increased linearly with increasing biodiesel percentage and the organic insoluble matter decreased with higher percentages of biodiesel. The rapeseed methyl ester had higher emission results than the soybean methyl ester, indicating some variability with source oil and corresponding emissions. The PM emission rates for B0 with and without a catalytic converter were 2 and 3 g/hr, respectively. For the B100, the PM emission rates with and without a catalytic converter were 5 and 9.5 g/hr.4 Increased PM concentration and NOx emissions with lower PAH emissions were also ascertained from a four-cylinder, 52 kW agriculture tractor diesel engine and 4.2 kW four-stroke direct injection test engine operating on rapeseed methyl ester. Higher percentages of sampled masses were

extracted from the filters from the biodiesel exhaust than those used for the petroleum diesel fuel. For the test engine equipped with a catalytic converter operating on rapeseed methyl ester, the PM emission rate for B0 was 2 g/hr and for B100 was 5 g/hr.20 Biodiesel is also known to have an effect on rubber parts within the engine.6 Biodiesel improves lubricity and because of its solvent properties may have the effect of cleaning out the fuel lines and fuel tank, resulting in dissolved material in the particulate matter emissions.

36

The increased PM results for the biodiesel fuels could also be attributed to the different experimental ambient air temperature and humidity conditions. The biodiesel fuel was tested during elevated ambient temperatures with low relative humidity whereas the ultralow sulfur petroleum fuel and B50 blend tests were completed during mild ambient temperature and relative humidity levels. Humidity and temperature may influence the nature of combustion. Sampling parameters, such as temperature consistency across the filter, may also influence the results.

The age of the engine, type of source oil, sampling method, environmental conditions, and control technology present on the engine all can affect the overall emission from the biodiesel and petroleum fuels. In a related dilution sampling research on a 2003 non-road diesel engine with current emission control devices, significant reductions in PM and CO with a slight increase in NOx were found from operating with soybean methyl ester biodiesel and pure methyl esters, methyl oleate, methyl palmitate, and methyl laurate. The PM emission rate while operating on petroleum diesel was 0.15 g/kW-hr and while operating on the methyl soyate was 0.03 g/kW-hr.23

3.3. Exhaust Gas Analysis Temperature, carbon monoxide (CO), carbon dioxide, oxides of nitrogen (NOx), and percent oxygen in the exhaust stream were measured utilizing the Testo Gas Analyzer.

37

3.3.1 Temperature The temperature of the engine exhaust was monitored continuously over the course of the experiments. Figure 3-11 illustrates the average exhaust temperature (C) recorded for each fuel over the varying loads. Ambient temperatures greatly influenced exhaust temperatures. The generator engine was operated on the B100 during elevated ambient temperatures, approximately 35C, in comparison to the B50 at 27C and B0 at 25C ambient conditions.

Figure 3-11: Temperature Profile of exhaust stream (C) for B0, B50, and B100 over sampling loads (kW)
Exhaust Stream Temperature (C)

400 350 300 250 200 150 100 0 20 40 Load (kW) 60 80 B0 B50 B100

Exhaust temperature increased linearly with increasing loading. The temperatures of the exhaust stream for B50 and B0 were extremely close for the higher loadings and the B50 was only about 7% higher at 0 and 25 kW than the B0. The B100 produced the highest exhaust temperatures, about 20% higher at the low loadings and about 8% higher at the higher loadings.

38

3.3.2. Carbon Monoxide Increasing loads on diesel engines leads to an increase in the combustion temperature and efficiency, resulting in lower carbon monoxide (CO) emissions when compared to lower loading conditions. Soot (the insoluble fraction of the particulate matter) is a product of incomplete combustion, which usually increases directly with fuel consumption.
Figure 3-12: Carbon Monoxide (ppm) in the exhaust stream for B0, B50, and B100 over sampling loads (kW)
300 250 CO (ppm) 200 150 100 50 0 0 20 40 Load (kW) 60 80 B0 B50 B100

Figure 3-12 illustrates that the biodiesel and biodiesel blend produced lower CO levels than the B0. B100 produced the most dramatic decrease in CO at the lowest and highest loadings, resulting in a 60% decrease at 0 kW and an 85% decrease at 75 kW from the B0, although the low CO concentrations at the high loading falls within the accuracy of the instrument (10 ppm).

39

3.3.3. Carbon Dioxide As the load increases with higher temperatures and higher fuel usage, more of the fuels carbon is oxidized to carbon dioxide (CO2), and carbon dioxide increases with increased loads. Complete combustion results in all carbon in the fuel to be converted to carbon dioxide, whereas carbon monoxide is a result of incomplete combustion. The increase in carbon dioxide for biodiesel over the petroleum diesel is shown in Figure 3-13. B50 resulted in about a 20% increase in CO2 emissions when compared to B0 and B100 resulted in an average 30% increase compared to B0.
Figure 3-13: Carbon Dioxide (%) in exhaust stream for B0, B50, and B100 over sampling loads (kW)
9 8 7 6 CO2 (%) 5 4 3 2 1 0 0 20 40 Load (kW) 60 80 B0 B50 B100

3.3.4. Oxides of Nitrogen (NOx) The 2002 U.S. EPA study established that NOx emissions for biodiesel and biodiesel blends are typically higher than the NOx emissions from petroleum diesel.19 As NOx is dependent on temperature, an increase in combustion temperature will lead to an increase in NOx, as is shown in Figure 3-14. The B100 and B50 operated at slightly higher

40

temperatures, which resulted in slightly higher NOx. NOx emissions were lower for B50 at 0 kW when compared to B0, but conversely were about 35% higher at the highest load. B100 resulted in NOx emissions about 25% higher than B0 at 0 and 50 kW and about 45% higher at 25 and 75 kW.
Figure 3-14: Oxides of Nitrogen (ppm) in exhaust stream for B0, B50, and B100 over sampling loads (kW)
1800 1600 1400 NOx (ppm) 1200 1000 800 600 400 200 0 0 20 40 Load (kW) 60 80 B0 B50 B100

3.3.5. Percent Oxygen Less oxygen and more carbon dioxide for the biodiesel and biodiesel blend indicates a more complete combustion, which is consistent with the CO results. Figure 3-15 shows that the biodiesels produced about a 7% decrease in the percent oxygen in the exhaust stream when compared to B0.

41

Figure 3-15: Percent Oxygen in exhaust stream for B0, B50, and B100 over sampling loads (kW)
22 20 18 O2 (%) 16 14 12 10 0 20 40 Load (kW) 60 80 B0 B50 B100

Table 3-7 outlines the averaged results for the gaseous emissions measured with the Testo Gas Analyzer. The data listed includes the exhaust temperature (C), carbon monoxide (ppm), percent carbon dioxide, NOx (ppm), and percent oxygen.
Table 3-7: Average Gaseous Emissions for B0, B50, and B100 over all loadings Load Exhaust CO, ppm CO2, % NOx, ppm O2, % Setting Temp. C (kW) B0 0 120 1.5 250 30 1.76 0.28 227 7 19.5 0.53 25 183 9.8 138 12 3.28 0.03 440 28 16.6 0.09 50 258 5.4 70 5 5.54 0.07 876 24 13.8 0.06 75 311 6.1 31 5.5 5.92 0.37 1079 95 12.1 1.49 B50 0 131 2 191 14.5 2.11 0.03 200 5 18.1 0.03 25 196 4.9 132 8.5 3.96 0.11 512 30.5 16.3 1.03 50 260 0.6 63 2.5 5.64 0.08 966 19.5 13.4 0.05 75 310 7.2 17 3 7.16 1550 11.4 0.02 B100 0 153 2.5 138 7.5 2.75 281 9.5 18.2 0.02 25 220 10 115 3.5 4.4 690 1.5 15.5 0.02 50 275 5 53 2.5 6.1 1185 13.3 75 342 8.5 12 0.5 7.9 1702 2 11.2 0.01

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3.4. Chemical Composition Analysis 3.4.1. Soluble Fractions of PM The soluble fraction or percent of volatile organics extracted is determined from the collected PM mass on the quartz fiber filters before and after extraction. The organics were extracted from the filters with dichloromethane (DCM) in order to perform the analysis. Figure 3-16 illustrates the results of the extraction percentages. The percent organics extracted was consistently higher for the B100 and B50 than for the B0. The organics extracted were highest at light engine loads when combustion temperatures are lower. The organic fraction of B50 is higher than for petroleum, and B100 is higher than B50, meaning that combustion of biodiesel and the biodiesel blend emit higher unburned hydrocarbons. Even though the emitted volatile concentrations were higher for biodiesel, the amount of soot emitted is higher for the petroleum diesel.
Figure 3-16: Percent Organics Extracted for B0, B50, and B100 over sampling loads (kW)
100 95

Percent Soluble (%)

90 85 80 75 70 65 60 0 20 40 Load (kW) 60 80 B0 B50 B100

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Table 3-8: Percent Organics Extracted for GC/MS analysis of B0, B50, and B100 at each sampling load (kW) Load Setting Percent Organic Extracted (kW) B0 B50 B100 0 93.6 1.9 95.3 2.8 93.8 25 91.7 1.5 95.8 1.5 95.5 1.3 50 77.8 6.1 92.1 4.7 94.9 0.1 75 65.4 1.7 81.3 7.2 76.9 0.4

Table 3-9 lists the average collected mass (mg) for each fuel at the various loads. This constitutes the mass dissolved in solvent utilized for subsequent thermal analysis.
Table 3-9: Total amount of mass collected (mg) for GC/MS analysis of B0, B50, and B100 at each sampling load (kW) Load Setting Collected Mass (mg) (kW) B0 B50 B100 0 41.6 2.3 56.8 15.7 57.8 25 38.5 1.8 112.5 20.7 178.3 0.8 50 31.1 7.6 48.2 3.9 100.2 1.3 75 10.7 1.0 18.5 3.1 57.2 0.1

The percentage in total extracted organic PM mass for each category decreases at the higher loadings, which corresponds to an increase in the insoluble fraction (soot). Biodiesel produced lower concentrations of emitted insoluble PM, but a larger amount of organic PM. The soluble gaseous emissions were determined from the combined

extraction of the XAD adsorbent and polyurethane foams.

3.4.2. n-Alkanes Normal alkanes account for a large fraction of the diesel fuel and the identifiable portion of diesel exhaust. An external standard of normal alkanes ranging from n-C10 to n-C25 was utilized to determine the concentration in the fuel and exhaust. The standard was obtained from Restek Corporation, DRO Mixture (Tennessee/Mississippi) Catalogue

44

Number 31214. The following table, Table 3-10, lists the components, elution order, and chemical properties of the n-alkane standard, as listed from Restek Corporation.
Table 3-10: n-Alkane standard elution order and chemical properties Elution Compound Formula Molecular Boiling Melting Density Order Weight Point Point (g/cm3) (g/gmol) (C) (C) 1 (C10) Decane C10H22 142.28 174 -30 0.73 2 (C11) Undecane C11H24 156.31 196 -26 0.74 3 (C12) Dodecane C12H26 170.33 216 -9.6 0.75 4 (C13) Tridecane C13H28 184.36 234 -5 0.76 5 (C14) Tetradecane C14H30 198.39 253 5.5 0.76 6 (C15) Pentadecane C15H32 212.41 270 9 0.77 7 (C16) Hexadecane C16H34 226.44 287 18 0.77 8 (C17) Heptadecane C17H36 240.47 302 21 0.78 9 (C18) Octadecane C18H38 254.49 317 28 0.78 10 (C19) Nonadecane C19H40 268.52 330 33 0.79 11 (C20) Eicosane C20H42 282.55 220 36 N/A 12 (C21) Heneicosane C21H44 296.57 100 40 N/A 13 (C22) Docosane C22H46 310.60 369 44 0.78 14 (C23) Tricosane C23H48 324.63 200 47 N/A 15 (C24) Tetracosane C24H50 338.65 391 50 N/A 16 (C25) Pentacosane C25H52 352.68 170 55 N/A

According to the World Health Organization, petroleum diesel fuel comprises of approximately 65% n-alkanes and about 2 to 30% aromatics.3 Figure 3-17 illustrates the n-alkane distribution (concentration percentage) for ULS petroleum diesel and B50 soybean methyl ester fuel utilized in this research. The petroleum fuel demonstrates a bell-shaped distribution from C10 (docane) to C23 (tricosane), with the most abundant occurring at C16 (hexadecane) to C21 (heneicosane). Since there are no alkanes present in biodiesel fuel, lower concentrations of these are expected in the PM and gas phase, and the relative concentration of the n-alkanes in B50 half that of the B0. Figure 3-17 shows that less than half the amount of n-alkanes is present in the biodiesel blend. Although biodiesel has been found to be completely miscible in petroleum fuel5, there may be some
45

amount of settling that occurs because of the differences in density and viscosity for the two fuels.
Figure 3-17: n-Alkanes Concentration (%) in B0 and B50 Fuel
18 16 14
Concentration (%)

12 10 8 6 4 2 0
de ca un ne de c d o an e de ca tri n e de c te tra ane de pe c n t ane ad ec he a x a ne de he c p t ane ad e o c can ta d e n o ecan na e de ca ei ne h e cos a ne ne ic os a do ne co sa tri ne co s te tra an e co pe s n t an e ac os an e

B0 B50

For all fuel types, the n-alkane concentration in both the particulate and gas phase was highest for the B0 fuel. The PM and gaseous compound concentration over the sampling volume (g/std m3) and emission rate (mg/hr) was highest at the 25 kW loading, except B100 gas phase which experienced the highest n-alkane concentration emission at 0 kW. Higher concentrations were emitted at the 0 and 25 kW load than 50 and 75 kW though fuel consumption rate increases linearly with load. The increase at 25 kW corresponds to the increase in mass collected for analysis. The lowest mass collected was at 75 kW, which resulted in the lowest concentrations. In addition, as the load increases, unburned fuel will be reduced due to improved fuel combustion at higher temperatures, which will also lead to the reduction of the compound concentration in the PM.

46

To quantify the results further, the emission rate is expressed in terms of milligram of compound emitted per kilogram of fuel consumed. The emission rate is also expressed in terms of nanogram of compound emitted per kilojoules of fuel consumed. For B0, these emission rates are the highest for each fuel type with a maximum in both the particulate phase and gaseous phase at 0 kW. For B50 and B100, the highest in the PM occurred at 25 kW and in the gaseous phase, 0 kW emitted the highest amount of n-alkane per amount of fuel consumed.

As exhaust gas temperatures increase with load, the higher combustion temperatures reduce the unburned hydrocarbons due to higher combustion efficiency. For all fuel types, the gas phase concentrations were higher than the particle phase concentration.

Lighter alkanes are present in the gas phase as opposed to the heavier alkanes found in the particle phase. There is a shift to heavier n-alkanes from diesel fuel to PM, as the result of the combustion process, as shorter-chained alkanes are more likely to undergo complete combustion than heavier alkanes.3 Figure 3-18 through Figure 3-21 shows the n-alkane distributions for B0 in the particulate phase.

47

Emission Rate (mg/hr)

Concentration (g/m)
100 120 20 40 60 80 0

10

15

20

25

30

35

40

Figure 3-18: n-Alkane PM Concentration (g/std m3) for B0 over sampling loads (kW)

Figure 3-19: n-Alkane PM Emission Rate (mg/hr) for B0 over sampling loads (kW)

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de c u n an e de c d o an e de c tri an e de c te tra ane p e dec n t an ad e h e e ca x a ne h e dec p t an ad e e o c can ta d e n o ec a na ne de ca ei ne co he n e s an ic e os a do ne co s tri ane co te s tr a a n e co pe n t san ac e os an e

de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e h e eca x a ne h e dec p t an ad e e o c can ta d e n o e ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te tra san e p e co s n t an ac e os an e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (ng/kJ)

0 1 2 3 4 5 6 7 200 180 160 140 120 100 80 60 40 20 0

mg Compound/kg fuel consumed

Figure 3-21: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)

Figure 3-22 through Figure 3-25 illustrates the n-alkane distribution in the gaseous phase.

Figure 3-20: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)

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de c u n an e de c d o an e de c tri an e de te c tra ane de pe n t can ad e h e e ca x a ne h e dec p t an ad e o c e ca ta ne d n o ec a na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te s tr a a n e co pe n t san ac e os an e

de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e h e e ca x a ne h e dec p t an ad e e o c can ta d e n o ec a na ne de ca ei ne h e cos n e an ic e os d o an e co s tri ane co te tra san e p e co sa nt ac n e os an e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (mg/hr)

Concentration (g/m)
100 200 300 400 500 600 700 800 0

100

150

200

250

50

Figure 3-22: n-Alkane Concentration in Gaseous Phase (g/std m3) for B0 over sampling loads (kW)

Figure 3-23: n-Alkane Gaseous Emission Rate (mg/hr) for B0 over sampling loads (kW)

50

de c u n an e de c d o an e de c tri an e de te tr a c a n e p e dec n t an ad e h e e ca x a ne h e dec p t an ad e e o c can ta de e n o ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te s tr a a n e co pe n t san ac e os an e de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e h e eca x a ne h e dec p t an ad e e o c can ta d e n o e ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te tra san e p e co s n t an ac e os an e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Figure 3-24: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)
mg Compound/kg fuel consumed

40 35 30 25 20 15 10 5 0
de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e h e e ca x a ne h e dec p t an ad e e o c can ta d e n o ec a na ne de ca ei ne h e cos n e an ic e os d o an e co s tri ane co te tra san e p e co sa nt ac n e os an e

0 kW 25 kW 50 kW 75 kW

Figure 3-25: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)
900 800
Emission Rate (ng/kJ)

700 600 500 400 300 200 100 0

de c u n an e de c d o an e de c tri an e de te c tra ane de pe n t can ad e h e e ca x a ne h e dec p t an ad e o c e can ta d e n o ec a na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te s tr a a n e co pe n t san ac e os an e

0 kW 25 kW 50 kW 75 kW

Figure 3-26 through Figure 3-29 display the results of the n-alkane distribution for B50 in the particulate phase over the various loadings. No heneicosane (C21) was detected in the B50 exhaust for either the PM or gas phase. This may be due to the presence of the methyl ester. The methyl esters elution occurs around the same time, as C21 and the
51

peaks are not separated. The n-alkane concentration and emission rate in the PM for B50 is about half that of the B0 except at the 25 kW loading where the decrease is only about 25%, which agrees with the reduction in n-alkane from the biodiesel fuel.

Figure 3-26: n-Alkane PM Concentration (g/std m3) for B50 over sampling loads (kW)
100 90 80 70 60 50 40 30 20 10 0
de c u n an e de c d o an e de c tri an e de te tr a c a n e p e dec n t an ad e h e e ca x a ne h e dec p t an ad e o c e can ta d e n o ec a na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te s tra an e co pe n t san ac e os an e

Concentration (g/m)

0 kW 25 kW 50 kW 75 kW

Figure 3-27: n-Alkane PM Emission Rate (mg/hr) for B50 over sampling loads (kW)
30
Emission Rate (mg/hr)

25 20 15 10 5 0
de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e e h e can xa e h e dec p t an ad e o c e can ta d e n o ec a na ne de ca ei ne h e cos n e an ic e os d o an e co s tri ane co s te tr a a n e co pe n t san ac e os an e

0 kW 25 kW 50 kW 75 kW

52

Emission Rate (ng/kJ)

0.5 1.5 2.5

mg Compound/kg fuel consumed

3.5

10
0 1 2

20

30

40

50

60

70

80

Figure 3-28: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)

Figure 3-29: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)

Figure 3-30 through Figure 3-33 shows the n-alkane distribution for B50 in the gaseous phase of exhaust.

53

de c u n an e de c d o an e de c tri an e de te c tra ane d p e eca nt ad ne h e e ca x a ne h e dec p t an ad e e o c can ta d e n o ec a na ne de ca ei ne co he n e s an e ic os d o an e co s tri ane co s te tr a a n e co pe n t san ac e os an e

de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e e h e can xa e h e dec p t an ad e e o c can ta d e n o e ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co s te tra an e co pe n t san ac e os an e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (mg/hr)

Concentration (g/m) 100 150 200 250 300 350 400 50 0

100 90 80 70 60 50 40 30 20 10 0

Figure 3-30: n-Alkane Concentration in Gaseous Phase (g/std m3) for B50 over sampling loads (kW)

Figure 3-31: n-Alkane Gaseous Emission Rate (mg/hr) for B50 over sampling loads (kW)

54

de c u n an e de c d o an e de c tri an e de te c tra ane de pe n t can ad e h e e ca x a ne h e dec p t an ad e o c e ca ta ne d n o ec a na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te tra san e p e co sa nt ac n e os an e de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e h e e ca x a ne h e dec p t an ad e o c e ca ta ne d n o ec a na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane c te osa tra n e p e co s n t an ac e os an e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Figure 3-32: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)
mg Compound/kg fuel consumed

25 20 15 10 5 0
de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e e h e can xa e h e dec p t an ad e o c e can ta d e n o ec a na ne de ca ei ne h e cos n e an ic e os d o an e co s tri ane co s te tr a a n e co pe n t san ac e os an e

0 kW 25 kW 50 kW 75 kW

Figure 3-33: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)
600
Emission Rate (ng/kJ)

500 400 300 200 100 0

de c u n an e de c d o an e de c tri an e de te c tra ane de pe n t can ad e h e eca x a ne h e dec p t an ad e e o c can ta de e n o ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te s tra an e co pe n t san ac e os an e

0 kW 25 kW 50 kW 75 kW

Figure 3-34 through Figure 3-37 display the results of the n-alkane distribution for B100 in the particulate phase over the various loadings. As with the B50 results, heneicosane (C21) was not detected in the B100 exhaust for either the PM or gas phase.

55

Emission Rate (mg/hr)

Concentration (g/m)

0.5 1 2 3 0 2 4 6 8

1.5

2.5

3.5

10

12

Figure 3-34: n-Alkane PM Concentration (g/std m3) for B100 over sampling loads (kW)

Figure 3-35: n-Alkane PM Emission Rate (mg/hr) for B100 over sampling loads (kW)

56

de c u n an e de c d o an e de c tri an e de te c tra ane d p e eca nt ad ne h e e ca x a ne h e dec p t an ad e e o c can ta d e n o ec a na ne de ca ei ne co he n e s an e ic os d o an e co s tri ane co s te tr a a n e co pe n t san ac e os an e de c u n an e de c d o an e de c tri an e de te c tra ane de pe n t can ad e h e eca x a ne h e dec p t an ad e e o c can ta de e n o ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te s tra an e co pe n t san ac e os an e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (ng/kJ)

mg Compound/kg fuel consumed

0.05

0.15

0.25

0.35

10 9 8 7 6 5 4 3 2 1 0
0.1 0.2 0

0.3

0.4

Figure 3-36: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)

Figure 3-37: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW)

Figure 3-38 through Figure 3-41 show the n-alkane distribution for B100 in the gaseous phase of exhaust.

57

de c u n an e de c d o an e de c tri an e de te c tra ane de pe n t can ad e h e e ca x a ne h e dec p t an ad e e o c can ta de e n o ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te s tr a a n e p e co sa nt ac n e os an e de c u n an e de c d o an e de c tri an e de te c tra ane de pe n t can ad e h e e ca x a ne h e dec p t an ad e e o c can ta de e n o ca na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane co te tra san e p e co sa nt ac n e os an e

0 kW

0 kW

75 kW

50 kW

25 kW

75 kW

50 kW

25 kW

Emission Rate (mg/hr)

Concentration (g/m)

10 100 20 40 60 80 0

15

20

25

30

35

40

120

140

Figure 3-38: n-Alkane Concentration in Gaseous Phase (g/std m3) for B100 over sampling loads (kW)

Figure 3-39: n-Alkane Gaseous Emission Rate (mg/hr) for B100 over sampling loads (kW)

58

de c u n an e de c d o an e de c tri an e de te c tra ane de pe c n t ane ad h e eca x a ne h e dec p t an ad e e o c can ta d e n o e ca na ne de ca ei ne co he n e s an e ic os d o an e co s tri ane co s te tra an e co pe n t san ac e os an e de c u n an e de c d o an e de c tri an e de te c tra ane p e dec n t an ad e h e e ca x a ne h e dec p t an ad e o c e ca ta ne d n o ec a na ne de ca ei ne co he n e s an ic e os d o an e co s tri ane c te osa tr a n e p e co sa nt ac n e os an e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Figure 3-40: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)
mg Compound/kg fuel consumed

8 7 6 5 4 3 2 1 0
de c u n an e de c d o an e de c tri an e de c te tra ane de pe n t can ad e h e e ca x a ne h e deca pt ad ne e o c can ta d e n o ec a na ne de ca ei ne h e cos n e an ic e os a do ne co s tri ane co te s tr a a n e co pe s n t an e ac os an e

0 kW 25 kW 50 kW 75 kW

Figure 3-41: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW)
200 180 160 140 120 100 80 60 40 20 0
de c u n an e de c d o an e de c tri an e de c te tra ane de pe n t can ad e h e e ca x a ne h e dec p t an ad e o c e can ta d e n o ec a na ne de ca ei ne co he n e s an ic e os a do ne co s tri ane co te tra san e p e co sa nt ac n e os an e

Emission Rate (ng/kJ)

0 kW 25 kW 50 kW 75 kW

There is a peak at heptadecane (C17) for all fuels. The amount of n-alkanes in the exhaust for the biodiesel is considerably less than the petroleum fuel. This is attributed to the absence of n-alkanes in the biodiesel fuel.

59

3.4.3. Polycyclic Aromatic Hydrocarbon The U.S. EPA 16-priority polycyclic aromatic hydrocarbons (PAHs) are important due to their carcinogenic and mutagenic properties. Fuel content of PAHs and mono-aromatics has the strongest influence on PAH emissions. The main source of PAH in the diesel exhaust is from unburned PAHs present in the fuel, pyrosynthesis during combustion, and the modification of one PAH into another.1 An external standard of the 16 PAHs was utilized to determine concentration in the fuel and exhaust. The standard was obtained from Restek Corporation, Catalogue Number 31011 SV Calibration Mix #5. The

following table lists the components, elution order, and chemical properties, as listed by Restek Corporation.
Table 3-11: U.S. EPA 16-priority PAH standard elution order and chemical property Molecular Boiling Melting Point Formula Elution Compound Weight Point (C) Order (g/gmol) (C) Naphthalene 1 C10H8 128.17 218 80 Acenaphthylene 2 C12H8 152.19 280 80 Acenaphthene 3 C12H10 154.21 279 93 Fluorene 4 C13H10 166.22 298 112 Phenanthrene 5 C14H10 178.23 340 99 Anthracene 6 C14H10 178.23 340 213 Fluoranthene 7 C16H10 202.25 384 108 Pyrene 8 C16H10 202.25 N/A 148 Benzo(a)anthracene 9 C18H12 228.29 N/A N/A Chrysene 10 C18H12 228.29 448 253 Benzo(b)fluoranthene 11 C20H12 252.31 N/A 164 Benzo(k)fluoranthene 12 C20H12 252.31 N/A 216 Benzo(a)pyrene 13 C20H12 252.31 495 178 Indeno(1,2,3-cd)pyrene 14 C22H12 276.33 N/A N/A Dibenzo(a,h)anthracene 15 C22H14 278.35 N/A N/A Benzo(g,h,i)perylene 16 C22H12 276.33 N/A N/A

60

The major component in petroleum diesel fuel is n-alkanes with about 2 to 30% in concentration consisting of aromatics. Figure 3-42 depicts the measured PAH

distribution (ppm) for B0 and B50 fuels. There are no PAHs present in B100 fuel.
Figure 3-42: PAH Concentration (%) in B0 and B50 Fuel

2.5
Concentration (%)

2 1.5 1 0.5 0
na ac p ht en h a a p le n ac hth y e e n le ap n e ht he f lu n e ph en o r an en e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne ry n z f lu o( o r sen k) an e flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e n z )an re n o( g, thra e h, ce i )p n er e yl en e

B0 B50

As with the n-alkane distribution in the fuel, less than half the PAHs present in ULS petroleum fuel is found in the 50/50 mixture of soybean methyl ester and ULS petroleum fuel. The B50 fuel sample was prepared by taking 1 mL of biodiesel and petroleum diesel and manually mixed before sampling.

The more volatile PAHs, such as phenanthrene, are not efficiently trapped on the quartz filter employed to collect particulate matter. The amounts of the PAH concentrations measured for the exhaust are believed to be less than the actual amounts emitted. As the vapor pressure of a PAH increases, it becomes more volatile and is trapped less efficiently on the filter.25

61

Emission Rate (mg/hr)

ac

Concentration (g/m)

ac

0 kW with the lowest amount at 75 kW.

10

35 30 25 20 15 10 5 0

Figure 3-43: PAH PM Concentration (g/std m3) for B0 over sampling loads (kW)

Figure 3-43 through Figure 3-46 illustrate the PAH concentration and emission rates for

B0 in the particulate phase. The particulate phase PAH for B0 was consistently higher at

Figure 3-44: PAH PM Emission Rate (mg/hr) for B0 over sampling loads (kW)

62

na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o re an n e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n n t d i o(1 zo(a h en be ,2 )p e nz ,3- y o c re b e (a,h d)py n e n z )an re n o( g, thra e h, i )p cen er e yl en e na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o re an n e t an hre th ne flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n n t d i o(1 zo(a h en be ,2 )p e nz ,3- y o c re b e (a,h d)py n e n z )an re n o( g, thra e h, i )p cen er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (ng/kJ)

ac ac

mg Compound/kg fuel consumed

0.5

1.5

2.5

70 60 50 40 30 20 10 0 0 1

B0 in the gas phase.

Figure 3-45: PAH PM Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)

Figure 3-46: PAH PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)

Figure 3-47 through Figure 3-50 illustrate the PAH concentration and emission rates for

The gaseous phase PAHs were considerably higher than the

63

na ph en th a a p le n ac hth y e en le ap n e ht he n p h flu e en o re an n e t an hre th ne f lu r a c o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e n z )an re n o( g, thra e h, i )p cen er e yl en e na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o r an en e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r sen k) an e flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e n z )an re n o( g, thra e h, i )p cen er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (mg/hr)

ac

Concentration (g/m)

ac

100

100

150

200

250

20 50 0

40

60

80

fuel consumed was highest at the low loadings.

amounts measured in the particulate phase. The amount of measured PAH for B0 per

Figure 3-47: PAH Concentration in Gaseous Phase (g/std m3) for B0 over sampling loads (kW)

Figure 3-48: PAH Gaseous Emission Rate (mg/hr) for B0 over sampling loads (kW)

64

na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o re an n e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n n t d i o(1 zo(a h en be ,2 )p e nz ,3- y o c re b e (a,h d)py n e n z )an re n o( g, thra e h, i )p cen er e yl en e na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o re an n e t an hre th ne flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n n t d i o(1 zo(a h en be ,2 )p e nz ,3- y o c re b e (a,h d)py n e n z )an re n o( g, thra e h, i )p cen er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (ng/kJ)

ac ac

mg Compound/kg fuel consumed

450 400 350 300 250 200 150 100 50 0

20 18 16 14 12 10 8 6 4 2 0

B50 was highest at 25 kW.

Figure 3-49: PAH Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0 over sampling loads (kW)

Figure 3-50: PAH Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0 over sampling loads (kW)

Figure 3-51 through Figure 3-54 display the PAH concentration emission for B50 at the

various loads for the PM phase of the exhaust. The concentration and emission rate for

65

na ph en th a a p le n ac hth y e en le ap n e ht he flu n e ph en o re an n e t an hren th e f lu r a c o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r sen k) an e flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r en o c b e (a,h d)py e n z )an re n o( g, thra e h, i )p cen er e yl en e na ph en th a ap le n ac hth y e e n le ap n e ht he f lu n e ph en o re an n e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r sen k) an e flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e n z )an re n o( g, thra e h, i )p cen er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (mg/hr)

ac ac

Concentration (g/m)

10

15

20

25

7 6 5 4 3 2 1 0 0 5

Figure 3-51: PAH PM Concentration (g/std m3) for B50 over sampling loads (kW)

Figure 3-52: PAH PM Emission Rate (mg/hr) for B50 over sampling loads (kW)

66

na ph en th a a p le n ac hth y e en le ap n e ht he flu n e ph en o re an n e t an hren th e f lu r a c o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n n t d i o(1 zo(a h en be ,2 )p e nz ,3- y o c re b e (a,h d)py n e n z )an re n o( g, thra e h, i )p cen er e yl en e na ph en th a a p le n ac hth y e e n le ap n e ht he f lu n e ph en o re an n e t an hre th ne flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n n t d i o(1 zo(a h en be ,2 )p e nz ,3- y o c re b e (a,h d)py n e n z )an re n o( g, thra e h, i )p cen er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (ng/kJ)

ac ac

mg Compound/kg fuel consumed

0.2

0.4

0.6

0.8

10

15

20

0 0

lowest amount of emitted compound as fuel is consumed at 0 kW.

Figure 3-53: PAH PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)

Figure 3-54: PAH PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)

Figure 3-55 through Figure 3-58 shows the PAH gas phase concentration and emission

for B50. The distribution is similar to the PAH amounts in the particulate phase, with the

67

na ph en th a a p le n ac hth y e e n le ap n e ht he f lu n e ph en o re an n e t an hre th ne flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z fl ry o( uo r se k) an ne flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r en o c b e (a,h d)py e n z )an re n o( g, thra e h, i )p cen er e yl en e na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o r an en e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r sen k) an e flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e )a nz r o( n th en e g, h , r a ce i )p n er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (mg/hr)

ac ac

Concentration (g/m)

100

150

200

10 50 0

20

30

40

50

60

Figure 3-55: PAH Concentration in Gaseous Phase (g/std m3) for B50 over sampling loads (kW)

Figure 3-56: PAH Gaseous Emission Rate (mg/hr) for B50 over sampling loads (kW)

68

na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o r an en e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r sen k) an e flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e n z )an re n o( g, thra e h, i )p cen er e yl en e na ph en th a a p le n ac hth y e e n le ap n e ht he n p h f lu e en o re an n e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n n t d i o(1 zo(a h en be ,2 )p e nz ,3- y o c re b e (a,h d)py n e n z )an re n o( g, thra e h, i )p cen er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

Emission Rate (ng/kJ)

ac

mg Compound/kg fuel consumed

100

150

200

250

50 0 2 4 6

10

12

Figure 3-58: PAH Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)

consistently less that the PAH emission for B0. Fluorene emission showed a small

Figure 3-57: PAH Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)

There are no PAHs present in biodiesel fuel and there were no PAHs detected in either

the particulate or the gaseous phase of B100 emission. The PAH emission for B50 was

69

na ac p ht en h a a p le n ac hth y e e n le ap n e ht he n p h f lu e or en an en e t an hren th e flu rac o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r sen k) an e flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e )a nz r o( n th en e g, h , r a ce i )p n er e yl en e na ph en th a a p le n ac hth y e en le ap n e ht he n p h flu e en o re an n e t an hre th ne f lu r a c o r en an e be th nz en o( a) p y e an re th ne be ra nz ce o( b e b) ch ne n z f lu r y o( o r se k) an ne flu th id b e o ra en e en n z n t d i o(1 o(a h en be ,2 )p e nz ,3- y r o en c b e (a,h d)py e n z )an re n o( g, thra e h, i )p cen er e yl en e

0 kW

75 kW

50 kW

25 kW

0 kW

75 kW

50 kW

25 kW

fluctuation for B50 over the B0 results. Phenanthrene, fluoranthene, and anthracene are the major PAHs found in PM for petroleum diesel.3 As the engine loads increases, the PAH concentration increases with a bell-type distribution for the particulate phase phases. The PAH emissions in the gas phase are considerably higher than those found in the PM. The major PAHs in total emissions are the lighter PAHs.

3.4.4. Methyl Esters An external standard was utilized to determine concentration of methyl esters in the fuel and exhaust. The standard was obtained from Restek Corporation, Catalogue Number 35024 AOCS Standard #3 Rapeseed Oil. The following table, Table 3-12, lists the components, elution order, and chemical properties, as listed from Restek Corporation.

Table 3-12: Methyl Ester Rapeseed Oil standard, elution order and chemical property Molecular Boiling Melting Density Formula Elution Compound Weight Point Point (g/cm3) Order (g/gmol) (C) (C) 1 (C16:0) Methyl Palmitate C17H34O2 270.45 185 34 0.852 (Hexadecanoic ME) 2 (C18:2) Methyl Linoleate C19H34O2 294.48 192 -35 0.889 (Octadecadienoic ME) 3 (C18:1) Methyl Oleate C19H36O2 296.49 218 N/A 0.874 (Octadecenoic ME) 4 (C18:0) Methyl Stearate C19H38O2 298.52 181 40 N/A (Octadecanoic ME) 5 (C18:3) Methyl Linolenate C19H32O2 292.46 182 N/A 0.895 (Octadecatrienoic ME)

There are no methyl esters in petroleum fuel. According to the National Biodiesel Board, soybean methyl ester biodiesel is comprised of 52% methyl linoleate, 25% methyl oleate, 12% methyl palmitate, 6% methyl linolenate, and 5% methyl stearate. Figure 3-67

70

depicts the measured methyl ester concentrations (ppm) determined from the GC/MS analysis. The Peter Cremer Nexsol Biodiesel was determined to have 42% methyl linoleate, 29% methyl palmitate, 20% methyl stearate, 5% methyl oleate, and 4% methyl linolenate.
Figure 3-59: Methyl Ester Concentration (%) in B50 and B100 Biodiesel Fuel

45 40
Concentration (%)

35 30 25 20 15 10 5 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

B50 B100

The B50 is approximately half the amount of B100 in the methyl ester content. This disagrees with the results of B50 being less than half the concentration of n-alkane and PAH in comparison to B0. In the identified compounds in the fuels, the petroleum diesel fuel is comprised of 89.1% n-alkanes and 10.9% aromatics. The B50 was comprised of 67% methyl esters, 30.1% n-alkanes, and 2.8% aromatics.

Figure 3-68 through Figure 3-71 represent the methyl ester distribution in the PM phase for B50. The methyl ester distributions are a similar bell-shape to the n-alkane

71

distributions. The highest amount of emitted matter per fuel consumed occurred at 0 kW and decreased as the sampling loads increased.
Figure 3-60: Methyl Ester PM Concentration (g/std m3) for B50 over sampling loads (kW)
900 800 Concentration (g/m) 700 600 500 400 300 200 100 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate
3

0 kW 25 kW 50 kW 75 kW

Figure 3-61: Methyl Ester PM Emission Rate (mg/hr) for B50 over sampling loads (kW)
250
Emission Rate (mg/hr)

200 150 100 50 0

methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

72

Figure 3-62: Methyl Ester PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)
40
mg Compound/kg fuel consumed

35 30 25 20 15 10 5 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

Figure 3-63: Methyl Ester PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)
1000 900 800 700 600 500 400 300 200 100 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

Emission Rate (ng/kJ)

0 kW 25 kW 50 kW 75 kW

Figure 3-72 through Figure 3-75 represent the methyl ester distribution in the gas phase exhaust for B50. The gas phase emission is lower than the particulate emission for the

73

methyl esters. The lowest amount occurred at 25 kW. The highest amount of emitted methyl ester in the gaseous phase per amount of fuel consumed occurred at 0 kW.
Figure 3-64: Methyl Ester Concentration in Gaseous Phase (g/std m3) for B50 over sampling loads (kW)
400 350 Concentration (g/m)
3

300 250 200 150 100 50 0

methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

Figure 3-65: Methyl Ester Gaseous Emission Rate (mg/hr) for B50 over sampling loads (kW)
120
Emission Rate (mg/hr)

100 80 60 40 20 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

74

Figure 3-66: Methyl Ester Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 over sampling loads (kW)
25
mg Compound/kg fuel consumed

20 15 10 5 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

Figure 3-67: Methyl Ester Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 over sampling loads (kW)
600
Emission Rate (ng/kJ)

500 400 300 200 100 0

methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

Figure 3-76 through Figure 3-79 represent the methyl ester distribution in the PM phase exhaust for B100. As with the B50 results, the methyl ester distributions for the The

particulate and gas phase are bell-shaped with a lower gas phase emission.

75

concentration (g/std m3) and emission rate (mg/hr) were highest at the 25 and 50 kW loading and the amount of emitted methyl ester per amount of fuel consumed was highest at the low loadings.
Figure 3-68: Methyl Ester PM Concentration (g/std m3) for B100 over sampling loads (kW)
1600 1400 Concentration (g/m)
3

1200 1000 800 600 400 200 0

methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

Figure 3-69: Methyl Ester PM Emission Rate (mg/hr) for B100 over sampling loads (kW)
500 450
Emission Rate (mg/hr)

400 350 300 250 200 150 100 50 0

methyl palmitate methyl linoleate methyl oleate methyl stearate

0 kW 25 kW 50 kW 75 kW

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Figure 3-70: Methyl Ester PM Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)
50
mg Compound/kg fuel consumed

45 40 35 30 25 20 15 10 5 0
methyl palmitate methyl linoleate methyl oleate methyl stearate

0 kW 25 kW 50 kW 75 kW

Figure 3-71: Methyl Ester PM Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW)
1400 1200
Emission Rate (ng/kJ)

1000 800 600 400 200 0

methyl palmitate methyl linoleate methyl oleate methyl stearate

0 kW 25 kW 50 kW 75 kW

Figure 3-80 through Figure 3-83 represent the methyl ester distribution in the gas phase exhaust for B100. The lowest amount of methyl ester gaseous phase occurred at 25 kW.

77

The highest amount of gaseous methyl ester emitted per amount of fuel consumed occurred at 0 kW.
Figure 3-72: Methyl Ester Concentration in Gaseous Phase (g/std m3) for B100 over sampling loads (kW)
600 Concentration (g/m) 500 400 300 200 100 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

Figure 3-73: Methyl Ester Gaseous Emission Rate (mg/hr) for B100 over sampling loads (kW)
200 180
Emission Rate (mg/hr)

160 140 120 100 80 60 40 20 0

methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

78

Figure 3-74: Methyl Ester Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B100 over sampling loads (kW)
30
mg Compound/kg fuel consumed

25 20 15 10 5 0
methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

Figure 3-75: Methyl Ester Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B100 over sampling loads (kW)
700 600
Emission Rate (ng/kJ)

500 400 300 200 100 0

methyl palmitate methyl linoleate methyl oleate methyl stearate methyl linolenate

0 kW 25 kW 50 kW 75 kW

The methyl ester content in the gaseous phase for the biodiesel emissions is lower than the methyl ester content in the particulate phase. The higher emission amount at 25 kW corresponds to the higher PM concentrations at 25 kW. The heavy methyl esters from the

79

unburned fuel favor the particulate phase. The methyl esters found in the exhaust are found in the same relative concentrations as are found in the fuel, with the major compound of methyl linoleate.

3.4.5. Compound Percentages in Total Identified Organics The n-alkane, PAH, and methyl ester concentration in the exhaust for each fuel were quantified over the total identified organic components throughout the loadings. Figure 3-84 illustrates the components in the n-alkane percentage in the particulate and gas phase for B0 and B50, Figure 3-85 shows the PAH percentage in the particulate and gas phase for B0 and B50, and Figure 3-86 illustrates the results for methyl ester emission percentage in the particulate and gas phase for B50 and B100.
Figure 3-76: Percentage of identified n-Alkanes PM and Gaseous Phase for B0 and B50
70
% n-Alkane in Identified Exhaust

60 50 40 30 20 10 0
0 25 50 75

B0 (PM) B0 (Gas) B50 (PM) B50 (Gas)

Load (kW)

80

Figure 3-77: Percentage of identified PAHs in PM and Gaseous Phase for B0 and B50
30
% PAH in Identified Exhaust

25 20 15 10 5 0
0 25 50 75

B0 (PM) B0 (Gas) B50 (PM) B50 (Gas)

Load (kW)

Figure 3-78: Percentage of identified Methyl Esters in PM and Gaseous Phase for B50 and B100
80

% ME in Identified Exhaust

60 B50 (PM) B50 (Gas) B100 (PM) B100 (Gas)

40

20

0
0 25 50 75

Load (kW)

The relative percentages in the identified components do not vary significantly with load. The major component in the ULS petroleum exhaust was the n-alkane in the gas phase, which comprised of 60% of the identified organic exhaust. The percentage of gas phase

81

n-alkane emission for B50 was about 38% and for B100 the percentage was 0.5%. The particulate phase n-alkane emission for B0 yielded 12% of the identified exhaust component, 6% for B50, and 14% for B100.

The PAH content in the PM was very low for each fuel type. For B0, the PM PAH emission was only 2%, and for B50 the relative percentage was 0.5%. The gas phase PAH emission had much higher results for the B0 at 25% and 15% for B50.

The gas phase emissions comprised most of the n-alkane and PAH emissions identified in the exhaust. Methyl ester species were found at twice the concentration in the particulate phase than in the gas phase. For B50, the PM methyl ester emission was 28% and the gas phase methyl ester 10%. For B100, 57% of the identified exhaust was particulate phase methyl ester and 23% was gas phase methyl ester exhaust.

4. Conclusion and Recommendations

Biodiesel is a diesel equivalent fuel that is a non-toxic, biodegradable, renewable, nonflammable, and may replace conventional petroleum diesel fuel. The overall goal of this study was to examine the emission from a diesel generator of selected air pollutants of biodiesel fuel blends in comparison to ultra-low sulfur petroleum diesel fuel. Results established increased total PM emissions (mostly soluble) for the biodiesel blends and increasing PM with increasing biodiesel blend concentration. A further comparison of the emitted PM emissions for the biodiesel and biodiesel blend (B50) show that the emitted petroleum PM contained a higher percentage of soot, as determined from the

82

dissolved solvent analysis. Within the higher amounts of PM concentration for the biodiesel and biodiesel blend, a decrease in carcinogenic polycyclic aromatic and nalkane hydrocarbon compounds was found for the biodiesel fuel emissions. The majority of the biodiesel organic emissions comprised of the methyl esters, which indicates unburned fuel in the exhaust.

For the petroleum fuel, the majority of the hydrocarbon emissions by mass were nalkanes found in the gaseous phase. For the biodiesel, the majority of the emissions were from the methyl esters found in the particulate matter. The higher amount of methyl esters in the PM contributes to the overall higher PM concentrations in the biodiesel blends. The biodiesel performed with higher fuel consumption and higher exhaust

temperatures. The higher fuel consumption for B100 and the non-linearity of the fuel consumption with increasing loads indicates a need for further research. The results of the fuel analysis indicate poor mixing and possible separation of the fuels, which may also attribute to inconsistent PM results. The exhaust profile of the biodiesel in

comparison to petroleum revealed higher NOx emissions; conversely lower carbon monoxide and higher carbon dioxide while operating the diesel engine generator. The higher carbon dioxide amounts for the B50 and B100 corresponds to the higher fuel consumption.

The dilution sampling system utilized was based on the general requirements of the Code of Federal Regulations, Title 40 Part 1065, Engine-Testing Procedures. Although the single dilution sampling employed did not meet the constant volume sampling criteria, it

83

was sufficient to characterize the exhaust emissions, as it would behave in the ambient environment. Constant total flow volume sampling may have been achieved with the use of a positive displacement pump or the use of a critical flow venturi for flow adjustment. Sampling conditions may be optimized for temperature consistency with minimal pressure drop across the filter, such as an increase in the dilution ratio with less exhaust and longer sampling times. In addition, control of temperature and humidity of the dilution air would alleviate environmental fluctuations.

For this study, the GC/MS was operated with a non-polar column. These results are based on retention time and should be considered preliminary data for further research. Since methyl esters are polar compounds, it is recommended that a polar column be used in conjunction with the non-polar compound for fuel and exhaust compound identification. Understanding the components in the exhaust can direct the development of appropriate control techniques. Since the majority of the biodiesel PM exhaust was condensed methyl esters, the installation of a particulate control device may significantly reduce the biodiesel PM emissions. Also, adjusting engine parameters to account for the difference in viscosity and density of the fuel will aide in optimizing the diesel engine to operate efficiently on biodiesel fuel. Such parameters may include altering the fuel injectors for improved atomization. Future research into biodiesel chemical kinetics will further develop the understanding about the biodiesel combustion process.

U.S. EPA Mobile Source Air Toxics include acetaldehyde, benzene, PM plus diesel exhaust, organic gases, formaldehyde, n-hexane, and naphthalene, all components present

84

in the biodiesel exhaust and others not addressed in this study.

A comprehensive

investigation on such components as benzene, aldehydes, and ketone as ozone precursors will assist in assessing the usage of biodiesel to the overall air quality and appropriate control technology. The results may be applied to air models in order to quantify the overall air quality impact of switching to biodiesel fuel.

As biodiesel is a renewable resource, advanced research is required in order to optimize the source oil yield. According to the United States Department of Energy and United States Department of Agriculture, soybean yields about 40 to 50 gallons per acre. Palm oil has a greater yield at about 650 gallons per acre. Algae as a source oil can yield up to 10,000 to 20,000 gallons per acre. Biodiesel may be formulated from a variety of sources that have yet found implementation.

In conclusion, the use of biodiesel in compression ignition engines has shown to be a viable alternative to petroleum diesel. Although biodiesel emissions were found to

increase the total particulate matter and oxides of nitrogen emissions, a decrease in polycyclic aromatic hydrocarbon emission and amount of soot may diminish the overall detrimental health effects of diesel-powered engines.

85

5. References

1) Turrio-Baldassarri, L., Battistelli, C., Conti, L., Crebelli, R., De Berardis, B., Iamiceli, A., Gambino, M., Iannaccone, S. (2003), Emission comparison of urban bus engine fueled with diesel oil and biodiesel blend, Science of the Total Environment, Vol. 327, pp. 147-162. 2) Liang, F., Lu, M, Keener, T., Liu, Z., Khang, S. (2005), The organic composition of diesel particulate matter, diesel fuel and engine oil of a non-road diesel generator, Journal of Environmental Monitoring, Vol. 7, pp. 983-988. 3) Liang, F., Lu, M., Keener, T., Birch, M., Sorial, G. (2006), Composition and Formation Mechanism of Diesel Particulate Matter Associated with Various Factors from A Non-road Diesel Generator, Dissertation submitted to University of Cincinnati. 4) Krahl, J., Baum, K., Hackbarth, U., Jeberien, H., Munack, A., Schtt, C., Schrder, O., Walter, N., Bnger, J., Mller, M., Weigel, A. (2001), Gaseous Compounds, Ozone Precursors, Particle Number and Particle Size Distributions, and Mutagenic Effects Due to Biodiesel, Transactions of the American Society of Agricultural Engineers, Vol. 44, Issue 2, pp. 179-191. 5) Graboski, M., McCormick, R. (1998), Combustion of fat and vegetable oil derived fuels in diesel engines, Progress in Energy and Combustion Science, Vol. 24, pp. 125-164. 6) Corporan, E., Reich, R., Monroig, O., DeWitt, M., Larson, V., Aulich, T., Mann, M., Seames, W. (2005), Impacts of Biodiesel on Pollutant Emissions of a JP-8Fueled Turbine Engine, Journal of Air & Waste Management Association, Vol. 55, 940-44. 7) Knothe, G., Steidley, K. (2005), Kinematic viscosity of biodiesel fuel components and related compounds. Influence of compound structure and comparison to petrodiesel fuel components, Fuel, Vol. 84, pp. 1059-1065. 8) zkan, M., Ergen, A., Denz, O. (2005), Experimental Performance Analysis of Biodiesel, Traditional Diesel and Biodiesel with Glycerin, Turkish Journal of Engineering and Environmental Science, Vol. 29, pp. 89-94. 9) Demrba, A. (2003), Chemical and Fuel Properties of Seventeen Vegetable Oils, Energy Source, Vol. 25, pp. 721-728. 10) Lee, S., Herage, T., Young, B. (2004), Emission reduction potential from the combustion of soy methyl ester fuel blended with petroleum distillate fuel, Fuel, Vol. 83, pp. 1607 1613.

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11) Wang, W., Lyons, D., Clark, N., Gautam, M. (2000), Emissions from Nine Heavy Trucks Fueled By Diesel and Biodiesel Blends without Engine Modification, Environmental Science and Technology, Vol. 34, No. 6, pp. 933939. 12) Zhang, Y., Dub, M., McLean, D., Kates, M. (2003), Biodiesel production from waste cooking oil: 1. Process design and technological assessment, Bioresource Technology, Vol. 89, pp. 1-16. 13) Serdari, A., Fragioudakis, K., Teas, C., Zannikos, F., Stournas, S., Lois, E. (1999), Effect of Biodiesel Addition to Diesel Fuel on Engine Performance and Emissions, Journal of Propulsion and Power, Vol. 15, No. 2, pp. 224-231. 14) Tate, R., Watts, K., Allen, C., Wilkie, K. (2006), The viscosities of three biodiesel fuels at temperatures up to 300C, Fuel, Vol. 85, pp. 1010-1015. 15) Schumacher, L., Peterson, C., Van Gerpen, J. (2001), Engine Oil Analysis of Diesel Engines Fueled with Biodiesel Blends, Presented at the 2001 Annual International Meeting sponsored by ASAE, Sacramento, California, Paper No. 016053, ASAE, 2950 Niles Rd., St. Joseph, MI 49085-9659 USA. 16) Tsolakis, A. (2006), Effects on Particle Size Distribution from the Diesel Engine Operating on RME-Biodiesel with EGR, Energy and Fuels, Vol. 20, pp. 1418 1424. 17) Usta, N., ztrk, E., Can, , Conkur, E., Nas, S., on, A., Can, A., Topcu, M. (2005), Combustion of biodiesel fuel produced from hazelnut soap stock/waste sunflower oil mixture in a Diesel engine, Energy Conversion and Management, Vol. 46, pp. 741-755. 18) Gomez, M., Howard-Hildige, R., Leahy, J., OReilly, T., Supple, B., Malone, M. (2000), Emission and performance characteristics of a 2-Litre Toyota diesel van operating on esterified waste cooking oil and mineral diesel fuel, Environmental Monitoring and Assessment, Vol. 65, pp. 13-20. 19) U.S. Environmental Protection Agency, Office of Transportation and Air Quality, Assessments and Standards Division (2002), A Comprehensive Analysis of Biodiesel Impacts on Exhaust Emissions Draft Technical Report, EPA420-P02-001. 20) Munack, A., Schrder, O., Krahl, J., Bnger, J. (2001), Comparison of Relevant Exhaust Gas Emissions from Biodiesel and Fossil Diesel Fuel, Agricultural Engineering International: the CIGR Journal of Scientific Research and Development, Manuscript EE 01 001, Vol. 3.

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21) Durbin, T., Collins, J., Norbeck, J., Smith, M. (2000), Effects of Biodiesel, Biodiesel Blends, and a Synthetic Diesel on Emissions from Light Heavy-Duty Diesel Vehicles, Environmental Science & Technology, Vol. 34, No. 3, pp. 349355. 22) Bol, M., Bhattacharya, T., Mishra, T. (2004), Studies on Fuel Properties of Refined Soybean Oil, Soybean Ethyl Ester and Their Blends with Diesel to Assess Usefulness as CI Engine Fuel, IE (I) Journal-ID, Vol. 85, pp. 17-20. 23) Knothe, G., Sharp, C., Ryan, T. (2006), Exhaust Emissions of Biodiesel, Petrodiesel, Neat Methyl Esters, and Alkanes in a New Technology Engine, Energy and Fuels, Vol. 20, pp. 403 408. 24) Sidhu, S., Graham, J., Striebich, R. (2001), Semi-volatile and particulate emissions from the combustion of alternative diesel fuels, Chemosphere, Vol. 42, pp. 681 690. 25) Kado, N.Y., Okamoto, R.A., Kuzmicky, P.A. (1996), Chemical and Bioassay Analysis of Diesel and Biodiesel Particulate Matter: Pilot Study, Department of Environmental Toxicology, University of California.

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Appendix A: n-Alkane Amount in Particulate and Gaseous Phase of Exhaust for B0, B50, and B100 Fuels Table A-1: n-Alkane PM Concentration (g/std m3) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Tetracosane Pentacosane

0 kW 0 0 0 0.53 1.43 7.92 32.95 96.11 88.23 92.22 65.23 24.69 7.57 0 0 0

B0 (g/std m3) 25 kW 50 kW 0 0 0 0 1.53 0 9.43 0 10.69 0.74 27.24 3.67 51.24 13.46 116.99 42.14 91.31 43.18 98.81 50.46 77.62 47.43 70.40 59.42 24.61 18.18 2.59 4.14 0 0 0 0

75 kW 0 0 0 0 1.6 4.16 12.83 32.58 47.82 64.55 65.04 60.87 16.19 2.93 0 0

0 kW 0 0 0 0 1.29 5.89 20.63 48.70 46.23 39.25 27.93 0 8.88 8.42 0 0

B50 (g/std m3) 25 kW 50 kW 0 0 0.65 0 0.70 0 5.88 0 3.88 1.08 16.38 3.27 47.14 9.37 92.97 19.04 75.30 19.07 61.23 18.91 26.28 14.69 0 0 4.46 5.57 1.91 2.27 0 0 0 0

75 kW 0 1.17 0 0.94 1.09 2.73 8.19 16.4 47.42 20.48 18.85 0 11.27 4.11 0 0

0 kW 0 0 0 0 0 0.75 3.15 4 5.05 2.55 5.95 0 0.1 1.9 0 0

B100 (g/std m3) 25 kW 50 kW 75 kW 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1.6 0.75 0.4 6.4 3.8 1.8 9.95 5.2 2.5 8.9 6.35 3.4 3.65 3.05 1.85 10.9 8.7 2.35 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

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Table A-2: n-Alkane PM Emission Rate (mg/hr) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Tetracosane Pentacosane

0 kW 0 0 0 0.14 0.37 2.08 8.66 25.27 23.20 24.25 17.15 6.49 1.99 0 0 0

B0 (mg/hr) 25 kW 50 kW 0 0 0 0 0.43 0 2.69 0 3.05 0.25 7.79 1.25 14.65 4.59 33.46 14.37 26.11 14.72 28.26 17.20 22.20 16.17 20.13 20.26 7.04 6.20 0.74 1.41 0 0 0 0

75 kW 0 0 0 0 0.61 1.58 4.90 12.44 18.26 24.65 24.84 23.25 6.18 1.12 0 0

0 kW 0 0 0 0 0.34 1.54 5.42 12.81 12.16 10.32 7.34 0 2.33 2.21 0 0

B50 (mg/hr) 25 kW 50 kW 0 0 0.18 0 0.20 0 1.68 0 1.11 0.36 4.68 1.11 13.48 3.19 26.59 6.49 21.53 6.50 17.51 6.45 7.51 5.01 0 0 1.27 1.90 0.54 0.77 0 0 0 0

75 kW 0 0.44 0 0.36 0.41 1.04 3.12 6.26 18.11 7.82 7.20 0 4.30 1.57 0 0

0 kW 0 0 0 0 0 0.20 0.83 1.05 1.33 0.67 1.56 0 0.03 0.50 0 0

B100 (mg/hr) 25 kW 50 kW 0 0 0 0 0 0 0 0 0 0 0.46 0.26 1.83 1.30 2.85 1.77 2.55 2.17 1.04 1.04 3.12 2.97 0 0 0 0 0 0 0 0 0 0

75 kW 0 0 0 0 0 0.15 0.69 0.96 1.30 0.71 0.90 0 0 0 0 0

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Table A-3: n-Alkane PM Emission Rate (mg emitted compound/kg fuel consumed) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Tetracosane Pentacosane

0 kW 0 0 0 0.04 0.11 0.65 2.70 7.88 7.24 7.57 5.35 2.02 0.621 0 0 0

B0 (mg/kg) 25 kW 50 kW 0 0 0 0 0.07 0 0.44 0 0.50 0.026 1.29 0.13 2.43 0.47 5.56 1.49 4.34 1.53 4.70 1.79 3.69 1.68 3.35 2.10 1.17 0.64 0.12 0.14 0 0 0 0

75 kW 0 0 0 0 0.047 0.12 0.37 0.94 1.39 1.88 1.89 1.77 0.47 0.085 0 0

0 kW 0 0 0 0 0.080 0.36 1.27 3.01 2.86 2.42 1.72 0 0.55 0.52 0 0

B50 (mg/kg) 25 kW 50 kW 0 0 0.022 0 0.024 0 0.20 0 0.13 0.026 0.55 0.08 1.60 0.23 3.16 0.46 2.56 0.46 2.08 0.46 0.89 0.36 0 0 0.15 0.13 0.065 0.055 0 0 0 0

75 kW 0 0.023 0 0.019 0.022 0.055 0.16 0.33 0.95 0.41 0.38 0 0.22 0.083 0 0

0 kW 0 0 0 0 0 0.04 0.18 0.23 0.29 0.15 0.34 0 0.01 0.11 0 0

B100 (mg/kg) 25 kW 50 kW 0 0 0 0 0 0 0 0 0 0 0.05 0.02 0.21 0.10 0.32 0.14 0.29 0.17 0.12 0.08 0.35 0.23 0 0 0 0 0 0 0 0 0 0

75 kW 0 0 0 0 0 0.01 0.04 0.06 0.08 0.04 0.05 0 0 0 0 0

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Table A-4: n-Alkane PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Tetracosane Pentacosane

0 kW 0 0 0 0.96 2.59 14.38 59.81 174.45 160.15 167.41 118.40 44.82 13.74 0 0 0

B0 (ng/kJ) 25 kW 50 kW 0 0 0 0 1.61 0 9.92 0 11.26 0.58 28.67 2.88 53.94 10.56 123.16 33.06 96.13 33.87 104.02 39.59 81.71 37.20 74.12 46.61 25.91 14.26 2.72 3.25 0 0 0 0

75 kW 0 0 0 0 1.04 2.68 8.26 20.99 30.81 41.60 41.91 39.22 10.43 1.88 0 0

0 kW 0 0 0 0 1.90 8.63 30.23 71.37 67.75 57.51 40.92 0 13.02 12.35 0 0

B50 (ng/kJ) 25 kW 50 kW 0 0 0.52 0 0.57 0 4.74 0 3.13 0.62 13.19 1.90 37.96 5.44 74.87 11.06 60.64 11.08 49.31 10.99 21.16 8.54 0 0 3.59 3.24 1.54 1.32 0 0 0 0

75 kW 0 0.56 0 0.45 0.52 1.30 3.91 7.83 22.66 9.78 9.01 0 5.38 1.96 0 0

0 kW 0 0 0 0 0 1.09 4.56 5.79 7.32 3.69 8.62 0 0.14 2.75 0 0

B100 (ng/kJ) 25 kW 50 kW 0 0 0 0 0 0 0 0 0 0 1.31 0.51 5.24 2.58 8.15 3.53 7.29 4.31 2.99 2.07 8.92 5.91 0 0 0 0 0 0 0 0 0 0

75 kW 0 0 0 0 0 0.23 1.04 1.44 1.96 1.07 1.36 0 0 0 0 0

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Table A-5: n-Alkane Concentration in Gaseous Phase (g/std m3) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Tetracosane Pentacosane

0 kW 37.41 8.90 241.28 262.44 428.79 161.27 346.44 288.57 27.80 67.91 29.42 0 0 0 0 0

B0 (g/std m3) 25 kW 50 kW 17.32 12.4 4.7 7.5 311.3 157.5 272.96 145.5 481.1 186.5 408.8 166.8 448.1 168.5 701.3 146.7 340.6 73.9 77.68 131.9 78.8 46 0 0 0 0 0 0 0 0 0 0

75 kW 22.2 11.6 208.4 162.1 245.7 238.3 246.6 195.9 127.6 90.4 9.1 0 0 0 0 0

0 kW 12.3 6.2 84.6 81.6 143.9 177.2 207.1 347.9 155.7 59.3 11.1 0 0 0 0 0

B50 (g/std m3) 25 kW 50 kW 12.5 9 4.61 4 132.8 62 148.8 50 229.5 88 202.3 100 240.2 118 214 115 122.7 55 75.4 30 5.9 15 0 0 0 0 0 0 0 0 0 0

75 kW 14.8 7.1 92.7 77.5 139.3 156.7 203.2 139.9 132.2 99.8 11.6 0 0 0 0 0

0 kW 0 0 0 44.2 79.3 102.7 130.2 8.5 63.8 24.8 9.6 0 0 0 0 0

B100 (g/std m3) 25 kW 50 kW 0 0 0 0 0 0 31.6 23.9 30.5 40.9 43.6 53.6 55.5 94.9 50.5 97.3 18.5 42.4 4.8 9.2 2.4 8.9 0 0 0 0 0 0 0 0 0 0

75 kW 0 0 0 14.6 29 36.2 67.6 42.2 37.3 11.1 4.6 0 0 0 0 0

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Table A-6: n-Alkane Gaseous Emission Rate (mg/hr) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound 0 kW 9.83 Decane 2.34 Undecane 63.45 Dodecane 69.02 Tridecane Tetradecane 112.77 Pentadecane 42.41 Hexadecane 91.11 Heptadecane 75.89 7.31 Octadecane Nonadecane 17.86 7.73 Eicosane 0 Heneicosane 0 Docosane 0 Tricosane 0 Tetracosane 0 Pentacosane

B0 (mg/hr) 25 kW 50 kW 4.95 4.22 1.34 2.55 89.03 53.70 78.06 49.61 137.59 63.59 116.91 56.87 128.15 57.45 200.57 50.02 97.41 25.19 22.21 44.97 22.53 15.68 0 0 0 0 0 0 0 0 0 0

75 kW 8.48 4.43 79.60 61.92 93.85 91.03 94.20 74.83 48.74 34.53 3.47 0 0 0 0 0

0 kW 3.23 1.63 22.25 21.46 37.85 46.60 54.47 91.50 40.95 15.60 2.92 0 0 0 0 0

B50 (mg/hr) 25 kW 50 kW 3.58 3.07 1.32 1.36 37.98 21.14 42.56 17.05 65.64 30.01 57.86 34.10 68.70 40.24 61.20 39.22 35.09 18.76 21.56 10.23 1.69 5.12 0 0 0 0 0 0 0 0 0 0

75 kW 5.65 2.71 35.41 29.61 53.21 59.86 77.62 53.44 50.50 38.12 4.43 0 0 0 0 0

0 kW 0 0 0 11.62 20.86 27.01 34.24 2.24 16.78 6.52 2.52 0 0 0 0 0

B100 (mg/hr) 25 kW 50 kW 0 0 0 0 0 0 9.04 8.15 8.72 13.95 12.47 18.28 15.87 32.36 14.44 33.18 5.29 14.46 1.37 3.14 0.69 3.03 0 0 0 0 0 0 0 0 0 0

75 kW 0 0 0 5.58 11.08 13.83 25.82 16.12 14.25 4.24 1.76 0 0 0 0 0

94

Table A-7: n-Alkane Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Tetracosane Pentacosane

0 kW 3.07 0.73 19.80 21.54 35.19 13.23 28.43 23.68 2.28 5.57 2.41 0 0 0 0 0

B0 (mg/kg) 25 kW 50 kW 0.82 0.43 0.22 0.26 14.81 5.58 12.99 5.16 22.90 6.61 19.46 5.91 21.33 5.97 33.38 5.20 16.21 2.62 3.69 4.67 3.75 1.63 0 0 0 0 0 0 0 0 0 0

75 kW 0.64 0.33 6.07 4.72 7.16 6.94 7.18 5.70 3.71 2.63 0.26 0 0 0 0 0

0 kW 0.76 0.38 5.24 5.05 8.91 10.97 12.82 21.53 9.64 3.67 0.69 0 0 0 0 0

B50 (mg/kg) 25 kW 50 kW 0.43 0.22 0.16 0.10 4.52 1.52 5.06 1.23 7.81 2.16 6.88 2.46 8.17 2.90 7.28 2.82 4.17 1.35 2.56 0.74 0.20 0.37 0 0 0 0 0 0 0 0 0 0

75 kW 0.30 0.14 1.87 1.56 2.81 3.16 4.10 2.82 2.67 2.01 0.23 0 0 0 0 0

0 kW 0 0 0 2.53 4.54 5.88 7.45 0.49 3.65 1.42 0.55 0 0 0 0 0

B100 (mg/kg) 25 kW 50 kW 0 0 0 0 0 0 1.02 0.64 0.99 1.10 1.41 1.44 1.80 2.55 1.63 2.61 0.60 1.14 0.16 0.25 0.078 0.24 0 0 0 0 0 0 0 0 0 0

75 kW 0 0 0 0.33 0.66 0.83 1.54 0.96 0.85 0.25 0.10 0 0 0 0 0

95

Table A-8: n-Alkane Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0, B50, and B100 over sampling loads (kW)

n-Alkane Compound Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Tetracosane Pentacosane

0 kW 67.90 16.16 437.99 476.40 778.36 292.74 628.89 523.83 50.47 123.27 53.40 0 0 0 0 0

B0 (ng/kJ) 25 kW 50 kW 18.23 9.72 4.94 5.88 327.71 123.55 287.35 114.14 506.47 146.30 430.35 130.85 471.73 132.18 738.28 115.08 358.56 57.97 81.77 103.47 82.95 36.08 0 0 0 0 0 0 0 0 0 0

75 kW 14.30 7.47 134.30 104.46 158.34 153.57 158.92 126.24 82.23 58.25 5.86 0 0 0 0 0

0 kW 18.02 9.08 123.96 119.56 210.85 259.64 303.45 509.76 228.14 86.89 16.26 0 0 0 0 0

B50 (ng/kJ) 25 kW 50 kW 10.07 5.23 3.71 2.33 106.94 36.04 119.83 29.06 184.82 51.15 162.91 58.13 193.43 68.59 172.33 66.85 98.81 31.97 60.72 17.44 4.75 8.72 0 0 0 0 0 0 0 0 0 0

75 kW 7.07 3.39 44.30 37.04 66.57 74.89 97.11 66.86 63.18 47.70 5.54 0 0 0 0 0

B100 (ng/kJ) 0 kW 25 kW 50 kW 0 0 0 0 0 0 0 0 0 64.02 25.87 16.23 114.87 24.97 27.77 148.76 35.69 36.39 188.60 45.44 64.43 12.31 41.34 66.06 92.42 15.15 28.79 35.92 3.93 6.25 13.91 1.96 6.04 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 0 0 0 8.43 16.74 20.90 39.02 24.36 21.53 6.41 2.66 0 0 0 0 0

96

Appendix B: Polycyclic Aromatic Hydrocarbon (PAH) Amount in Particulate and Gaseous Phase of Exhaust for B0 and B50 Fuels Table B-1: PAH PM Concentration (g/std m3) for B0 and B50 over sampling loads (kW) 0 kW 0 Naphthalene 0.26 Acenaphthylene 1.42 Acenaphthene 9.08 Fluorene 17.77 Phenanthrene 33.90 Anthracene 0 Fluoranthene 0 Pyrene 0 Benzo(a)anthracene 0 Chrysene 0 Benzo(b)fluoranthene 0 Benzo(k)fluoranthene 0 Benzo(a)pyrene 0 Ideno(1,2,3-cd)pyrene 0 Dibenzo(a,h)anthracene 0 Benzo(g,h,i)perylene

PAH Compound

B0 (g/std m3) 25 50 kW kW 0 0 0.47 0.65 1.53 0.73 6.82 1.67 20.37 8.33 26.99 16.29 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

B50 (g/std m3) 75 0 25 50 kW kW kW kW 0 0 0 0 4.95 0.37 1.99 0.48 1.34 0.92 3.16 0.65 7.52 3.66 12.22 2.84 6.72 6.34 13.30 3.10 10.36 11.74 22.77 2.64 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 0 5.51 1.63 8.58 4.48 2.76 0 0 0 0 0 0 0 0 0 0

97

Table B-2: PAH PM Emission Rate (mg/hr) for B0 and B50 over sampling loads (kW) 0 kW 0 Naphthalene 0.07 Acenaphthylene 0.37 Acenaphthene 2.39 Fluorene 4.67 Phenanthrene 8.92 Anthracene 0 Fluoranthene 0 Pyrene 0 Benzo(a)anthracene 0 Chrysene 0 Benzo(b)fluoranthene 0 Benzo(k)fluoranthene 0 Benzo(a)pyrene 0 Ideno(1,2,3-cd)pyrene 0 Dibenzo(a,h)anthracene 0 Benzo(g,h,i)perylene

PAH Compound

B0 (mg/hr) 25 50 kW kW 0 0 0.13 0.22 0.44 0.25 1.95 0.57 5.83 2.84 7.72 5.56 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 0 1.89 0.51 2.87 2.57 3.96 0 0 0 0 0 0 0 0 0 0

0 kW 0 0.10 0.24 0.96 1.67 3.09 0 0 0 0 0 0 0 0 0 0

B50 (mg/hr) 25 50 kW kW 0 0 0.57 0.16 0.90 0.22 3.50 0.97 3.80 1.06 6.51 0.90 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 0 2.11 0.62 3.28 1.71 1.06 0 0 0 0 0 0 0 0 0 0

98

Table B-3: PAH PM Emission Rate (mg emitted compound/kg fuel consumed) for B0 and B50 over sampling loads (kW) 0 kW 0 Naphthalene 0.02 Acenaphthylene 0.12 Acenaphthene 0.75 Fluorene 1.46 Phenanthrene 2.78 Anthracene 0 Fluoranthene 0 Pyrene 0 Benzo(a)anthracene 0 Chrysene 0 Benzo(b)fluoranthene 0 Benzo(k)fluoranthene 0 Benzo(a)pyrene 0 Ideno(1,2,3-cd)pyrene 0 Dibenzo(a,h)anthracene 0 Benzo(g,h,i)perylene

PAH Compound

B0 (mg/kg) 25 50 kW kW 0 0 0.02 0.02 0.07 0.03 0.32 0.06 0.97 0.30 1.28 0.58 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 0 0.14 0.04 0.22 0.20 0.30 0 0 0 0 0 0 0 0 0 0

0 kW 0 0.02 0.06 0.23 0.39 0.73 0 0 0 0 0 0 0 0 0 0

B50 (mg/kg) 25 50 kW kW 0 0 0.07 0.01 0.11 0.02 0.42 0.07 0.45 0.08 0.77 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 0 0.11 0.03 0.17 0.09 0.06 0 0 0 0 0 0 0 0 0 0

99

Table B-4: PAH PM Emission Rate (ng emitted compound/kJ fuel consumed) for B0 and B50 over sampling loads (kW)

B0 (ng/kJ) 0 25 50 kW kW kW 0 0 0 Naphthalene 0.47 0.49 0.51 Acenaphthylene 2.58 1.61 0.57 Acenaphthene 16.49 7.18 1.31 Fluorene 32.26 21.44 6.53 Phenanthrene 61.54 28.41 12.78 Anthracene 0 0 0 Fluoranthene 0 0 0 Pyrene 0 0 0 Benzo(a)anthracene 0 0 0 Chrysene 0 0 0 Benzo(b)fluoranthene 0 0 0 Benzo(k)fluoranthene 0 0 0 Benzo(a)pyrene 0 0 0 Ideno(1,2,3-cd)pyrene 0 0 0 Dibenzo(a,h)anthracene 0 0 0 Benzo(g,h,i)perylene PAH Compound

75 0 kW kW 0 0 3.19 0.54 0.86 1.34 4.85 5.37 4.33 9.29 6.68 17.20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

B50 (ng/kJ) 25 50 kW kW 0 0 1.60 0.28 2.55 0.38 9.84 1.65 10.71 1.80 18.34 1.53 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 0 2.63 0.78 4.10 2.14 1.32 0 0 0 0 0 0 0 0 0 0

100

Table B-5: PAH Concentration in Gaseous Phase (g/std m3) for B0 and B50 over sampling loads (kW) 0 kW 185.4 Naphthalene 69.8 Acenaphthylene 88.95 Acenaphthene 169.3 Fluorene 22.43 Phenanthrene 122.2 Anthracene 214.9 Fluoranthene 0 Pyrene 0 Benzo(a)anthracene 0 Chrysene 0 Benzo(b)fluoranthene 0 Benzo(k)fluoranthene 0 Benzo(a)pyrene 0 Ideno(1,2,3-cd)pyrene 0 Dibenzo(a,h)anthracene 0 Benzo(g,h,i)perylene

PAH Compound

B0 (g/std m3) 25 50 kW kW 171.8 147.8 147.9 54.1 94.3 31.9 192.7 45.5 134.7 2.9 85.4 10.8 178.7 177.2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

B50 (g/std m3) 75 0 25 50 75 kW kW kW kW kW 238 121.6 82.1 45 141.8 126.3 56.9 110.5 20 79.6 64.6 48 72.7 45 46.1 101.4 69.5 91.2 59 34.5 24.7 26.9 62.9 10 27.6 17.4 32.6 21.9 15 68.8 148.6 155.3 184.4 61 126.1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

101

Table B-6: PAH Gaseous Emission Rate (mg/hr) for B0 and B50 over sampling loads (kW) 0 kW 48.76 Naphthalene 18.35 Acenaphthylene 23.39 Acenaphthene 44.52 Fluorene 5.89 Phenanthrene 32.13 Anthracene 56.51 Fluoranthene 0 Pyrene 0 Benzo(a)anthracene 0 Chrysene 0 Benzo(b)fluoranthene 0 Benzo(k)fluoranthene 0 Benzo(a)pyrene 0 Ideno(1,2,3-cd)pyrene 0 Dibenzo(a,h)anthracene 0 Benzo(g,h,i)perylene

PAH Compound

B0 (mg/hr) 25 50 kW kW 49.13 50.4 42.29 18.44 26.97 10.87 55.11 15.51 38.52 0.98 24.42 3.68 51.10 60.42 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 90.91 48.24 24.67 38.73 9.43 6.64 56.76 0 0 0 0 0 0 0 0 0

0 kW 31.98 14.96 12.62 18.28 7.07 8.57 40.84 0 0 0 0 0 0 0 0 0

B50 (mg/hr) 25 50 kW kW 23.48 15.35 31.60 6.82 20.79 15.35 26.08 20.12 17.99 3.41 6.26 5.12 52.74 20.80 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 54.17 30.41 17.61 13.18 10.54 26.28 48.17 0 0 0 0 0 0 0 0 0

102

Table B-7: PAH Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B0 and B50 over sampling loads (kW)

PAH Compound
Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Ideno(1,2,3-cd)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene

0 kW 15.22 5.73 7.30 13.90 1.84 10.03 17.64 0 0 0 0 0 0 0 0 0

B0 (mg/kg) 25 50 kW kW 8.18 5.24 7.04 1.92 4.49 1.13 9.17 1.61 6.41 0.10 4.07 0.38 8.51 6.29 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 6.94 3.68 1.88 2.95 0.72 0.51 4.33 0 0 0 0 0 0 0 0 0

0 kW 7.53 3.52 2.97 4.30 1.66 2.02 9.61 0 0 0 0 0 0 0 0 0

B50 (mg/kg) 25 50 kW kW 2.79 1.10 3.76 0.49 2.47 1.10 3.10 1.45 2.14 0.25 0.74 0.37 6.27 1.50 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 2.86 1.61 0.93 0.70 0.56 1.39 2.55 0 0 0 0 0 0 0 0 0

103

Table B-8: PAH Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B0 and B50 over sampling loads (kW) 0 kW 336.55 Naphthalene 126.71 Acenaphthylene 161.47 Acenaphthene 307.32 Fluorene 40.72 Phenanthrene 221.83 Anthracene 390.10 Fluoranthene 0 Pyrene 0 Benzo(a)anthracene 0 Chrysene 0 Benzo(b)fluoranthene 0 Benzo(k)fluoranthene 0 Benzo(a)pyrene 0 Ideno(1,2,3-cd)pyrene 0 Dibenzo(a,h)anthracene 0 Benzo(g,h,i)perylene

PAH Compound

B0 (ng/kJ) B50 (ng/kJ) 25 50 75 0 25 50 kW kW kW kW kW kW 180.86 115.95 153.38 178.18 66.11 26.16 155.70 42.44 81.40 83.37 88.99 11.63 99.27 25.03 41.63 70.33 58.54 26.16 202.86 35.69 65.35 101.84 73.44 34.29 141.80 2.28 15.92 39.42 50.65 5.81 89.90 8.47 11.21 47.77 17.64 8.72 188.12 139.01 95.77 227.55 148.50 35.46 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

75 kW 67.77 38.04 22.03 16.49 13.19 32.88 60.26 0 0 0 0 0 0 0 0 0

104

Appendix C: Methyl Ester Amount in Particulate and Gaseous Phase of Exhaust for B50 and B100 Fuels Table C-1: Methyl Ester PM Concentration (g/std m3) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (g/std m3) 25 kW 50 kW 131.25 798.50 85.88 41.13 0 59.98 483.37 61.68 31.33 0

75 kW

0 kW

B100 (g/std m3) 25 kW 50 kW

75 kW

100.25 612.55 79.85 45.98 0

62.31 538.36 82.44 74.43 0

84.55 143.00 97.50 66.00 819.65 1447.65 1265.05 766.35 98.95 155.80 132.20 87.35 58.55 72.50 61.45 45.50 0 0 0 0

Table C-2: Methyl Ester PM Emission Rate (mg/hr) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (mg/hr) 25 kW 50 kW 37.54 228.37 24.56 11.76 0 20.45 164.83 21.03 10.68 0

75 kW

0 kW

B100 (mg/hr) 25 kW 50 kW 40.90 414.03 44.56 20.74 0 33.25 431.38 45.08 20.95 0

75 kW

26.37 161.10 21.00 12.09 0

23.80 205.65 31.49 28.43 0

22.24 215.57 26.02 15.40 0

25.21 292.75 33.37 17.38 0

105

Table C-3: Methyl Ester PM Emission Rate (mg emitted compound/kg fuel consumed) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (mg/kg) 25 kW 50 kW 4.46 27.16 2.92 1.40 0 1.47 11.87 1.51 0.77 0

75 kW

0 kW

B100 (mg/kg) 25 kW 50 kW 4.63 46.84 5.04 2.35 0 2.62 33.95 3.55 1.65 0

75 kW

6.20 37.91 4.94 2.85 0

1.26 10.87 1.66 1.50 0

4.84 46.93 5.67 3.35 0

1.51 17.49 1.99 1.04 0

Table C-4: Methyl Ester PM Emission Rate (ng emitted compound/kJ fuel consumed) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (ng/kJ) 25 kW 50 kW 105.69 643.03 69.16 33.12 0 34.87 280.96 35.85 18.21 0

75 kW

0 kW

B100 (ng/kJ) 25 kW 50 kW 66.20 858.88 89.75 41.72 0

75 kW

146.89 897.54 117.00 67.38 0

29.78 257.29 39.40 35.57 0

122.47 117.07 1187.28 1185.12 143.33 127.55 84.81 59.35 0 0

38.10 442.39 50.42 26.27 0

106

Table C-5: Methyl Ester Concentration in Gaseous Phase (g/std m3) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (g/std m3) 25 kW 50 kW 31 95 8 2 0 102 300 21 4 0

75 kW

0 kW

B100 (g/std m3) 25 kW 50 kW 75 kW 46.9 159.6 16.1 4.2 0 116.7 503.9 55.4 9.98 0 130 377.2 50.4 7.5 0

163 375 40 5 0

120 245 45 12 0

151.8 448.1 59.3 8.7 0

Table C-6: Methyl Ester Gaseous Emission Rate (mg/hr) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (mg/hr) 25 kW 50 kW 8.87 27.17 2.29 0.57 0 34.78 102.30 7.16 1.36 0

75 kW

0 kW

B100 (mg/hr) 25 kW 50 kW 13.41 45.65 4.60 1.20 0 39.79 171.83 18.89 3.40 0

75 kW

42.87 98.63 10.52 1.32 0

45.84 93.59 17.19 4.58 0

39.92 117.85 15.60 2.29 0

49.66 144.09 19.25 2.87 0

107

Table C-7: Methyl Ester Gaseous Emission Rate (mg emitted compound/kg fuel consumed) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (mg/kg) 25 kW 50 kW 1.05 3.23 0.27 0.07 0 2.50 7.37 0.52 0.10 0

75 kW

0 kW

B100 (mg/kg) 25 kW 50 kW 1.52 5.16 0.52 0.14 0 3.13 13.52 1.49 0.27 0

75 kW

10.09 23.21 2.48 0.31 0

2.42 4.95 0.91 0.24 0

8.69 25.66 3.40 0.50 0

2.97 8.61 1.15 0.17 0

Table C-8: Methyl Ester Gaseous Emission Rate (ng emitted compound/kJ fuel consumed) for B50 and B100 over sampling loads (kW)

Methyl Ester Compound Methyl palmitate Methyl linoleate Methyl oleate Methyl stearate Methyl linolenate

0 kW

B50 (ng/kJ) 25 kW 50 kW 24.96 76.50 6.44 1.61 0 59.29 174.38 12.21 2.33 0

75 kW

0 kW

B100 (ng/kJ) 25 kW 50 kW 38.39 130.66 13.18 3.44 0 79.23 342.11 37.61 6.78 0

75 kW

238.84 549.47 58.61 7.33 0

57.35 117.09 21.51 5.73 0

219.89 649.08 85.90 12.60 0

75.04 217.75 29.09 4.33 0

108