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Technical Paper

Analysis of the Physical Characteristics of Diesel Particulate Matter Using Transmission Electron Microscope Techniques

An Andersen Impactor was used to collect particulate samples in both the undiluted and diluted exhaust from a Caterpillar 3150 diesel engine operated on the EPA 13-mode cycle. A total of 24 samples were examined using the transmission electron microscope and approximately 300 photomicrographs were taken. The microscope analysis and photomicrographs revealed details concerning the physical characteristics of the particulate and permitted a direct visual comparison of the samples collected. The photomicrographs were used to obtain diameter measurements of the basic individual spherical particles that comprise the much larger aggregates/agglomerates. Nearly 11,000 basic particles were measured and the observed range of diameters was 70-1200 Å. The mean particle diameters in the undiluted and diluted exhaust samples were 479 Å and 436 Å respectively. respectively. A respectively. 436 A respectively.
Technical Paper

Cooperative Study of Heavy Duty Diesel Emission Measurement Methods

A cooperative test program was conducted by the CRC-APRAC CAPI-1-64 Composition of Diesel Exhaust Program Group to evaluate the technical aspects of a proposed EPA recommended Heavy Duty Diesel Emission Measurement and Test Procedure. The proposed changes affected the sampling configurations and the types of instruments used. Six participants studied the effects of a number of variables on the proposed changes and evaluated some alternative systems that included both CHEMI and NDIR instruments. The tests were conducted at one site using a multi-cylinder engine operating on the 13-Mode Cycle. Equivalency of systems was demonstrated and the best performance was obtained with a special NDIR system.
Technical Paper

Effects of a Catalyzed Particulate Filter on Emissions from a Diesel Engine: Chemical Characterization Data and Particulate Emissions Measured with Thermal Optical and Gravimetric Methods

A wide range of emissions were characterized from a heavy-duty diesel engine operated on conventional low sulfur (∼375 ppm) fuel, equipped with manually controlled EGR and a catalyzed particulate filter (CPF). The effect of the CPF and engine load was studied, along with a comparison of results between the gravimetric and thermal optical methods (TOM) for determining diesel particulate levels. Data were obtained from four of the EPA old 13 mode test cycle steady-state operating conditions, i.e., Modes 11, 10, 9, and 8 using a 1995 Cummins M11-330E engine with a Corning EX-80 cordierite particulate filter, coated with a platinum catalyst (5 g/ft3).
Technical Paper

Effects of a Ceramic Particle Trap and Copper Fuel Additive on Heavy-Duty Diesel Emissions

This research quantifies the effects of a copper fuel additive on the regulated [oxides of nitrogen (NOx), hydrocarbons (HC) and total particulate matter (TPM)] and unregulated emissions [soluble organic fraction (SOF), vapor phase organics (XOC), polynuclear aromatic hydrocarbons (PAH), nitro-PAH, particle size distributions and mutagenic activity] from a 1988 Cummins LTA10 diesel engine using a low sulfur fuel. The engine was operated at two steady state modes (EPA modes 9 and 11, which are 75 and 25% load at rated speed, respectively) and five additive levels (0, 15, 30, 60 and 100 ppm Cu by mass) with and without a ceramic trap. Measurements of PAH and mutagenic activity were limited to the 0, 30 and 60 ppm Cu levels. Data were also collected to assess the effect of the additive on regeneration temperature and duration. Copper species collected within the trap were identified and exhaust copper concentrations quantified.
Technical Paper

Modeling Study of Active Regeneration of a Catalyzed Particulate Filter Using One-Dimensional DOC and CPF Models

The catalyzed particulate filter (CPF), used in conjunction with a diesel oxidation catalyst (DOC) is an important aftertreatment device used to meet Environmental Protection Agency (EPA) heavy-duty diesel emission standards for particulate matter (PM). Numerical modeling of these exhaust after-treatment devices decreases the time and cost of development involved. Modeling CPF active regeneration gives insight into the PM oxidation kinetics, which helps in reducing the regeneration fuel penalty. As seen from experimental data, active regeneration of the CPF results in a significant temperature increase into the CPF (up to 8°C/sec) which affects the oxidation rate of particulate matter (PM). PM oxidation during active regeneration was determined to be a function of filter PM loading, inlet temperature and inlet hydrocarbon concentration.
Technical Paper

Oxidation Catalytic Converter and Emulsified Fuel Effects on Heavy-Duty Diesel Engine Particulate Matter Emissions

The effects of an oxidation catalytic converter (OCC), an emulsified fuel, and their combined effects on particle number and volume concentrations compared to those obtained when using a basefuel were studied. Particle size and particulate emission measurements were conducted at three operating conditions; idle (850 rpm, 35 Nm), Mode 11 (1900 rpm, 277 Nm) and Mode 9 (1900 rpm, 831 Nm) of the EPA 13 mode cycle. The individual effects of the emulsified fuel and the OCC as well as their combined effects on particle number and volume concentrations were studied at two different particle size ranges; the nuclei (less than or equal to 50 nm) and accumulation (greater than 50 nm) modes. An OCC loaded with 10 g/ft3 platinum metal (OCC1) and a 20% emulsified fuel were used for this study and a notable influence on the particle size with respect to number and volume distributions was observed.
Technical Paper

Physical Size Distribution Characterization of Diesel Particulate Matter and the Study of the Coagulation Process

Diesel particulate matter in both the diluted and undiluted state is subject to the processes of coagulation, condensation or evaporation, and nucleation which causes continuous changes in its physical characteristics. The Electrical Aerosol Analyzer (EAA) is used to measure the diesel particle size distribution in the MTU dilution tunnel for a naturally aspirated direct-injection diesel engine operated on the EPA 13 mode cycle. The design and development of accurate and repeatable sampling methods using the EAA are presented. These methods involve both steady-state tunnel and bag measurements. The data indicate a bimodal nature within the 0.001 to 1 μm range. The first mode termed the “embroynic mode” has a saddle point between 0.005 to 0.015 μm and the second mode termed the “aggregation mode” lies between .08 to .15 μm for the number distribution.
Technical Paper

The Characterization of the Hydrocarbon and Sulfate Fractions of Diesel Particulate Matter

One of the more objectionable aspects of the use of diesel engines has been the emission of particulate matter. A literature review of combustion flames, theoretical calculations and dilution tunnel experiments have been performed to elucidate the chemical and physical processes involved in the formation of diesel particulate matter. A comparative dilution tunnel study of diluted and undiluted total particulate data provided evidence supporting calculations that indicate hydro-carbon condensation should occur in the tunnel at low exhaust temperatures. The sample collection system for the measurement of total particulate matter and soluble sulfate in particulate matter on the EPA 13 mode cycle is presented. A method to correct for hydrocarbon interferences in the EPA barium chloranilate method for the determination of sulfate in particulate matter is discussed.
Technical Paper

The Characterization of the Soluble Organic Fraction of Diesel Particulate Matter

This paper is concerned with the demonstration of a methodology for chemically characterizing diesel particulate organic matter (POM) emissions. The procedure begins with a Soxhlet extraction of the POM with dichloromethane to obtain a soluble organic fraction (SOF). The acidic and basic portions of the SOF are isolated by liquid-liquid extraction techniques with aqueous base and aqueous acid, respectively. The neutral portion of the extract is separated into paraffin, aromatic, transitional and oxygenated fractions by column chromatography on silica gel. Two additional fractions, the ether insoluble and hexane insoluble fractions, are also separated by the procedure. Quantitative mass data are presented on the extraction and fractionation of twelve particulate samples from the exhaust of a medium-duty diesel engine collected in a dilution tunnel at a volume dilution ratio of 8 to 1.
Technical Paper

The Effect of Low Sulfur Fuel and a Ceramic Particle Filter on Diesel Exhaust Particle Size Distributions

Diesel exhaust particle size distributions were measured using an Electrical Aerosol Analyzer (EAA) with both conventional (0.31 wt. pet sulfur) and low sulfur fuel (0.01 wt pet sulfur) with and without a ceramic diesel particle filter (DPF). The engine used for this study was a 1988 heavy-duty diesel engine (Cummins LTA10-300) operated at EPA steady-state modes 9 and 11. The particle size distribution results indicated the typical bi-modal distribution; however, there were clear differences in the number of particles in each mode for all conditions. For the baseline conditions with no DPF, there was more than one order of magnitude greater number of particles in the nuclei mode for the conventional fuel as compared to the low sulfur fuel, while the accumulation modes for each fuel were nearly identical.
Technical Paper

The Effect of a Diesel Oxidation Catalyst and a Catalyzed Particulate Filter on the Emissions from a Heavy Duty Diesel Engine

The objective of this research was to study the effects of a CCRT®, henceforth called Diesel Oxidation Catalyst - Catalyzed Particulate Filter (DOC-CPF) system on particulate and gaseous emissions from a heavy-duty diesel engine (HDDE) operated at Modes 11 and 9 of the old Environmental Protection Agency (EPA) 13-mode test cycle Emissions characterized included: total particulate matter (TPM) and components of carbonaceous solids (SOL), soluble organic fraction (SOF) and sulfates (SO4); vapor phase organics (XOC); gaseous emissions of total hydrocarbons (HC), carbon monoxide (CO), oxides of nitrogen (NOx), nitric oxide (NO) and nitrogen dioxide (NO2), oxygen (O2) and carbon dioxide (CO2); and particle size distributions at normal dilution ratio (NDR) and higher dilution ratio (HDR). Significant reductions were observed for TPM and SOL (>90%), SOF (>80%) and XOC (>70%) across the DOC-CPF at both modes.
Technical Paper

The Effects of Fuel Sulfur Concentration on Regulated and Unregulated Heavy-Duty Diesel Emissions

The effects of fuel sulfur concentration on heavy-duty diesel emissions have been studied at two EPA steady-state operating conditions, mode 9 (1900 RPM, 75% Load) and mode 11(1900 RPM, 25% Load). Data were obtained using one fuel at two sulfur levels (Low Sulfur, LS = 0.01 wt% S and Doped Low Sulfur DS = 0.29 wt% S). All tests were conducted using a Cummins LTA10-300 heavy-duty diesel engine. No significant changes were found for the nitrogen oxides (NOx), soluble organic fractions (SOF) and XAD-2 (a copolymer of styrene and divinylbenzene) organic component (XOC) due to the fuel sulfur level increase at either engine mode. The hydrocarbon (HC) levels were not significantly affected by sulfur at mode 9; however, at mode 11 the HC levels were reduced by 16%. The total particulate matter (TPM) levels increased by 17% at mode 11 and by 24% at mode 9 (both significantly different).
Technical Paper

The Effects of Fuels on Diesel Oxidation Catalyst Performance and the Physical, Chemical, and Biological Character of Diesel Particulate Emissions

The effect of fuel changes on diesel oxidation catalyst performance was studied by comparing the physical, chemical and biological character of the particulate emissions using three different fuels. Baseline (uncatalyzed) emissions were also compared for these same fuels. The fuels used for this study were: a typical No. 2 fuel, a No. 1 fuel, and a shale oil-derived diesel fuel. Comparisons of NOX, NO, NO2, HC and particulate mass emissions using each fuel were made using selected modes from the EPA 13 mode cycle. Changes in the chemical and biological character of the soluble organic fraction (SOF) were also studied. Fuel properties, most notably fuel sulfur content, were found to affect the performance of the oxidation catalyst used. Fuel sulfur content should be kept as low as possible if catalytic converters are used on diesel powered equipment.
Technical Paper

The Effects of a Catalyzed Particulate Filter and Ultra Low Sulfur Fuel on Heavy Duty Diesel Engine Emissions

The objective of this research was to study the effect of a catalyzed particulate filter (CPF) with a high loading of catalyst (50 gms/ft3) and ultra low sulfur fuel (ULSF -0.57 ppm of sulfur) on the emissions from a heavy duty diesel engine. The particulate emissions were measured using two different analytical methods, i.e., the gravimetric method and the thermal optical method (TOM). The results from the two different methods of analyses were compared. The experiments were performed at four different operating conditions chosen from the old Environmental Protection Agency (EPA) 13-mode test cycle. A 1995 Cummins M11 heavy-duty engine with manually controlled exhaust gas recirculation (EGR) was used to perform the emission characterization experiments. The emission characterization included total particulate matter (TPM), which is composed of the solids (SOL), soluble organic fractions (SOF) and sulfates (SO4) analyzed using the gravimetric method.
Technical Paper

The Effects of a Porous Ceramic Particulate Trap on the Physical, Chemical and Biological Character of Diesel Particulate Emissions

Physical, chemical, and biological characterization data for the particulate emissions from a Caterpillar 3208 diesel engine with and without Corning porous ceramic particulate traps are presented. Measurements made at EPA modes 3,4,5,9,lO and 11 include total hydrocarbon, oxides of nitrogen and total particulate matter emissions including the solid fraction (SOL), soluble organic fraction (SOF) and sulfate fraction (SO4), Chemical character was defined by fractionation of the SOF while biological character was defined by analysis of Ames Salmonella/ microsome bioassay data. The trap produced a wide range of total particulate reduction efficiencies (0-97%) depending on the character of the particulate. The chemical character of the SOF was significantly changed through the trap as was the biological character. The mutagenic specific activity of the SOF was generally increased through the trap but this was offset by a decrease in SOF mass emissions.