New Catalytic Stripper System for the Measurement of Solid Particle Mass, Number, and Size Emissions from Internal Combustion Engines Imad A. Khalek, Ph.D. Southwest Research Institute Department of Emissions Research, 6220 Culebra Road San Antonio, Texas, 78238, Ikhalek@Swri.org 7 th ETH Conference on Combustion Generated Particles, Zurich, Switzerland, August 18-20, 2003 Particulate matter (PM) emitted from combustion sources, particularly diesel engines, is typically composed of volatile and solid material. The solid material ("soot") consists mainly of carbon and a small amount of inorganic ash. The volatile material consists of unburned and partially burned fuel and lubricating oil, and sulfur compounds. Dry soot particles are formed in the combustion chamber of an engine while most of the volatile material enters the particle phase from the gas phase as the exhaust cools. Hence, particulate matter is a combined measure of solid and volatile particles. It is important to be able to distinguish between the two components because the mechanism of their formation and control are different. Such information can also be useful for researchers investigating the effect of particulate emissions on human health. A catalytic stripper system referred to in this work as the solid particle measurement system (SPMS), Patent Pending, was designed to allow for the measurement of real time solid particle mass, size, and number in the size range from 10 nm to 500 nm. The SPMS consists of a heated mini oxidation catalyst and a micro-dilution system to cool the heated sample by dilution and prevent particle thermophoretic deposition downstream of the oxidation catalyst. The SPMS is equipped with two 47 mm filter holders for the measurement of solid particle mass and total (volatile plus solid) particle mass. Similarly, the SPMS is also equipped with sample ports for total and solid particle size and number measurements. The SPMS is a stand-alone system on a moving laboratory cart. All that is needed is an electric power outlet. Vacuum and compressed air sources are available on-board. The SPMS is also equipped with a Labview data acquisition system and a laptop computer for data processing and data analysis. The SPMS was characterized with sodium chloride, ammonium sulfate, and engine oil particles. The SPMS removed more than 99 percent of engine oil without generating sulfuric acid particles. The SPMS had better than 99 percent penetration of sodium chloride solid particles. The SPMS was applied to measure particle number and size distributions from a 1998 DDC Series 60 heavy-duty on-highway diesel engine operating at high
and low engine load. The total particle number-weighted size distribution was bimodal in nature with a nuclei mode at about 20 nm and an accumulation mode at about 50 nm. The solid particle number-weighted size distribution in the accumulation mode was similar to that of total, suggesting that the majority of accumulation mode particles for this engine are solid in nature. For the nuclei mode, a significant reduction in particle number was obtained downstream of the SPMS, suggesting that the majority of particles in the nuclei mode are volatile and were removed by the catalyst used in the SPMS. The SPMS also revealed, however, that under most engine operating conditions the solid fraction, the ratio of solid to total particle number in the sub 20 nm diameter range increased and exceeded 100 percent for particles between 9nm and 11 nm in diameter. By the definition of the solid fraction, it is not surprising to have a solid fraction over 100 percent. The following example explains how that can be possible. Suppose 50 percent of one hundred 10 nm solid particles present in the exhaust grew by the absorption of volatile material to a size above 10 nm. For the total size distribution, one would measure 50 particles with size 10 nm and 50 particles above 10 nm. If one applies the SPMS, one would measure a 100 solid particles for 10 nm particles. The solid fraction for 10 nm particles will then be 200 percent. This new findings suggest the presence of a solid core in the sub 20 nm particle size range that may go down to below 9 nm, the lower detection limit of the instrument used on this program. The nature of this solid core may be solid carbon or possibly metallic ash from the engine lubricating oil. Such information is extremely important to the health authorities trying to understand the effect of particles on human health. The application of the SPMS in future work is expected to generate significant information as to the composition and characteristics of particulate emissions from combustion sources. Coupled with a Nano-SMPS or similar devices that can measure particle size and number down to 3 nm, the use of the SPMS is expected to provide significant information as to the generation and growth of even the smallest of particles.
New Catalytic Stripper System for the measurement of Solid Particle mass, Number and Size Imad A. Khalek, Southwest Research Institute, San Antonio, Texas 7th ETH Conference on Combustion Generated Particles, Zurich, Switzerland, August 18-20, 2003 Acknowledgments This work was funded by SwRI Committee for Internal Research and Development. 1
Note The new catalytic stripper system will be referred to as the solid particle measurement system (SPMS) throughout this presentation Outline What is the SPMS? Characterization with Laboratory Aerosol Application on A Heavy-Duty Diesel Engine Conclusions 2
SPMS Development Objectives To Develop a Stand-Alone Laboratory Instrument that Facilitates the Measurement of Solid Exhaust Particle Mass (Filter and Non-Filter based), Number, Size, and Other Physical PM Characteristics Using Different Real Time Instruments To Minimize Solid Particle Losses and Achieve Near a 100 Percent Penetration of Solid Particles To Maximize the Removal of Volatile to Near 100 percent To Prevent the Potential Formation of Sulfuric Acid Particles To be Capable of Measuring Total PM (Solid and Volatile) So Volatile PM can be Determined To be Used Either with Diluted or Undiluted Exhaust Stream SPMS Principle of Operation Raw or Dilute Exhaust Temperature Probe Oxidation Catalyst Cool Clean Compressed Air Dilution Tunnel Heater Temperature Probe Temperature Controller To Particle Measurement System 3
Example of Gas Diffusion and Flow Optimization In Catalyst Square Channel Molecular Penetration, % 100.0000% 10.0000% 1.0000% 0.1000% 0.0100% 0.0010% 0.0001% Region of Interest 0.025 slpm 0 200 400 600 800 Molecular Penetration, % 100.0000% 10.0000% 1.0000% 0.1000% 0.0100% 0.0010% 0.0001% 0.10 slpm Region of Interest 0 200 400 600 800 Temperature, K Temperature, K C10H22 C19H40 C40H82 C10H22 C19H40 C40H82 Example of Particle Penetration and Flow Optimization In Catalyst Square Channel Particle Penetration, % 100% 95% 90% 85% 80% 75% 70% 0.025 slpm Number Mean Diameter Region Mass Mean Diameter Region 65% 10 100 1000 293 K 393 K 493 K 573 K 623 K 673 K Particle Penetration, % 100% 95% 90% 85% 80% 75% 0.10 slpm Number Mean Diameter Region 70% Mass Mean Diameter Region 65% 10 100 1000 293 K 393 K 493 K 573 K 623 K 673 K 4
Example of Dilution Ratio and Temperature Requirement at the Exit of Catalyst at Temperature of 300 o C 200 Dilution Air Temperature, C 100 0-100 -200 Practical Dilution -300 Range for PM Filter Measurement -400 0 10 20 30 40 Dilution Ratio MT: 25 C MT: 47 C MT: 75 C MT: 100 C Cutting The Appropriate Size Catalyst from The Stock Catalyst 5
Partial View of the SPMS Vortex Tube Diesel Oxidation Catalyst Clean Air Inlet (Optional) Sample Inlet CSS Outlet Particle Number and Size Ports Particle Mass Filter Holder Location Micro Dilution System Total Flow Out Laminar Flow Element Compressed Air In Laminar Flow Element Particle Number and Size Sample Ports Total Flow Tube Stand-Alone SPMS 6
SPMS Characterization with Laboratory Aerosol (Nominal Flow and Dilution Ratio) Unheated CSS Flow Conditions Total Flow (slpm) Air Flow (slpm) Sample Flow (slpm) Dilution Ratio 1 65.2 49.4 15.8 4.12 2 73.9 49.2 24.7 2.99 3 80.4 49.2 30.2 2.57 Heated CSS (300 /C) 1 70.7 49.7 21.0 3.36 2 64.3 49.2 15.1 4.25 3 60.0 50.0 10.0 6.00 SPMS Performance with NaCl Particles at 300 o C Particle Size-Specific Penetration (PSSP) 1.4 1.2 1 0.8 0.6 0.4 0.2 0 10 100 1000 Flow 1- New Flow 2-New Flow 3-New Theory 7
SPMS Performance With Engine Oil Droplets Particle Number Concentration, Part./cm³ 1.E+05 1.E+04 1.E+03 1.E+02 1.E+01 Engine Oil Droplet Residue Flow 1 1.E+00 1 10 100 1000 NC S-200 C S-250 C S-300 C S-350 C S-400 C Particle Volume Concentration, nm³/cm³ 1.00E+11 1.00E+10 1.00E+09 1.00E+08 1.00E+07 Engine Oil 1.00E+06 Droplet 1.00E+05 Residue Flow 1 1.00E+04 1 10 100 1000 NC S-200 C S-250 C S-300 C S-350 C S-400 C SPMS Performance with Ammonium Sulfate Particles Particle Number Concentration Part./cm³ 1.00E+05 1.00E+04 1.00E+03 1.00E+02 1.00E+01 Flow 1 1.00E+00 1 10 100 1000 NC S-200 C S-250 C S-300 C S-350 C S-400 C Particle Volume Concentration, nm³/cm³ 1.00E+11 1.00E+10 1.00E+09 1.00E+08 1.00E+07 1.00E+06 1.00E+05 Flow 1 1.00E+04 1 10 100 1000 NC S-200 C S-250 C S-300 C S-350 C S-400 C 8
Particle Penetration for Engine Oil Droplets Based on Number and Volume 100.0% Particle Number Total Particle Penetration, % 10.0% 1.0% Particle Volume 0.1% 0 50 100 150 200 250 300 350 400 450 CSS Inlet Temperature, C Flow 1- N Flow 2-N Flow 3-N Flow 1-V Flow 2-V Flow 3-V Engine Test Matrix Mode Speed, rpm Load, % of Load at Rated Speed Number of Repeats 1 1800 65 6 2 900 25 6 3 1800 35 6 4 600 0 6 1998 DDC Series 60 Heavy-Duty Diesel Engine 9
Total and Solid Particle Size Distributions Using SPMS (Heavy-Duty Diesel Engine Operating at High Load, Rated Speed, Mode 1) 1.00E+11 Particle Concentration (Part/cm³ and nm³/cm³) 1.00E+10 1.00E+09 1.00E+08 1.00E+07 1.00E+06 1.00E+05 1.00E+04 1.00E+03 1.00E+02 1.00E+01 Volume Reduction : 34 % Number Reduction : 93 % 1.00E+00 1 10 100 1000 Total Number Solid Number Total Volume Solid Volume Solid Fraction, % Total and Solid Particle Size Distributions Using SPMS (Heavy-Duty Diesel Engine Operating Near Low Idle, Mode 4) Particle Concentration (Part/cm³ and nm³/cm³) 1.00E+11 1.00E+10 1.00E+09 1.00E+08 Volume Reduction : 42 % 1.00E+07 1.00E+06 Number Reduction : 86 % 1.00E+05 1.00E+04 1.00E+03 1.00E+02 1.00E+01 1.00E+00 1.00E-01 1.00E-02 1 10 100 1000 Total Number Solid Number Total Volume Solid Volume Solid Fraction, % 10
Summary A Stand-Alone SPMS was developed for Solid and Total Particle Mass, Number, and Size. Solid Particle Losses were at minimum level and no correction is need in the size range from 10 nm to 300 nm. The SPMS removed more than 99 percent of oil droplets No apparent formation of sulfuric acid particles Engine Emissions Data revealed that some of the volatile droplets contain a solid core. It is possible to attribute such core to Ash derived from the lube oil. This instrument Can be a very useful for Assessing Solid,Volatile, and Total Particles in Real Time. More Detail Description and Analysis of the SPMS will be available in future publications 11
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