1、American Petroleum I Institute VEHICLE EMISSIONS TESTING OF RAPIDLY AGED CATALYSTS Health and Environmental Sciences Department Publication Number 4667 November 1997 STD-APIIPETRO PUBL ibb“ENGL L777 I 0732270 ObOL244 “IT3 P American Petroleum Institute American Petroleum Institute Environmental, Hea
2、lth, and Safety Mission and Guiding Principles MISSION The members of the American Petroleum Institute are dedicated to continuous efforts to improve the compatibility of our operations with the environment while economically developing energy resources and supplying high quality products und servic
3、es to consumers. We recognize our responsibility to work with the public, the government, and others to develop and to use natural resources in an environmentally sound manner while protecting the health and safety of our employees and the public. To meet these responsibilities, API members pledge t
4、o manage our businesses according to the following principles using sound science to prioritize risks and to implement cost-effective management practices: PRINCIPLES o To recognize and to respond to community concerns about our raw materials, products and operations. o To operate our plants and fac
5、ilities, and to handle our raw materials and products in a manner that protects the environment, and the safety and health of our employees and the public. 0 To make safety, health and environmental considerations a priority in our planning, and our development of new products and processes. o To ad
6、vise promptly, appropriate officials, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures. o To counsel customers, transporters and others in the safe use, transportation and disposal of our
7、 raw materials, products and waste materials. o To economically develop and produce natural resources and to conserve those resources by using energy efficiently. o To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products
8、, processes and waste materials. o To commit to reduce overall emission and waste generation. o To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. 0 To participate with government and others in creating responsible laws, regulations
9、and standards to safeguard the community, workplace and environment. o To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes. Vehicle Emissions Testing
10、of Rapidly Aged Catalysts Health and Environmental Sciences Department API PUBLICATION NUMBER 4667 PREPARED UNDER CONTRACT BY: JAMES A. RUTHERFORD, CHEVRON RESEARCH AND TECHNOLOGY COMPANY CHARLES H. SCHLEYER, MOBIL RESEARCH AND DEVELOPMENT DAVID H. LAX, AMERICAN PETROLEUM INSTITUTE MARK L. SZTENDERO
11、WICZ, CHEVRON PRODUCTS COMPANY NOVEMBER 1997 American Petroleum Institute FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES
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15、oshington. D.C. 2000s. Copyright Q 1997 Amcrican Petroleum Institute iii ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: PLpI STAFF CONTACT David Lax, Health and Environmental Sciences Departme
16、nt MBERS OF THE VEHICLE MISSIONS TASK FORCE J. Steve Welstand, Chairperson, Chevron Products Company Bill Bandy, Amoco Research Center John Eckstrom, Amoco Research Center King Eng, Texaco, Inc. Dennis Fiest, Shell Development Company Ana Rodriguez-Forker, Arco Products Company Frank S. Gerry, BP Am
17、erica, Inc. Albert M. Hochhauser, Exxon Research and Engineering Company George S. Musser, Exxon Research and Engineering Company Rick Riley, Phillips Petroleum Charles H. Schleyer, Mobil Research and Development We would also like to acknowledge the following people for their contributions: James A
18、. Rutherford, Chevron Research and Technology Company Mark L. Sztenderowicz, Chevron Products Company Jeff Jetter, Honda R (b) two stock replacement catalysts which had been artificially aged to 100,000 miles on gasolines with 40 ppm sulfur and 1000 ppm sulfur, respectively; and (c) a “field-aged” c
19、atalyst obtained from an “in-use” 1993 Honda Civic VX TLEV with approximately 100,000 odometer miles. The results of this test program show the following: The effects of sulfur on exhaust emissions of a 1993 Honda Civic certified to California TLEV standards were similar to those seen in other vehic
20、le test programs such as those conducted by PERF and the Auto/Oil AQIRP. (1) (3) Emissions were lower on the 35 ppm sulfur fuel than on the gasoline with 600 ppm sulfr. The differences in emissions between fuels were statistically significant for the group of four test catalysts as a whole, but diff
21、erences between fuels in individual catalysts were often not significant. Averaging over all catalysts, lowering fuel sulfur content from 600 to 35 ppm reduced FTP emissions by 21 to 27% depending on the pollutant. Exhaust emissions were lowest for the original catalyst and highest for the field-age
22、d, 100,000 mile in-use catalyst (Mg). The differences in emissions between the original catalyst and M9 were statistically significant for all pollutants over the FTP. I Numbers in ( ) denote references listed at the end of the report. ES- 1 Fuel sulfur content did not have an effect on the long-ter
23、m emissions performance of catalysts which had been artificially aged using the RAT-A cycle. Catalysts M7 and M8 were aged for 1 O0 hours on a dynamometer using the RAT-A cycle for 1 O0 hours on 40 and 1 O00 ppm sulfur fuels, respectively. There was no difference in overall emissions or sulfur effec
24、ts between these two catalysts. Rapid catalyst aging did not have a large effect on sulfur response compared to in-use aging. All catalysts responded directionally the same to sulfur and there was no difference in the magnitude of the sulfur effect among the four catalysts. An identical catalyst fro
25、m a Honda TLEV was tested in the CRC Sulfur/OBD-II laboratory reactor program. A comparison of the data generated from the two programs suggests that laboratory results may (a) overstate sulfur effects as measured from a vehicle and (b) represent hot vehicle performance better than cold operation. R
26、educing fuel sulfur content from 600 to 40 ppm in the CRC laboratory reactor program lowered the Honda TLEV HC and NO, emissions by 57% or more than twice the percentage effect seen over the FTP in the present study. However, the sulfur effects on HC that were observed during the warmed-up phases of
27、 the FTP (Bags 2 and 3) of the present study were similar to those measured in the CRC lab reactor program under steady-state, warmed-up conditions. Gasoline sulfur content did not have a significant effect on catalyst oxygen storage capacity. Differences in OSC between the original and the aged cat
28、alysts were much larger than any differences attributable to fuel sulfur content. OSC was roughly twice as high in the original catalyst compared to the three aged catalysts, all of which had similar OSC. ES-2 Section 1 INTRODUCTION Over the past several years, interest in evaluating the effect of f
29、uel sulfur content on motor vehicle emissions has prompted the initiation of a number of test programs which have focused on advanced technology vehicles. In 1993, for example, the Petroleum Environmental Research Forum (PERF) sponsored a study to evaluate the effect of fuel sulfur content on exhaus
30、t emissions from low-mileage production vehicles designed to meet Californias Transitional Low Emission Vehicle (TLEV) standards. (1) One of the TLEVs tested as part of that program was a 1993 Honda Civic VX. An identical catalyst from a 1993 Honda Civic VX TLEV model also was tested as part of a re
31、cent study sponsored by the Coordinating Research Council (CRC). (2) The CRC project was designed to measure the effect of fuel sulfur level on the conversion efficiencies and oxygen storage capacities of various rapidly aged automobile emissions control catalysts. The measurements in that program w
32、ere performed using a steady-state bench reactor because three of the four catalyst formulations that were tested were prototypes for which no suitable vehicle platforms were available at the time for FTP emissions tests. Equivalent fuel sulfur levels were obtained in the CRC program by varying the
33、content of the SO, feedgas to the bench reactor. However, this raised the question as to whether the results of steady-state emissions tests performed in a laboratory bench reactor were truly representative of those which would occur under in-use transient conditions as measured by the Federal Test
34、Procedure. Since identical catalysts were used in the CRC and PERF studies, the 1993 Honda Civic VX TLEV model provided an opportunity for a further program to compare sulfur effects in “real world” conditions on a vehicle which had accumulated a history of emissions testing to those observed in a s
35、teady-state bench reactor. It aiso provided a means to determine if the catalyst aging procedures in the CRC program impacted the sulfur responses differently from vehicle aging of catalysts. This program was performed under contract to the American Petroleum Institute (API) by Chevron Research and
36、Technology Co. 1-1 Section 2 TEST VEHICLES, CATALYSTS AND FUELS TEST VEHICLES Two vehicles were used in this test program and are described in Table 2-1. The first vehicle was a 1993 Honda Civic VX that was certified as a California Transitional Low Emissions Vehicle (TLEV). It is the same vehicle t
37、hat was used in Petroleum Environmental Research Forum (PERF) Project 93-12. (1) At the time of the PERF testing, the odometer on this vehicle showed between 4,000 and 5,000 miles. In the current program, accumulated mileage on the 1993 Honda Civic VX was between 10,000 and 1 1,000 miles. The 1993 H
38、onda Civic VX was instrumented to permit exhaust samples to .be drawn upstream of the catalyst and to measure temperature and oxygen content of exhaust before and after the catalyst. Since the vehicle was not equipped for California on-board diagnostics (OBD II), this included installation of a seco
39、nd exhaust gas oxygen sensor. Table 2-1: Description of Test Vehicles Model Year LEV (OBD II) TLEV California Emissions Standard Certification Honda Civic LX Honda Civic VX Model 1996 1993 The second vehicle was a 1996 Honda Civic LX loaned to the project by Honda R po zzu c( (d E .r. 2 O S 5-5 STD-
40、API/PETRO PUBL qbb7-ENGL L777 0732270 DbOL272 3b8 W Table 5-2: Reduction In Honda Tlev Ftp Emissions In Switching From High To Low Sulfur Fuel (600a35 Ppm) And Comparison To Results From Perf Tlev Program M8 M9 Catalyst Pollutant M7 THC NMHC NO, CO THC NMHC NO, CO THC NMHC NOx CO Original THC NMHC N
41、Ox CO ALL THC NMHC NOX CO PERF TLEV, 60025 mm NMHC NO, CO Grams per mile 0.032 i 0.012 0.01%0.027 0.08M.125 0.36644.538 0.01w.012 0.01 W0.027 0.131M.125 O. 14W0.538 0.046iO.012 0.025*0.027 0.181O.125 0.44W0.538 0.04W.015 0.028*0.034 0.077*0.152 0.45!&0.659 0.035M.004 0.021M.008 0.1 lW.038 0.351M.164 0.028 0.025 O. 193 Percent Reduction 24.8% 21.2% 20.6% 24.1 yo 15.8% 13.8% 28.2% 9.9% 26.1 YO 3 1.9% 22.9% 37.6% 32.3% 23.9% 4 1.7% 19.9% 26.2% 2 1.9% 26.9% 23.6% 19.1% 15.1% 26.9% 95% confidence intervals are shown. Significant differences are bolded 5-6
