1、American 1220 L Street, Northwest PetrOkUm Washington, D.C. 20005-4070 Institute 202-682-8000 Gas Fired Heater-Test Report Site B Characterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion Sources Regulatory and Scientific Affairs PUBL
2、ICATION NUMBER 4704 AUGUST 2001 Gas Fired Heater-Test Report Site B Characterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion Sources Regulatory and Scientific Affairs API PUBLICATION NUMBER 4704 AUGUST 2001 PREPARED UNDER CONTRACT BY
3、: GE ENERGY AND ENVIRONMENTAL RESEARCH CORPORATION 18 MASON IRVINE, CA 9261 8 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 N
4、OT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY
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6、SURING ANYONE AGAINST LIABIL- All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher. Contact the publisher; APIPublishi
7、ng Services, I220 L Street, N. K, Washington, D.C. 20005. Copyright O 2001 American Petroleum Institute II ACKNOWLEDGMENTS The following people are recognized for their contributions of time and expertise during this study and in the preparation of this report: API STAFF CONTACT Karin Ritter, Regula
8、tory and Scientific Affairs MEMBERS OF THE PM SOURCE CHARACTERIZATION WORKGROUP Lee Gilmer, Equilon Enterprises LLC, Stationary Source Emissions Research Committee, Chairperson Karl Loos, Equilon Enterprises LLC Jeff Siegell, ExxonMobil Research and Engineering GE ENERGY AND ENVIRONMENTAL RESEARCH C
9、ORPORATION PROJECT TEAM MEMBERS Glenn England, Project Manager Stephanie Wien, Project Engineer Bob Zimperman, Field Team Leader Barbara Zielinska, Desert Research Institute Jake McDonald, Desert Research Institute . 111 TABLE OF CONTENTS Section Pag.e EXECUTIVE SUMMARY . ES- 1 1 .O PROJECT DESCRIPT
10、ION 1 . 1 PROJECT OVERVIEW . 1 . 1 PROJECT OBJECTIVES . 1-2 Primary Objectives . . 1-2 Secondary Objective . 1-2 TEST OVERVIEW . . 1-2 Source Level (In-Stack) Samples . 1-2 Dilution Stack Gas Samples . . 1-3 Process Samples 1-4 KEY PERSONNEL . . 1-5 PROCESS DESCRIPTION 2. 1 SAMPLING LOCATIONS . 2. 1
11、 TEST PROCEDURES . 3. 1 2.0 3.0 STACK GAS FLOW RATE, MOISTURE CONTENT AND MOLECULAR WEIGHT . 3 . 1 02, COZ, CO, NOx AND SO2 . 3. 1 IN-STACK METHOD TESTS . 3-5 In-Stack Total Filterable PM, PM10 and PM2.5 3-6 Condensible Particulate Matter Mass and Chemical Analysis 3 . 11 DILUTION TUNNEL TESTS 3-14
12、PM2.5 Mass 3-16 Elements . 3 . 16 Sulfate, Nitrate, Chloride and Ammonium . 3 . 17 Organic and Elemental Carbon 3-18 Volatile Organic Compounds 3 . 19 Semivolatile Organic Compounds . 3-19 TABLE OF CONTENTS (CONTINUED) Section Pag.e 4.0 TEST RESULTS 4-1 PROCESS OPERATING CONDITIONS . 4. 1 PRELIMINAR
13、Y TEST RESULTS . 4-4 STACK GAS CONDITIONS AND FLOW RATE . 4-4 CO, NO,. AND SO2 EMISSIONS 4-4 IN-STACK AND IMPINGER METHOD RESULTS . 4.6 Particulate Mass 4.6 OC. EC and SVOCs 4-9 DILUTION TUNNEL RESULTS . 4. 11 Particulate Mass 4. 11 Sulfate, Chloride. Nitrate and Ammonium . 4. 12 OC. EC and Organic
14、Species . 4. 13 Elements . 4. 17 5.0 EMISSIONS FACTORS AND SPECIFICATION PROFILES . 5. 1 UNCERTAINTY 5 . 1 EMISSION FACTORS . 5. 1 PM2.5 SPECIATION PROFILES 5.5 Dilution Tunnel . 5.5 Method 20 1 N202 . 5.9 6.0 QUALITY ASSURANCE 6. 1 SAMPLE STORAGE AND SHIPPING 6. 1 DILUTION TUNNEL FLOWS 6. 1 GRAVIME
15、TRIC ANALYSIS 6. 1 Dilution Tunnel Filters 6. 1 In-Stack Filters 6-3 ELEMENTAL (XRF) ANALYSIS . 6.4 ORGANIC AND ELEMENTAL CARBON ANALYSIS . 6-5 SULFATE. NITRATE. CHLORIDE. AND AMMONIUM ANALYSIS . 6-6 TABLE OF CONTENTS (CONTINUED) Section Pag.e SVOC ANALYSIS . 6-7 VOC ANALYSIS . 6-9 CEMS ANALYSIS . 6
16、. 12 DISCUSSION AND FINDINGS 7-1 PM2.5 MASS MEASUREMENTS . 7. 1 CHEMICAL SPECIATION OF PRIMARY PM2.5 EMISSIONS . 7.5 SECONDARY PM2.5 PRECURSOR EMISSIONS . 7.9 7.0 REFERENCES . R- 1 Appendix A GLOSSARY A-1 Appendix B SI CONVERSION FACTORS B- 1 Fime E- 1 2- 1 3-1 3 -2 3-3 3 -4 3-5 3-6 3 -7 3-8 3 -9 5-
17、 1 5-2 5-3 7- 1 7-2 7-3 7-4 7-5 LIST OF FIGURES Pag.e Speciation Profile For Primary Particulate Emissions From Gas-Fired Process Heater (Refinery Site B) e5-9 Heater Process Overview and Samplinghonitoring Locations . 2.2 Chronology for Gas-Fired Process Heater Tests (Refinery Site B) 3-3 Continuou
18、s Emissions Monitoring System . 3-4 PM2.5/PM 1 O Train Configuration for Method 20 1 A/202 . 3-7 Method 201A (Modified) Sample Recovery Procedure 3-8 Method 201A (Modified) Sample Analysis Procedure 3-9 Sampling Train configuration for EPA Method 17 . 3-10 Method 202 Sample Recovery Procedure . 3-12
19、 Method 202 Sample Analysis Procedure (Modified) . 3 . 13 Dilution Tunnel Sampling System 3-15 PM2.5 Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel Results (Refinery Site B) 5-9 PM2.5 Speciation Profile for Gas-Fired Process Heater - Method 201/202 Results (Refinery Site B) 5-11 S
20、VOC Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel Results (Refinery Site B) 5-14 Method 202 Inorganic Fraction Residue Analysis for Gas-Fired Process Heater Tests (Refinery Site B) . 7-2 Results of Laboratory Tests Showing Effect of SO2 and Purge on Method 202 Sulfate Bias 7-4 In
21、-Stack and Ambient Species Concentrations For Gas-Fired Process Heater - Dilution Tunnel Results (Refinery Site B) 7-6 Comparison of Species Concentrations to Detection Limits for Gas-Fired Process Heater - Dilution Tunnel Results (Refinery Site B) . 7-7 Mean Species Concentrations and Standard Devi
22、ation for Gas-Fired Process Heater Tests - Dilution Tunnel Results (Refinery Site B) . 7-8 Table E- 1 E-2 E-3 E-4 1-1 1-2 2- 1 2-2 3-1 3 -2 4- 1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 LIST OF TABLES Pag.e Summary of Primary Particulate Emissions Factors for Gas-Fired Process Heater e5-4 Summary of Semivola
23、tile Organic Species Emissions Factors for Gas-Fired Process Heater . e5-5 Summary of Secondary Particulate Precursor Emission Factors for Gas-Fired Process Heater . e5-7 Substances of Interest not Detected in Stack Emissions from Gas-Fired Process Heater . e5-8 Overview of Sampling Scope . 1-3 Summ
24、ary of Analytical Targets . . l -4 Overview of Sampling Scope . 2-2 Summary of Analytical Targets 2.3 Summary of Test Procedures 3-2 CEMS Instrumentation Used for Gas-Fired Process Heater Test (Refinery Site B) . 3-5 Approximate In-Stack Detection Limits Achieved for Gas-Fired Process Heater Tests (
25、Refinery Site B) 4-2 Process Operating Conditions for Gas-Fired Process Heater (Refinery Site B) . 4.3 Fuel Gas Analysis for Gas-Fired Process Heater Tests (Refinery Site B) 4-3 Average Stack Gas Parameters for Gas-Fired Process Heater Tests (Refinery Site B) . 4-5 NOx, SOZ. and CO Results for Gas-F
26、ired Process Heater (Refinery Site B) 4-5 Filterable Total Particulate. PM10. and PM2.5 Results for Gas-Fired Process Heater (Refinery Site B) 4.6 Method 17 Total Particulate Matter Results for Gas-Fired Process Heater (Refinery Site B) 4-7 Condensible Particulate Matter for Gas-Fired Process Heater
27、 (Refinery Site B) 4.8 Analysis of Method 202 Residue for Process Heater Tests (Refinery Site B) 4-10 LIST OF TABLES (CONTINUED) Table 4-10 4-1 1 4-12 4-13 4-14 4-15 4-16 4-17 5- 1 5-2 5-3 5-4 5-5 5-6 5-7 In-Stack Filter Semivolatile Organic Compound Results for Gas-Fired Process Heater (Refinery Si
28、te B, mg/dscm) . .4- 1 1 Dilution Tunnel PM2.5 Results for Gas-Fired Process Heater (Refinery Site B) . 4-12 Ambient PM2.5 Results for Refinery Site B .4- 12 Dilution Tunnel Sulfate, Nitrate, Chloride and Ammonia Results for Gas-Fired Process Heater (Refinery Site B) . .4- 13 Dilution Tunnel Organic
29、 and Elemental Carbon Results for Gas-Fired Process Heater (Refinery Site B) 4- 14 Dilution Tunnel SVOC Results for Gas-Fired Process Heater (Refinery Site B, mg/dscm) . .4- 15 Dilution Tunnel VOC Results for Gas-Fired Process Heater (Refinery Site B) .4- 1 8 Dilution Tunnel Elemental Results for Ga
30、s-Fired Process Heater (Refinery Site B) .4- 19 Particulate Mass, Element, and Ion Emission Factors for Gas-Fired Process Heater (Refinery Site B) . 5-2 Carbon and Semivolatile Organic Compound Emission Factors for Gas- Fired Process Heater (Refinery Site B) .5-3 Volatile Organic Compound Emission F
31、actors for Gas-Fired Process Heater (Refinery Site B) . 5-6 NO, and SO2 Emission Factors for Gas-Fired Process Heater (Refinery Site B) . 5-8 PM2.5 Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel Results (Refinery Site B) 5-8 PM2.5 Speciation Profile for Gas-Fired Process Heater -
32、Method 201N202 Results (Refinery Site B) . .5- 1 O SVOC Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel Results (Refinery Site B) . .5- 12 LIST OF TABLES (CONTINUED) Table 6- 1 6-2 6-3 6-4 6-5 6-6 6-7 6-8 Pre- and Post-test Flow Checks for Dilution Tunnel for Gas-Fired Process Heat
33、er Tests (Refinery Site B) 6-2 Method 20 M202 Blank Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-3 Acetone Blank Results for Gas-Fired Process Heater (Refinery Site B) . . . .6-4 Blank Results for Elements . . . . . . . . . . . . .
34、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-5 Organic and Elemental Carbon Blank Results for Gas-Fired Process Heater (Refinery Site B) 6-6 Ion Blank Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
35、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6-7 SVOC Blank and Replicate Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6- 1 O VOC Blank Results . . . . . . . . . . . . . . . . . . . . . . .
36、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6- 1 1 EXECUTIVE SUMMARY In 1997, the United States Environmental Protection Agency (EPA) promulgated new ambient air standards for particulate matter smaller than 2.5 micrometers in diameter (PM2.5
37、). Source emissions data are needed to assess the contribution of petroleum industry combustion sources to ambient PM2.5 concentrations for receptor modeling and PM2.5 standard attainment strategy development. There are few existing data on emissions and characteristics of fine aerosols from petrole
38、um industry combustion sources, and the limited information that is available is incomplete and outdated. The American Petroleum Institute (API) developed a test protocol to address this data gap, specifically to: Develop emission factors and speciation profiles for emissions of primary fine particu
39、late matter (i.e., particulate present in the stack flue gas including condensible aerosols), especially organic aerosols from gas-fired combustion devices; and Identi and characterize secondary particulate (i.e., particulate formed via reaction of stack emissions in the atmosphere) precursor emissi
40、ons. This report presents results of a pilot project to evaluate the test protocol on a 1 14 million British thermal unit (MMBtu) per hour gas-fired refinery process heater. The process heater has a refractory-lined rectangular box furnace with a single row of burners on two opposing sides of the fu
41、rnace with a tubular process fluid heat exchanger located at the top of the furnace. The unit has no controls for NO, emissions. The flue gas temperatwe at the stack was approximately 680F during the tests. The particulate measurements at the stack were made using both a dilution tunnel research tes
42、t method and traditional methods for regulatory enforcement of particulate regulations. The dilution tunnel method is attractive because the sample collection media and analysis methods are identical to those used for ambient air sampling. Thus, the results are directly comparable with ambient air d
43、ata. Also, the dilution tunnel method is believed to provide representative results for condensible aerosols. Regulatory methods are attractive because they are readily accepted by regulatory agencies and have been used extensively on a wide variety of source ES- 1 types; existing regulatory methods
44、 for condensible aerosols may be subject to significant bias, however, and sampling/analytical options are limited. Emission factors for all species measured were extremely low, which is expected for gas-fired sources. Emission factors for primary particulate, including: total particulate, PM 1 O (p
45、articles smaller than nominally 10 micrometers), and PM2.5; elements; ionic species; and organic and elemental carbon are presented in Table E- 1. Since the process heater was firing refinery process gas with a heating value different from natwal gas, emission factors are expressed in pounds of poll
46、utant per million British thermal units of gas fired (lb/MMBtu). All tests were performed in triplicate. As a measure of the bias, precision, and variability of the results, the uncertainty and 95% confidence upper bound also are presented. Emission factors for semi-volatile organic species are pres
47、ented in Table E-2. The sum of semi- volatile organic species is approximately 3% of the organic carbon. Emission factors for secondary particulate precursors (NO, S02, and volatile organic species with carbon number of 7 or greater) are presented in Table E-3. The preceding tables include only thos
48、e substances that were detected in at least one of the three test runs. Substances of interest that were not present above the minimum detection limit for these tests are listed in Table E-4. A single ambient air sample was collected at the site. In some cases, the emission factors reported in Table
49、s E-1 to E-3 resulted from in-stack concentrations that were near ambient air concentrations. Those in-stack species concentrations that are within a factor of 10 of the ambient air concentration are indicated on the table by an asterisk (*). The primary particulate results presented in Table E-1 also may be expressed as a PM2.5 speciation profile, which is the mass fraction of each species contributing to the total PM2.5 mass. The speciation profile is presented in Figure E-1 . ES-2 The main findings of these tests are: Particulate mass emissions from the process heater were extremely l
