1、 Gas Fired BoilerTest Report Refinery Site ACharacterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion SourcesRegulatory and Scientific AffairsPUBLICATION NUMBER 4703JULY 2001Gas Fired BoilerTest Report Refinery Site ACharacterization
2、of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion SourcesRegulatory and Scientific AffairsAPI PUBLICATION NUMBER 4703JULY 2001PREPARED UNDER CONTRACT BY:GE ENERGYANDENVIRONMENTALRESEARCHCORPORATION18 MASONIRVINE, CA 92618FOREWORDAPI PUBLICATIO
3、NS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE.WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERALLAWS AND REGULATIONS SHOULD BE REVIEWED.API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS,MANUFACTURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIPTHEIR EMPLOYEES, AND O
4、THERS EXPOSED, CONCERNING HEALTH AND SAFETYRISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDERLOCAL, STATE, OR FEDERAL LAWS.NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED ASGRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THEMANUFACTURE, SALE, OR USE OF ANY METHOD, APPARA
5、TUS, OR PRODUCTCOVERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED INTHE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABILITYFOR INFRINGEMENT OF LETTERS PATENT.All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted byany means, ele
6、ctronic, mechanical, photocopying, recording, or otherwise, without prior writtenpermission from the publisher. Contact the publisher, API Publishing Services, 1220 L Street, N.W.,Washington, D.C. 20005.ACKNOWLEDGMENTSThe following people are recognized for their contributions of time and expertise
7、duringthis study and in the preparation of this report:API STAFF CONTACTKarin Ritter, Regulatory and Scientific AffairsMEMBERS OF THE PM SOURCE CHARACTERIZATION WORKGROUPLee Gilmer, Equilon Enterprises LLC, Stationary Source Emissions Research Committee, ChairpersonKarl Loos, Equilon Enterprises LLC
8、Jeff Siegell, ExxonMobil Research and EngineeringGE ENERGY AND ENVIRONMENTAL RESEARCH CORPORATIONPROJECT TEAM MEMBERSGlenn England, Project ManagerStephanie Wien, Project EngineerBob Zimperman, Field Team LeaderBarbara Zielinska, Desert Research InstituteJake McDonald, Desert Research InstituteTABLE
9、 OF CONTENTSSection PageEXECUTIVE SUMMARY ES-11.0 PROJECT DESCRIPTION .1-1PROJECT OVERVIEW 1-1PROJECT OBJECTIVES 1-2Primary Objectives.1-2Secondary Objectives.1-2TEST OVERVIEW .1-2Source Level (In-Stack) Samples1-2Dilution Stack Gas Samples .1-3Process Samples.1-4KEY PERSONNEL.1-52.0 PROCESS DESCRIP
10、TION.2-1SAMPLING LOCATIONS2-13.0 TEST PROCEDURES 3-1STACK GAS FLOW RATE, MOISTURE CONTENT ANDMOLECULAR WEIGHT3-1O2, CO2, CO, NOXAND SO23-1IN-STACK METHOD TESTS 3-6In-Stack Filterable Total PM, PM10 and PM2.5.3-7Condensible Particulate Matter Mass and Chemical Analysis. 3-12DILUTION TUNNEL TESTS. 3-1
11、5PM2.5 Mass. 3-17Elements 3-17Sulfate, Nitrate, Chloride and Ammonium 3-18Organic and Elemental Carbon. 3-19Volatile Organic Compounds . 3-19Semivolatile Organic Compounds 3-204.0 TEST RESULTS.4-1PROCESS OPERATING CONDITIONS 4-1PRELIMINARY TEST RESULTS4-1STACK CONDITIONS AND FLOW RATE.4-5CO, NOXAND
12、SO2EMISSIONS4-6IN-STACK AND IMPINGER METHOD RESULTS 4-7Particulate Mass.4-7OC, EC and SVOCs . 4-12DILUTION TUNNEL RESULTS 4-14Particulate Mass. 4-14Sulfate, Chloride, Nitrate and Ammonium 4-15OC, EC and Organic Species 4-15Elements 4-195.0 EMISSION FACTORS AND SPECIATION PROFILES5-1UNCERTAINTY.5-1EM
13、ISSION FACTORS FOR PRIMARY EMISSIONS .5-1PM2.5 SPECIATION PROFILES5-5Dilution Tunnel5-5Method 201A/202 5-8SPECIATION PROFILES FOR ORGANIC AEROSOLS .5-8Dilution Tunnel Organic Speciation .5-8Method 201A/202 Organic Speciation 5-106.0 QUALITY ASSURANCE.6-1SAMPLE STORAGE AND SHIPPING.6-1DILUTION TUNNEL
14、 FLOWS .6-1GRAVIMETRIC ANALYSIS .6-1ELEMENTAL (XRF) ANALYSIS6-3ORGANIC AND ELEMENTAL CARBON ANALYSIS 6-4SULFATE, NITRATE, CHLORIDE AND AMMONIUMANALYSIS.6-5SVOC ANALYSIS6-6VOC ANALYSIS6-8TABLE OF CONTENTS (CONTINUED)Section PageCEMS ANALYSIS 6-127.0 DISCUSSION AND FINDINGS.7-1PM2.5 MASS MEASUREMENTS7
15、-1CHEMICAL SPECIATION OF PRIMARY PM2.5 EMISSIONS7-5SECONDARY PM2.5 PRECURSOR EMISSIONS 7-11REFERENCES R-1Appendix AGLOSSARY . A-1Appendix BSI CONVERSION FACTORS. B-1LIST OF FIGURESFigure PageE-1 Speciation Profile for Primary Particulate Emissions from Gas-Fired Boiler(Refinery Site A). ES-102-1 Boi
16、ler Process Overview and Sampling/Monitoring Locations .2-23-1 Chronology for Gas-Fired Boiler (Refinery Site A) 3-33-2 CEMS Schematic .3-53-3 PM2.5/PM10 Train Configuration for Method 201A/202 .3-83-4 Method 201A (Modified) Sample Recovery Procedure 3-93-5 Method 201A Modified Sample Analysis Proce
17、dure 3-103-6 Sampling Train Configuration for EPA Method 17.3-113-7 Method 202 Sample Recovery Procedure .3-133-8 Method 202 Sample Modified Analysis Procedure .3-143-9 Dilution Tunnel Sampling System3-165-1 Speciation Profile-Dilution Tunnel PM2.5 Fractions 5-95-2 Speciation Profile-Method 201A/202
18、 .5-115-3 Organic Aerosol Mass Fraction Speciation.5-145-4 In-Stack Organic Aerosol Mass Fraction Speciation.5-177-1 Speciation of Inorganic Impinger Fraction Reanalysis (Refinery Site A) 7-27-2 Results of Laboratory Tests Showing Effect of SO2and Purge onMethod 202 Sulfate Bias 7-47-3 In-Stack and
19、Ambient Species Concentrations (Dilution Tunnel)(Refinery Site A)7-67-4 Comparison of Species Concentrations to Detection Limits (Dilution Tunnel)7-77-5 Mean Species Concentrations and Standard Deviation (Dilution Tunnel) .7-8LIST OF TABLESTable PageE-1 Summary of Primary Particulate Emission Factor
20、s for Gas-Fired RefineryBoiler . ES-4E-2 Summary of Semivolatile Organic Species Emission Factors for Gas-FiredRefinery Boiler ES-5E-3 Summary of Secondary Particulate Precursor Emission Factors for Gas-FiredRefinery Boiler. ES-8E-4 Substances of Interest Not Detected in Stack Emissions from Gas-Fir
21、ed Boiler ES-91-1 Overview of Sampling Scope 1-31-2 Summary of Analytical Targets.1-43-1 Summary of Test Procedures.3-23-2 Description of CEMS Instrumentation Used for Gas-FiredBoiler Test (Refinery Site A).3-64-1 Approximate In-Stack Detection Limits Achieved for Gas-FiredBoiler Tests (Refinery A)
22、4-24-2 Process Data for Gas-Fired Boiler (Refinery Site A)4-34-3 Fuel Gas Analyses for Gas-Fired Boiler (Refinery Site A).4-44-4 Stratification Data for Gas-Fired Boiler (Refinery Site A) .4-54-5 Stack Gas Summary for Gas-Fired Boiler (Refinery Site A) 4-64-6 CEMS Data For Gas-Fired Boiler (Refinery
23、 Site A)4-74-7 Filterable Particulate Matter (Method 201A) for Gas-Fired Boiler(Refinery Site A).4-84-8 Condensible Particulate for Gas-Fired Boiler (Refinery Site A).4-94-9 Method 202 Inorganic Residue Analysis . 4-114-10 In-Stack Organic and Elemental Carbon Results for Gas-Fired Boiler(Refinery S
24、ite A) 4-134-11 In-Stack SVOC Results for Gas-Fired Boiler (Refinery Site A) 4-134-12 Stack Gas PM2.5 Results for Gas-Fired Boiler (Refinery Site A) . 4-144-13 Ambient Air PM2.5 Results for Gas-Fired Boiler (Refinery Site A) 4-14LIST OF TABLES (CONTINUED)Table Page4-14 Dilution Tunnel Sulfate, Nitra
25、te, Chloride and Ammonium Results forGas-Fired Boiler (Refinery Site A) 4-154-15 Dilution Tunnel Organic and Elemental Carbon Results for Gas-FiredBoiler (Refinery Site A) 4-164-16 Dilution Tunnel SVOC Results for Gas-Fired Boiler (Refinery Site A) . 4-174-17 Dilution Tunnel VOC Results for Gas-Fire
26、d Boiler (Refinery Site A) . 4-204-18 Dilution Tunnel Elemental Results for Gas-Fired Boiler (Refinery Site A) 4-215-1 Primary Emissions - Particulate Mass and Elements5-25-2 Primary Emissions - Carbon and Semivolatile Organic Compounds 5-35-3 Emission Factors for Secondary Organic Aerosol Precursor
27、s (VOC).5-65-4 Emission Factors for Secondary Organic Aerosol Precursors - NOxand SO2.5-65-5 Speciation Profile for Dilution Tunnel Primary Emissions for Gas-FiredBoiler (Refinery Site A) 5-75-6 Speciation Profile for PM2.5 for Gas-Fired Boiler (Refinery Site A)(Method 201 A/202) 5-105-7 Organic Aer
28、osol Speciation Profile . 5-125-8 Organic Aerosol Speciation Profile (Method 201A/202) 5-166-1 Pre- and Post- Test Dilution Tunnel Flow Checks for the Gas-Fired Boiler(Refinery Site A).6-26-2 Method 201A/202 Blank Results.6-36-3 Results from Field Blank Acetone Rinses6-36-4 Field Blank for Elements.
29、6-46-5 Organic and Elemental Carbon Blanks and Replicate Sample (mg/dscm) 6-56-6 Ion Blank Results6-66-7 SVOC/PUF/XAD Field Blank Results 6-96-8 SVOC PUF/XAD Replicate Analysis Results 6-10ES-1EXECUTIVE SUMMARYIn 1997, the United States Environmental Protection Agency (EPA) promulgated new ambientai
30、r standards for particulate matter smaller than 2.5 micrometers in diameter (PM2.5). Sourceemissions data are needed to assess the contribution of petroleum industry combustion sources toambient PM2.5 concentrations for receptor modeling and PM2.5 standard attainment strategydevelopment. There are f
31、ew existing data on emissions and characteristics of fine aerosols frompetroleum industry combustion sources, and the limited information that is available isincomplete and outdated. The American Petroleum Institute (API) developed a test protocol toaddress this data gap, specifically to: Develop em
32、ission factors and speciation profiles for emissions of primary fineparticulate matter (i.e., particulate present in the stack flue gas includingcondensible aerosols), especially organic aerosols from gas-fired combustiondevices; and Identify and characterize secondary particulate (i.e., particulate
33、 formed viareaction of stack emissions in the atmosphere) precursor emissions.This report presents results of a pilot project to evaluate the test protocol on 550,000 pounds perhour steam (approximately 650 x 106British thermal units per hour) boiler firing refinery processgas. The tangentially fire
34、d boiler has a waterwall furnace with two rows of burners in eachcorner of the furnace. The unit has no controls for NOxemissions. The boiler operated atapproximately 57 percent of capacity, and flue gas temperature at the stack was approximately345 degrees Fahrenheit during the tests.The particulat
35、e measurements at the stack were made using both a dilution tunnel research testmethod and traditional methods for regulatory enforcement of particulate regulations. Thedilution tunnel method is attractive because the sample collection media and analysis methodsare identical to those used for ambien
36、t air sampling. Thus, the results are directly comparablewith ambient air data. Also, the dilution tunnel method is believed to provide representativeresults for condensible aerosols. Regulatory methods are attractive because they are readilyaccepted by regulatory agencies and have been used extensi
37、vely on a wide variety of sourceES-2types; existing regulatory methods for condensible aerosols may be subject to significant bias,however, and sampling/analytical options are limited.Emission factors for all species measured are extremely low, which is expected for gas-firedsources. Emission factor
38、s for primary particulate, including: total particulate, PM10 (particlessmaller than nominally 10 micrometers), and PM2.5; elements; ionic species; and organic andelemental carbon are presented in Table E-1. Since the boiler was firing refinery process gaswith a heating value different from natural
39、gas, emission factors are expressed in pounds ofpollutant per million British thermal units of gas fired (lb/MMBtu). All tests were performed intriplicate. As a measure of the bias, precision, and variability of the results, the uncertainty and95 percent confidence upper bound also are presented.Emi
40、ssion factors for semivolatile organic species are presented in Table E-2. The sum ofsemivolatile organic species is approximately three percent of the organic carbon. Emissionfactors for secondary particulate precursors (NOx, SO2, and volatile organic species with carbonnumber of 7 or greater) are
41、presented in Table E-3.The preceding tables include only those substances that were detected in at least one of the threetest runs. Substances of interest that were not present above the minimum detection limit forthese tests are listed in Table E-4.A single ambient air sample was collected at the s
42、ite. In some cases, the emission factorsreported in Tables E-1 to E-3 resulted from in-stack concentrations that were near ambient airconcentrations. Those species concentrations that are within a factor of 10 of the ambient airconcentration are indicated on the table by an asterisk (*).The primary
43、particulate results presented in Table E-1 also may be expressed as a PM2.5speciation profile, which is the mass fraction of each species contributing to the total PM2.5mass. The speciation profile is presented in Figure E-1.ES-3The main findings of these tests are: Particulate mass emissions from t
44、he boiler were extremely low, consistent with levelsexpected for gaseous fuel combustion. Two methods for determining the average emission factor for primary PM2.5 massgave results which differed in magnitude by a factor of 27: 0.000358 lb/MMBtu usingthe dilution tunnel; and 0.00974 lb/MMBtu using c
45、onventional in-stack methods forfilterable and condensible particulate. Sampling and analytical artifacts principally caused by gaseous SO2in the stack gaswere shown to produce a relatively large positive bias in condensible particulate asmeasured by conventional in-stack methods. Most of the differ
46、ence between thedilution tunnel and conventional method results can be explained by thesemeasurement artifacts. The results using conventional EPA methods are nominallyconsistent with published EPA emission factors for external combustion of naturalgas (U. S. EPA, 1998). Therefore, the published EPA
47、 emission factors derived fromtests using similar measurement methods also may be positively biased. Chemical species accounting for 74 percent of the measured PM2.5 mass werequantified. Organic and elemental carbon comprise 68 percent of the measured primary PM2.5mass. Sulfates, iron, copper, chlor
48、ide, and smaller amounts of other elements account foranother 6 percent of the measured PM2.5 mass. Less than 26 percent of the measured PM2.5 mass is unspeciated. Most elements are not present at levels significantly above the background levels inthe ambient air or the minimum detection limits of t
49、he test methods. Most organic species are not detected at levels significantly above background levelsin the ambient air or field blanks. All detected organics are present at extremely lowlevels consistent with gaseous fuel combustion. Emissions of secondary particle precursors are low and consistent with levelsexpected for gaseous fuel combustion.ES-4Table E-1. Summary of Primary Particulate Emission Factors for Gas-Fired Refinery Boiler.Substance Emission Uncertainty 95% ConfidenceParticulate Condensible Particulate (inorganic) 9.07E-3 107 1.58E-2Condensible Particulate (or
