1、 Gas-Fired Steam GeneratorTest Report Site CCharacterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion SourcesRegulatory and Scientific AffairsPUBLICATION NUMBER 4712JULY 2001Gas-Fired Steam GeneratorTest Report Site CCharacterization
2、of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion SourcesRegulatory and Scientific AffairsAPI PUBLICATION NUMBER 4712JULY 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, orransmitted by any means, elec
6、tronic, mechanical, photocopying, recording, or otherwise,without prior written permission from the publisher. Contact the publisher,API Publishing Services, 1220 L Street, N.W., Washington, D.C. 20005.Copyright 2001 American Petroleum InstituteACKNOWLEDGMENTSThe following people are recognized for
7、their contributions of time and expertise 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 Task Force,ChairpersonK
8、arl Loos, Equilon Enterprises LLCMiriam Lev-On, BPJeff 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 Inst
9、ituteJake McDonald, Desert Research InstituteiTABLE OF CONTENTSSection Page1.0 PROJECT DESCRIPTION1-1PROJECT OVERVIEW.1-1PROJECT OBJECTIVES 1-2Primary Objectives.1-2Secondary Objective 1-2TEST OVERVIEW1-2Source Level (In-Stack) Samples.1-2Dilution Stack Gas Samples.1-3Process Samples.1-5KEY PERSONNE
10、L1-52.0 PROCESS DESCRIPTION .2-1SAMPLING LOCATIONS .2-13.0 TEST PROCEDURES .3-1STACK GAS FLOW RATE, MOISTURE CONTENT ANDMOLECULAR WEIGHT3-1O2, CO2, CO, NOX.3-1SULFUR DIOXIDE (SO2).3-6IN-STACK METHOD TESTS 3-6In-Stack Total Filterable PM, PM10 and PM2.5 .3-6Condensible Particulate Matter Mass and Che
11、mical Analysis.3-12DILUTION TUNNEL TESTS .3-15PM2.5 Mass3-17Elements.3-17Sulfate, Nitrate, and Chloride.3-18Organic and Elemental Carbon3-18Volatile Organic Compounds.3-19Semivolatile Organic Compounds .3-19iiTABLE OF CONTENTS (CONTINUED)Section Page4.0 TEST RESULTS 4-1PROCESS OPERATING CONDITIONS.4
12、-1PRELIMINARY TEST RESULTS4-1STACK GAS CONDITIONS AND FLOW RATE.4-4CO, NOx, AND SO2 EMISSIONS.4-4IN-STACK AND IMPINGER METHOD RESULTS.4-5Particulate Mass .4-5OC and EC .4-10DILUTION TUNNEL RESULTS .4-11Particulate Mass .4-11Sulfate, Chloride, and Nitrate.4-12OC, EC and Organic Species .4-13Elements.
13、4-145.0 EMISSIONS FACTORS AND SPECIFICATION PROFILES 5-1UNCERTAINTY.5-1EMISSION FACTORS5-1PM2.5 SPECIATION PROFILES .5-5Dilution Tunnel5-5Organic Aerosols5-8Method 201A/202 5-86.0 QUALITY ASSURANCE.6-1SAMPLE STORAGE AND SHIPPING6-1DILUTION TUNNEL FLOWS.6-1GRAVIMETRIC ANALYSIS .6-1Dilution Tunnel Fil
14、ters.6-1In-Stack Filters.6-2ELEMENTAL (XRF) ANALYSIS6-3iiiTABLE OF CONTENTS (CONTINUED)Section PageORGANIC AND ELEMENTAL CARBON ANALYSIS 6-4SULFATE, NITRATE, AND CHLORIDE, AND ANALYSIS6-5SVOC ANALYSIS 6-6VOC ANALYSIS.6-8CEMS ANALYSIS6-8INORGANIC RESIDUE ANALYSIS.6-97.0 DISCUSSION AND FINDINGS .7-1PO
15、TENTIAL EMISSIONS MARKER SPECIES .7-6REFERENCESR-1ivLIST OF FIGURESFigure Page2-1 Generator Process Overview and Sampling/Monitoring Locations.2-23-1 Chronology for Gas-Fired Steam Generator Tests (Site C). 3-33-2 Continuous Emissions Monitoring System3-43-3 Modified SCAQMD Method 6.1 - Sulfur Oxide
16、s Sampling Train3-73-4 PM10/PM2.5 Train Configuration for Method 201A/202.3-83-5 Method 201A (Modified) Sample Recovery Procedure 3-93-6 Method 201A (Modified) Sample Analysis Procedure3-113-7 Method 202 Sample Recovery Procedure3-133-8 Modified Method 202 Sample Analysis Procedure .3-143-9 Dilution
17、 Tunnel Sampling System.3-165-1 PM2.5 Speciation, as Measured by the Dilution Tunnel (Site C)5-95-2 Organic Aerosol Speciation (Site C)5-125-3 Method 201/202 PM2.5 Mass Speciation Profile (Site C).5-157-1 Inorganic CPM Residue Speciation Results.7-27-2 Mass Speciation for Dilution Tunnel Ambient and
18、 Stack Samples (Site C).7-87-3 Comparison of Average Sample Concentration and Detection Limits (Site C)7-97-4 Average Sample Concentration Minus Ambient Concentration (Site C)7-10vLIST OF TABLESTable Page1-1 Overview of Sampling Scope.1-31-2 Summary of Analytical Targets .1-43-1 Summary of Test Proc
19、edures .3-23-2 CEMS Instrumentation Used for Gas-Fired Steam Generator Test (Site C).3-54-1 Approximate In-Stack Detection Limits Achieved for Gas-Fired SteamGenerator Tests (Site C).4-24-2 Process Operating Conditions (Site C).4-34-3 Fuel Gas Analysis for Gas-Fired Steam Generator Tests (Site C).4-
20、34-4 Average Stack Gas Conditions (Site C).4-44-5 CEMS Data (Site C).4-54-6 Method 6 Results (Site C)4-54-7 Filterable Particulate Matter (EPA Method 201A) Results (Site C)4-64-8 Condensible Particulate Matter (Method 202) Results (Site C).4-74-9 Speciation (mg/dscm) of Back-Half Impinger Catch (Sit
21、e C).4-94-10 OC/EC as Measured on the In-Stack Filters (Site C).4-114-11 Dilution Tunnel PM2.5 Results (Site C)4-114-12 Dilution Tunnel Sulfate, Nitrate, and Chloride Results (Site C)4-124-13 OC/EC as Measured by the Dilution Tunnel (Site C)4-134-14 Semi-Volatile Organic Compound Results as Measured
22、 by the Dilution Tunnel(mg/dscm) (Site C).4-154-15 Volatile Organic Compound (VOC) Results (Site C)4-174-16 Elements, as Measured by the Dilution Tunnel (Site C)4-185-1 Primary Emissions Particulate Mass and Elements (Site C).5-25-2 Primary Emissions Carbon and SVOCs (Site C)5-35-3 Secondary Organic
23、 Aerosol Precursors (VOCs) (Site C) 5-65-4 Secondary Particulate Precursors NOx and SO2 (Site C).5-75-5 Speciation Profile for Primary Emissions Dilution Tunnel Results (Site C)5-75-6 Organic Aerosol Speciation Profile (Site C)5-10viLIST OF TABLES (CONTINUED)Table Page5-7 Speciation Profile for PM2.
24、5 Measured by Method 201A/202 (Site C)5-146-1 Pre- and Post-Test Flow Checks for the Dilution Tunnel6-26-2 Filter and Reagent Blank Results.6-36-3 Results from Acetone Blank Rinses.6-36-4 XRF Elemental Analysis Field Blank Results .6-46-5 Organic and Elemental Carbon Field Blank Results6-56-6 PUF/XA
25、D Field Blank and Replicate Results (mg/dscm).6-86-7 Method 202 Water Reagent Blank Results (mg/dscm)6-97-1 Comparison of Sulfate Measurements (mg/dscm).7-37-2 Comparison of Data from Corio and Sherwell (2000) and API PM2.5 Program7-57-3 Comparison of EPA AP-42 Database and API PM2.5 Program Data.7-
26、67-4 Average Organic Aerosol Emission Factor Comparison (lb/MMBtu) 7-111-1Section 1PROJECT DESCRIPTIONPROJECT OVERVIEWIn 1997, the United States Environmental Protection Agency (EPA) promulgated new ambientair standards for particulate matter, including for the first time particles with aerodynamicd
27、iameters smaller than 2.5 micrometers (PM2.5). There are few existing data regardingemissions and characteristics of fine aerosols from petroleum industry combustion sources, andthe information that is available is old. Traditional stationary source air emission samplingmethods tend to underestimate
28、 or overestimate the contribution of the source to ambient aerosolsbecause they do not properly account for primary aerosol formation, which occurs after the gasesleave the stack. This issue was extensively reviewed by the American Petroleum Institue (API)in a recent report (England et al., 1997), w
29、hich concluded that dilution sampling techniques aremore appropriate for obtaining a representative sample from combustion systems. Thesetechniques have been widely used in research studies (Hildemann et al., 1994; McDonald et al.,1998) and use clean ambient air to dilute the stack gas sample and pr
30、ovide 80-90 secondsresidence time for aerosol formation prior to sample collection for determination of mass andchemical speciation.As a result of the API review, a test protocol was developed based on the dilution samplingsystem described in this report. The dilution sampling protocol was used to c
31、ollect particulateemissions data from petroleum industry combustion sources, along with emissions data obtainedfrom conventional sampling methods. This test program is designed to provide reliable sourceemissions data for use in assessing the contribution of petroleum industry combustion sources toa
32、mbient PM2.5 concentrations. The goals of this test program were to: Develop emission factors and speciation profiles for emissions of fineparticulate matter, especially organic aerosols; and Identify and characterize PM2.5 precursor compound emissions.This test report describes the results of tests
33、 performed on a gas-fired steam generator at Site Con October 21, 22 and 25, 1999.1-2PROJECT OBJECTIVESThe specific objectives of this test were to:Primary Objectives Compare PM2.5 mass measured using an in-stack filter and an iced impingertrain (EPA Method 201A/202), and mass measured using a dilut
34、ion tunnel; Develop emission factors and speciation profiles for organic aerosols andPM2.5 mass; Characterize sulfate, nitrate, ammonium, inorganic elements, elementalcarbon (EC) and organic carbon (OC) in particulate matter collected on filtermedia in the dilution sampler; Characterize key secondar
35、y particle precursors in stack gas samples: volatileorganic compounds (VOC) with carbon number of 7 and above; sulfur dioxide(SO2); and oxides of nitrogen (NOX); and Document the relevant process design characteristics and operating conditionsduring the test.Secondary Objective Characterize ions (su
36、lfate, nitrate and ammonium), OC, and EC in particulatecollected on filter media in stack gas sampling trains.TEST OVERVIEWThe scope of testing is summarized in Table 1-1. The emissions testing included simultaneouscollection and analysis of both in-stack and diluted stack gas samples. All emission
37、sampleswere collected from the stack of the unit. The samples were analyzed for the compounds listedin Table 1-2. Process data and fuel gas samples were collected during the tests to documentoperating conditions.Source Level (In-stack) SamplesIn-stack sampling and analysis for filterable (total, PM1
38、0 and PM2.5) and condensibleparticulate matter (CPM), NOx, oxygen (O2), carbon dioxide (CO2), carbon monoxide (CO) andSO2 was performed using traditional EPA methods. In-stack cyclones and filters were used forfilterable particulate matter. Sample analysis was expanded to include OC, EC and organics
39、pecies on the in-stack quartz filters.1-3Table 1-1. Overview of Sampling Scope.Sampling Location Number of SamplesFuel Gas Header Stack Ambient AirEPA Method 201A/202 train - 3 -EPA Method 6 train - 3 -Dilution tunnel - 3 1Teflon filterTIGF/PUF/XAD-4Quartz filterTenaxFuel sample 3 - -NOx, CO, O2, CO
40、2 - Continuous -Process monitoring - Hourly -TIGF - Teflon-impregnated glass fiber filterPUF - polyurethane foamXAD-4 - Amberlite sorbent resinDilution Stack Gas SamplesDilution sampling was used to characterize PM2.5 including aerosols formed in the near-fieldplume. The dilution sampler extracted a
41、 sample stream from the stack into a mixing chamber,where it was diluted approximately 21:1 with purified ambient air. Because PM2.5 behavesaerodynamically like a gas at typical stack conditions, the samples were extractednonisokinetically. A slipstream of the mixed and diluted sample was extracted
42、into a residencetime chamber where it resided for approximately 80 seconds to allow time for low-concentrationaerosols, especially organics, to condense and grow. The diluted and aged sample then passedthrough cyclone separators sized to remove particles larger than 2.5 microns, after whichsamples w
43、ere collected on various media: high-purity quartz, Teflon membrane filters (TMF),and Teflon-impregnated glass fiber (TIGF) filters; a polyurethane foam (PUF)/Amberlitesorbent resin (XAD-4)/PUF cartridge to collect gas phase semivolatile organic compounds; and aTenax cartridge to capture VOCs. Three
44、 samples were collected on three sequential test days.1-4Table 1-2. Summary of Analytical Targets.In-Stack Dilution TunnelParameters Cyclones QuartzFilterImpingers Gases QuartzFilterTIGF/XAD-4TMF Tenax GasesTotal PM mass X XPM10 mass X XPM2.5 mass X X XCondensibleparticulate massXSulfate X XChloride
45、 X XAmmonium XNitrate X XElements X XOrganic carbon X XElemental carbon X XSemivolatileorganic compoundsX XVolatile organiccompounds*XNOx XSO2 XCO XO2 XCO2 XMoisture or relativehumidityX XVelocity XTemperature X XTMF - Teflon membrane filterTIGF - Teflon-impregnated glass fiber filter*Carbon number
46、of 7 or greaterAn ambient air sample was collected to establish background concentrations of measuredsubstances. The same sampling and analysis procedures used for the dilution tunnel wereapplied for collecting ambient air samples.1-5Process SamplesA sample of the fuel gas burned in the steam genera
47、tor was collected on each day of testing andanalyzed for specific gravity, heating value, and hydrocarbon speciation.KEY PERSONNELGE Energy and Environmental Research Corporation (GE EER) had primary responsibility forthe test program. Key personnel involved in the tests were: Glenn England (GE EER)
48、 - Program Manager (949) 859-8851 Stephanie Wien (GE EER) - Project Engineer (949) 859-8851 Bob Zimperman (GE EER) - Field Team Leader (949) 552-1803 Barbara Zielinska (Desert Research Institute) - Dilution Sampling andLaboratory Analysis (775) 674-7066 Karl Loos (Equilon Enterprises LLC) - API Work
49、 Group Chairman (281) 544-7264 Karin Ritter (API) - API Project Officer (202) 682-84722-1Section 2PROCESS DESCRIPTIONThe tests were performed on a gas-fired steam generator at Site C. The generator has amaximum heat input of 62.5 MMBtu/hr with an average rate of approximately 50 MMBtu/hr.The unit is an oil field steam generator with a single burner and retrofitted with flue gasrecirculation. The generator was designed to fire both crude oil and natural gas, but is now onlyfired on natural gas. The generator appeared to be in good working condition d
