1、 Test Report: Fluidized Catalytic Cracking Unit at a Refinery (Site A)Characterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion SourcesRegulatory and Scientific AffairsAPI PUBLICATION 4713MARCH 2002Test Report: Fluidized Catalytic Cra
2、cking Unit at a Refinery (Site A)Characterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion SourcesRegulatory and Scientific AffairsAPI PUBLICATION 4713MARCH 2002PREPARED UNDER CONTRACT BY:GE Energy however, theInstitute makes no repre
3、sentation, warranty, or guarantee in connection with this publicationand hereby expressly disclaims any liability or responsibility for loss or damage resultingfrom its use or for the violation of any federal, state, or municipal regulation with which thispublication may conflict.Suggested revisions
4、 are invited and should be submitted to the Regulatory and ScientificAffairs department, American Petroleum Institute, 1220 L Street, N.W., Washington, D.C.20005.All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic, mechan
5、ical, 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 2002 American Petroleum InstituteACKNOWLEDGMENTSThe following people are recognized for their contri
6、butions of time and expertise during thisstudy and in the preparation of this report:API STAFF CONTACTKarin Ritter, RASAMEMBERS OF THE PM SOURCE CHARACTERIZATION WORKGROUPKarl Loos, Equilon Enterprises LLC, ChairpersonLee Gilmer, Equilon Enterprises LLCJeff Siegell, ExxonMobil Research and Engineeri
7、ngLyman Young, Chevron TexacoGE 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 OF CONTENTSSection
8、Page ACKNOWLEDGMENTSEXECUTIVE SUMMARY . E-1FINDINGS E-91.0 PROJECT DESCRIPTION1-1PROJECT OVERVIEW 1-1PROJECT OBJECTIVES1-2Primary Objectives 1-2Secondary Objectives1-2TEST OVERVIEW1-2Source Level (In-Stack) Samples .1-3Dilution Stack Gas Samples1-4Process Samples.1-5KEY PERSONNEL .1-52.0 PROCESS DES
9、CRIPTION .2-1SAMPLING LOCATIONS .2-13.0 TEST PROCEDURES .3-1STACK GAS FLOW RATE, MOISTURE CONTENT ANDMOLECULAR WEIGHT3-1O2,CO2, CO, NOx AND SO23-1IN-STACK METHOD TESTS .3-6In-Stack Total Filterable PM, PM10 and PM2.5.3-6Particle Size Distribution 3-10Condensible Particulate Matter Mass and Chemical
10、Analysis .3-10SO3and NH3.3-14DILUTION TUNNEL TESTS 3-16PM2.5 Mass .3-19Elements.3-19Sulfate, Nitrate, Chloride and Ammonium Emissions3-20Organic and Elemental Carbon.3-20Volatile Organic Compounds .3-21Semivolatile Organic Compounds3-224.0 TEST RESULTS 4-1PROCESS OPERATING CONDITIONS. 4-1PRELIMINARY
11、 TEST RESULTS 4-1STACK CONDITIONS AND FLOW RATE4-3CO, NOxAND SO2EMISSIONS .4-5IN-STACK AND IMPINGER METHOD RESULTS 4-6Particulate Mass.4-6Particle Size Distribution 4-7OC, EC, and SVOCs (In-Stack Filters)4-9SO3and NH3.4-15TABLE OF CONTENTS (CONTINUED)Section Page DILUTION TUNNEL RESULTS 4-15Particul
12、ate Mass.4-15SO4=, NO3-, Cl-and NH4+.4-17OC, EC and Organic Species4-18Elements.4-23PROCESS SAMPLES .4-23ESP Fines .4-23Spent and Regenerated Catalyst Samples 4-235.0 EMISSION FACTORS AND SPECIATION PROFILES 5-1IN-STACK AND IMPINGER METHOD RESULTS 5-1DILUTION TUNNEL RESULTS 5-56.0 QUALITY ASSURANCE
13、.6-1DILUTION TUNNEL QA/QC RESULTS 6-1Dilution Tunnel Flows.6-1Blank Results Dilution Tunnel 6-1QA Checks Dilution Tunnel Particulate Mass6-1Precision Dilution Tunnel 6-4IN-STACK AND IMPINGER METHOD QA/QC RESULTS 6-7CEMS Analysis6-8PROCESS SAMPLE QA/QC RESULTS 6-8ANALYTICAL QA/QC PROCEDURES6-8Particu
14、late Mass.6-8Elemental (XRF) Analysis 6-10Organic and Elemental Carbon Analysis .6-10Sulfate, Nitrate, Chloride and Ammonium Analysis.6-11SVOC Analysis6-12VOC Analysis 6-13SAMPLE STORAGE AND SHIPPING 6-147.0 DISCUSSION AND FINDINGS 7-1PRIMARY PM2.5 MASS EMISSIONS 7-1PARTICLE SIZE DISTRIBUTION .7-3SP
15、ECIATION OF PRIMARY PM2.5 EMISSIONS.7-3PM2.5 PRECURSOR EMISSIONS .7-9FINDINGS7-9REFERENCE R-1Appendix AGLOSSARY A-1Appendix BSI CONVERSION FACTORS B-1LIST OF FIGURESFigure Page E-1 Primary Particulate Speciation Profile . E-82-1 FCCU Process Overview and Sampling/Monitoring Locations2-23-1 Chronolog
16、y for Testing at FCCU (Refinery Site A) 3-33-2 Continuous Emissions Monitoring System.3-53-3 Method 201A (Modified)/202 Sampling Train .3-73-4 Method 201A (Modified) Sample Recovery Procedure 3-83-5 Method 201A (Modified) Sample Analysis Procedure3-93-6 Hot and Cooled Cascade Impactor Train Configur
17、ations3-113-7 Method 202 Sample Recovery Procedure.3-123-8 Method 202 Sample Analysis Procedure 3-133-9 Illustration of Draft EPA Method 206 Sampling Train Assembly3-153-10 Controlled Condensation Sampling Train Configuration 3-163-11 Dilution Tunnel Sampling System 3-174-1 In-Stack Particle Size Di
18、stribution for FCCU (Refinery Site A) 4-124-2 Particle Volume Distribution for FCCU (Refinery Site A) .4-135-1 PM2.5 Speciation Profile In-Stack and Impinger Methods5-45-2 Organic Carbon Speciation Profile In-Stack Filter .5-45-3 PM2.5 Speciation Profile Dilution Tunnel Methods.5-95-4 PM2.5 Speciati
19、on Profile Dilution Tunnel Methods.5-147-1 Average Concentrations of Detected Substances in the FCCU Stack Gas(FCCU, Refinery Site A)7-57-2 Comparison of Average Sample Concentration and Detection Limits(FCCU, Refinery Site A) .7-77-3 Comparison of Stack and Ambient Air Results (FCCU, Refinery Site
20、A).7-8LIST OF TABLESTable Page E-1 Summary of Primary Particulate Emission Factors for FCCU. E-3E-2 SVOC Emission Factors for FCCU E-4E-3 Summary of Secondary Particulate Precursor Emission Factors for FCCU E-6E-4 Substances of Interest Not Detected in Stack Emissions from FCCU. E-71-1 Overview of S
21、ampling Scope for FCCU (Refinery Site A).1-31-2 Summary of Analytical Targets for the FCCU Tests (Refinery A) 1-43-1 Summary of Test Procedures.3-23-2 Continuous Emissions Monitoring System Instrumentation 3-64-1 Detection Limits for Target Compounds 4-24-2 FCCU Process Data (Refinery Site A)4-34-3
22、Stratification Test Results for the FCCU (Refinery Site A) 4-44-4 Stack Summary for FCCU (Refinery Site A) .4-44-5 NOx, SO2, and CO Test Results for FCCU (Refinery Site A)4-54-6 Filterable Particulate Matter (Method 201A) for FCCU (Refinery Site A)4-64-7 Condensible Particulate Emissions for FCCU (R
23、efinery Site A)4-84-8 Particle Size Distribution from the Cooled Cascade Impactor at FCCU(Refinery Site A).4-104-9 Particle Size Distribution for the Hot Cascade Impactor at FCCU(Refinery Site A).4-114-10 Organic and Elemental Carbon Results for the FCCU (Refinery Site A),as Measured on the In-Stack
24、 Filter (Method 201A).4-144-11 SVOC Results for Method 201A Filters at the FCCU (Refinery Site A)(mg/dscm) 4-144-12 Controlled Condensation Train Results for the FCCU (Refinery Site A) 4-154-13 EPA Method 206 Ammonia Train Results for the FCCU (Refinery Site A) .4-154-14 Dilution Tunnel PM2.5 Result
25、s for the FCCU (Refinery Site A) .4-164-15 Dilution Tunnel Sulfate, Nitrate, Chloride and Ammonium Results forthe FCCU 4-184-16 Organic and Elemental Carbon Results for the FCCU (Refinery Site A), asMeasured by the Dilution Tunnel4-194-17 Dilution Tunnel VOC Results for the FCCU (Refinery Site A) (m
26、g/dscm).4-204-18 Dilution Tunnel SVOC Results for the FCCU (Refinery Site A) (mg/dscm) 4-214-19 Dilution Tunnel Elemental Results for the FCCU (Refinery Site A) (mg/dscm).4-244-20 Elemental Analysis of ESP Fines from the FCCU (Refinery Site A) (mg/kg).4-254-21 Regenerated Catalyst Fines Analysis Res
27、ults.4-264-22 Spent Catalyst Fines Analysis Results 4-265-1 Emission Factors In-Stack and Impinger Methods .5-25-2 PM2.5 Speciation Profile In-Stack and Impinger Methods .5-35-3 Emission Factors Dilution Tunnel (Mass, Elements and Ions) 5-65-4 PM2.5 Speciation Profile Dilution Tunnel (Elements, Ions
28、 and Carbon) .5-85-5 Emission Factors Dilution Tunnel (Carbon and SVOC).5-105-6 PM2.5 Speciation Profile Dilution Tunnel (SVOC) .5-12LIST OF TABLES (CONTINUED)Table Page 5-7 Emission Factors Dilution Tunnel (VOC C7+).5-156-1 Pre- and Post-Test Dilution Tunnel Flow Checks for the FCCU(Refinery Site A
29、).6-26-2 Blank Results for Dilution Methods6-36-3 Replicate Analysis Results for Dilution Tunnel (SVOCs).6-56-4 Blank Results for In-Stack and Impinger Methods 6-76-5 QA Results for ESP Fines Analysis 6-96-6 Internal Standards for SVOC Analysis .6-13E-1EXECUTIVE SUMMARYIn 1997, EPA promulgated new a
30、mbient air standards for particulate matter smaller than 2.5micrometers (PM2.5). Source emissions data are needed to assess the contribution of petroleumindustry combustion sources to ambient PM2.5concentrations for receptor modeling and PM2.5standard attainment strategy development. There are few e
31、xisting data on emissions andcharacteristics of fine aerosols from petroleum industry combustion sources, and the limitedinformation that is available is incomplete and outdated. The American Petroleum Institute(API) developed a test protocol to address this data gap, specifically to: Develop emissi
32、on 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 for
33、med viareaction of stack emissions in the atmosphere) precursor emissions.This report presents results of a pilot project to evaluate the test protocol on a refinery fluidcatalytic cracking unit (FCCU). The FCCU tested is a partial combustion unit with a processcapacity of 47,000 barrels per day. Th
34、e CO-rich offgas from the regenerator is combusted withrefinery process gas in a process heater, which preheats the FCCU process feed. The processheater flue gases pass through an electrostatic precipitator to recover catalyst fines, which alsoreduces particulate emissions. The unit has no controls
35、for NOxor SO2emissions. The FCCUwas operating at approximately 94 percent of capacity and the flue gas temperature at the stackwas approximately 579 F during the tests.The tests included comparison of a dilution tunnel research test method for sample collection andtraditional methods used for regula
36、tory enforcement of particulate regulations. The dilutiontunnel method is attractive because the sample collection media and analysis methods areidentical to those used for ambient air sampling. Thus the results are directly comparable withambient air data. Also, the dilution tunnel method is believ
37、ed to provide representative resultsfor condensible aerosols. Regulatory methods are attractive because they are readily acceptedby regulatory agencies and have been used extensively on a wide variety of source types;E-2however, existing regulatory methods for condensible aerosols may have significa
38、nt biasproblems for some source types and analytical options are limited.In addition to a standard EPA particulate sampling train, hot and cold cascade impactors wereused to measure particle size distribution. Ammonia (by EPA Method 206) and sulfur trioxide(by controlled condensation) emissions also
39、 were measured.The results of these tests demonstrated that the test protocol developed by API could be appliedsuccessfully to refinery sources. The results also were used to refine the test protocol leading tolower costs for future tests. Emission factors for primary particles including: total part
40、iculatemass, PM10 (mass of particles smaller than 10 micrometers), and PM2.5; elements; ionicspecies; sulfuric acid; and organic and elemental carbon are presented in Table E-1. Emissionfactors are expressed in pounds of pollutant per thousand pounds of coke burned in theregenerator. The tables incl
41、ude only those substances that were detected in at least one of thethree test runs. The uncertainty and upper 95 percent confidence bound also are presented.Emission factors for semivolatile organic species that comprise organic carbon are presented inTable E-2. The sum of semivolatile organic speci
42、es totals approximately three percent of theorganic carbon. Emission factors for secondary particulate precursors (NOx, SO2, volatileorganic species, and ammonia) are presented in Table E-3. Substances of interest that were notpresent above the minimum detection limit for these tests are listed in T
43、able E-4.A single ambient air sample also was collected at the site. 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 with concentrations within a factor of 10 of the measured ambientair con
44、centration are indicated on the table by an asterisk (*).The primary particulate matter 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
45、.E-3Table E-1. Summary of Primary Particulate Emission Factors for FCCU.SubstanceAverage Emission Factor (lb/1000 lb coke burned)Uncertainty (%)95% Confidence Upper Bound (lb/1000 lb coke burned)CPM (inorganic) 0.51 279 1.5CPM (organic) 4.7E-3 160 0.01Total CPM (blank corrected) 0.51 281 1.5Total FP
46、M (in-stack method) 0.50 69 0.74Filterable PM10 (in-stack method) 0.47 72 0.71Filterable PM2.5 (in-stack method) 0.44 72 0.65PM2.5 (Dilution Tunnel) 0.11 68 0.16Elements Aluminum 3.9E-3 80 6.1E-3Antimony 8.5E-5 80 1.3E-4Barium 2.0E-5 49 2.7E-5Bromine * 3.3E-7 54 4.6E-7Calcium 1.3E-4 73 1.9E-4Chromiu
47、m 4.3E-5 60 6.1E-5Cobalt 7.9E-6 146 1.6E-5Copper 4.6E-4 375 1.6E-3Gallium 2.3E-6 142 4.5E-6Iron 9.2E-4 80 1.4E-3Lanthanum 8.5E-4 80 1.3E-3Lead 9.7E-6 74 1.5E-5Manganese 1.6E-5 78 2.5E-5Molybdenum 9.3E-6 84 1.5E-5Nickel 2.1E-4 74 3.2E-4Potassium 7.7E-5 70 1.1E-4Rubidium 6.9E-7 48 9.2E-7Selenium 5.9E-
48、7 61 8.4E-7Silicon 6.8E-3 78 1.0E-2Strontium 8.1E-6 79 1.3E-5Sulfur 1.3E-3 124 2.4E-3Thallium 6.1E-7 n/a n/aTin 3.5E-6 n/a n/aTitanium 4.2E-4 83 6.5E-4Uranium 8.1E-7 254 1.8E-6Vanadium 4.1E-4 87 6.6E-4Yttrium 1.0E-6 118 1.8E-6Zinc 3.3E-5 57 4.6E-5Zirconium 7.6E-6 78 1.2E-5Ions Chloride 2.0E-4 71 3.0
49、E-4Nitrate ND n/a n/aSulfate 9.7E-2 72 1.5E-1Ammonium 8.9E-4 82 1.4E-3Sulfuric Acid SO3 (as H2SO4) 1.4 92 2.3Carbon Organic Carbon (dilution tunnel) 9.9E-4 53 1.4E-3Elemental Carbon (dilution tunnel) * 2.0E-4 n/a n/aTotal Carbon (dilution tunnel) 1.1E-3 52 1.5E-3Organic Carbon (in-stack) B 1.5E-4 66 2.2E-4Elemental Carbon (in-stack) 3.2E-5 153 6.6E-5Total Carbon (in-stack) B 1.8E-4 77 2.8E-4* 10x ambientB 10x blank(1) 10x detection limit, ambient=ND(2) 10x detection limit, blank=NDParticulate MassE-4Table E-2. SVOC Emission Factors for FCCU.Average Em
