1、 API PUBL*4612 94 m 0732290 0533300 930 m 1993 Study of Refinery Fugitive Emissions from Equipment Leaks Volume I: Data Analysis, Conclusions and Recommendations Prepared for: American Petroleum Institute Health and Environmental Sciences Department and Western States Petroleum Association API PUBLI
2、CATION NUMBER 461 2 PREPARED UNDER CONTRACT BY: RADIAN CORPORATION SACRAMENTO, CALIFORNIA APRIL 1994 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 SHOUL
3、D BE REVIEWED. API IS NOT 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. NO
4、THING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETTERS PATENT. GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- THE PUBLICA
5、TION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- NOTE: This is to advise the reader that these studies are now under review by the U.S. Environmental Protection Agency. The Agencys review may be complete by summer 1994. Copyright Q 1994 Amencan Pciroleum Insiiiuie II API PUBLx4b12 94 0732290 053
6、3102 793 = 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 CONTACTS: Karin Ritter, Health and Environmental Affairs Department Paul Wakim, Statistics Department MEMBERS OF THE AIR TOX
7、ICS MULTIYEAR STUDY WORKGROUP : Julian Blomley, UNOCAL Miriam Lev-On, ARCO Products Company Richard Russell, API Consultant Hai Taback, API Consultant Daniel VanDerZanden, Chevron Research and Technology Company This study was co-funded by the Western States Petroleum Association (WSPA). The followi
8、ng members of the WSPA Fugitive Emissions Project Steering Committee are recognized for their connibutions of time and expertisc: Frank Giles, Ultramar Matt Marusich, Tosco Refining Company Julian Blomley, UNOCAL Miriam Lev-On, ARCO Products Company Daniel Van Der Zanden, Chevron Research and Techno
9、logy Company In addition the U.S. EPA Ofice of Air Quality Planning and Standards, Emission Inventory Branch, Research Triangle Park, North Carolina; South Coast Air Quality Management District; Bay Area Air Quality Management District; and, California Air Resources Board are gratefully recognized f
10、or providing oversight, additional review of draft reports and concurrent QA/QC of final measurements during this study. . 111 API PUBL*4632 94 D 0732290 0533303 b2T ABSTRACT The Western States Petroleum Association (WSPA) and the American Petroleum Institute (MI) commissioned this “1993 Study of Re
11、finery Fugitive Emissions from Equipment Leaks,“ called the I 1993 Refinery Study“ in this document. The results of this study are new emission correlation equations that relate the mass of hydrocarbon emissions to specific emission rates measured by screening components with an Organic Vapor Analyz
12、er (OVA). Emission correlation equations were developed for valves, pumps, connectors, and open-ended lines, based on established statistical methodologies recommended by the United States Environmental Protection Agency (U.S. EPA). An alternative statistical methodology called the measurement error
13、 method (MEM) was also examined. The emission correlation equa- tions from the MEM technique account for variabilities in screening values and in the measured mass emissions. Additional evaluation of this methodology is still in progress. The emission correlation equations from the 1993 Refinery Stu
14、dy result in emission calcula- tions that are significantly lower than emission calculations based on published emission correlation equations developed from data in Radians Assessment of Atmospheric Emissions fiom Petroleum Refining, called the 1980 Refinery Study in this document. However, much of
15、 the difference in emission correlation equations is based on different data collection and data analysis techniques in the two studies. Changes in equipment and operating procedures may also have contributed to the differences in emission correlation equations. New “zero component emission factors“
16、 were developed for components that screen at background hydrocarbon levels and were compared to the zero component emission factors published in the U.S. EPA Protocols Document. Depending on the component category, the factors developed in this study were similar, higher, or lower than those in the
17、 EPA document New emission factors were also developed for components that have screening values above the range of the screening instrument (pegged components). These factors are significantly lower than those published in the EPA document. API PUBL*4b32 94 0732290 0533304 5bb Several special studi
18、es were also conducted as part of the 1993 Refinery Study as a quality assurance measure and to investigate the variability of factors used to develop the emission correlation equations, zero component emission factors, and pegged component emission factors. The special studies discussed in this rep
19、ort include: o Effects of potentially leaking OVA probes; Screening variability; o Nitrogen flow rate variability; o Benefits of additional bagging; Effects of dilution probe data; and Effects of high screening variability data. o The results of these special studies increase the understanding of th
20、e emission correlation equations, zero component emission factors, and pegged component emission factors, but do not indicate that any changes to these equations or emission factors are required. API PUBL84bL2 94 0732290 0533305 4T2 W . TABLE OF CONTENTS Section Executive Summary e5-1 Emission Corre
21、lation Equations . e5-2 Vapor Leak Composition Compared with Liquid Stream Composition e5-9 Special Studies . e5-10 Data Applicability . e5-14 1 . Introduction . 1-1 Study Objectives . 1-1 Project Description . 1-2 Historical Perspective . 1-2 Report Organization . 1-4 Data Analysis 2-1 Emission Rat
22、e Calculation 2-1 Emission Correlation Equations . 2-3 Multivariate Analysis . 2-3 Leut-Squares (OLS) Approach . 2-27 Statistical Approach 2-34 Comparison to Other Studies 2-58 Zero Component Emission Factors . 2-77 Comparison of New Zero Component Emission Factors With Established U.S. EPA Zero Com
23、ponent Emission Factors 2-79 Zero Component Emission Factors and Pegged Component Emission Factors . ES-6 DataQuality . e5-12 2 . Emission Correlation Equations Using the Ordinary Emission Correlation Equations Using an Alternative Pegged Component Emission Factors 2-83 Composition . 2-88 Conclusion
24、s and Recommendations . 3-1 Emission Correlation Equations . 3-1 Comparison of Vapor Leak Composition with Liquid Stream 3 . TABLE OF CONTENTS (Continued) Section Page 3 . Conclusions and Recommendations (Continued) Zero Component Emission Factors and Pegged Component Emission Factors 3-3 Vapor Leak
25、 Composition Compared with Liquid Stream Composition 3-3 Special Studies for Additional Data Analysis . 3-3 Impact of Potentially Leaking OVA Probes . 3-4 Screening Variability . 3-4 Benefits of Additional Bagging 3-4 Nitrogen Flow Rate During Component Bagging . 3-4 Dilution Probe Data . 3-5 Effect
26、s of High Screening Variability Data 3-5 DataQuality 3-5 Data Applicability 3-6 Recommendations for Future Data Analysis 3-6 Evaluate Component Design Data and Stream characteristics . 3-7 Compare Vapor Leak Composition to Liquid Stream Composi- tion in a Controlled Laboratory Setting 3-8 Reanalyze
27、the 1980 Refinery Study Data Based on Comparable OVA Readings and Without the Pegged Components 3-8 Additional Research of the Measurement Error Method (MEM) Technique 3-9 4 . References 4-1 Figure ES- 1 2- 1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 2-1 1 API PUBL*4bL2 94 0732290 0533107 275 LIST OF FIG
28、URES Comparison of 1980 Refinery Study and 1993 Refinery Study Regression Lines, 95% Confidence Intervals, and Data for Valves in Light Liquid Service - Excludes Two Low Screening Values from 1980 Refinery Study . ES-7 Mass Emission Calculation Procedure for Tented Leak Rate 2-2 Comparison of Emissi
29、on Rate/Screening Value Data Pairs and Regression Lines for Flange and Non-Flange Connectors . 2-12 Comparison of Emission Rate/Screening Value Data Pairs and Regression Lines for Small and Large Open-Ended Lines - 1993 Marketing Terminal and 1993 Refinery Studies Combined. . 2-16 Comparison of Emis
30、sion Rate/Screening Value Data Pairs and Regression Lines for Pump Seals in Heavy Liquid and Light Liquid Services . 2-18 Comparison of Emission RateKcreening Value Data Pairs for Valves in All Services by Size . 2-20 Comparison of Emission RatejScreening Value Data Pairs for Valves in Light Liquid,
31、 Heavy Liquid, and Gas Services . 2-24 Comparison of Emission Rate/Screening Value Data Pairs and Regression Lines for Light Liquid Valves by Refinery . 2-25 Comparison of Emission Rate/Screening Value Data Pairs and Regression Lines for Light Liquid Manual Versus Control Valves . 2-26 THC Mass Emis
32、sion Rate Versus OVA Screening Value at the Surface: Ordinary Least-Squares Emission Correlation Equation, and 95% Confidence Intervals for the Mean Emission Rate and for Individual Values - Connectors (Flanges) in All Services . 2-36 THC Mass Emission Rate Versus OVA Screening Value at the Surface:
33、 Ordinary Least-Squares Emission Correlation Equation, and 95% Confidence Intervals for the Mean Emission Rate and for Individual Values - Connectors (Non-Flanges) in All Services 2-37 THC Mass Emission Rate Versus OVA Screening Value at the Surface: Ordinary Least-Squares Emission Correlation Equat
34、ion, and 95% Confidence Intervals for the Mean Emission Rate and for Individual Values - Open-Ended Lines in All Services 2-38 API PUBLb4bL2 94 W 0732290 0533LOB 101 LIST OF FIGURES (Continued) Figure 2-12 2-13 2-14 2-15 2-16 2-17 2-18 2-19 THC Mass Emission Rate Versus OVA Screening Value at the Su
35、rface: Ordinary Least-Squares Emission Correlation Equation, and 95% Confidence Intervals for the Mean Emission Rate and for Individual Values - Pump Seals in Heavy Liquid Service 2-39 THC Mass Emission Rate Versus OVA Screening Value at the Surface: Ordinary Least-Squares Emission Correlation Equat
36、ion, and 95% Confidence Intervals for the Mean Emission Rate and for Individual Values - Pump Seals in Light Liquid Service 2-40 THC Mass Emission Rate Versus OVA Screening Value at the Surface: Ordinary Least-Squares Emission Correlation Equation, and 95% Confidence Intervals for the Mean Emission
37、Rate and for Individual Values - Valves in All Services . 2-41 THC Mass Emission Rate Versus OVA Screening Value at the Surface: MEM Emission Correlation Equation and 95% Confidence Intervals for the Mean Emission Rate Overlaid with Ordinary Least-Squares Emission Conelation Equations . Connectors (
38、Flanges) in Al1 Services 2-52 THC Mass Emission Rate Versus OVA Screening Value at the Surface: MEM Emission Correlation Equation and 95% Confidence Intervals for the Mean Emission Rate Overlaid with Ordinary Least-Squares Emission Correlation Equations . Connectors (Non-Flanges) in All Services . 2
39、-53 THC Mass Emission Rate Versus OVA Screening Value at the Surface: MEM Emission Correlation Equation and 95% Confidence Intervals for the Mean Emission Rate Overlaid with Ordinary Least-Squares Emission Correlation Equations . Open-Ended Lines in All Services 2-54 THC Mass Emission Rate Versus OV
40、A Screening Value at the Surface: MEM Emission Correlation Equation and 95% Confidence Intervals for the Mean Emission Rate Overlaid with Ordinary Least-Squares Emission Correlation Equations . Pump Seals in Heavy Liquid Service 2-55 THC Mass Emission Rate Versus OVA Screening Value at the Surface:
41、MEM Emission Correlation Equation and 95% Confidence Intervals for the Mean Emission Rate Overlaid with Ordinary Least-Squares Emission Correlation Equations . Pump Seals in Light Liquid Service . 2-56 2-20 2-2 1 2-22 2-23 2-24 2-25 2-26 2-27 2-28 2-29 API PUBLx4b12 94 0732290 0533109 048 LIST OF FI
42、GURES (Continued) Page THC Mass Emission Rate Versus OVA Screening Value at the Surface: MEM Emission Correlation Equation and 95% Confidence Intervals for the Mean Emission Rate Overlaid with Ordinary Least-Squares Emission Correlation Equations . Valves in All Services 2-57 1993 THC Emission Corre
43、lation Equation and 95% Confidence Intervals for the Mean Overlaid on the Marketing Terminals Study and 1980 Refinery Study Emission Correlation Equations Connectors in All Services 2-63 1993 THC Emission Correlation Equation and 95% Confidence Intervals for the Mean Overlaid on the Marketing Termin
44、als Study Emission Correlation Equation Open-Ended Lines in All Services 2-64 1993 THC Emission Correlation Equation and 95% Confidence Intervals for the Mean Overlaid on the 1980 Refinery Study Emission Correlation Equations Pump Seals in Heavy Liquid Service . 2-65 1993 THC Emission Correlation Eq
45、uation and 95% Confidence Intervals for the Mean Overlaid on the Marketing Terminals Study and 1980 Refinery Study Emission correlation Equations Pump Seals in Light Liquid Service . 2-67 1993 THC Emission Correlation Equation and 95% Confidence Intervals for the Mean Overlaid on the Marketing Termi
46、nals Study Data Pairs and the 1980 Refinery Study Emission Correlation Equations - Valves in Gas Vapor Service . 2-68 1993 THC Emission Correlation Equation and 95% Confidence Intervals for the Mean Overlaid on the Marketing Terminals Study and 1980 Refinery Study Emission Correlation Equations Valv
47、es in Light Liquid Service . 2-70 1993 THC Emission Correlation Equation and 95% Confidence Intervals for the Mean Overlaid on the Adjusted 1980 Refinery Emission Correlation Equations Valves in Light Liquid Service 2-75 1993 Data Pairs, Emission Correlation Equation and 95% Confidence Intervals for
48、 the Mean Overlaid on the 1980 Refinery Data Pairs, Emission Correlation Equation, and 95% Confidence Intervals for the Mean Adjusted for OVA Screening Values at the Surface Valves in Light Liquid Service 2-76 1993 Data Pairs and 1980 Refinery Data Pairs Overlaid on the 1993 and 1980 Combined Emissi
49、on Correlation Equation, 95% Confidence Intervals for the Mean, and 95% Confidence Intervals for Individual Values - Valves in Light Liquid Service . 2-78 API PUBL+4612 74 rn 0732270 0533110 8bT = LIST OF TABLES - Table Pane ES-1 Number of Valid Bagged Samples and High Screening Variability Bagged Samples in 1993 Refinery Study ES-3 ES-2 1993 Refinery Study Emission Correlation Equations ES-4 ES-3 Comparison of 1993 Refinery Study Emission Correlation Equations With Established Emission Correlation Equations ES-5 ES-4 1993 Refinery Study Zero Component and Pegged Compone
