1、American 0732290 Ob15185 bT2 $11 Petroleum Institute FUGITIVE EMISSIONS FROM REFINERY PROCESS DRAINS VOLUME I FUGITIVE EMISSION FACTORS FOR REFINERY PROCESS DRAINS One or More Drain Pipes Process Unit Drain Hub/Drain Funnel Opening HEALTH AND ENVIRONMENTAL SCIENCES DEPARTMENT Reducer PUBLICATION NUM
2、BER 4677 APRIL 1999 Unsealed Drain Discharge from Process Unit One or More Drain Pipes Drain Hub/Drain Funnel Opening 4- Reducer Grade Sealed (Trapped) Drain STD-API/PETRO PUBL 4b77-ENGL L777 Il 0732270 ObL5LBb 539 m.l American Petroleum Institute American Petroleum Institute Environmental, Health,
3、and Safety Mission and Guiding Principles MISSION The members of the American Petroleum Institute are dedicuted to continuous eforts to improve the compatibility of our operations with the environment while economically developing energy resources and supplying high quality products and services to
4、consumers. We recognize our responsibility to work with the public, the government, and others to develop and to use natural resources in un environmentally sound manner while protecting the health and safety of our employees and the public. To meet these responsibilities, API members pledge to mana
5、ge our businesses according to the following principles using sound science to prioritize risks and to implement cost-effective management practices: . PRINCIPLES o o To recognize and to respond to community concerns about our raw materials, products and operations. To operate our plants and facilit
6、ies, and to handle our raw materials and products in a manner that protects the environment, and the safety and health of our employees and the public. To make safety, health and environmental considerations a priority in our planning, and our development of new products and processes. To advise pro
7、mptly, appropriate officials, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures. To counsel customers, transporters and others in the safe use, transportation and disposal of our raw mater
8、ials, products and waste materials. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes an
9、d waste materials. To commit to reduce overall emission and waste generation. To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. To participate with government and others in creating responsible laws, regulations and standards to saf
10、eguard the community, workplace and environment. To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes. Fugitive Emissions From Refinery Process Drains
11、Volume I Fugitive Emission Factors For Refinery Process Drains Health and Environmental Sciences Department API PUBLICATION NUMBER 4677 PREPARED UNDER CONTRACT BY: 100 WEST HARRISON STREET SEATTLE, WASHINGTON 981 19-4186 BROWN AND CALDWELL ENVIROMEGA LTD. 7 INNOVATION DRIVE HAM I LTO N , ONTARIO CAN
12、ADA L9J1 K3 APRIL 1999 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 NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFAC
13、- 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 API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGH
14、T, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LEITERS PAENT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- AU rights reserved. No par
15、t 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 publishex Contact the publisher, API Publishing Services, 1220 L Street, N.W, Washington, D.C. 20005.
16、Copyright O 1999 American Petroleum institute iii STD.API/PETRO PUBL 4677-ENGL 1999 0732290 ObLSL89 248 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 Paul Martino, Health and
17、 Environmental Sciences Department MEMBERS OF THE REFINERY DRAINS EMISSIONS PROJECT GROUP Nick Spiridakis, Chairman, Chevron Research and Technology Kare1 Jelinek, BP Oil Company Minam Lev-On, Arco Gary Morris, Mobil Technology Company Chris Rabideau, Texaco Manuel Cano, Shell Development Company Ac
18、har Ramachandra, Amoco Corporation Jeff Siegell, Exxon Research and Engineering Ron Wilkniss, Western States Petroleum Association Jenny Yang, Marathon Oil Company Brown and Caldwell would also like to thank Hugh Monteith (Enviromega, Ltd.) for his assistance in the completion of this work. iv STD.A
19、PI/PETRO PUBL 4b77-ENGL 1993 E 0732290 ObL5L90 TbT PREFACE The results of this study are presented in three separate reports. 0 Volume I entitled Fugitive Emission Factors for Refinery Process Drains“ (API Publication Number 4677) contains simplified emission factors that can be used to quickly esti
20、mate total volatile organic compound (VOC) emissions from refinery process drains. 0 Volume II entitled “Fundamentals of Fugitive Emissions from Refinery Process Drains (API Publication Number 4678) describes theoretical concepts and equations that may be used in a model (APIDRAIN) to estimate speci
21、ated VOC emissions. The model can provide insight on. how to change process drain variables (flow rate, temperature, etc.) to reduce emissions. 0 Volume 111 entitled “APIDRAIN Version 7.0, Process Drain Emission Calcuhtor“ (API Publication Number 4681) is the computer model with users guide to estim
22、ate emissions from refinery process drains. The software allows users to calculate VOC emissions based on the emission factors in Volume I and equations for speciated emissions in Volume II. All three volumes of this study can be purchased separately; however, it is suggested that the user consider
23、purchase of the entire set to gain a complete understanding of fugitive emissions from refinery process drains. STD.API/PETRO PUBL 4b77-ENGL 1999 I 0732290 ObL5L91 9Tb I ABSTRACT Fugitive emissions are estimated using USEPAs emission factors from the publication known as AP-42. The factor for refine
24、ry process drains was first developed in 1979. Drain modifications and sewer system improvements have reduced emissions, with the result that the AP-42 emission factor may overestimate drain emissions. The refinery process drain emission factor has also been applied to non-process drains, with the r
25、esult that drain emissions are now a significant component of refinery emissions. This work was undertaken to address these concerns. Laboratory- and pilot-scale drain systems were constructed and tests were conducted to develop emission factors and to evaluate the mechanics of emissions from active
26、, trapped process drains. A model was developed to estimate emissions from process drains. STD=API/PETRO PUBL 4677-ENGL I 0732290 0615192 832 II Table of Contents Page EXECUTIVE SUMMARY ES-I 1 . INTRODUCTION 1-1 2 . PILOT SCALE DETERMINATION OF DRAIN BAGGING PROTOCOL 2-1 EXPERIMENTAL PROCEDURE . 2-1
27、 Analyte Selection and Characteristics 2-1 Apparat us . 2.2 No Bag 2.2 Vacuum Method 2.2 Blow-Through Method . 2-3 Dosing Procedure . 2-7 Wastewater Sampling and Analysis 2.7 OVA Calibration 2.7 Experimental Schedule . 2.8 RESULTS . 2-9 Sample Results for Each Experiment - Analysis of Duplicate Subm
28、issions 2-9 Percentage Emissions 2-9 Mass Emissions . 2-11 Organic Vapor Analyzer Results . 2.13 OVA Concentrations 2.13 Mass Emissions . 2.1 4 Statistical Analysis of Results . 2-15 DISCUSSION OF RESULTS 2-17 3 . PILOT SCALE DETERMINATION OF STRIPPING EFFICIENCIES 3-1 EXPERIMENTAL PROCEDURE . 3-1 A
29、nalyte Selection and Characteristics 3-1 Experimental Apparatus . 3.2 Emission Factor Drain Structure 3.2 Emission Factor Drain Structure . No Bag . 3-5 Emission Factor Drain Structure . Vacuum Method . 3-5 Aligned Drain Structure 3-6 University of Texas Drain Structure . 3-8 Dosing Procedure . 3-9
30、Sample Analysis . 3-9 OVA Calibration 3-10 Experimental Plan and Methodology 3-10 Drain Emission Factor Study . 3-10 Aligned Drain Emissions 3-12 Duplication of University of Texas Experiments . 3-12 Experimental Schedule . 3-13 STD.API/PETRO PUBL 9677-ENGL L999 m 0732290 ObL5L93 779 Table of Conten
31、ts RESULTS 3-14 Duplicate Sample Analysis . 3-14 Discharge Column of Water Description . 3-15 Drain Emission Factors Experiments (misaligned drain) . 3-16 Calculation of Experimental Percentage Emissions . 3-1 6 Emission Factor Tables . 3-18 Organic Vapor Analyzer Results 3-20 Aligned Drain Structur
32、e 3-22 Duplication of University of Texas Experiments 3-23 DISCUSSION OF RESULTS 3-25 SIMPLIFIED EMISSION FACTOR TABLES . 3-26 Using the Simplified Emission Factor Tables 3-31 Example Use of the Emission Factor Tables . 3-32 User Input: Look-up Table Mass Emissions . 3-33 User Input Data 3-32 Calcul
33、ations 3-34 4 . CONCLUSIONS AND RECOMMENDATIONS . 4.1 5 . REFERENCES . 5-1 Appendix A Analytical Data From Drain Bagging Protocol Experiments Appendix B WQC . Duplicate Sample Submission From Drain Bagging Protocol Experiments Appendix C Analytical Data From Stripping Efficiency Experiments Appendix
34、 D Emission Factors (Misaligned Drain) for Individual Contaminants From Stripping Efficiency Experiments Appendix E Degree of Saturation in Gas Phase During Bagged Experiments From Stripping Efficiency Experiments Appendix F Mass Emission Calculations Based on OVA Readings STD.API/PETRO PUBL 4b77-EN
35、GL 1999 0732290 ObL5L94 bo5 = Table of Contents LIST OF TABLES Table 2.1 . Table 2.2 . Table 2.3 . Table 2-4 . Table 2.5 . Table 2.6 . Table 2.7 . Table 2.8 . Table 2.9 . Table 2.10 . Table 2-1 I . Table 2-1 2 . Table 2-1 3 . Table 3.1 . Table 3.2 . Table 3.3 . Table 3-4 . Table 3.5 . Table 3.6 . Ta
36、ble 3.7 . Table 3.8 . Table 3.9 . Table 3.10 . Table 3-1 I . Table 3.12 . Table 3-1 3 . Table 3.14 . Table 3.15 . Table 3.16 . Table 3.17 . Table 3.18 . Table 3.19 . Table 3.20 . Table 3.21 . Table 3.22 . Table 3.23 . Table 4.1 . Henrys Law Coefficients for Test Compounds . 2-2 Experimental Schedule
37、 . 2.8 Summary of Drain Emissions (%) . No Bag 2-10 Summary of Drain Emissions (%) - Vacuum 2-10 Comparison of Blow-Through Bag Results for Phase 1 (API, 1996) and Phase 2 (Current Work ) 2-11 Summary of Drain Emissions (pg/min) - No Bag 2-12 Summary of Drain Emissions (pg/min) - Vacuum . 2-13 Obser
38、ved OVA Readings . 2-1 5 Total Drain Emissions Based on OVA Measurements - Vacuum . 2-15 Comparing Vacuum and Blow-Through Methods -2-1 6 Comparing Combined Vacuum and Blow-Through Methods To No Bag Method 2-17 Summary of Drain Emissions (%) - Blow-Through . 2-11 Summary of Drain Emissions (pg/min)
39、- Blow-Through 2-13 Henrys Law Coefficients for Test Compounds . 3.2 Inactive Drain Sampling Schedule 3-12 Experimental Schedule . 3-13 Inactive Drain Liquid Temperature 3-16 Emission Factors: 1.23 I Hc I 7.17 3-19 Emission Factors: 0.32 I Hc c 1.23 3-19 Emission Factors: O . 13 I Hc c 0.32 3-20 Emi
40、ssion Factors: 0.02 5 Hc 0.1 3 3-20 Organic Vapor Analyzer Results . 3-21 Drain Emissions Based OVA Measurements - Bagged Experiments 3-21 Drain Emission Factor Experimental Plan . 3-11 Drain Emission Factor Experimental Process Variation 3-11 University of Texas Replication Experiments . Process Co
41、nditions 3-13 Aligned Drain Percentage Emissions 3-23 University of Texas Experiments - Percentage Emissions 3-24 Study Emissions and University of Texas Model Emissions . 3-25 Simplified Emission Factor Table Summary of Drain Operating Conditions 3-28 High Volatility Compounds (I . 23 I Hc I 7.17)
42、3-29 Medium Volatility Compounds (0.1 3 I Hc 0.32) . 3-29 Low Volatility Compounds (I 0.02 Hc c O . 13) . 3-29 Simplified Emissions Factor Table - High Volatility . 3-30 Simplified Emissions Factor Table - Medium Volatility 3-30 Simplified Emissions Factor Table - Low Volatility 3-30 Conservative Us
43、e of Emission Factor Tables . 4-1 sTD.API/PETRO PUBL 4677-ENGL 1777 I 0732270 Ob15L75 541 Table of Contents LIST OF FIGURES Figure 2-1 Figure 2-2 Figure 2-3 Figure 3.1 . Figure 3.2 . Figure 3.3 . Figure 3-4 . Figure 3.5 . Figure 3.6 . Schematic of Pilot Drain Structure 2-4 Vacuum Bag Apparatus 2-5 P
44、ressure Bag Apparatus . 2-6 Drain Emission Factor Drain Structure 3-3 Drain Emission Factor Hub Structure 34 Aligned Drain Discharge . 3-7 Drain Emission Structure - Vacuum Bag . 3-6 Replication of University of Texas Drain Structure 3-8 Mass Emissions as a Function of OVA Reading . 3-22 STD-API/PET
45、RO PUBL 4b77-ENGL L999 H 0732290 ObL5Lb 488 I EXECUTIVE SUMMARY This investigation was initiated by the American Petroleum Institute (API) to update the AP-42 emission factor for refinery process drains, which may overestimate refinery process drain fugitive emissions. Changes in refinery process dr
46、ains have been implemented in response to United States Environmental Protection Agency (USEPA) regulations, including benzene waste operations National Emission Standards for Hazardous Air Pollutants (NESHAP) and New Source Performance Standards (NSPS) Subpart QQQ. Sealed drains have led to lower r
47、efinery process drain emission conditions, compared with conditions when the AP-42 emission factor was developed. The results of this study indicate that the AP-42 emission factor for refinery process drains should be modified. The work reported in this report is the second phase of an effort to dev
48、elop new emission factors to improve the estimate of drain emissions. This report presents new emission factors based on the flow and loadings into laboratory- and pilot-scale process drains. The emission factors require a knowledge of the concentrations of various constituents in the process wastew
49、ater discharged to the refinery drains. Specific project activities are summarized below. Protocols for field bagging and measuring drain emissions were tested. Results indicated that vacuum and blow-through bagging protocols give the same results. For the least volatile constituents, emissions were statistically greater for a drain with no bag than for a drain enclosed by a bag. A series of emission factor tables were developed, which are more appropriate for estimating drain emissions than using a single emission factor. The emission factor tables require a knowledge of the volatil
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