1、I Estimation of Fugitive Emissions from Petroleum ! Refinery Process Drains I Phase I Report Health and Environmental Sciences Department Publication Number 4639 April 1996 API PUBL*4639 96 = 0732290 0557233 930 W -b- One of the most significant long-term trends affecting the future vitality of the
2、petroleum industry is the publics concerns about the environment. Recognizing this trend, API member companies have developed a positive, forward-looking strategy called STEP: Strategies for Todays Environmental Partnership. This program aims to address public concerns by improving our industrys env
3、ironmental, health and safety peiformance; documenting performance improvements; and communicating them to the public. The foundation of STEP is the API Environmental Mission and Guiding Environmental Principles. API ENVIRONMENTAL MISSION AND GUIDING ENVIRONMENTAL PRINCIPLES The members of the Ameri
4、can Petroleum Institute are dedicated to continuous efforts to improve the compatibility of our operations with the environment while economically developing energy resources and supplying high quality products and services to consumers. The members recognize the importance of efficiently meeting so
5、cietys needs and our responsibility to work with the public, the government, and others to develop and to use natural resources in an environmentally sound manner while protecting the health and safety of our employees and the public. To meet these responsibilities, API members pledge to manage our
6、businesses according to these principles: 9 To recognize and to respond to community concerns about our raw materials, products and operations. O To operate our plants and facilities, and to handle our raw materials and products in a manner that protects the environment, and the safety and health of
7、 our employees and the public. 9 To make safety, health and environmental considerations a priority in our planning, and our development of new products and processes. 4. To advise promptly, appropriate officials, employees, customers and the public of information on significant industry-related saf
8、ety, health and environmental hazards, and to recommend protective measures. 9 To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materials, products and waste materials. 4. To economically develop and produce natural resources and to conserve those
9、 resources by using energy efficiently. 9 To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials. 9 To commit to reduce overall emission and waste generation. 4 To work with others to reso
10、lve problems created by handling and disposal of hazardous substances from our operations. 9 To participate with government and others in creating responsible laws, regulations and standards to safeguard the community, workplace and environment. 4 To promote these principles and practices by sharing
11、 experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes. Estimation of Fugitive Emissions from Petroleum Refinery Process Drains Phase I Report Health and Environmental Sciences Department API PUBLICATION N
12、UMBER 4639 PREPARED UNDER CONTRACT BY: BROWN AND CALDWELL 1 O0 WEST HARRISON STREET, SUITE 205 SEATTLE, WASHINGTON 981 19-41 86 WITH UNIVERSITY OF TEXAS AT AUSTIN DEPARTMENT OF CIVIL ENGINEERING AUSTIN, TEXAS 7871 2-1 076 ENVIROMEGA, LTD. 7 INNOVATION DRIVE HAMILTON, ONTARIO CANADA L9 J 1 K3 AND AUG
13、UST 1995 American Petroleum Institute API PUBL*4639 96 m 0732290 0557233 703 m 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
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15、STRUED AS GRANTING ANY RIGHT, 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 LETTERS PAm. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- C
16、opyright O 1996 American Petroleum institute i ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: - Paul Martino, Health and Environmental Sciences Department S OF THE REmRY DRm EMISSIONS PROJECT
17、GROUP Nick Spiridakis, Chairman, Chevron Research and Technology Kare1 Jelinek, BP Oil Company Miriam Lev-On, Arco Jan Nguyen, UNOCAL Chris Rabideau, Texaco S. Rajagopalan, Shell Development Company Achar Ramachandra, Amoco Corporation Ron Wilkniss, Western States Petroleum Assocation Jenny Yang, Ma
18、rathon Oil Company Brown and Caldwell would also like to thank Dr. Richard Corsi (University of Texas) and Dr. J.P. Bell (Enviromega, Ltd.) for their assistance in the completion of this work. API PUBL*4639 96 m 0732290 0557235 586 m ABSTRACT Fugitive emissions are commonly estimated using USEPAs AP
19、-42 emission factors. The factor for refinery process drains was developed in 1979. Since that time, modifications to drains, canied out in response to regulatory requirements, have reduced emissions, with the result that the AP-42 factor may be over-estimating actual drain emissions. This work was
20、undertaken to address these concerns by developing a protocol to improve estimates of drain emissions. A survey of process drains was conducted at three refineries, and an evaluation carried out of the capability of existing models to predict drain emissions and important variables influencing drain
21、 emissions. Laboratory scale and pilot scale equipment were assembled to facilitate the measurement of VOC emissions fi-om simulated drain structures under controlled conditions. Testing demonstrated almost complete mass balance closures, and repeatability of analytical determination of target compo
22、unds and their stripping efficiencies, confirming the suitability of the protocol for measuring VOC emissions from drain structures. API PUBLX4639 96 0732290 0557236 412 TABLE OF CONTENTS Section mis EXECUTIVE SUMMARY ES- 1 1 . INTRODUCTION 1 . 1 OBJECTIVE . 1 . 1 PROBLEM DEFINITION 1-1 LITERATURE R
23、EVIEW . 2-1 INTRODUCTION 2-1 2 . Objectives . 2-1 General Approach . 2-1 summary . 2-2 FACTORS AFFECTING EMISSIONS . 2-3 FIELD STUDIES 2-4 Frequency of Outgassing Drains . 2-4 Fugitive Emissions Measurements . 2-5 EMISSION MODELS 2-7 Emission Factors . 2-7 Equilibrium-Based Models . 2-9 Kinetics-Bas
24、ed Models . 2-9 EXPERIMENTAL STUDIES 2-10 SUMMARY OF EXISTING KNOWLEDGE BASE . 2-11 SURVEY OF REFINERY PROCESS DRAINS 3-1 APPROACH . 3-1 MAJOR FINDINGS . 3-2 Number of Drains . 3-2 Types of Drain Structures . 3-2 Active Drains 3-4 Type of Discharge . 3-9 Temperature 3-9 3 . RECOMMENDATIONS 3- 1 1 TA
25、BLE OF CONTENTS (continued) Section m 4 . MODEL AND INFLUENCING FACTORS 4-1 CONCEPTUAL SYSTEM . 4-1 AIR EXCHANGE WITHIN A PROCESS UNIT 4-2 PARAMETERS AND INFLUENCING FACTORS 4-4 SUMMARY OF PROPOSED MODEL . 4-6 PHASE II PROTOCOL 5-1 LABORATORY SCALE 5-4 5 . Test System . 5-4 Dosing Procedure 5-7 Flui
26、d Simulation . 5-7 Oxygen Uptake Rate Determination . 5-8 Liquid Sampling and Analysis 5-8 Gas Sampling and Analysis 5-8 Recommendations for Laboratory Scale Phase II Work 5-8 PILOT SCALE . 5-9 Drain Stnicture 5-10 Fluid Sirnulation . 5-10 Dosing Procedure 5-11 Wastewater Sampling and Analysis 5-11
27、Gas Sampling and Analysis 5-11 Recommendations for Pilot Scale Phase II Work . 5-13 ALTERNATIVE PROCEDURE FOR FIELD MEASUREMENTS . 5-14 Wastewater Sampling and Analysis 5-14 Wastewater Flow 5-14 TESTING OF PHASE II PROTOCOL 6-1 LABORATORY SCALE ASSESSMENT . 6-1 Experimental Conditions 6-1 6 . TABLE
28、OF CONTENTS (continued) Section Pas 6 . TESTING OF PHASE II PROTOCOL (continued) Results . 6-2 Duplicate Sample Analysis . 6-2 Mass Balance Closure . 6-2 Stripping EMiciencies 6-3 Conclusions . 6-5 PILOT SCALE ASSESSMENTS . 6-5 Experimental Plan . 6-5 Results . 6-6 Mass Balance Closure . 6-9 Strippi
29、ng Efficiency 6-11 Conclusions . 6-12 ASSESSMENT OF ALTERNATIVE PROCEDURES . 6-12 Wastewater Flowrate . 6-12 Wastewater Sampling . 6-13 7 . RECOMMENDATIONS FOR PHASE II WORK . 7-1 REFERENCES . R- I API PUBL*q639 96 0732290 0557239 121 = LIST OF APPENDICES Appendix A LITERATURE REVIEW BRIEFS . A- 1 A
30、ppendix B SUPPLEMENTARY REFERENCES B- 1 Appendix C SURVEY OF PROCESS DRAINS REPORTS . C-1 Appendix D MODEL DEVELOPMENT FOR REFINERY PROCESS DRAINS D- 1 MASS TRANSFER ABOVE HUB D-1 MASS TRANSFER BELOW HUB AND ABOVE TRAP/CHA“EL D-3 MASS TRANSFER WITHIN A TRAP . D-5 MASS TRANSFER BELOW A TRAP D-5 Appen
31、dix E RECOMMENDED LABORATORY SCALE TASKS FOR PHASE II . E- 1 TASK 1 MODEL DEVELOPMENT AND SENSITIVITY ANALYSIS . E- 1 TASK 2: MODEL PARAMETER ESTIMATION . E-1 TASK 3: EVALUATION OF THE EFFECTS OF DRAIN CONFIGURATIONS AND CHEMICAL EQUILIBRIUM . E-3 FINAL PRODUCTS . E-3 API PUBL*4b39 96 m 0732290 0557
32、240 943 m LIST OF FIGURES Fieure rn 2.1 . Schematic of Sample Train for Baggable Source (Vacuum Method) 2-6 2.2 . Schematic of Sample Train for Blow-Through Method . 2-7 3.1 . Major Components of a Drain Structure 3-3 3.2 . Drain Structures at the West Coast Refinery 3-5 3.3 . P-Trap Water Sealed Dr
33、ain at the Midwest Refinery . 3-6 3-4 . Unsealed Drain Funnel at the Midwest Refinery . 3-7 3-5 . P-Trap Types at the East Coast Refinery 3-8 3.6. Running P-Traps at the East Coast Refinery 3-10 4-1 . Mass Transfer Mechanisms in Process Drains . 4-2 4-2 . Illustration of Co-current Cumulative Ventil
34、ation Model 4-4 5-1 . Schematic of Pilot Drain System 5-5 5-2 . Schematic of Recirculating Batch Reactor . 5-6 5-3 . Schematic of Pilot Drain Structure . 5-10 5-4 . Schematic of Gas Sampling Apparatus 5-12 6- 1 . Acetone Calibration Curve . 6-3 API PUBL*4639 96 0732290 0557241 88T W LIST OF TABLES T
35、able 2.1 . Major Reports Related to Emissions from Process Drains 2-3 2.2 . Factors Affecting Mass Transfer Reported in Existing Literature 2-3 2.3 . Factors Affecting Ventilation Reported in Existing Literature . 2-4 3.1 . Summary of Drain Survey Data 3-2 5-1 . Henrys Law Coefficients for Target VO
36、Cs at 22C 5-7 5-2 . Number of Experiments at Each Operating Condition 5-13 6-1 . Summary of Experimental Conditions 6-1 6-2 . Stripping Efficiencies 6-3 6-3 . Experimental Conditions . 6-5 6-4 . Dosed Contaminants 6-6 6-5 . Sampling Schedule 6-6 6-6 . Analytical Data - Experiment 1 . 6-7 6-7 . Analy
37、tical Data - Experiment 2 6-8 6-8 . Analytical Data - Experiment 3 6-8 6-9 . Mass Balance Closures 6- 10 6- 1 O . Percent Air Emissions/Stripping Efficiency from Drain Structures 6- 10 6- 1 1 . Comparison of Flowrate Measurements 6- 13 6-1 2 . Comparison of Wastewater Sampling Results 6- 14 API PUBL
38、x4b39 b M O732290 0557242 716 M EXECUTIVE SUMMARY This investigation was initiated by the American Petroleum Institute (API) to address the apparent inadequacy of the AP-42 factor in estimating correctly the fugitive emissions from refinery process drains. Significant modifications have been made to
39、 refinery drain installations over the last few years in response to regulatory requirements introduced during this period. These changes have resulted in reductions in emissions from drains such that the AP-42 factor is now thought to overestimate these emissions. The work reported here was the fir
40、st phase of an investigation to develop predictive correlations that can be used to improve the estimate of drain emissions. This report presents and discusses a protocol which would facilitate the measurement and modeling of volatile organic compound (VOC) emissions from refinery process drains. It
41、 includes a comprehensive literature review on fugitive emissions from process drains, the results of a survey of process drains at three refineries, a review of models that describe VOC emissions from drain structures and the results from a series of tests that were carried out to evaluate, at labo
42、ratory scale and pilot scale, the suitability of the equipment and procedures that make up the protocol. LITERATURE REVIEW The literature review revealed that, of 220 publications related to VOC emissions, only 19 addressed VOC emissions from process drains. The current base of knowledge on process
43、drain emissions is based on five of these publications, the remaining 14 borrowing heavily from the first five. It was found that current methods for estimating VOC emissions from process drains are both conservative (overestimate) and characterized by a high degree of uncertainty. Factors affecting
44、 VOC emissions from drains were divided into those affecting mass transfer and those affecting ventilation. Important factors affecting mass transfer were identified as volatility, liquid concentration, diffusion rate through air and water, and drain diameter. Factors affecting ventilation included
45、wastewater drag, wind eduction, temperature differentials, barometric pressure, wastewater levels, and drain dimensions. The review differentiated between emission 1 Volatile Organic Compounds (VOC), in general, means any compound of carbon which participates in atmospheric photochemical reactions,
46、excluding certain compounds determined to have negligible photochemical reactivity (e.g., methane and ethane). A more complete and precise definition is given in 40 CFR 5 1.100 (S). ES- 1 API PUBLX4639 96 m O732290 0557243 b52 factors, equilibrium-based models, and kinetics-based models. Existing em
47、ission factors were found to be outdated and needed to be revised to reflect advances in process drain configurations. Equilibrium-based models represent the state-of-the-art in emissions estimation methods for process drains. Improvement of such models will depend upon improvements in methods to me
48、asure and estimate air exchange rates between drains and the ambient atmosphere. The USEPA raised the concern that ventilation rate can impact emissions from process drains as a result of air exchange between the drains and a collection system suggesting that a modeling analysis of drain emissions s
49、hould incorporate the collection system. However, the petroleum industry, through the Petroleum Environmental Research Forum (PERF), intends to address this concern by modeling the collection system and its component parts. This project, sponsored by API, is an integral part of the overall PERF investigation to estimate VOC emissions from petroleum refineries. The drain model to be developed in Phase II of this API study intends to provide boundary conditions to allow the drain model to be incorporated into collection models such as SEAM, or fate models such as WATER 8. REFINERY SUR
