1、STD.API/PETRO PUBL 4b98-ENGL 3999 0732290 0638509 380 RI American Petroleum Institute - A REVIEW OF TECHNOLOGIES TO MEASURE THE OIL AND GREASE CONTENT OF PRODUCED WATER FROM OFFSHORE OIL AND GAS PRODUCTION OPERATIONS REGULATORY AND SCIENTIFIC AFFAIRS PUBLICATION NUMBER 4698 NOVEMBER 1999 STD.API/PET
2、RO PUBL 4698-ENGL 1999 W 0732270 ObL85LU UT2 8 American Petroleum Institu#e -b American Petroleum Institute Environmental, Health, and Safety Mission and Guiding Principles MISSION The members of the American Petroleum Institute are dedicated to continuous efforts to iiiiprovi the compatibility of o
3、ur operations with the environment while economically developing energy resources and supplying high quality products and services to consumers. We recognize our responsibility to work with the public, the government, and others to develop and to use natural resources in an enironmentally sound mann
4、er while protecting the health and safety of our employees and the public. To meet these responsibilities, API members pledge to manage our businesses according to the following principles using sound science to prioritize risks and to implement cost-effective management practices: PRINCIPLES O O a
5、To recognix and to respond to community concerns about our raw materials, products and opcrations. 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 our employees and the public. To make safety,
6、health and environmental considerations a priority in our planning, and our dcvclopment of new products and processes. To advise promptly, appropriate officials, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recomm
7、end protective measures. To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materials, products and waste materials. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowlcd
8、ge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials. o commit to rcduce overall emission and waste generation To work with others to resolve problems created by handling and disposal of hazardous substa
9、nces from our operations. To participate with govcrnment and others in creating responsible laws, regulations and standards to safeguard the community, workplace and environment. To promote these principles and practices by sharing experiences and offering assistance to others who produce, handlc, u
10、se, transport or dispose of similar raw materials, petroleum products and wastes. STD.API/PETRO PUBL 4698-ENGL 1799 0732290 ObL85Ll T39 A Review of Technologies to Measure the Oil and Grease Content of Produced Water From Offshore Oil and Gas Production Operations Regulatory and Scientific Affairs A
11、PI PUBLICATION NUMBER 4698 PREPARED UNDER CONTRACT BY: JAMES FRASER DAN CAUDLE WATER TECHNOLOGY INTERNATIONAL CORP. 867 LAKESHORE ROAD BURLINGTON, ONTARIO, CANADA L7R 4L7 SOUND ENVIRONMENTAL SOLUTIONS 11 11 1 KAw FREEWAY SUITE 104 HOUSTON, TEXAS 77079 JOSEPH RAIA J. C. RAIA CONSULTING SERVICES 15402
12、 PARK ESTATES LANE HOUSTON, TX 77062 EDITED BY: ROGER CLAFF, AMERICAN PETROLEUM INSTITUTE KRIS BANSAL, CONOCO, INCORPORATED NOVEMBER 1999 American Petroleum I Institute STD-APIIPETRO PUBL 4b98-ENGL 1999 9 0732290 Ob18512 975 FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE.
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16、ng, recording, or otherwise, without prior written permissionfrom the publisher Contact the publisher, API Publishing Services, i220 L Street, N.W, Washington, D.C. 20005. Copyright O 1999 American Petroleum Institute iii STD.API/PETRO PUBL 4b98-ENGL 1999 0732i90 bLB513 BOL I ACKNOWLEDGMENTS THE FOL
17、LOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT API STAFF CONTACTS Roger Claff, Regulatory and Scientific Affairs Alexis Steen, Regulatory and Scientific Affairs MEMBERS OF THE PRODUCED WATER OIL AND GREASE WORKGROUP
18、Sung-I Johnson, Phillips Petroleum Company, Chairperson Syed Ali, Chevron USA Production Company Kris Bansal, Conoco, Incorporated Larry Henry, Chevron USA, Incorporated Zara Khatib, Shell Development Company David LeBlanc, Texaco Exploration and Production, Incorporated James Ray, Equilon Enterpris
19、es LLC Joseph Smith, Exxon Production Research Company Steve Tink, VASTAR Resources, Incorporated Donna Stevison, Marathon Oil Company iv STD.API/PETRO PUBL 4b98-ENGL 1999 m 0732290 Ob185L4 748 m ABSTRACT The traditional monitoring methods for monitoring oil and grease, EPA Methods 413.1 and 4 13.2,
20、 rely on Freon 1 13 extraction of oil and grease. Owing to the phase-out of Freon 1 13 use mandated by the Montreal Protocol and 1990 Clean Air Act Amendments, these methods can no longer be considered viable and hence a new method must be sought. This study identified and evaluated practical altern
21、ative methods for routine offshore monitoring of oil and grease in produced waters. Three methods were addressed in this study: 1) an infrared absorption method in which transmitted infrared radiation is measured and correlated to the oil and grease content; 2) an infrared absorption method in which
22、 reflected infrared radiation is measured and correlated to the oil and grease content; and 3) an ultraviolet fluorescence (UV) method in which the fluorescent radiation from the sample or sample extract is measured at a specific wavelength and correlated to the oil and grease content. The two infra
23、red absorption methods employed two different configurations of a particular analytical instrument, and the ultraviolet fluorescence method was conducted using two different analytical instruments. All instruments and methods were found capable of measuring oil and grease in produced water. They dem
24、onstrated acceptable performance in terms of linear response, analytical sensitivity, sensitivity to changes in crude oil composition, interferences, flexibility, ease of use, and correlation of results to the EPA hexane extraction method, EPA Method 1664. TABLE OF CONTENTS SECTION . PAGE EXECUTIVE
25、SUMMARY ES- 1 1 2 3 4 INTRODUCTION 1 . 1 PHASE I . COMPARISON OF EPA METHODS 413.1 AND 1664 . 2-1 PHASE II . SURVEY OF CANDIDATE METHODS . 3- 1 PHASE III . LABORATORY PERFORMANCE TESTING . 4- 1 Laboratory Performance Testing 4- 1 Instrument Calibration 4-2 Working Range . 4. 16 Precision . 4- 16 Eff
26、ect of Water Soluble Organics . 4- 18 Effect of Iron on Direct Reading UV Analyses 4- 19 5 CONCLUSIONS 5- 1 APPENDIX A A COMPARISON OF EPA METHOD 4 13.1 AND EPA METHOD 1664 FOR THE DETERMINATION OF OIL AND GREASE IN PRODUCED WATER FROM OFFSHORE PRODUCTION OPERATIONS A- 1 APPENDIX B A REVIEW OF TECHN
27、OLOGIES TO MEASURE THE OIL AND GREASE CONTENT OF PRODUCED WATER FROM OFFSHORE OIL AND GAS PRODUCTION OPERATIONS B. 1 1 LIST OF FIGURES 4.1 Measured vs. Defined concentration: UV Instrument B, Calibrated with Crude #2 Simulated Produced Water, Measuring Oil and Grease in Crude # 1 and Crude #2 Simula
28、ted Produced Water . 4-5 UV Instrument A Calibrated with Crude #4 Simulated Extracts: Measured Oil and Grease Concentrations in Crude #3 and #4 Simulated Extracts . 4-8 Crude #I Concentration vs. RFUs 4-9 Average Measured Oil and Grease Concentration from Simulated Extracts, Determined by IR-ABS, vs
29、. Defined Concentration 4-14 Comparison of IR-HATR and IR-ABS Oil and Grease Concentrations Measured in Simulated Produced Water Samples Containing Crude #2 . . . . . 4- 16 Concentration Ration vs. Ferric Ion Concentration 4-2 1 4.2 4.3 4-4 4-5 4-6 STD.API/PETRO PUBL 4b98-ENGL 1999 = O732290 Oh18517
30、 457 2.1 2.2 3.1 4.1 4.2 4.3 4.4 4.5 4-6 4-7 4- 8 4-9 4-10 4-1 1 4-12 4-13 4-14 4-15 4-16 4-17 4-18 4-19 LIST OF TABLES Produced Water Oil and Grease Data from Five Offshore Platforms (mg/L) 2-2 Summary Statistics for the Phase I Produced Water Data 2-3 Analytical Instruments for Oil and Grease Meas
31、urement 3-2 UV Analysis of Simulated Produced Water Samples Using Instruments Calibrated with Crude #2 Simulated Produced Water . 4-4 Oil and Grease in Produced Water Samples from Platforms SPW and CPW 4-6 Averages and Standard Deviations for Replicate Samples 4-6 Oil and Grease Concentrations Deter
32、mined by UV Instrument A Calibrated with Crude #4 Simulated Extracts 4-7 Correlation of Fluorescence Units and Crude #1 Concentrations with Dye Concentrations Used to Calibrate Instruments A . 4-8 Analyses of a Natural Produced Water Using Instrument A With a Dye Calibration and Various Analytical F
33、actors . 4-10 Goodness of Fit for Fluorescence Analyses of a Natural Water 4-10 Comparison of Fluorescence Analyses on a Natural Water Sample Analyzed Directly and by Extraction . 4-11 Comparison of EPA Method 1664 Results to UV Fluorescence Results on Defined Concentrations of Crude Oil in Hexane .
34、 4-12 Oil and Grease Concentrations Determined by IR-ABS7 Calibrated with Crude #1 in Hexane 4-13 Comparison of UV Instrument A vs . IR-HATR in the Analyses of Oil and Grease in Actual Produced Water Samples 4-15 Comparison of IR-HATR and IR-ABS Methods in Analyzing Oil and Grease in Simulated Produ
35、ced Water Samples Containing Crude #2 4-15 Precision Study of UV Instrument A 4-17 Precision Study of IR-ABS and IR-HATR 4-18 Sample Matrix for WSO Studies 4-18 Effect of Ferric Ion on Direct Reading UV Determinations by Instrument A, Recorded as Raw Fluorescent Units . 4-19 Effect of Ferric Ion on
36、Direct Reading UV Determinations by Instrument A, Recorded as Oil and Grease Concentration 4-19 Ferric Ion Effect on UV Instrument A Determinations of Oil and Grease in Simulated Produced Water Samples 4-20 Ratio of Measured to Defined Oil and Grease Concentration at Various Ferric Ion Concentration
37、s . 4-20 EXECUTIVE SUMMARY The objective of this study is to identifj practical alternative methods for routine monitoring of oil and grease in produced waters. The traditional monitoring methods, EPA Methods 41 3.1 and 41 3.2, rely on Freon 1 13 extraction of oil and grease. Owing to the phase-out
38、of Freon 1 13 use mandated by the Montreal Protocol and 1990 Clean Air Act Amendments, these methods can no longer be considered viable and hence a new method must be sought. The United States Environmental Protection Agency (EPA) is soon to promulgate a new method for oil and grease, EPA Method 166
39、4. This method entails hexane extraction of the sample, followed by separation of the oil and grease from the hexane by evaporation, and weighing of the oil and grease remaining behind. Although this method will be required for compliance monitoring, it is generally unsuitable for routine monitoring
40、 on offshore platforms. The method is not simple to conduct, requires access to fume hoods and other equipment, and requires a quiescent and physically stable environment for weighing the samples. Since Method 1664 is considered impractical for routine offshore monitoring of produced water oil and g
41、rease, an alternative method must be sought for routine monitoring and verification of compliance. Offshore operators charged with this important compliance verification task must have an analytical method that is reliable and relatively easy to conduct, while at the same time consistently provides
42、analytical results that can be accurately correlated to EPAs compliance method, Method 1664. The American Petroleum Institutes (APIs) Produced Water Oil and Grease Workgroup (Workgroup) initiated this study to identifj and evaluate promising practical alternatives. The study was conducted in three p
43、hases. In the first phase of this study, EPA Methods 4 13.1 and 1664 were compared using five sets of replicate produced water samples from production operations in Louisiana and California. The results by the two methods appeared to be weakly related; however, because of high variability between re
44、plicates, a statistically defensible relationship between the results of the two methods could not be established. ES- 1 STD-APIIPETRO PUBL 4bq-ENGL 1999 W 0732290 ObL85L9 22T = In the second phase of the study, field-proven alternative methods and instruments that might be successfully used for rou
45、tine offshore produced water monitoring were identified. Viable methods and associated instruments must: Give a significant response to oil and grease; Give a linear response to oil and grease over the concentration range of interest; Measure oil and grease with acceptable precision; Provide analyti
46、cal results which can be correlated to results by the official EPA method using hexane extraction, EPA Method 1664; Be easy to calibrate and operate on offshore platforms; Provide consistent performance; and 0 Be rugged, durable, and require infrequent repair and adjustment. In consideration of thes
47、e criteria, three methods were recommended: Infrared absorption (IR-ABS) method in which the sample extract is deposited on a sapphire window, infrared radiation is passed through the sample, and transmitted radiation is measured and correlated to the oil and grease content. Infrared absorption (IR-
48、HATR) method in which the sample extract is deposited on a sapphire plate or zinc sulfide surface, infrared radiation is passed through the sample, and reflected radiation is measured and correlated to the oil and grease content. Ultraviolet fluorescence (UV) method in which ultraviolet radiation fr
49、om the sample or sample extract is measured and correlated to the oil and grease content. In the third phase of the study, the performance of these methods was evaluated in the laboratory, using two UV fluorescence instruments and two modifications of a single IR instrument. All instruments and methods were found capable of measuring oil and grease in produced water. In evaluating the performance of these methods and instruments, the following observations were made: 0 Linear Response - All instruments provided a linear response to oil and grease concentration ove
