1、 TECHNOLOGIESTOREDUCEOILANDGREASECONTENTOFWELLTREATMENT, WELLCOMPLETION, ANDWORKOVERFLUIDSFOROVERBOARDDISPOSALRegulatory and Scientific AffairsPublication Number 4702March 2001American Petroleum InstituteEnvironmental, Health and Safety Missionand Guiding PrinciplesMISSIONThe members of the American
2、 Petroleum Institute are dedicated to continuousefforts to improve the compatibility of our operations with the environment whileeconomically developing energy resources and supplying high quality products andservices to consumers. We recognize our responsibility to work with the public, thegovernme
3、nt, and others to develop and to use natural resources in an environmen-tally sound manner while protecting the health and safety of our employees and thepublic. To meet these responsibilities, API members pledge to manage our busi-nesses according to the following principles using sound science to
4、prioritize risksand to implement cost-effective management practices:PRINCIPLES To recognize and to respond to community concerns about our raw materials,products and operations. To operate our plants and facilities, and to handle our raw materials and products in a manner that protects the environm
5、ent, and the safety and health of our employees and the public. To make safety, health and environmental considerations a priority in our plan-ning, and our development of new products and processes. To advise promptly, appropriate ofcials, employees, customers and the public of information on signi
6、cant industry-related safety, health and environmental haz-ards, and to recommend 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
7、and to conserve those resources by using energy efciently. To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials. To commit to reduce overall emission and waste generation. To work with o
8、thers to resolve problems created by handling and disposal of haz-ardous substances from our operations. To participate with government and others in creating responsible laws, regula-tions and standards to safeguard the community, workplace and environment. To promote these principles and practices
9、 by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes.Technologies to Reduce Oil and GreaseContent of Well Treatment, WellCompletion, and Workover Fluidsfor Overboard DisposalRegulatory and Sci
10、entific Affairs DepartmentAPI Publication Number 4702PREPARED UNDER CONTRACT BY:Marc Halevy, ing.Conor Pacific Environmental Technologies, Inc.Mississauga, OntarioCanadaJULY 2000FOREWORDAPI publications necessarily address problems of a general nature. With respect to particular circum-stances, loca
11、l, state, and federal laws and regulations should be reviewed.API is not undertaking to meet the duties of employers, manufacturers, or suppliers to warn and prop-erly train and equip their employees, and others exposed, concerning health and safety risks and precau-tions, nor undertaking their obli
12、gations under local, state, or federal laws.Nothing contained in any API publication is to be construed as granting any right, by implication orotherwise, for the manufacture, sale, or use of any method, apparatus, or product covered by letterspatent. Neither should anything contained in the publica
13、tion be construed as insuring anyone against lia-bility for infringement of letters patent.All rights reserved. No part 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 per-
14、mission from the publisher. Contact the Publisher, API Publishing Services, 1220 L Street, N.W., Washington, D.C. 20005.Copyright 2001 American Petroleum InstituteACKNOWLEDGMENTSTHE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIMEAND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION
15、OF THISREPORT:API STAFF CONTACTRoger E. Claff, Regulatory and Scientific Affairs DepartmentMEMBERS OF THE PRODUCED WATER OIL AND GREASE WORKGROUPSyed Ali, Chevron Petroleum Technology CompanyKris Bansal, Conoco Inc.Larry Henry, Chevron USA, Inc.Sung-I Johnson, Phillips Petroleum CompanyZara Khatib,
16、Shell Development CompanyDavid LeBlanc, Texaco Exploration and Production, Inc.James Ray, Equilon Enterprises LLCJoseph Smith, Exxon Production Research CompanyDonna Stevison, Marathon Oil CompanySteve Tink, VASTAR Resources, Inc.The following colleagues were an essential part of this project and th
17、eir contributions weregreatly appreciated: Abbas Zaidi, Dan Caudle, Samira Nawar, Nadine Toscani, and FanjianMeng.ABSTRACTThe flowback of non-produced fluids to surface de-oiling facilities on offshore platforms cancreate severe process upsets. Consequently, meeting oil and grease (O technology revi
18、ew and screening at laboratory scale; and bench scaletechnology development of the most promising technology.To properly simulate NPF flowback, the first phase targeted the collection and review ofchemical use procedures. A reduced-scale sand pack column simulated a downhole sandstoneformation. Form
19、ulation and fluid preparation procedures were established for produced water,well stimulation solutions, and non-produced fluids. A nitrogen gas flotation process was usedto simulate produced water de-oiling operations. Experimental protocols and O Polymer-modified clay adsorption; Iron-catalyzed hy
20、drogen peroxide advanced oxidation; Liquid-liquid extraction; Electro-coagulation; and Membrane filtration.Based on laboratory scale treatability data, two processes were initially retained: granularactivated carbon (GAC) adsorption and iron-catalyzed hydrogen peroxide oxidation. Althoughboth techno
21、logies demonstrated similar performance at laboratory scale, chemical oxidation wasabandoned in favor of adsorption. This decision was based on technical and logistic scale-upconsiderations, safety requirements, process flexibility, process control needs, and capital costs.Bench scale technology dev
22、elopment activities were pursued on GAC adsorption. A polymer-modified clay adsorbent (PCA) was also included in the bench scale experimental work since ithas recently been introduced to offshore operations for the treatment of non-produced fluidsfrom acidizing operations. The performance of PCA ads
23、orption was evaluated both as analternative to the GAC process and as a pretreatment step.Two discharge options for the treated NPF were investigated: 1) direct overboard discharge, and2) indirect overboard discharge entailing controlled blending of treated NPF with produced waterprior to final de-o
24、iling treatment by flotation. Adsorption performance was investigated on rawNPF (R-NPF), characterized by high dissolved O and on produced waterspiked NPF (PW-NPF), characterized byhigh dissolved and emulsified O Ali, 1997; Caudle, 1996): Acidizing additives, such as mutual solvents, surfactants, an
25、d corrosion inhibitors; Precipitates formed during acidizing, including colloidal ferric hydroxides; Iron (III) interactions with asphaltenes; Oil-wetted solids, including corrosion and scale compounds and formation fines; and Acidity of return non-produced fluids.Although the industry is engineerin
26、g well stimulation formulations and procedures forsatisfactory formation acidizing while reducing the impact of fluid returns on de-oiling facilities,these measures alone are not capable of eliminating operational problems (Bansal, 1993; Ali andHill, 1997; Hebert and Khatib, 1996). As part of the de
27、velopment of these integrated systemapproaches, effective point-source treatment processes, designed to selectively removecontaminants responsible for stabilizing emulsions and inducing process upsets, need to bedeveloped.Based on current industry needs, the American Petroleum Institute (API) initia
28、ted thisindependent study to identify effective technologies for the point-source treatment of non-produced fluids. The study was structured into four phases: Phase I consisted of collecting and reviewing current chemical use and procedures. Phase II targeted the laboratory simulation of produced wa
29、ter (PW), non-produced fluids(NPF), and a blend of PW and NPF (termed “combined fluids,” CF). It also included the set-up of a sand pack column simulating a sandstone formation, and the set-up of an induced gasflotation process for produced water de-oiling. Oil and grease (O 2) produced water, follo
30、wing treatment inthe flotation cell; 3) well stimulation solutions and fluids; and 4) non-produced fluids.Table 6 presents Freon-extractable O&G data for the 0.5% solutions of each wellstimulation chemical formulation in a 100 g/L salt solution (35 g/L sea salt and 65 g/Lsodium chloride). Table 6 il
31、lustrates that even at 0.5% concentration, high O&Gconcentrations (193-721 mg/L) were measured for the corrosion inhibitor, anti-sludge, andsurfactant formulations. Significantly lower O&G concentrations (1246 mg/L) weremeasured for the clay and iron stabilizer formulations.Table 7 presents Freon-ex
32、tractable O&G data for each of the four well stimulation solutionsprior to contacting the sand pack. High O&G concentrations (1166-4648 mg/L) were measuredfor each well stimulation stock solution. These high O&G concentrations primarily reflect thehigh concentrations of organic solvents and surfacta
33、nts present in well stimulation formulations.These measurements were made on raw stock solutions prior to downflow contacting of the sandpack.The stock solutions were pumped downflow through the sand pack. Each well stimulation fluidwas collected in a separate container following downflow contacting. An aliquot of each fluid,