油田水管线结垢机理及阻垢缓蚀新技术研究
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摘要
油田采油进入高含水开发后期,长期回注开发过程带来大量的含油污水使注水管网系统严重的腐蚀结垢,为此对绿色环保阻垢缓蚀剂聚天冬氨酸进行系统地研究具有重要意义。研究油田注水管线的结垢过程和结垢机理以及各种影响结垢的因素,可以有效地预防结垢。通过分析在三元复合驱过程中油田注入水和产出水在管线中的结垢特点,合成适用于大庆油田注水管线的聚天冬氨酸产品,以降低管线的结垢和腐蚀程度。研究合成聚天冬氨酸的路线和最佳合成条件、产品的阻垢缓蚀效果;同时为降低药品投放成本,对聚天冬氨酸与其他阻垢剂进行了复配阻垢实验,并且聚天冬氨酸与其他缓蚀剂进行了复配缓蚀实验,收效很好。
本文介绍以马来酸酐与铵盐或胺类物质为原料,采用热聚合法生成(聚)琥珀酰亚胺后水解生成聚天冬氨酸的方法,其产物热稳定性优异、聚合效果好,工艺流程简单。然后通过油田水的阻垢实验来筛选聚天冬氨酸的最佳合成条件、最佳投放量,由此来选择效果最佳的聚天冬氨酸样品。在此结论基础上,研究了不同分子量的聚天冬氨酸的缓蚀效果,聚天冬氨酸与其他盐类的复配作用,以及不同水温、盐度对缓蚀率的影响,验证了具有实际的应用价值的环保型的聚天冬氨酸-钨酸盐复合阻垢缓蚀水处理剂配方,其阻垢缓蚀性能优良。同时为提高投放药剂的利用率,对药剂缓释方法进行了调研,有利于进一步指导药剂的使用。
While the oil extraction turns into the last period of high water containing in oilfield, large numbers of sewage containing oil was recycled to infuse which mades scale and corrosion seriously in watering pipeline system, so it means great significance to systemiclyresearch the polyasparticacid, which is a new kind of environmental-friend antiscale. Research the process and mechanism of scale and the influencing factor in oilfield watering pipeline is available to prevend scale. In order to synthesize the polyasparticacid production which is suit for Daqing oilfield watering pipeline and this production would reduce the degree of scale and corrosion, the character of water scale in pipeline was analyzed in the process of alkaline-surfactant-polymer. The synthesize route, best synthesize condition and antiscale effect of polyasparticacid were researched. And in order to reduce the cost of added materia agent, the compounding scale inhibition experiment of polyasparticacid and other kinds of antiscale were carried through, at the same time, the compounding corrosion inhibition and scale inhibition experiment of polyasparticacid and other kinds of antiscale were also carried out, the effect is very good.
Maleic anhydride was used as raw material, and was polymerized to create PSI, then PSI was hydrolyzing to creat polyasparticacid. The method was introduced in this text, caloric stability of the production and the effect of aggregation are excellent, and the technological folwsheet is simple. The best synthesize condition and quantity of polyasparticacid was filtrated from oilfiled water experimentation, then the best polyasparticacid production was choosed. The corrosion inhibition effect of polyasparticacid with different molecular weight, compounding effect of polyasparticacid and other salts,and the rate of corrosion inhibition in the water with different temperature and salinity were researched. The compound environmental-friend formulation of polyasparticacid tungstate was testified to be practical value, and its capability of scale inhibition and corrosion inhibition is excellent. At the same time, the method of medicament slowly released was researched to enhance utilizing rate of used medicament, and the method will guide medicament utilizing.
本文介绍以马来酸酐与铵盐或胺类物质为原料,采用热聚合法生成(聚)琥珀酰亚胺后水解生成聚天冬氨酸的方法,其产物热稳定性优异、聚合效果好,工艺流程简单。然后通过油田水的阻垢实验来筛选聚天冬氨酸的最佳合成条件、最佳投放量,由此来选择效果最佳的聚天冬氨酸样品。在此结论基础上,研究了不同分子量的聚天冬氨酸的缓蚀效果,聚天冬氨酸与其他盐类的复配作用,以及不同水温、盐度对缓蚀率的影响,验证了具有实际的应用价值的环保型的聚天冬氨酸-钨酸盐复合阻垢缓蚀水处理剂配方,其阻垢缓蚀性能优良。同时为提高投放药剂的利用率,对药剂缓释方法进行了调研,有利于进一步指导药剂的使用。
While the oil extraction turns into the last period of high water containing in oilfield, large numbers of sewage containing oil was recycled to infuse which mades scale and corrosion seriously in watering pipeline system, so it means great significance to systemiclyresearch the polyasparticacid, which is a new kind of environmental-friend antiscale. Research the process and mechanism of scale and the influencing factor in oilfield watering pipeline is available to prevend scale. In order to synthesize the polyasparticacid production which is suit for Daqing oilfield watering pipeline and this production would reduce the degree of scale and corrosion, the character of water scale in pipeline was analyzed in the process of alkaline-surfactant-polymer. The synthesize route, best synthesize condition and antiscale effect of polyasparticacid were researched. And in order to reduce the cost of added materia agent, the compounding scale inhibition experiment of polyasparticacid and other kinds of antiscale were carried through, at the same time, the compounding corrosion inhibition and scale inhibition experiment of polyasparticacid and other kinds of antiscale were also carried out, the effect is very good.
Maleic anhydride was used as raw material, and was polymerized to create PSI, then PSI was hydrolyzing to creat polyasparticacid. The method was introduced in this text, caloric stability of the production and the effect of aggregation are excellent, and the technological folwsheet is simple. The best synthesize condition and quantity of polyasparticacid was filtrated from oilfiled water experimentation, then the best polyasparticacid production was choosed. The corrosion inhibition effect of polyasparticacid with different molecular weight, compounding effect of polyasparticacid and other salts,and the rate of corrosion inhibition in the water with different temperature and salinity were researched. The compound environmental-friend formulation of polyasparticacid tungstate was testified to be practical value, and its capability of scale inhibition and corrosion inhibition is excellent. At the same time, the method of medicament slowly released was researched to enhance utilizing rate of used medicament, and the method will guide medicament utilizing.
引文
[1] Low K C, Wheeler A P,Koskan L P. Green chemistry applied to corrosion and scale inhibiors[J].Adv.Chem.Ser, 1996,248:99~111
[2] Robert J Ross, Kim C Low, James E Shannon. Green chemistry applied to corrosion and scale inhibiors[J].Material Performance, 1997,(4):52~57
[3] Koskan Larry P. Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor [P]. 1991, US: 5116513
[4]杨士林,黄君礼,张玉玲等.聚天冬氨酸制造工艺研究进展[J].环境污染治理技术与设备,2002,3(9):38~41
[5] Haroda K, Matsuyama M, Kokufuta E.[J].Polym Bull,1978,1(3):177~180
[6] Low K C, Wheeler A P, Koskan L P.[J]. Adv Chem Ser, 1996,248:99
[7]王朝阳,任碧野,童真.可生物降解材料聚天冬氨酸的研究进展[J].高分子通报,2002,5:29~34
[8] Haroda K.. Org Chem[P], 1959,24(11):1662~1666
[9] Kovacs, et al.. J Org Chem[P], 1961,25:1084
[10]杨士林,黄君礼,陶虎春等.聚天冬氨酸液相催化合成及其阻垢性能研究[J].哈尔滨工业大学学报,2004,36(2):234
[11] Boehmake Guenther.[P]. 1989, US: 4839461,
[12] Barney Vallno, Daniel A, Batzel Skokie. [P]. 1997, US: 5681920
[13]韶晖,冷一欣.以马来酸为原料合成的聚天冬氨酸的阻垢性能[J].江苏石油化工学院学报,2001,13(1):18~20
[14]杨红健,赵新强,王延吉.以马来酐为原料合成聚琥珀酰亚胺的反应机理研究[J].精细石油化工,2004,5:41~43
[15]董雪玲,熊蓉春.聚天冬氨酸的合成工艺研究[J].石油化工,2004, 33 (12):1173~1175
[16]韶晖,冷一欣,蒋俊杰.新型绿色钻井液降粘剂-聚天冬氨酸[J].江苏石油化工学院学报,2002, 14(1):4~6
[17] Kinncrsley Alan M, Koskan Larry P. Method for more efficient uprake of plant growth nutrients [P]. 1997,US:5593947
[18] Kroner Matthias, Schornick Gunnar, Baur Richard, Kud Alexander, Schwendmann Volker. Use of polyaspartic acid in detergents and cleaners[P]. 1998, US:5770553
[19] Yueting Chou. Superabsorbing fibers and films and processes for preparing same[P]. 2002, US: 6465536
[20] K.Prompruk, T. Govender, S. Zhang, C.D. Xiong,S. Stolnik. Synthesis of a novel PEG-block-poly (aspartic acid-stat-pHenylalanine) copolymer shows potential for formation of a micellar drug carrier[J]. International Journal of pHarmaceutics ,2005, 297(2):242~253
[21]冷一欣,韶晖,欧阳平凯.绿色化学品聚天冬氨酸的合成与应用进展[J].江苏工业学院学报,2004, 16(3):46~49
[22] J. Bolze, D. Pontoni, M. Ballauff, T. Narayanan , H. C?lfen. Time-resolved SAXS study of the effect of a double hydropHilic block-copolymer on the formation of CaCO3 from a supersaturated salt solution [J]. Journal of Colloid and Interface Science ,2004, 277 (1):84~94
[23]王吉龙,王亭,郦和生等.含膦酰基聚天冬氨酸的阻垢性能研究[J].工业水处理,2004,24 (9):22~24
[24]朱义吾,赵作糍.油田开发中的结垢机理及其防治技术[M].陕西科学技术出版社,1995: 242~246
[25]李学文.吉林油田英台注水系统结垢与腐蚀防治对策[M].石油化工腐蚀与防护.2005,22(2): 34~36
[26]赵长久,李新峰,周淑华.大庆油区三元复合驱矿场结垢状况分析.油气地质与采收率,2006,13(4):93~95
[27] NAJIBI SH, STEINHAGENHM, JAMIALAHMADIM. Calcium sulpHate scale formation during sub-cooled flow boiling [J]. Chem EngSci, 1997, 52: 1265~1284.
[28] HASSON D, AVRIEL M, RESNICK W, et al.Mechanism of calciumcarbonate scale deposition on heat transfer surfaces[J]. Ind Eng ChemFund. 1968, 7: 59~65.
[29] ANDRITSOS N. Calcium carbonate deposit formation under isothermal conditions[J]. The Canadian journal of chemical engineering. 1996,74:911~919.
[30]邢晓凯,荆冬锋.CaCO3结垢过程控制机理分析[J].热能动力工程,2007, 22(3):336~339
[31]王鑫,张玉奎,朱平生等.榆树林油田注水井结垢及机理研究[J].油田化学,1997,14(2):139~142
[32]杨士林,黄君礼,陶虎春等.影响聚天冬氨酸相对分子质量的因素分析[J].哈尔滨工业大学学报,2004,36(2):234~237
[33]王永丽,黄少斌,胡和平.聚天冬氨酸合成及其阻垢性能[J].工业用水与废水,2004,35(5):74~76
[34]赵子刚,徐启,史连杰等.高温高压下碳酸钙的溶解度及朝阳沟注水油田低渗透储层结垢问题[J].油田化学,2003,20(1):4~6
[35]徐耀军,杨文忠,唐永明等.聚天冬氨酸的阻垢缓蚀性能[J].南京工业大学学报,2002, 24 (1):87~89
[36]王正文.中国钨的应用与消费[J].中国钨业,2000,13 (2):10~12
[37]陈旭俊.不锈钢局部腐蚀缓蚀剂及其作用机理的研究[J].化工机械,1986.13(1):50~60
[38] Batroff H.P.,Tosmann K.H. Inhibition of pitting corrosion by heteropoly acids Ann.Univ.Ferrara. Sez.S Suppl. 1980, 7:1103~1110
[39] Kurita Water Industries Ltd. Sanyo Chemical Industries Ltd. Corrosion inhibitors for metals in water. 1P 58,171,577 1983 Oct Spp
[40]郭良生,黄霓裳.自来水中碳钢缓蚀剂研究的进展[J].腐蚀与防腐,1999,20( 8 ): 337~338
[41] P.R.P.Rodrigues. Benzotrizole as corrosion inhibitors for type 304 stainless steel in water ethanol media containing H2SO4[J]. Br. Corros. 1998, 33(3):258~261
[42] L Niu C.N.; Cao H.C.; G.L.Song. Inhibitive effect of Benzotrizole on the stress corrosion cracking of 18Cr-9Ni-Ti stainless steel in acidre chloriodl solution[J]. Corrosion Sci 1998, 40(7):1109
[43]文明通.水系统中锌离子稳定性试验研究[J].工业水处理,1998.5: 813~817
[44] Nakato T, Oshitake M Y, Matsubara K. Relationships between structure and properties of poly(aspartic acid)s[J]. Macromolecules, 1998, 31(7):2107~2213
[45] Machael Schwamborn.[J]. Polym Degard Stab, 1998, 59:39~45
[46]熊蓉春,董雪玲,魏刚.绿色生物高分子聚天冬氨酸的合成及其阻垢性能研究[J].工业水处理,2001,21(1):17~20
[47]祝志峰,卓仁禧.淀粉囊化农药控释缓释技术[J].高分子通报,2003,2:8~14
[2] Robert J Ross, Kim C Low, James E Shannon. Green chemistry applied to corrosion and scale inhibiors[J].Material Performance, 1997,(4):52~57
[3] Koskan Larry P. Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor [P]. 1991, US: 5116513
[4]杨士林,黄君礼,张玉玲等.聚天冬氨酸制造工艺研究进展[J].环境污染治理技术与设备,2002,3(9):38~41
[5] Haroda K, Matsuyama M, Kokufuta E.[J].Polym Bull,1978,1(3):177~180
[6] Low K C, Wheeler A P, Koskan L P.[J]. Adv Chem Ser, 1996,248:99
[7]王朝阳,任碧野,童真.可生物降解材料聚天冬氨酸的研究进展[J].高分子通报,2002,5:29~34
[8] Haroda K.. Org Chem[P], 1959,24(11):1662~1666
[9] Kovacs, et al.. J Org Chem[P], 1961,25:1084
[10]杨士林,黄君礼,陶虎春等.聚天冬氨酸液相催化合成及其阻垢性能研究[J].哈尔滨工业大学学报,2004,36(2):234
[11] Boehmake Guenther.[P]. 1989, US: 4839461,
[12] Barney Vallno, Daniel A, Batzel Skokie. [P]. 1997, US: 5681920
[13]韶晖,冷一欣.以马来酸为原料合成的聚天冬氨酸的阻垢性能[J].江苏石油化工学院学报,2001,13(1):18~20
[14]杨红健,赵新强,王延吉.以马来酐为原料合成聚琥珀酰亚胺的反应机理研究[J].精细石油化工,2004,5:41~43
[15]董雪玲,熊蓉春.聚天冬氨酸的合成工艺研究[J].石油化工,2004, 33 (12):1173~1175
[16]韶晖,冷一欣,蒋俊杰.新型绿色钻井液降粘剂-聚天冬氨酸[J].江苏石油化工学院学报,2002, 14(1):4~6
[17] Kinncrsley Alan M, Koskan Larry P. Method for more efficient uprake of plant growth nutrients [P]. 1997,US:5593947
[18] Kroner Matthias, Schornick Gunnar, Baur Richard, Kud Alexander, Schwendmann Volker. Use of polyaspartic acid in detergents and cleaners[P]. 1998, US:5770553
[19] Yueting Chou. Superabsorbing fibers and films and processes for preparing same[P]. 2002, US: 6465536
[20] K.Prompruk, T. Govender, S. Zhang, C.D. Xiong,S. Stolnik. Synthesis of a novel PEG-block-poly (aspartic acid-stat-pHenylalanine) copolymer shows potential for formation of a micellar drug carrier[J]. International Journal of pHarmaceutics ,2005, 297(2):242~253
[21]冷一欣,韶晖,欧阳平凯.绿色化学品聚天冬氨酸的合成与应用进展[J].江苏工业学院学报,2004, 16(3):46~49
[22] J. Bolze, D. Pontoni, M. Ballauff, T. Narayanan , H. C?lfen. Time-resolved SAXS study of the effect of a double hydropHilic block-copolymer on the formation of CaCO3 from a supersaturated salt solution [J]. Journal of Colloid and Interface Science ,2004, 277 (1):84~94
[23]王吉龙,王亭,郦和生等.含膦酰基聚天冬氨酸的阻垢性能研究[J].工业水处理,2004,24 (9):22~24
[24]朱义吾,赵作糍.油田开发中的结垢机理及其防治技术[M].陕西科学技术出版社,1995: 242~246
[25]李学文.吉林油田英台注水系统结垢与腐蚀防治对策[M].石油化工腐蚀与防护.2005,22(2): 34~36
[26]赵长久,李新峰,周淑华.大庆油区三元复合驱矿场结垢状况分析.油气地质与采收率,2006,13(4):93~95
[27] NAJIBI SH, STEINHAGENHM, JAMIALAHMADIM. Calcium sulpHate scale formation during sub-cooled flow boiling [J]. Chem EngSci, 1997, 52: 1265~1284.
[28] HASSON D, AVRIEL M, RESNICK W, et al.Mechanism of calciumcarbonate scale deposition on heat transfer surfaces[J]. Ind Eng ChemFund. 1968, 7: 59~65.
[29] ANDRITSOS N. Calcium carbonate deposit formation under isothermal conditions[J]. The Canadian journal of chemical engineering. 1996,74:911~919.
[30]邢晓凯,荆冬锋.CaCO3结垢过程控制机理分析[J].热能动力工程,2007, 22(3):336~339
[31]王鑫,张玉奎,朱平生等.榆树林油田注水井结垢及机理研究[J].油田化学,1997,14(2):139~142
[32]杨士林,黄君礼,陶虎春等.影响聚天冬氨酸相对分子质量的因素分析[J].哈尔滨工业大学学报,2004,36(2):234~237
[33]王永丽,黄少斌,胡和平.聚天冬氨酸合成及其阻垢性能[J].工业用水与废水,2004,35(5):74~76
[34]赵子刚,徐启,史连杰等.高温高压下碳酸钙的溶解度及朝阳沟注水油田低渗透储层结垢问题[J].油田化学,2003,20(1):4~6
[35]徐耀军,杨文忠,唐永明等.聚天冬氨酸的阻垢缓蚀性能[J].南京工业大学学报,2002, 24 (1):87~89
[36]王正文.中国钨的应用与消费[J].中国钨业,2000,13 (2):10~12
[37]陈旭俊.不锈钢局部腐蚀缓蚀剂及其作用机理的研究[J].化工机械,1986.13(1):50~60
[38] Batroff H.P.,Tosmann K.H. Inhibition of pitting corrosion by heteropoly acids Ann.Univ.Ferrara. Sez.S Suppl. 1980, 7:1103~1110
[39] Kurita Water Industries Ltd. Sanyo Chemical Industries Ltd. Corrosion inhibitors for metals in water. 1P 58,171,577 1983 Oct Spp
[40]郭良生,黄霓裳.自来水中碳钢缓蚀剂研究的进展[J].腐蚀与防腐,1999,20( 8 ): 337~338
[41] P.R.P.Rodrigues. Benzotrizole as corrosion inhibitors for type 304 stainless steel in water ethanol media containing H2SO4[J]. Br. Corros. 1998, 33(3):258~261
[42] L Niu C.N.; Cao H.C.; G.L.Song. Inhibitive effect of Benzotrizole on the stress corrosion cracking of 18Cr-9Ni-Ti stainless steel in acidre chloriodl solution[J]. Corrosion Sci 1998, 40(7):1109
[43]文明通.水系统中锌离子稳定性试验研究[J].工业水处理,1998.5: 813~817
[44] Nakato T, Oshitake M Y, Matsubara K. Relationships between structure and properties of poly(aspartic acid)s[J]. Macromolecules, 1998, 31(7):2107~2213
[45] Machael Schwamborn.[J]. Polym Degard Stab, 1998, 59:39~45
[46]熊蓉春,董雪玲,魏刚.绿色生物高分子聚天冬氨酸的合成及其阻垢性能研究[J].工业水处理,2001,21(1):17~20
[47]祝志峰,卓仁禧.淀粉囊化农药控释缓释技术[J].高分子通报,2003,2:8~14