HAc/CO_2体系中的缓蚀剂研究
摘要
醋酸是深井采油、采气酸化液的重要组成成分,也是油气田中伴生的低分子量有机酸。在油气田产出水中常伴有CO_2、Cl~-及水等多种腐蚀物质,这些腐蚀性物质也常与醋酸共存。本文针对醋酸、二氧化碳共存体系中的金属腐蚀,设计了硫脲基双咪唑啉、硫脲基咪唑啉以及酰胺咪唑基硫脲衍生物三种缓蚀剂分子。
本文分别以油酸、月桂酸、二乙烯三胺、二硫化碳为原料合成了硫脲基双咪唑啉;以油酸、二乙烯三胺、硫脲为原料合成了硫脲基咪唑啉;以硫脲、多乙烯多胺、有机酸为原料合成了酰胺咪唑基硫脲衍生物(酰胺咪唑硫酮),并探讨了酰胺基咪唑基硫脲衍生物的最佳合成条件。
通过动电位扫描技术对硫脲基双咪唑啉、硫脲基咪唑啉的缓蚀性能进行了评价,并采用动电位扫描技术、失重法和电化学渗氢实验探讨了酰胺咪唑基硫脲衍生物的吸附行为和缓蚀性能。研究表明硫脲基双咪唑啉在X52钢表面的吸附满足Langmuir吸附等温式,主要通过改变阳极过程起到缓蚀作用;酰胺咪唑基硫脲衍生物在较低的浓度下即对X52钢在醋酸、CO_2体系中的腐蚀和氢渗透有较好的抑制作用,是一种以控制阳极过程为主的缓蚀剂,在X52钢表面的吸附亦满足Langmuir吸附等温式。
通过动电位扫描技术、失重法,研究了酰胺咪唑基硫脲衍生物与六次甲基四胺、碘化钾、丁炔醇、磷酸三钠、磷酸酯等几种缓蚀剂的缓蚀协同效应。研究结果表明酰胺咪唑基硫脲衍生物与KI之间存在着一定的协同作用。
Acetic acid is an important component of acidizing fluids in oil and gas production industry and a lower molecular organic acid as associated products in producing fluids of gas and oil fields, which coexists mostly with CO_2, Cl~- containing in the producing fluids. So, three molecular structures as corrosion inhibitors, such as symmetrical N,N’- disubstituted thioureido imidazolines, substituted thioureido imidazolines and a new imidazolyl thioureas derivative, were designed.
Symmetrical N,N’-disubstituted thioureido imidazolines were synthesized from oleic acid, lauric acid, diethylenetriamine and carbon disulfide. Substituted thioureido imida zolines were synthesized by oleic acid,diethylenetriamine and thiourea. A new imidazolyl thioureas derivative was prepared from thiourea, tetraethylene pentamine, organic acid, and the optimum synthesis condition was investigated.
Their inhibiting behavior on X52 steel in saturated CO_2, 0.1mol/LCH3COOH and 0.5%NaCl solutions were investigated by weight loss, potentiodynamic polarization and electrochemical hydrogen permeation measurement. The results showed that symmetrical N,N’-disubstituted thioureido imidazolines’s adsorption behavior obeyed Langmuir equation, and which worked mainly by changing the anodic process of corrosion reaction; amido imidazolyl thiourea is a good inhibitor for inhibiting corrosion and hydrogen permeation even at a low concentration. It also mainly controlled the anodic process of corrosion reaction, and it’s adsorption behavior obeyed Langmuir equation too.
The inhibition synergistic effect between amino imidazolyl thiourea and some inhibitors, such as hexamethylenamine, potassium iodide, butynol, trisodium phosphate and organic phosphate, was investigated by potentiodynamic polarization and weight-loss method. The results showed that there was synergistic effect between amino imidazolyl thiourea and KI.
本文分别以油酸、月桂酸、二乙烯三胺、二硫化碳为原料合成了硫脲基双咪唑啉;以油酸、二乙烯三胺、硫脲为原料合成了硫脲基咪唑啉;以硫脲、多乙烯多胺、有机酸为原料合成了酰胺咪唑基硫脲衍生物(酰胺咪唑硫酮),并探讨了酰胺基咪唑基硫脲衍生物的最佳合成条件。
通过动电位扫描技术对硫脲基双咪唑啉、硫脲基咪唑啉的缓蚀性能进行了评价,并采用动电位扫描技术、失重法和电化学渗氢实验探讨了酰胺咪唑基硫脲衍生物的吸附行为和缓蚀性能。研究表明硫脲基双咪唑啉在X52钢表面的吸附满足Langmuir吸附等温式,主要通过改变阳极过程起到缓蚀作用;酰胺咪唑基硫脲衍生物在较低的浓度下即对X52钢在醋酸、CO_2体系中的腐蚀和氢渗透有较好的抑制作用,是一种以控制阳极过程为主的缓蚀剂,在X52钢表面的吸附亦满足Langmuir吸附等温式。
通过动电位扫描技术、失重法,研究了酰胺咪唑基硫脲衍生物与六次甲基四胺、碘化钾、丁炔醇、磷酸三钠、磷酸酯等几种缓蚀剂的缓蚀协同效应。研究结果表明酰胺咪唑基硫脲衍生物与KI之间存在着一定的协同作用。
Acetic acid is an important component of acidizing fluids in oil and gas production industry and a lower molecular organic acid as associated products in producing fluids of gas and oil fields, which coexists mostly with CO_2, Cl~- containing in the producing fluids. So, three molecular structures as corrosion inhibitors, such as symmetrical N,N’- disubstituted thioureido imidazolines, substituted thioureido imidazolines and a new imidazolyl thioureas derivative, were designed.
Symmetrical N,N’-disubstituted thioureido imidazolines were synthesized from oleic acid, lauric acid, diethylenetriamine and carbon disulfide. Substituted thioureido imida zolines were synthesized by oleic acid,diethylenetriamine and thiourea. A new imidazolyl thioureas derivative was prepared from thiourea, tetraethylene pentamine, organic acid, and the optimum synthesis condition was investigated.
Their inhibiting behavior on X52 steel in saturated CO_2, 0.1mol/LCH3COOH and 0.5%NaCl solutions were investigated by weight loss, potentiodynamic polarization and electrochemical hydrogen permeation measurement. The results showed that symmetrical N,N’-disubstituted thioureido imidazolines’s adsorption behavior obeyed Langmuir equation, and which worked mainly by changing the anodic process of corrosion reaction; amido imidazolyl thiourea is a good inhibitor for inhibiting corrosion and hydrogen permeation even at a low concentration. It also mainly controlled the anodic process of corrosion reaction, and it’s adsorption behavior obeyed Langmuir equation too.
The inhibition synergistic effect between amino imidazolyl thiourea and some inhibitors, such as hexamethylenamine, potassium iodide, butynol, trisodium phosphate and organic phosphate, was investigated by potentiodynamic polarization and weight-loss method. The results showed that there was synergistic effect between amino imidazolyl thiourea and KI.
引文
[1] J L Crolet, N Thevenot, A Dugstad. Role of Free Acetic Acid on the CO2 Corrosion of Steels[A]. in: CORROSION. Houston Texas: NACE International, 1999. paper no.24
[2] K S Georeg, S Nesic. Investigation of Carbon Dioxide Corrosion of Mild Steel in the Presence of Acetic Acid[J]. Corrosion, 2007, 63(2): 178
[3] Vanessa F, Christian C, Bruce B, et al. Effect of organic acids in CO2 corrosion[A]. in: CORROSION. Houston: NACE International, 2007. paper no.07661
[4] Singer M, Brown B, Camacho A, et al. Combined effect of CO2, H2S and acetic acid on bottom of the line corrosion[A]. in: CORROSION. Houston Texas:NACE International, 2007. paper no.07661
[5] Yannich G, Derek P. The role of acetate in CO2 corrosion of carbon steel: studies related to oilfield conditions[A]. in: CORROSION. Houston Texas: NACE International, 2003. paper no.03324
[6]张天胜.缓蚀剂[M].北京:化学工业出版社, 2002
[7]张宝宏,丛文博,杨萍.金属电化学腐蚀与防护[M].北京:化学工业出版社, 2005, 6
[8]李金桂,吴再思.防腐蚀表面工程技术[M].北京:化学工业出版社, 2002, 12
[9]张磊.化学清洗缓蚀剂的选择及影响因素的分析[J].工业技术经济, 1998(2): 120
[10] Hackerman N. Review of corrosion inhibition science and technology[J]. Material Performance, 1990, 29(2): 44~47
[11] Desai M N. Corrosion inhibitors for Cu[J]. Anti-corrosion, 1971, 18(2): 19~24
[12] Eldaker N. Effect of substituted BTA on the anod discussion of iron in H2SO4[J]. Corrosion, 1981, 37(5): 27~31
[13]郭稚弧.几种植物萃取液对碳钢腐蚀的抑制作用[J].材料保护, 1989, 30(2): 103~ 107
[14] Lorenz W J, Mansfeld F. International conference on corrosion Inhibition. Dallas: 1983, 2
[15] Dakes D. Historical review of inhibitor, mechanisms[J]. Corrosion, 1981, 248
[16] Henry L. Review of proposed mechanisms for corrosion inhibition and passivation by metallic cations[J]. Corrosion, 1980, 36(7): 339~345
[17] Lorenz W J, Mansfeld F. Determination of corrosion rates by electrochemical DC and AC methods[J]. Corrosion Science, 1981, 21(9): 647~672
[18]曹楚南.缓蚀剂研究中的电化学测量技术[J].材料保护, 1990, 23(1~2): 40~42
[19]曹楚南,张鸣镝,林海潮.铁在盐酸中的缓蚀剂的两种作用类型的研究[J].腐蚀科学与防护技术, 1992, 4(1): 1~8
[20] A S Fouda, M N Moussa, F I Taha, et al. The role of some thiosemicarbazide derivatives in the corrosion inhibition of aluminium in hydrochloric acid[J]. Corrosion Science, 1986, 26(9): 719~726
[21]郭兴蓬,俞敦义,叶康民.缓蚀剂研究中的电化学方法--某些问题与新方法[J].材料保护, 1992, 25(10): 24~27
[22] Sykes J M, Dawson J L, Williams D E. Electrochemic Noise: The Technique for the′90s?[J]. Br Corros J, 1991, 26(4): 238
[23] Monticelli C, Brunoro G. Evaluation of corrosion inhibitors by electrochemical noise analysis[J]. Electrochem. Society, 1992, 139(3): 706~711
[24]李欣,齐晶瑶.用电化学噪声测量法进行缓蚀剂的性能测试及筛选[J].工业水处理, 1996, 16(6):27~33
[25] Cottis R A. Interpretation of electrochemical noise data[J]. Corrosion, 2001, 57(3): 265
[26] Zilong T, Shizhe S. The potentiostatic-galvanostatic transient response character of a passive system with adsorption[J]. Corrosion Science, 1993, 34(10): 1607~1616
[27]唐子龙.孔蚀过程动力学及其缓蚀作用机理研究: [博士学位论文].天津:天津大学, 1996
[28]徐群杰,周国定.光电化学方法在铜缓蚀剂作用机理研究中的应用.见:第十二届全国缓蚀剂学术讨论会论文集.青岛: 2001, 129
[29]徐群杰,周国定,陆柱等.缓蚀剂对铜作用的激光扫描微区光电化学研究[J].化学学报, 2000, 58(9): 1079~1084
[30] Shah S. Surface and Interface Characterization. In: CORROSION. Houston. Texas: NACE International, 1994
[31] Olsson C A, Agarwal P, Frey M, et al, An XPS study of the adsorption of organic inhibitors on mild steel surfaces[J]. Corrosion Science, 2000, 42(7): 1197~1211
[32] Zhou S, Zheng J, Mossbauer. Spectroscopic Studies on the Oxida—tion of Iron Immersed in Hydrochloric Acid and Anti—Oxidation by Corrosion Inhibitors [J]. Corrosion, 1991, 47(3): 197~199
[33]旷亚非,夏笑虹,李国希.聚丙烯酸钠在腐蚀产物羟基氧化铁上的吸附行为.见:第十二届全国缓蚀剂学术讨论会论文集.青岛: 2001, 57
[34]黄宗卿,张胜涛,谢上芬.椭圆偏振光谱方法对电化学的研究及应用[J].电化学, 1999, 5(3): 247~252
[35] Poling G W J. Studies of protective films formed by acetylenic corrosion inhibitors [J]. Electrochem. Society, 1967, 114(12): 1209~1214
[36]田中群,任斌,佘春兴等.电化学原位拉曼光谱的应用及进展[J].电化学, 1999, 5(1): 1~13
[37]严川伟,余家康,林海潮等.激光拉曼光谱在金属腐蚀研究中的应用[J].腐蚀科学与防护技术, 1998, 10(3): 163~170
[38]李瑛,曹楚南,林海潮.扫描隧道显微镜在腐蚀电化学研究中的应用[J].腐蚀科学与防护技术, 1998, 10(5): 284~289
[39]俞春福,徐久军,黑祖昆.电化学扫描探针显微镜在腐蚀电化学研究中的应用[J].腐蚀与防护, 2002, 23(1): 1~5
[40] Streicher M A. Corrosion of stainless steel in boiling acids and its suppression by ferricsalts[J]. Corrosion, 1958, 14(2): 59~70
[41]熊登谷武纪.铜及铜合金.腐蚀抑制剂[J].防蚀技术, 1978, 27(12): 661~662
[42]黄魁元.醋酸的腐蚀特性及缓蚀剂[J].应用化工, 2001, 30(2): 1~6
[43]刘鹤霞,郑家燊.气田气井缓蚀剂研究[J].四川化工与腐蚀控制, 2003, 6(2): 24~25
[44]吕战鹏,郑家燊,刘江鸿等.硫脲衍生物对CO2饱和水溶液中碳钢缓蚀性能的研究[J].腐蚀与防护, 1999, 20(1): 18~21.
[45]蒋秀,郑玉贵.油气井缓蚀剂研究进展[J].腐蚀科学与防护技术, 2003, 15(3): 164~168
[46] J M Hallen, L S Zamudio, E Arce, et al. Surface analysis of inhibior films formed by imidazolines and amides on mild steel in an acidic environment[J]. Applied Surface Science, 2006, 252: 2139~2152
[47]王慧龙,韩秀丽,郑家燊.高级脂肪酸酰胺基烷基咪唑啉的合成及缓蚀研究[J].郑州工业大学学报, 2001, 22(3): 62~64
[48]段长强,孟庆芳等.现代化学试剂手册[M].北京:化学工业出版社, 1988, 6
[49] Marco B, Roberto B, France B, et al. Synthesis of Symmetrical N,N'-Disubstituted Thioureas and Heterocyclic Thiones from Amines and CS2 over a ZnO/Al2O3 Composite as Heterogeneous and Reusable Catalyst[J]. Journal of Organic Chemistry, 1999, 64: 1029~1032
[50]曾涵,许国强. 2-硫代四氢咪唑酮的合成及其对碳钢缓蚀性能测试[J].新疆师范大学学报, 2006, 25(2): 40~44
[51] Penieres G C,Bonifas I A,Lopez J G C, et al. Synthesis of benzimidazoles in dry medium[J]. Synthetic Communications, 2000, 30(12): 2191~2195
[52] L Jun, Y Bingqin, B Yinjuan. Microwave irradiation synthesis of 2-substituted benzimidazoles using PPA as a catalyst under solvent-free conditions[J]. Synthetic Communications, 2002, 32(24): 3703~3709
[53]李静.油管钢CO2腐蚀行为与机理研究: [北京科技大学博士论文].北京:北京科技大学, 2001
[2] K S Georeg, S Nesic. Investigation of Carbon Dioxide Corrosion of Mild Steel in the Presence of Acetic Acid[J]. Corrosion, 2007, 63(2): 178
[3] Vanessa F, Christian C, Bruce B, et al. Effect of organic acids in CO2 corrosion[A]. in: CORROSION. Houston: NACE International, 2007. paper no.07661
[4] Singer M, Brown B, Camacho A, et al. Combined effect of CO2, H2S and acetic acid on bottom of the line corrosion[A]. in: CORROSION. Houston Texas:NACE International, 2007. paper no.07661
[5] Yannich G, Derek P. The role of acetate in CO2 corrosion of carbon steel: studies related to oilfield conditions[A]. in: CORROSION. Houston Texas: NACE International, 2003. paper no.03324
[6]张天胜.缓蚀剂[M].北京:化学工业出版社, 2002
[7]张宝宏,丛文博,杨萍.金属电化学腐蚀与防护[M].北京:化学工业出版社, 2005, 6
[8]李金桂,吴再思.防腐蚀表面工程技术[M].北京:化学工业出版社, 2002, 12
[9]张磊.化学清洗缓蚀剂的选择及影响因素的分析[J].工业技术经济, 1998(2): 120
[10] Hackerman N. Review of corrosion inhibition science and technology[J]. Material Performance, 1990, 29(2): 44~47
[11] Desai M N. Corrosion inhibitors for Cu[J]. Anti-corrosion, 1971, 18(2): 19~24
[12] Eldaker N. Effect of substituted BTA on the anod discussion of iron in H2SO4[J]. Corrosion, 1981, 37(5): 27~31
[13]郭稚弧.几种植物萃取液对碳钢腐蚀的抑制作用[J].材料保护, 1989, 30(2): 103~ 107
[14] Lorenz W J, Mansfeld F. International conference on corrosion Inhibition. Dallas: 1983, 2
[15] Dakes D. Historical review of inhibitor, mechanisms[J]. Corrosion, 1981, 248
[16] Henry L. Review of proposed mechanisms for corrosion inhibition and passivation by metallic cations[J]. Corrosion, 1980, 36(7): 339~345
[17] Lorenz W J, Mansfeld F. Determination of corrosion rates by electrochemical DC and AC methods[J]. Corrosion Science, 1981, 21(9): 647~672
[18]曹楚南.缓蚀剂研究中的电化学测量技术[J].材料保护, 1990, 23(1~2): 40~42
[19]曹楚南,张鸣镝,林海潮.铁在盐酸中的缓蚀剂的两种作用类型的研究[J].腐蚀科学与防护技术, 1992, 4(1): 1~8
[20] A S Fouda, M N Moussa, F I Taha, et al. The role of some thiosemicarbazide derivatives in the corrosion inhibition of aluminium in hydrochloric acid[J]. Corrosion Science, 1986, 26(9): 719~726
[21]郭兴蓬,俞敦义,叶康民.缓蚀剂研究中的电化学方法--某些问题与新方法[J].材料保护, 1992, 25(10): 24~27
[22] Sykes J M, Dawson J L, Williams D E. Electrochemic Noise: The Technique for the′90s?[J]. Br Corros J, 1991, 26(4): 238
[23] Monticelli C, Brunoro G. Evaluation of corrosion inhibitors by electrochemical noise analysis[J]. Electrochem. Society, 1992, 139(3): 706~711
[24]李欣,齐晶瑶.用电化学噪声测量法进行缓蚀剂的性能测试及筛选[J].工业水处理, 1996, 16(6):27~33
[25] Cottis R A. Interpretation of electrochemical noise data[J]. Corrosion, 2001, 57(3): 265
[26] Zilong T, Shizhe S. The potentiostatic-galvanostatic transient response character of a passive system with adsorption[J]. Corrosion Science, 1993, 34(10): 1607~1616
[27]唐子龙.孔蚀过程动力学及其缓蚀作用机理研究: [博士学位论文].天津:天津大学, 1996
[28]徐群杰,周国定.光电化学方法在铜缓蚀剂作用机理研究中的应用.见:第十二届全国缓蚀剂学术讨论会论文集.青岛: 2001, 129
[29]徐群杰,周国定,陆柱等.缓蚀剂对铜作用的激光扫描微区光电化学研究[J].化学学报, 2000, 58(9): 1079~1084
[30] Shah S. Surface and Interface Characterization. In: CORROSION. Houston. Texas: NACE International, 1994
[31] Olsson C A, Agarwal P, Frey M, et al, An XPS study of the adsorption of organic inhibitors on mild steel surfaces[J]. Corrosion Science, 2000, 42(7): 1197~1211
[32] Zhou S, Zheng J, Mossbauer. Spectroscopic Studies on the Oxida—tion of Iron Immersed in Hydrochloric Acid and Anti—Oxidation by Corrosion Inhibitors [J]. Corrosion, 1991, 47(3): 197~199
[33]旷亚非,夏笑虹,李国希.聚丙烯酸钠在腐蚀产物羟基氧化铁上的吸附行为.见:第十二届全国缓蚀剂学术讨论会论文集.青岛: 2001, 57
[34]黄宗卿,张胜涛,谢上芬.椭圆偏振光谱方法对电化学的研究及应用[J].电化学, 1999, 5(3): 247~252
[35] Poling G W J. Studies of protective films formed by acetylenic corrosion inhibitors [J]. Electrochem. Society, 1967, 114(12): 1209~1214
[36]田中群,任斌,佘春兴等.电化学原位拉曼光谱的应用及进展[J].电化学, 1999, 5(1): 1~13
[37]严川伟,余家康,林海潮等.激光拉曼光谱在金属腐蚀研究中的应用[J].腐蚀科学与防护技术, 1998, 10(3): 163~170
[38]李瑛,曹楚南,林海潮.扫描隧道显微镜在腐蚀电化学研究中的应用[J].腐蚀科学与防护技术, 1998, 10(5): 284~289
[39]俞春福,徐久军,黑祖昆.电化学扫描探针显微镜在腐蚀电化学研究中的应用[J].腐蚀与防护, 2002, 23(1): 1~5
[40] Streicher M A. Corrosion of stainless steel in boiling acids and its suppression by ferricsalts[J]. Corrosion, 1958, 14(2): 59~70
[41]熊登谷武纪.铜及铜合金.腐蚀抑制剂[J].防蚀技术, 1978, 27(12): 661~662
[42]黄魁元.醋酸的腐蚀特性及缓蚀剂[J].应用化工, 2001, 30(2): 1~6
[43]刘鹤霞,郑家燊.气田气井缓蚀剂研究[J].四川化工与腐蚀控制, 2003, 6(2): 24~25
[44]吕战鹏,郑家燊,刘江鸿等.硫脲衍生物对CO2饱和水溶液中碳钢缓蚀性能的研究[J].腐蚀与防护, 1999, 20(1): 18~21.
[45]蒋秀,郑玉贵.油气井缓蚀剂研究进展[J].腐蚀科学与防护技术, 2003, 15(3): 164~168
[46] J M Hallen, L S Zamudio, E Arce, et al. Surface analysis of inhibior films formed by imidazolines and amides on mild steel in an acidic environment[J]. Applied Surface Science, 2006, 252: 2139~2152
[47]王慧龙,韩秀丽,郑家燊.高级脂肪酸酰胺基烷基咪唑啉的合成及缓蚀研究[J].郑州工业大学学报, 2001, 22(3): 62~64
[48]段长强,孟庆芳等.现代化学试剂手册[M].北京:化学工业出版社, 1988, 6
[49] Marco B, Roberto B, France B, et al. Synthesis of Symmetrical N,N'-Disubstituted Thioureas and Heterocyclic Thiones from Amines and CS2 over a ZnO/Al2O3 Composite as Heterogeneous and Reusable Catalyst[J]. Journal of Organic Chemistry, 1999, 64: 1029~1032
[50]曾涵,许国强. 2-硫代四氢咪唑酮的合成及其对碳钢缓蚀性能测试[J].新疆师范大学学报, 2006, 25(2): 40~44
[51] Penieres G C,Bonifas I A,Lopez J G C, et al. Synthesis of benzimidazoles in dry medium[J]. Synthetic Communications, 2000, 30(12): 2191~2195
[52] L Jun, Y Bingqin, B Yinjuan. Microwave irradiation synthesis of 2-substituted benzimidazoles using PPA as a catalyst under solvent-free conditions[J]. Synthetic Communications, 2002, 32(24): 3703~3709
[53]李静.油管钢CO2腐蚀行为与机理研究: [北京科技大学博士论文].北京:北京科技大学, 2001