噻吩水热裂解反应机理研究
|
摘要
针对注蒸汽开采稠油过程中出现的H_2S现象,以稠油中含硫化合物噻吩为研究对象,在室内耐高温高压反应釜中开展了热裂解和水热裂解实验。通过检测反应后的气相产物和液相产物组成,探讨了噻吩热裂解和水热裂解反应的反应路径、断键机理。结果表明:噻吩水热裂解的主要烃类产物是甲烷和丁烷;噻吩水热裂解的液相中除了大量未反应的噻吩,还包括极少量的烷基噻吩、噻吩基噻吩等噻吩衍生物。质子化作用、一次水解以及二次水解在噻吩水热裂解生成H_2S的过程中具有重要作用,C-S键断裂是噻吩水热裂解反应和热裂解反应的重要步骤。
In this paper,aiming at the phenomenon of hydrogen sulfide(H_2S) formation in heavy oil recovery by steam injection,thiophene was selected as the model compound,then the experiments of pyrolysis and aquathermolysis were carried out in the reaction kettle with high temperature and high pressure in lab.Based on testing the content of gas products and liquid products,the reaction paths and broken bond mechanism of pyrolysis and aquathermolysis of thiophene were discussed.The results show that the main hydrocarbon products are methane and butane during the aquathermolysis of thiophene;besides a large number of unreacted thiophene,liquid products include a little of alkylthiophene,thienyl-thiophene and some derivatives.The protonation,primary hydrolysis and secondary hydrolysis are very important in the formation of H_2S.The cleavage of the C-S bond is an important step in the aquathermolysis and pyrolysis reaction of thiophene.
In this paper,aiming at the phenomenon of hydrogen sulfide(H_2S) formation in heavy oil recovery by steam injection,thiophene was selected as the model compound,then the experiments of pyrolysis and aquathermolysis were carried out in the reaction kettle with high temperature and high pressure in lab.Based on testing the content of gas products and liquid products,the reaction paths and broken bond mechanism of pyrolysis and aquathermolysis of thiophene were discussed.The results show that the main hydrocarbon products are methane and butane during the aquathermolysis of thiophene;besides a large number of unreacted thiophene,liquid products include a little of alkylthiophene,thienyl-thiophene and some derivatives.The protonation,primary hydrolysis and secondary hydrolysis are very important in the formation of H_2S.The cleavage of the C-S bond is an important step in the aquathermolysis and pyrolysis reaction of thiophene.
引文
[1] 刘春天, 刘永建, 程显彪. 稠油水热裂解反应中有机硫化合物的转化研究[J]. 石油与天然气化工, 2004, 33(6): 424-426.
[2] 戴金星, 胡见义, 贾承造, 等. 科学安全勘探开发高硫化氢天然气田的建议[J]. 石油勘探与开发, 2004, 31(2): 1-4.
[3] 张星, 李兆敏, 徐林静, 等. 含硫化氢油气井完井工艺技术现状与发展趋势[J]. 特种油气藏, 2010, 17(1): 12-14.
[4] 刘伟, 蒲晓林, 白小东, 等. 油田硫化氢腐蚀机理及防护的研究现状及进展[J]. 石油钻探技术, 2008, 36(1): 83-86.
[5] 马强. 稠油热采油田硫化氢生成机理研究[J]. 吐哈油气, 2012, 17(3): 274-278.
[6] 吴拓, 杨俊印, 林仲, 等. 稠油注蒸汽开发区块H2S成因研究[J]. 特种油气藏, 2008, 15(3): 80-83.
[7] LILLIE W H E, SPRINGER F P. Status of the steam drive pilot in the Georgsdorf field, federal republic of Germany[J]. Journal of Petroleum Technology, 1981, 33(1): 173-180.
[8] 于波. 辽河稠油催化降黏研究[D]. 青岛: 中国石油大学(华东), 2007.
[9] BRICKER J C, NAGEL C C, BHATTACHARYYA A A, et al. Hydride donating properties of (HRu3(CO)11)- in the presence of carbon monoxide; Chemistry of ruthenium carbonyl anions relevant to the catalysis of the water gas shift reaction[J]. ChemInform, 1985, 16(21).
[10] HENDERSON J H, WEBER L. Physical upgrading of heavy crude oils by the application of heat[J]. Journal of Canadian Petroleum Technology, 1965, 4(4): 206-212.
[11] LILLIE W H E, SPRINGER F P. Status of the steam drive pilot in the Georgsdorf field, federal republic of Germany[J]. Journal of Petroleum Technology, 1981, 33(1): 173-180.
[12] 吕慧. 孤岛油田热采油井硫化氢生成规律研究[D]. 青岛: 中国石油大学(华东), 2014.
[13] 朱根权, 夏道宏, 阙国和. 催化裂化过程中含硫化合物转化规律的研究[J]. 燃料化学学报, 2000, 28(6): 522-526.
[14] 朱根权, 夏道宏, 阙国和. 含硫化合物热解规律的研究[J]. 燃料化学学报, 2000, 28(6): 518-521.
[15] CORMA A, MARTINEZ C, KETLEY G, et al. On the mechanism of sulfur removal during catalytic cracking[J]. Applied Catalysis A: General, 2001, 208(1-2): 135-152.
[16] 郑柯文, 高金森, 徐春明. 噻吩催化裂化脱硫机理的量子化学分析[J]. 化工学报, 2004, 55(1): 87-90.
[17] SHAN H H, LI C Y, YANG C H, et al. Mechanistic studies on thiophene species cracking over USY zeolite[J]. Catalysis Today, 2002, 77(1-2): 117-126.
[18] 范洪富, 刘永建, 赵晓非. 稠油在水蒸汽作用下组成变化研究[J]. 燃料化学学报, 2001, 29(3): 269-272.
[19] CLARK P D, HYNE J B, TYRER J D. Some chemistry of organosulphur compound types occurring in heavy oil sands: 2. Influence of pH on the high temperature hydrolysis of tetrahydrothiophene and thiophene[J]. Fuel, 1984, 63(1): 125-128.
[20] CLARK P D, DOWLING N I, LESAGE K L, et al. Chemistry of organosulphur compound types occurring in heavy oil sands: 5. Reaction of thiophene and tetrahydrothiophene with aqueous Group VIIIB metal species at high temperature[J]. Fuel, 1987, 66(12): 1699-1702.
[2] 戴金星, 胡见义, 贾承造, 等. 科学安全勘探开发高硫化氢天然气田的建议[J]. 石油勘探与开发, 2004, 31(2): 1-4.
[3] 张星, 李兆敏, 徐林静, 等. 含硫化氢油气井完井工艺技术现状与发展趋势[J]. 特种油气藏, 2010, 17(1): 12-14.
[4] 刘伟, 蒲晓林, 白小东, 等. 油田硫化氢腐蚀机理及防护的研究现状及进展[J]. 石油钻探技术, 2008, 36(1): 83-86.
[5] 马强. 稠油热采油田硫化氢生成机理研究[J]. 吐哈油气, 2012, 17(3): 274-278.
[6] 吴拓, 杨俊印, 林仲, 等. 稠油注蒸汽开发区块H2S成因研究[J]. 特种油气藏, 2008, 15(3): 80-83.
[7] LILLIE W H E, SPRINGER F P. Status of the steam drive pilot in the Georgsdorf field, federal republic of Germany[J]. Journal of Petroleum Technology, 1981, 33(1): 173-180.
[8] 于波. 辽河稠油催化降黏研究[D]. 青岛: 中国石油大学(华东), 2007.
[9] BRICKER J C, NAGEL C C, BHATTACHARYYA A A, et al. Hydride donating properties of (HRu3(CO)11)- in the presence of carbon monoxide; Chemistry of ruthenium carbonyl anions relevant to the catalysis of the water gas shift reaction[J]. ChemInform, 1985, 16(21).
[10] HENDERSON J H, WEBER L. Physical upgrading of heavy crude oils by the application of heat[J]. Journal of Canadian Petroleum Technology, 1965, 4(4): 206-212.
[11] LILLIE W H E, SPRINGER F P. Status of the steam drive pilot in the Georgsdorf field, federal republic of Germany[J]. Journal of Petroleum Technology, 1981, 33(1): 173-180.
[12] 吕慧. 孤岛油田热采油井硫化氢生成规律研究[D]. 青岛: 中国石油大学(华东), 2014.
[13] 朱根权, 夏道宏, 阙国和. 催化裂化过程中含硫化合物转化规律的研究[J]. 燃料化学学报, 2000, 28(6): 522-526.
[14] 朱根权, 夏道宏, 阙国和. 含硫化合物热解规律的研究[J]. 燃料化学学报, 2000, 28(6): 518-521.
[15] CORMA A, MARTINEZ C, KETLEY G, et al. On the mechanism of sulfur removal during catalytic cracking[J]. Applied Catalysis A: General, 2001, 208(1-2): 135-152.
[16] 郑柯文, 高金森, 徐春明. 噻吩催化裂化脱硫机理的量子化学分析[J]. 化工学报, 2004, 55(1): 87-90.
[17] SHAN H H, LI C Y, YANG C H, et al. Mechanistic studies on thiophene species cracking over USY zeolite[J]. Catalysis Today, 2002, 77(1-2): 117-126.
[18] 范洪富, 刘永建, 赵晓非. 稠油在水蒸汽作用下组成变化研究[J]. 燃料化学学报, 2001, 29(3): 269-272.
[19] CLARK P D, HYNE J B, TYRER J D. Some chemistry of organosulphur compound types occurring in heavy oil sands: 2. Influence of pH on the high temperature hydrolysis of tetrahydrothiophene and thiophene[J]. Fuel, 1984, 63(1): 125-128.
[20] CLARK P D, DOWLING N I, LESAGE K L, et al. Chemistry of organosulphur compound types occurring in heavy oil sands: 5. Reaction of thiophene and tetrahydrothiophene with aqueous Group VIIIB metal species at high temperature[J]. Fuel, 1987, 66(12): 1699-1702.