稠油模型化合物水热裂解生成H_2S实验研究
|
摘要
针对注汽热采过程产生硫化氢(H_2S)现象,以稠油的4种模型化合物(2-甲基噻吩、苯并噻吩、二苯并噻吩及噻蒽)作为稠油水热裂解的模型化合物,通过实验探究不同类型含硫有机物的水热裂解过程及铝离子的催化作用。实验研究结果表明:(1)4种模型化合物在280℃时不会发生水热裂解反应;(2)由于S原子的密度云不同,生成H2_S速率也不相同,且其由大到小的顺序为2-甲基噻吩>苯并噻吩>二苯并噻吩>噻蒽;(3)Al 3+对模型化合物具有催化作用。最后,探讨了4种模型化合物的水热裂解途径。结果表明:H2_S主要由二次水解产生;在含氧条件下,反应过程中醛首先被氧化为羧酸而不是水热裂解生成CO。
During the thermal enhanced oil recovery(EOR)process,the existence of H2_S among the produced gase brings great trouble to petroleum exploration and development.Four model compounds of heavy oil(2-methylthiophene,BBT,DBT,and thianthrene)were carried out to study the pyrolysis process of different types of sulfur containing organic compounds and the catalysis of aluminum ions. The results showed that the pyrolysis reaction of 2-methylthiophene,benzothiophene,dibenzothiophene and thianthrene wouldn't occur under the reaction temperature of280 ℃.Due to the different electron cloud density of the S atom,the production of H2_S is in order of2-methylthiophene>benzothiophene>dibenzothiophene>thianthrene.Al 3+had a catalytic effect on the model compound.The aquathermolysis path of four kinds of model compounds was discussed.The results indicated that the secondary hydrolysis plays an important role in the process of generating H2_S by aquthermolysis.In the presence of oxygen,aldehydes were first oxidized to carboxylic acids instead of generating CO by aquathermolysis.
During the thermal enhanced oil recovery(EOR)process,the existence of H2_S among the produced gase brings great trouble to petroleum exploration and development.Four model compounds of heavy oil(2-methylthiophene,BBT,DBT,and thianthrene)were carried out to study the pyrolysis process of different types of sulfur containing organic compounds and the catalysis of aluminum ions. The results showed that the pyrolysis reaction of 2-methylthiophene,benzothiophene,dibenzothiophene and thianthrene wouldn't occur under the reaction temperature of280 ℃.Due to the different electron cloud density of the S atom,the production of H2_S is in order of2-methylthiophene>benzothiophene>dibenzothiophene>thianthrene.Al 3+had a catalytic effect on the model compound.The aquathermolysis path of four kinds of model compounds was discussed.The results indicated that the secondary hydrolysis plays an important role in the process of generating H2_S by aquthermolysis.In the presence of oxygen,aldehydes were first oxidized to carboxylic acids instead of generating CO by aquathermolysis.
引文
[1]王大为,周耐强,牟凯.稠油热采技术现状及发展趋势[J].西部探矿工程,2008,20(12):129-131.
[2]王弥康.热力采油与提高原油采收率[J].油气采收率技术,1994,1(1):6-11.
[3]刘喜林.难动用储量开发稠油开采技术[M].北京:石油工业出版社,2005:151-162.
[4]IBATULLIN T,YANG T,PETERSEN E B,et al.Simulation of hydrogen sulfide and carbon dioxide production during thermal recovery of bitumen[C]//SPE Reservoir Characterisation and Simulation Conference and Exhibition.Abu Dhabi,UAE:Society of Petroleum Engineers,2011.
[5]张水昌,帅燕华,朱光有.TSR促进原油裂解成气:模拟实验证据[J].中国科学:地球科学,2008,38(3):307-311.
[6]THIMM H F.Aquathermolysis and sources of produced gases in SAGD[C]//SPE Heavy Oil Conference-Canada.Calgary,Alberta:Society of Petroleum Engineers,2014.
[7]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.
[8]HYNE J B,GREIDANUS J W.Aquathermolysis of heavy oil[C]//Proceedings of the 2nd International Conference on Heavy Crude and Tar Sands.Caracas,Venezuela,1982:25-30.
[9]CLARK P D,HYNE J B,TYRER J D.Chemistry of organosulphur compound types occurring in heavy oil sands:1.High temperature hydrolysis and thermolysis of tetrahydrothiophene in relation to steam stimulation processes[J].Fuel,1983,62(8):959-962.
[10]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.
[11]KAPADIA P R,WANG J Y,KALLOS M S,et al.New thermalreactive reservoir engineering model predicts hydrogen sulfide generation in Steam Assisted Gravity Drainage[J].Journal of Petroleum Science and Engineering,2012,94-95:100-111.
[12]HYNE J B.Aquathermolysis:a synopsis of work on chemical reaction between water(steam)and heavy oil sands during simulated steam stimulation[M].Edmonton:Alberta Oil Sands Technology and Research Authority Library and information Service,1986.
[13]范洪富,刘永建,赵晓非,等.金属盐对辽河稠油水热裂解反应影响研究[J].燃料化学学报,2001,29(5):430-433.
[14]樊泽霞,赵福麟,王杰祥,等.超稠油供氢水热裂解改质降黏研究[J].燃料化学学报,2006,34(3):315-318.
[15]CHAO K,CHEN Y L,LI J,et al.Upgrading and visbreaking of super-heavy oil by catalytic aquathermolysis with aromatic sulfonic copper[J].Fuel Processing Technology,2012,104:174-180.
[16]MARCANO N,LARTER S R,SNOWDON L R,et al.An overview of the origin,pathways and controls of H2S productionduring thermal recovery operations of heavy oil and extra-heavy oil[C]//Geoconvention 2013;CSPG,CSEG&CWLS.2013.
[17]刘永建,刘春天,程显彪.噻吩水热裂解平衡计算及反应过程分析[J].化工学报,2005,56(1):6-10.
[18]程显彪,刘春天.四氢噻吩水热裂解反应化学平衡分析[J].石油天然气学报(江汉石油学院学报),2005,27(增刊5):715-717.
[19]段新平.磷化镍(钼)催化剂的制备、改性以及加氢精制性能的研究[D].大连:大连理工大学,2010.
[20]CLARK P D,CLARKE R A,HYNE J B,et al.Studies on the chemical reactions of heavy oils under steam stimulation conditions[J].AOSTRA Journal of Research,1990,6(1):29-39.
[21]陈传平,梅博文,贾发敬,等.生油岩产生低分子量有机酸的模拟实验研究[J].地球化学,1994,23(2):155-160.
[22]陈传平,梅博文.原油的有水热解产生低分子量有机酸的研究[J].地球化学,1997,26(1):85-91.
[2]王弥康.热力采油与提高原油采收率[J].油气采收率技术,1994,1(1):6-11.
[3]刘喜林.难动用储量开发稠油开采技术[M].北京:石油工业出版社,2005:151-162.
[4]IBATULLIN T,YANG T,PETERSEN E B,et al.Simulation of hydrogen sulfide and carbon dioxide production during thermal recovery of bitumen[C]//SPE Reservoir Characterisation and Simulation Conference and Exhibition.Abu Dhabi,UAE:Society of Petroleum Engineers,2011.
[5]张水昌,帅燕华,朱光有.TSR促进原油裂解成气:模拟实验证据[J].中国科学:地球科学,2008,38(3):307-311.
[6]THIMM H F.Aquathermolysis and sources of produced gases in SAGD[C]//SPE Heavy Oil Conference-Canada.Calgary,Alberta:Society of Petroleum Engineers,2014.
[7]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.
[8]HYNE J B,GREIDANUS J W.Aquathermolysis of heavy oil[C]//Proceedings of the 2nd International Conference on Heavy Crude and Tar Sands.Caracas,Venezuela,1982:25-30.
[9]CLARK P D,HYNE J B,TYRER J D.Chemistry of organosulphur compound types occurring in heavy oil sands:1.High temperature hydrolysis and thermolysis of tetrahydrothiophene in relation to steam stimulation processes[J].Fuel,1983,62(8):959-962.
[10]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.
[11]KAPADIA P R,WANG J Y,KALLOS M S,et al.New thermalreactive reservoir engineering model predicts hydrogen sulfide generation in Steam Assisted Gravity Drainage[J].Journal of Petroleum Science and Engineering,2012,94-95:100-111.
[12]HYNE J B.Aquathermolysis:a synopsis of work on chemical reaction between water(steam)and heavy oil sands during simulated steam stimulation[M].Edmonton:Alberta Oil Sands Technology and Research Authority Library and information Service,1986.
[13]范洪富,刘永建,赵晓非,等.金属盐对辽河稠油水热裂解反应影响研究[J].燃料化学学报,2001,29(5):430-433.
[14]樊泽霞,赵福麟,王杰祥,等.超稠油供氢水热裂解改质降黏研究[J].燃料化学学报,2006,34(3):315-318.
[15]CHAO K,CHEN Y L,LI J,et al.Upgrading and visbreaking of super-heavy oil by catalytic aquathermolysis with aromatic sulfonic copper[J].Fuel Processing Technology,2012,104:174-180.
[16]MARCANO N,LARTER S R,SNOWDON L R,et al.An overview of the origin,pathways and controls of H2S productionduring thermal recovery operations of heavy oil and extra-heavy oil[C]//Geoconvention 2013;CSPG,CSEG&CWLS.2013.
[17]刘永建,刘春天,程显彪.噻吩水热裂解平衡计算及反应过程分析[J].化工学报,2005,56(1):6-10.
[18]程显彪,刘春天.四氢噻吩水热裂解反应化学平衡分析[J].石油天然气学报(江汉石油学院学报),2005,27(增刊5):715-717.
[19]段新平.磷化镍(钼)催化剂的制备、改性以及加氢精制性能的研究[D].大连:大连理工大学,2010.
[20]CLARK P D,CLARKE R A,HYNE J B,et al.Studies on the chemical reactions of heavy oils under steam stimulation conditions[J].AOSTRA Journal of Research,1990,6(1):29-39.
[21]陈传平,梅博文,贾发敬,等.生油岩产生低分子量有机酸的模拟实验研究[J].地球化学,1994,23(2):155-160.
[22]陈传平,梅博文.原油的有水热解产生低分子量有机酸的研究[J].地球化学,1997,26(1):85-91.