An experiment on the influences of non-sulfur-bearing metal salt on hydrogen sulfide formation by aquathermolysis reaction of heavy oils

doi:10.7623/syxb201602010

Acta Petrolei Sinica ›› 2016, Vol. 37 ›› Issue (2): 237-241.DOI: 10.7623/syxb201602010

• Oil Field Development • Previous Articles Next Articles

An experiment on the influences of non-sulfur-bearing metal salt on hydrogen sulfide formation by aquathermolysis reaction of heavy oils

Lin Riyi¹, Luo Jianjun¹, Wang Xinwei¹, Xie Fengjia¹, Song Duopei², Gai Zheng³, Tian Xin⁴

1. College of Architecture & Storage Engineering, China University of Petroleum, Shandong Qingdao 266580, China;
2. Zhundong Oil Production Plant, PetroChina Xinjiang Oilfield Company, Xinjiang Fukang 831511, China;
3. Beijing Branch, CNPC Engineering Company Limited, Beijing 100085, China;
4. Jinma Oilfield Company, PetroChina Liaohe Oilfield Company, Liaoning Panjin 124000, China

Received:2015-09-23 Revised:2016-01-12 Online:2016-02-25 Published:2016-03-11

非含硫金属盐对稠油水热裂解生成硫化氢影响实验

林日亿¹, 罗建军¹, 王新伟¹, 谢逢佳¹, 宋多培², 盖争³, 田鑫⁴

1. 中国石油大学储运与建筑工程学院山东青岛 266580;
2. 中国石油新疆油田公司准东采油厂新疆阜康 831511;
3. 中国石油集团工程设计有限责任公司北京分公司北京 100085;
4. 中国石油辽河油田公司金马油田开发公司辽宁盘锦 124000

通讯作者: 林日亿,男,1973年4月生,1996年获石油大学(华东)热能工程专业学士学位,2007年获中国石油大学(华东)油气田开发工程专业博士学位,现为中国石油大学(华东)储运与建筑工程学院副教授、硕士生导师,主要从事热力采油和热能利用方面的教学和科研工作。Email:linry@upc.edu.cn
作者简介:林日亿,男,1973年4月生,1996年获石油大学(华东)热能工程专业学士学位,2007年获中国石油大学(华东)油气田开发工程专业博士学位,现为中国石油大学(华东)储运与建筑工程学院副教授、硕士生导师,主要从事热力采油和热能利用方面的教学和科研工作。Email:linry@upc.edu.cn
基金资助:
国家重大科技专项(2011ZX05017-004-HZ05)和中央高校基本科研业务费专项资金项目(15CX05002A)资助。

Abstract

Abstract:

In the exploitation of high-sulfur heavy oil using steam injection method, aquathermolysis and thermochemical sulfate reduction occur among heavy oil, steam and rock matrix, thus forming the reaction product H₂S. To avoid H₂S formation by thermochemical sulfate reduction, the catalytic effect of metallic ions on H₂S formation by aquathermolysis of high-sulfur heavy oil was studied here. Meanwhile, the aquathermolysis reaction experiments between four non-sulfur-bearing metal salts(AlCl₃, MgCl₂, CaCl₂ and ZnCl₂) and heavy oil were also carried out. The experimental results show that within the temperature range of 240-300℃, Al³⁺, Mg²⁺, Ca²⁺ and Zn²⁺ all have certain catalytic effect on H₂S formation by aquathermolysis reaction of heavy oil, and Al³⁺ shows the optimal catalytic effect. The lower the pH value is, the stronger the aquathermolysis reaction will be. It results from the enhanced H⁺ protonation due to the acidity of metal salt solutions, and metal ions has catalytic effect on the intermediate reactions in aquathermolysis, such as C-S bond breaking, hydrodesulfsurizing and water-gas shift reaction. Within a certain density range, the higher the metal salt concentration is, the lower the pH value will be, the higher the chance of metal ions to contact reactants will be, the more significant the catalytic effect on aquathermolysis will be, and the more the generated H₂S will be.

Key words: metal salt, hydrogen sulfide, aquathermolysis, catalytic effect, heavy oil thermal recovery

摘要：

高含硫稠油注蒸汽开采过程中,稠油、水蒸气和岩石基质间将发生水热裂解和硫酸盐热化学还原反应,并产生H₂S。为排除硫酸盐热化学还原生成H₂S反应,研究了金属离子对高含硫稠油水热裂解反应生成H₂S的催化作用,开展了AlCl₃、MgCl₂、CaCl₂和ZnCl₂这4种不含硫金属盐与稠油的水热裂解反应实验。实验结果表明:在240~300℃范围内,Al³⁺、Mg²⁺、Ca²⁺、Zn²⁺对稠油水热裂解反应生成H₂S均有催化作用,且Al³⁺的催化效果最好;pH值越低水热裂解生成H₂S反应越强烈,这是因为金属盐溶液呈酸性使H⁺质子化作用加强,而且金属离子对水热裂解中间反应包括C-S键断裂、加氢脱硫、水气转换等反应有催化作用;在一定浓度范围内,金属盐浓度越高,溶液pH值就越低,且金属离子与反应物接触几率增加,对水热裂解催化效果越明显,生成的H₂S越多。

关键词: 金属盐, 硫化氢, 水热裂解, 催化作用, 稠油热采

CLC Number:

TE357.4

Lin Riyi, Luo Jianjun, Wang Xinwei, Xie Fengjia, Song Duopei, Gai Zheng, Tian Xin. An experiment on the influences of non-sulfur-bearing metal salt on hydrogen sulfide formation by aquathermolysis reaction of heavy oils[J]. Acta Petrolei Sinica, 2016, 37(2): 237-241.

林日亿, 罗建军, 王新伟, 谢逢佳, 宋多培, 盖争, 田鑫. 非含硫金属盐对稠油水热裂解生成硫化氢影响实验[J]. 石油学报, 2016, 37(2): 237-241.

References

[1] Ibatullin T,Yang Tao,Petersen E B,et al.Simulation of hydrogen sulfide and carbon dioxide production during thermal recovery of bitumen[R].SPE 147934,2011.
[2] 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D辑:地球科学,2008,38(3):307-311.
Zhang Shuichang,Shuai Yanhua,Zhu Guangyou.TSR promotes the formation of oil-cracking gases:evidence from simulation experiments[J].Science in China Series D:Earth Sciences,2008,51(3):451-455.
[3] Thimm H F.Aquathermolysis and sources of produced gases in SAGD[R].SPE 170058,2014.
[4] 林日亿,宋多培,周广响,等.热采过程中硫化氢成因机制[J].石油学报,2014,35(6):1153-1159.
Lin Riyi,Song Duopei,Zhou Guangxiang,et al.Hydrogen sulfide formation mechanism in the process of thermal recovery[J].Acta Petrolei Sinica,2014,35(6):1153-1159.
[5] Akstinat M H.Gas evolution and change of oil composition during steam flooding of oil reservoirs[J].Journal of Petroleum Geology,1983,5(4):363-388.
[6] Clark P D,Hyne J B.Chemistry of organosulphur compound types occurring in heavy oil sands:3.Reaction of thiophene and tetrahydrothiophene with vanadyl and nickel salts[J].Fuel,1984,63(12):1649-1654.
[7] Clark P D,Dowling N I,Hyne J B,et al.The chemistry of organosulphur compound types occurring in heavy oils:4.The high-temperature reaction of thiophene and tetrahydrothiophene with aqueous solutions of aluminium and first-row transition-mental cations[J].Fuel,1987,66(10):1353-1357.
[8] 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.
[9] 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.
Fan Hongfu,Liu Yongjian,Zhao Xiaofei,et al.Studies on effect of metal ions on aquathermolysis reaction of Liaohe heavy oils under steam treatment[J].Journal of Fuel Chemistry and Technology,2001,29(5):430-433.
[10] 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.
Fan Zexia,Zhao Fulin,Wang Jiexiang,et al.Upgrading and viscosity reduction of super heavy oil by aquathermolysis with hydrogen donor[J].Journal of Fuel Chemistry and Technology,2006,34(3):315-318.
[11] Chao Kun,Chen Yanling,Li Jian,et al.Upgrading and visbreaking of super-heavy oil by catalytic aquathermolysis with aromatic sulfonic copper[J].Fuel Processing Technology,2012,104:174-180.
[12] 张静岩,朱光有,田建波,等.注蒸汽开采稠油过程中H₂S的形成[J].天然气地球科学,2007,18(6):798-802.
Zhang Jingyan,Zhu Guangyou,Tian Jianbo,et al.Formation of H₂S during thermal recovery for viscous oil by steam[J].Natural Gas Geoscience,2007,18(6):798-802.
[13] Kowalewski I,Lamoureux V V,Lorant F.Geochemical factors controlling H₂S production in petroleum reservoirs during steam injection process:TSR experimental simulation[J].Organic Geochemistry Challenges for the 21th Century,2005,1:368-369.
[14] Hyne J B.Aquathermolysis:a synopsis work on the chemical reaction between water(steam) and heavy oil sands during simulated stimulation[M].Synopsis Report:Alberta Oil Sands Technology and Research Authority,1986.
[15] Hamedi-Shokrlu Y,Babadagli T.In-situ upgrading of heavy oil/bitumen during steam injection by use of metal nanoparticles:a study on In-situ catalysis and catalyst transportation[J].SPE Reservoir Evaluation & Engineering,2013,16(3):333-344.
[16] 刘永建,钟立国,蒋生健,等.水热裂解开采稠油技术研究的进展[J].燃料化学学报,2004,32(1):117-122.
Liu Yongjian,Zhong Liguo,Jiang Shengjian,et al.Research progress of recovering heavy oil by aquathermolysis[J].Journal of Fuel Chemistry and Technology,2004,32(1):117-122.
[17] Lin Riyi,Song Duopei,Wang Xinwei,et al.Experimental evaluation of H2S yields during thermal recovery processes[R].SPE 174486,2015.
[18] 刘永建,钟立国,范洪富,等.稠油的水热裂解反应及其降粘机理[J].大庆石油学院学报,2002,26(3):95-98.
Liu Yongjian,Zhong Liguo,Fan Hongfu,et al.Study on the aquathermolysis and viscosity reduced mechanism of heavy oil[J].Journal of Daqing Petroleum Institute,2002,26(3):95-98.
[19] 代金友,陈安定,何顺利.模拟硫化氢生成的热化学还原反应实验研究[J].石油实验地质,2008,30(2):200-202.
Dai Jinyou,Chen Anding,He Shunli.Experimental study of thermochemical sulfate reduction on the sulfureted hydrogen[J].Petroleum Geology & Experiment,2008,30(2):200-202.
[20] 岳长涛,李术元,丁康乐,等.硫酸盐热化学还原反应体系实验研究[J].科学技术与工程,2004,4(1):44-45.
Yue Changtao,Li Shuyuan,Ding Kangle,et al.Study of Thermo-chemical sulfate reduction using simulation experiments[J].Science Technology and Engineering,2004,4(1):44-45.

An experiment on the influences of non-sulfur-bearing metal salt on hydrogen sulfide formation by aquathermolysis reaction of heavy oils

非含硫金属盐对稠油水热裂解生成硫化氢影响实验

PDF

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Li Le, Hu Yuanqing, Peng Xiaogui, Wang Wei, Yu Haoyu, Cui Yasheng. Research progress of hydrogen sulfide genesis in shale gas reservoirs [J]. Acta Petrolei Sinica, 2024, 45(2): 461-476.
[2]	Shang Ting, Tian Jingchun, Liu Xin, Xie Xiankui, Zhang Xiaolei, Yu Wei, Guo Yixuan, Wang Feng, Chen Jiangmeng. Genesis analysis of the petroleum associated H₂S: a case study of Pengyang oilfield in Ordos Basin [J]. Acta Petrolei Sinica, 2022, 43(5): 595-604.
[3]	Wu Xiaoli, Xu Wanglin, Li Rongxi, Li Ningxi, Liu Qi, Zhao Di, Zhao Bangsheng, Qin Xiaoli, Bai Ying. Genesis of hydrogen sulfide in Ordovician Majiagou Formation, mid-eastern Ordos Basin: evidence from fluid inclusions [J]. Acta Petrolei Sinica, 2022, 43(2): 250-261.
[4]	Guo Jianying, Fu Lixin, Xiao Xin, Wang Dongliang, Li Jian, Zhang Lu, Xiao Dunqing, Xie Zengye, Liu Xiaoxuan, Wang Jinyou. Geochemical characteristics and genesis of high-H₂S natural gas in the Dagang exploration area,Huanghua depression [J]. Acta Petrolei Sinica, 2016, 37(S2): 31-38.
[5]	Tang Donglin, Ke Zhijun, Dai Zhiyong, Dou Chunxia, Jia Pinyuan. Optical fiber evanescent sensing technology of hydrogen sulfide gas concentration in oil and gas fields [J]. Acta Petrolei Sinica, 2016, 37(1): 106-110.
[6]	He Congge, Mu Longxin, Xu Anzhu, Fang Sidong. A new model of steam soaking heating radius and productivity prediction for heavy oil reservoirs [J]. Acta Petrolei Sinica, 2015, 36(12): 1564-1570.
[7]	Lin Riyi, Song Duopei, Zhou Guangxiang, Wang Xinwei, Tian Xin, Yang Kai. Hydrogen sulfide formation mechanism in the process of thermal recovery [J]. ACTA PETROLEI SINICA, 2014, 35(6): 1153-1159.
[8]	ZHUO Lubin GE Yunhua ZHANG Fucheng WANG Haige YUAN Zhi LONG ping . An early identification technique for gas cut in carbonate reservoirs [J]. Editorial office of ACTA PETROLEI SINICA, 2012, 33(S2): 174-180.
[9]	JI Youjun CHENG Linsong LIU Qicheng LIU Zhibo. Digital experiment on steam and in-condensable gas push for extra heavy oil reservoir [J]. Editorial office of ACTA PETROLEI SINICA, 2010, 31(4): 602-606.
[10]	CHEN Sheng JIANG Tianhan DENG Yunfeng XI Xuejun GUO Zaifu. Approach to evaluate emergency planning zones for the sour gas wells in the mountain areas of China based on H₂S toxic load [J]. Editorial office of ACTA PETROLEI SINICA, 2010, 31(4): 668-671.
[11]	CHEN Sheng, WU Qingshan, JIANG Tianhan, XI Xuejun, GUO Zaifu, WANG Jianguang. Probabilistic distribution model for release rates of H²S in sour gas wells of Sichuan and Chongqing areas [J]. Editorial office of ACTA PETROLEI SINICA, 2009, 30(5): 774-777.
[12]	SHI Xiaobing, GAN Yifeng, ZHONG Shuiqing, XIONG Jiyou, ZHANG Shiqiang. Study on hydrogen sulfide gas cutting in high-sulfur geological environment [J]. Editorial office of ACTA PETROLEI SINICA, 2008, 29(4): 601-604.
[13]	LUO Yinyu, JIANG Tianhan, DENG Yunfeng, XI Xuejun, WU Binbin. Classification method for hazard levels of hydrogen sulfide dispersion in sour gas wells [J]. Editorial office of ACTA PETROLEI SINICA, 2008, 29(3): 447-450.
[14]	Zhang Shuichang, Zhu Guangyou. Gas accumulation characteristics and exploration potential of marine sediments in Sichuan Basin [J]. Editorial office of ACTA PETROLEI SINICA, 2006, 27(5): 1-8.
[15]	ZHU Guang-you, ZHANG Shui-chang, LIANG Ying-bo, DAI Jin-xing, LI Jian. Alteration of thermochemical sulfate reduction to hydrocarbons [J]. Editorial office of ACTA PETROLEI SINICA, 2005, 26(5): 48-52.