引用本文:马强,林日亿,冯一波,罗建军. 稠油模型化合物水热裂解生成H2S实验研究[J]. 石油与天然气化工, 2018, 47(4): 6-13, 17.
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稠油模型化合物水热裂解生成H2S实验研究
马强1,林日亿1,冯一波2,罗建军3
1.中国石油大学(华东)储运与建筑工程学院 ;2.中国石化西北油田分公司石油工程技术研究院 ;3.中船重工重庆智能装备工程设计有限公司
摘要:
针对注汽热采过程产生硫化氢(H2S)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:①4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H2S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;③Al3+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:H2S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。
关键词:  模型化合物  水热裂解  H2S  热化学
DOI:10.3969/j.issn.1007-3426.2018.04.002
分类号:
基金项目:国家“十三五”重大科技专项“改善SAGD开发效果技术研究与应用”(2016ZX05012-002);山东省自然基金“基于稠油水热裂解反应的硫化氢生成机制研究”(ZR2017MEE030)
Experimental study on the formation of H2S by aquathermolysis of heavy oil model compounds
Ma Qiang1, Lin Riyi1, Feng Yibo2, Luo Jianjun3
1. China University of Petroleum, Qingdao, Shandong, China;2. Engineering Institute of Sinopec Northwest Branch, Urumchi, Xinjiang, China;3. China Shipbuilding Heavy Industry Chongqing Intelligent Equipment Engineering Design Co., Ltd., Chongqing, China
Abstract:
During the thermal enhanced oil recovery (EOR) process, the existence of H2S 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 of 280 ℃. Due to the different electron cloud density of the S atom, the production of H2S is in order of 2-methylthiophene >benzothiophene>dibenzothiophene>thianthrene. Al3+ 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 H2S by aquthermolysis. In the presence of oxygen, aldehydes were first oxidized to carboxylic acids instead of generating CO by aquathermolysis.
Key words:  model compound  aquathermolysis  H2S  thermochemica