| 摘要: |
| 稠油注汽热采过程中通常伴随着H2S的产生,针对此现象,以稠油非含硫模型化合物正十六烷及4种金属盐(MgSO4、Al2(SO4)3、Na2SO4及CaSO4)为研究对象,开展热模拟实验,对稠油热采过程中硫酸盐热化学还原(TSR)生成H2S机理进行研究。实验表明:反应产物以烃类(C1～C5)、无机气体(H2、CO2、H2S)、MgO以及噻吩类、硫醇和硫醚类物质为主；4种金属盐TSR生成H2S量顺序为:Al2(SO4)3＞CaSO4＞MgSO4＞Na2SO4；生成CO2量顺序为:Al2(SO4)3＞Na2SO4＞MgSO4＞CaSO4。原因在于金属阳离子电荷数越大自催化作用越强,产生H2S越多；不同硫酸盐体系反应路径不同。推导了正十六烷与MgSO4的TSR反应过程:包括质子化作用、热解反应、硫代硫酸盐向有机硫化物转化、H2S自催化作用及硫化物热解和水解等反应,其中自催化作用是生成H2S的主要途径。最后,通过计算得到正十六烷与MgSO4的TSR反应活化能为61.498 kJ /mol。 |
| 关键词: 正十六烷 H2S TSR 反应动力学 |
| DOI：10.3969/j.issn.1007-3426.2019.04.014 |
| 分类号: |
| 基金项目:国家自然科学基金“稠油水热裂解生成硫化氢反应机制研究”(51874333)；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) |
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| Experimental study on H2S formation by thermochemical reduction of sulfate and n-hexadecane |
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Ma Qiang1,2, Lin Riyi1, Han Chaojie3, Liu Hao1
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1. College of Pipeline and Civil Engineering, China University of Petroleum, Qingdao, Shandong, China;2. China Petroleum Pipeline Engineering Co., Ltd, Langfang, Hebei, China;3. Weifang Municipal Engineering Design & Research Institute Co., Ltd., Weifang, Shandong, China
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| Abstract: |
| It will produce acid gas such as H2S and CO2 in heavy oil recovery by steam injection because of the complicated reaction which induced by thermochemical sulfate reduction (TSR) between stream and heavy oil in reservoir. In this paper, model compound of heavy oil (n-hexadecane) and four metal salts (MgSO4, Al2(SO4)3, Na2SO4 and CaSO4 were taken as research objects, and the H2S formation mechanism of TSR experiments was studied. The results show that the products are carbonyl sulfide, mercaptan, thiophene, thioether and gases (H2, CO2, H2S,MgO, hydrocarbons). The order of H2S formation in different reaction systems is Al2(SO4)3＞CaSO4＞MgSO4＞Na2SO4 , but the order of CO2 is Al2(SO4)3＞Na2SO4＞MgSO4＞CaSO4. By comparing the generation order of H2S and CO2 in different systems, it is known that the greater the number of metal cation charges is, the stronger the autocatalytic effect is, and the reaction paths of different sulfate systems are different. The TSR way of n-hexadecane with magnesium sulfate was discussed, including protonation, hydrocarbon elimination reaction, thiosulfate conversion to organic sulfide, hydrogen sulfide autocatalysis, pyrolysis and hydrolysis of sulfide, in which hydrogen sulfide autocatalysis is the main process. Finally, the reaction kinetics was studied and the calculated activation energy is 61.498 kJ/mol. |
| Key words: n-hexadecane H2S TSR reaction dynamics |
