不同硫酸盐引发的热化学还原作用对原油裂解气生成的影响

doi:10.7623/syxb201304012

石油学报 ›› 2013, Vol. 34 ›› Issue (4): 720-726.DOI: 10.7623/syxb201304012

不同硫酸盐引发的热化学还原作用对原油裂解气生成的影响

何坤¹, 张水昌¹, 米敬奎¹, 毛榕^1,2, 帅燕华¹, 毕丽娜¹

1. 中国石油勘探开发研究院提高石油采收率国家重点实验室北京 100083;
2. 长江大学地球化学系湖北荆州 434023

收稿日期:2012-12-29 修回日期:2013-03-18 出版日期:2013-07-25 发布日期:2013-07-04
通讯作者: 何坤
作者简介:何坤,男,1982年6月生,2005年获南京大学学士学位,2008年获南京大学硕士学位,2011获中国石油勘探开发研究院博士学位,现为中国石油勘探开发研究院工程师,主要从事油气地球化学及生烃模拟实验方面的研究工作。Email:hekun1@petrochina.com.cn
基金资助:
国家重大科技专项 "天然气生成机理、资源潜力评价与战略选区" (2011ZX05007-001);中国石油天然气股份有限公司科技项目"不同地质条件下油气生成排驱模型及在资源评价中的应用" (2011A-0201);中石油咨询公司科技项目(2010D-5003-04)资助。

Effects of thermochemical reduction initiated by different sulfates on the generation of oil cracking gas

HE Kun¹, ZHANG Shuichang¹, MI Jingkui¹, MAO Rong^1,2, SHUAI Yanhua¹, BI Lina¹

1. State Key Laboratory of Enhanced Oil Recovery, PetroChina Research Institute of Petroleum Exploration & Development, Beijing 100083, China;
2. Department of Geochemistry, Yangtze University, Jingzhou 434023, China

Received:2012-12-29 Revised:2013-03-18 Online:2013-07-25 Published:2013-07-04

摘要/Abstract

摘要：

由于反应途径或机制不同于裂解反应,硫酸盐热化学还原作用(TSR)很可能会改变油藏中原油的热稳定性和裂解气产量。为了阐明TSR作用对原油裂解气生成的影响,利用黄金管热模拟装置开展了一系列不同硫酸盐和原油的升温热解实验。非烃气体,包括H₂S的大量生成表明,石膏和硫酸镁的加入引发了原油的TSR反应,其中,石膏参与的TSR作用对烃类气体的产量和生成活化能无明显影响;相对而言,硫酸镁参与的TSR反应引起了最终甲烷产量约13.1% 的降低和大分子气态烃(C₂₊)稳定性的明显降低;氯化镁的加入导致了硫酸镁体系中H₂S产量进一步的增加和烃类气体产量进一步的降低。可以证实,在硫酸镁热解体系中,C₂₊与活性结构HSO₄^-发生了氧化还原反应,这也是导致烃类气体产量降低的重要原因。因此,TSR作用对裂解气生成的影响很大程度上受控于地层水中的硫酸盐类型和活性结构的浓度。

关键词: 硫酸盐热化学还原作用, 原油, 裂解气, 接触离子对, 活化能

Abstract:

Thermochemical sulfate reduction (TSR) might alter the stability of oils and the yield of cracked gas in reservoirs because its reaction pathway or mechanism differs from that of oil cracking. In order to ascertain the effect of TSR on the generation of cracked gas from oils, we performed a series of non-isothermal pyrolysis experiments involving different sulfates and an oil (QB3) with a gold-tube system. The generation of considerable amounts of non-hydrocarbon gases (including H₂S) indicates that TSR is initiated by the presence of gypsum and magnesium sulfate (MgSO₄). Comparatively, the yield and generation activation energy of gaseous hydrocarbons are not obviously affected by TSR involving gypsum. Whereas TSR involving MgSO₄ leads to about 13.1% decrease in the methane yield and also a remarkable decrease in the stability of C₂₊, and the addition of MgCl₂ to the MgSO₄ system results in a further increase in the H₂S yield but a further decrease in the hydrocarbon gas yield. Moreover, the redox reaction between C₂₊ and actively structured HSO₄^- can take place in the MgSO₄ pyroysis system, which is attributed to an important cause for decreasing the yield of gaseous hydrocarbons. Therefore, the effect of TSR on the generation of cracked gas is significantly dominated by sulfate types and the concentration of active species in formation water.

Key words: thermochemical sulfate reduction, crude oil, cracked gas, contact ion-pair, activation energy

中图分类号:

TE124.1

何坤, 张水昌, 米敬奎, 毛榕, 帅燕华, 毕丽娜. 不同硫酸盐引发的热化学还原作用对原油裂解气生成的影响[J]. 石油学报, 2013, 34(4): 720-726.

HE Kun, ZHANG Shuichang, MI Jingkui, MAO Rong, SHUAI Yanhua, BI Lina. Effects of thermochemical reduction initiated by different sulfates on the generation of oil cracking gas[J]. Editorial office of ACTA PETROLEI SINICA, 2013, 34(4): 720-726.

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不同硫酸盐引发的热化学还原作用对原油裂解气生成的影响

Effects of thermochemical reduction initiated by different sulfates on the generation of oil cracking gas

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