不同油品注空气氧化动力学特征
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摘要
基于热分析技术确定稀油、普通稠油、特稠油3种油品注空气过程中4个反应阶段的温度区间,阐述不同油品在不同氧化阶段的氧化反应特征,根据动力学模型,采用微分法计算3种油品各反应阶段的氧化动力学参数。结果表明:低温阶段,稀油质量损失率最多,放热峰值最高,随着黏度增加,3种油品初始放热点升高,自燃点降低,高温氧化阶段特稠油放热峰为稀油的4.4倍;稠油相对稀油活化能整体偏高,低温氧化阶段活化能随着原油黏度增加而增加,高温氧化阶段活化能随着稠油黏度增加而减小;不同类型油藏可选择不同的注空气开发方式:轻质油藏低温氧化反应比高温燃烧更明显,推荐采用稀油注空气提高采收率,随着黏度增加,稠油油藏高温下放热峰值增加,更适合火驱开采实现高温氧化。
Based on the thermal analyzing technique, the temperature ranges were determined during four reaction stages in the air injection process of thin oil, general heavy oil and extra-heavy oil, the oxidation reaction features were described for different oils at different oxidation stages. Based on the kinetic model, the differential method was employed to calculate the oxidation kinetic parameters of the three oils in different reaction stages. The results show that the thin oil has the most mass lost relative to the others in low temperature stage, while its exothermic value is the highest. With the rise of the viscosity, their initial hot spots increase, the spontaneous combustion points decrease, the exothermic peak of the extra-heavy oil is 4.4 times of the thin oil in high temperature oxidation stage; the heavy oil has pretty higher activation energy than the thin oil, with the increase of the crude oil viscosity, the activation energy increases in low temperature oxidation stage, while the activation energy decreases with the rise of the heavy oil viscosity in high temperature oxidation stage; for different types of the oil reservoir, the air injection developing methods can be selected as follows:the low temperature oxidation reaction is more obvious than high temperature combustion for the light oil reservoir, thus the thin-oil air injection is recommended to enhance the oil recovery, with the increase of the viscosity, the value of the exothermic peak increases in high temperature for the heavy oil reservoir, so in-situ combustion development is more suitable for high temperature oxidation.
Based on the thermal analyzing technique, the temperature ranges were determined during four reaction stages in the air injection process of thin oil, general heavy oil and extra-heavy oil, the oxidation reaction features were described for different oils at different oxidation stages. Based on the kinetic model, the differential method was employed to calculate the oxidation kinetic parameters of the three oils in different reaction stages. The results show that the thin oil has the most mass lost relative to the others in low temperature stage, while its exothermic value is the highest. With the rise of the viscosity, their initial hot spots increase, the spontaneous combustion points decrease, the exothermic peak of the extra-heavy oil is 4.4 times of the thin oil in high temperature oxidation stage; the heavy oil has pretty higher activation energy than the thin oil, with the increase of the crude oil viscosity, the activation energy increases in low temperature oxidation stage, while the activation energy decreases with the rise of the heavy oil viscosity in high temperature oxidation stage; for different types of the oil reservoir, the air injection developing methods can be selected as follows:the low temperature oxidation reaction is more obvious than high temperature combustion for the light oil reservoir, thus the thin-oil air injection is recommended to enhance the oil recovery, with the increase of the viscosity, the value of the exothermic peak increases in high temperature for the heavy oil reservoir, so in-situ combustion development is more suitable for high temperature oxidation.
引文
[1]唐君实, 关文龙, 蒋有伟, 等. 稀油火烧油层物理模拟[J].石油学报, 2015, 36(9): 1135-1140.TANG Junshi, GUAN Wenlong, JIANG Youwei, et al. Physical simulation of light oil in-situ combustion[J].Acta Petrolei Sinica, 2015, 36(9): 1135-1140.
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[7]唐晓东, 魏宇涛, 李晶晶, 等. 原油注空气氧化反应及其动力学研究进展[J].化工进展, 2016, 35(1): 83-90. TANG Xiaodong, WEI Yutao, LI Jingjing ,et al. Advances in oxidation reaction of air injection and its kinetics[J].Chemical Industry and Engineering Progress, 2016, 35(1): 83-90.
[8]ABDUL J A G, HAN Y, BRIGNOLI O, et al. Heavy fuel oil pyrolysis and combustion: Kinetics and evolved gases investigated by TGA-FTIR[J].Journal of Analytical and Applied Pyrolysis, 2017, 127: 183-195.
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[12]CLARA C, DURANDEAU M, QUENAULT G, et al. Laboratory studies for light-oil air injection projects:Potential application in Handil Field[J].SPE Reservoir Evaluation & Engineering, 2000, 3(3): 239-248.
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[16]宋薇, 刘建国, 聂永丰, 等. 含油污泥热解和燃烧的反应过程[J].清华大学学报(自然科学版), 2008, 48(9):1453-1457. SONG Wei, LIU Jianguo, NIE Yongfeng, et al. Comparative study of pyrolysis and combustion process of oil sludge by TG-FTIR analysis[J].Journal of Tsinghua University(Science and Technology),2008, 48(9):1453-1457.
[17]杜建芬, 郭平, 王仲林, 等. 轻油油藏高压注空气油与空气反应的活性研究[J].西南石油大学学报(自然科学版),2008, 30(6):92-96. DU jianfen, GUO Ping, WANG Zhonglin, et al. Research on reactivity of oil with air in high-pressure air injection at light oil reservoirs[J].Journal of Southwest Petroleum University(Science & Technology Edition) , 2008, 30(6):92-96.
[18]刘少敏, 陈明强, 胡青松, 等. 固定床反应器中生物油水溶性组分热解反应动力学[J].石油学报(石油加工), 2013, 29(3):422-426. LIU Shaomin, CHEN Mingqiang, HU Qingsong, et al. Pyrolysis kinetic analysis for water-soluble fraction of bio-oil in fixed bed reactor[J].Acta Petrolei Sinica( Petroleum Processing Section), 2013, 29(3): 422-426.
[19]唐君实, 关文龙, 梁金中, 等. 热重分析仪求取稠油高温氧化动力学参数[J].石油学报,2013, 34(4):775-779. TANG Junshi, GUAN Wenlong, LIANG Jinzhong et al. Determination on high-temperature oxidation kinetic parameters of heavy oils with thermogravimetric analyzer[J].Acta Petrolei Sinica, 2013, 34(4):775-779.
[2]唐晓东, 苏旭, 崔盈贤, 等. 空气低温氧化体系对稠油组成的影响[J].西南石油大学学报(自然科学版), 2011, 33(4): 149-152. TANG Xiaodong, SU Xu, CUI Yingxian, et al. Effect of low temperature air oxidation on the composition of heavy oil[J].Journal of Southwest Petroleum University (Science & Technology Edition), 2011, 33(4): 149-152.
[3]MURUGAN P, MANI T, MAHINPEY N, et al. The low temperature oxidation of Fosterton asphaltenes and its combustion kinetics[J].Fuel Processing Technology, 2011, 92(5) : 1056-1061.
[4]陈艳茹, 郭平, 张建东, 等. 低渗透油藏注空气原油低温氧化机理[J].重庆科技学院学报(自然科学版), 2013, 15(1): 101-103.CHEN Yanru, GUO Ping, ZHANG Jiandong, et al. Research on the low temperature oxidation process in low permeability light oil reservoirs[J].Journal of Chongqing Institute of Science and Technology (Science & Technology Edition), 2013, 15(1): 101-103.
[5]张方礼. 火烧油层技术综述[J].特种油气藏, 2011, 18(6): 1-5. ZHANG Fangli. An overview of in situ combustion technology[J].Special Oil & Gas Reservoirs, 2011, 18(6): 1-5.
[6]刘其成. 火烧油层室内实验及驱油机理研究[D].大庆:东北石油大学, 2011.LIU Qicheng. Study on indoor experiment and oil displacement mechanism of fire flooding[D].Daqing: Northeast Petroleum University, 2011.
[7]唐晓东, 魏宇涛, 李晶晶, 等. 原油注空气氧化反应及其动力学研究进展[J].化工进展, 2016, 35(1): 83-90. TANG Xiaodong, WEI Yutao, LI Jingjing ,et al. Advances in oxidation reaction of air injection and its kinetics[J].Chemical Industry and Engineering Progress, 2016, 35(1): 83-90.
[8]ABDUL J A G, HAN Y, BRIGNOLI O, et al. Heavy fuel oil pyrolysis and combustion: Kinetics and evolved gases investigated by TGA-FTIR[J].Journal of Analytical and Applied Pyrolysis, 2017, 127: 183-195.
[9]KOK M V. Use of thermal equipment to evaluate crude oils[J].Thermochimica Acta, 1993, 214(2) : 315-324.
[10]侯胜明, 刘印华, 于洪敏, 等. 注空气过程轻质原油低温氧化动力学[J].中国石油大学学报(自然科学版), 2011, 35(1): 169-173. HOU Shengming, LIU Yinhua, YU Hongmin,et al. Kinetics of low temperature oxidation of light oil in air injection process[J].Journal of China University of Petroleum (Edition of Natural Science), 2011, 35(1): 169-173.
[11]蒋海岩, 袁士宝, 李杨,等. 稠油氧化阶段划分及活化能的确定[J].西南石油大学学报(自然科学版), 2016, 38(4): 136-142.JANG Haiyan, YUAN Shibao, LI Yang, et al. Division of oxidation stage of heavy oil in the process of in-situ combustion[J].Journal of Southwest Petroleum University( Science & Technology Edition), 2016,38(4): 136-142.
[12]CLARA C, DURANDEAU M, QUENAULT G, et al. Laboratory studies for light-oil air injection projects:Potential application in Handil Field[J].SPE Reservoir Evaluation & Engineering, 2000, 3(3): 239-248.
[13]MURUGAN P, MAHINPEY N, MANI T, et al. Pyrolysis and combustion kinetics of Fosterton oil using thermogravimetric analysis[J].Fuel, 2009, 88(9): 1708-1713.
[14]胡荣祖, 史启桢. 热分析动力学[M].北京: 科学出版社, 2001. HU Rongzu, SHI Qizhen. Thermal analysis dynamics[M].Beijing: Science Press, 2001.
[15]油气田开发专业标准化技术委员会.稠油高温氧化动力学参数测定方法: 热重法 SY/T 6954—2013 [S].北京: 石油工业出版社, 2014.Professional Committee for Standardization of Oil and Gas Field Development.standard test method for high temperature oxidation kinetic parameters for heavy oil—Thermogravimetric method:SY/T 6954—2013[S].Beijing: Petroleum Industry Press, 2014.
[16]宋薇, 刘建国, 聂永丰, 等. 含油污泥热解和燃烧的反应过程[J].清华大学学报(自然科学版), 2008, 48(9):1453-1457. SONG Wei, LIU Jianguo, NIE Yongfeng, et al. Comparative study of pyrolysis and combustion process of oil sludge by TG-FTIR analysis[J].Journal of Tsinghua University(Science and Technology),2008, 48(9):1453-1457.
[17]杜建芬, 郭平, 王仲林, 等. 轻油油藏高压注空气油与空气反应的活性研究[J].西南石油大学学报(自然科学版),2008, 30(6):92-96. DU jianfen, GUO Ping, WANG Zhonglin, et al. Research on reactivity of oil with air in high-pressure air injection at light oil reservoirs[J].Journal of Southwest Petroleum University(Science & Technology Edition) , 2008, 30(6):92-96.
[18]刘少敏, 陈明强, 胡青松, 等. 固定床反应器中生物油水溶性组分热解反应动力学[J].石油学报(石油加工), 2013, 29(3):422-426. LIU Shaomin, CHEN Mingqiang, HU Qingsong, et al. Pyrolysis kinetic analysis for water-soluble fraction of bio-oil in fixed bed reactor[J].Acta Petrolei Sinica( Petroleum Processing Section), 2013, 29(3): 422-426.
[19]唐君实, 关文龙, 梁金中, 等. 热重分析仪求取稠油高温氧化动力学参数[J].石油学报,2013, 34(4):775-779. TANG Junshi, GUAN Wenlong, LIANG Jinzhong et al. Determination on high-temperature oxidation kinetic parameters of heavy oils with thermogravimetric analyzer[J].Acta Petrolei Sinica, 2013, 34(4):775-779.
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