马瑞原油在空气和氮气中的热解-氧化性能

doi:10.11944/j.issn.1000-0518.2018.12.180029

摘要/Abstract

摘要：

低温氧化是注空气采油及原位燃烧采油技术中的重要化学反应,为深入认识原油在有氧环境下复杂热反应过程中的低温氧化特性,我们采用热重/差热分析法(TG/DTA)研究了线性升温和等温条件下马瑞(Merey)原油的热反应行为。结果表明,Merey原油在空气及线性升温条件下的受热过程分4个阶段:气化段、低温氧化段、热解段和高温氧化段;相邻阶段的物理、化学主导过程的重叠增加了分析原油热反应特征的难度。升温速率提高,气化段和低温氧化段的终止温度不变;热解段和高温氧化段的终止温度以及热解段的峰温随升温速率的增加而升高。 N₂气与空气下Merey原油的热重/微分热重(TG/DTG)数据对比表明,升温速率越高,空气下的高温氧化段与热解段重叠程度越大,这有利于燃烧但会降低原油采收率。空气下等温时的TG/DTA结果表明随升温速率增加,升温至300 ℃时的失重率降低,不利于原油轻组分的气化。反应温度越高,气化过程时间越长,失重分数越大。 Merey原油在低于300℃时低温氧化反应不是主导反应。

关键词: 低温氧化, 热重/差热分析, 原油, 热解

Abstract:

Low-temperature oxidation is an important chemical reaction in air injection and in-situ combustion processes for enhanced oil recovery. To further understand the low temperature oxidation mechanism of intricate thermal reactions of crude oil in aerobic environment, the thermal behavior of Merey crude oil was investigated by thermogravimetry/differential thermal analysis(TG/DTA) in air and under nitrogen atmosphere. The results show that the four reaction intervals including gasification, low temperature oxidation, pyrolysis and high temperature oxidation are observed for the thermal process of Merey crude oil in air with a linear heating rate. The overlap of dominant physical and chemical processes in adjacent intervals sophisticates the characteristics of the oil thermal reaction. The invariant final temperature of gasification and low temperature oxidation intervals as well as the elevated final temperature of pyrolysis and high temperature oxidation intervals along with a raised peak temperature of pyrolysis interval are obtained as the heating rate increases. The comparison of TG/DTG experiments in air and under N₂ atmosphere show that an increasing overlap of high temperature oxidation and pyrolysis intervals is observed as the heating rate increases, which is in favor of coke combustion but adverse to the enhanced oil recovery. The isothermal TG/DTA results show that the ratio of mass loss at temperature 300 ℃ decreases with the increase of the heating rate in air, which is not conducive to the gasification of light components of oil. The higher isothermal reaction temperature corresponds to the longer process of gasification and the greater mass loss. The oxidation is not the main reaction for Merey crude oil below 300 ℃.

Key words: low-temperature oxidation, thermogravimetry/differential thermal analysis, crude oil, pyrolysis

张庆轩, 李金涛, 张梦. 马瑞原油在空气和氮气中的热解-氧化性能[J]. 应用化学, 2018, 35(12): 1470-1477.

ZHANG Qingxuan, LI Jintao, ZHANG Meng. Characteristics of Pyrolysis-Oxidation Reactions of Merey Crude Oil in Air and Nitrogen[J]. Chinese Journal of Applied Chemistry, 2018, 35(12): 1470-1477.

参考文献

[1]	Castanier L M,Brigham W E.Upgrading of Crude Oil via in Situ Combustion[J]. J Pet Sci Eng,2003,39(1):125-136.
[2]	Manrique E,Thomas C,Ravikiran R,et al. EOR:Current Status and Opportunities[C]//2010 SPE Improved Oil Recovery Symposium. Society of Petroleum Engineers,Tulsa,Oklahoma,USA,2010:1-21.
[3]	Turta A T,Chattopadhyay S K,Bhattacharya R N,et al. Current Status of Commercial in Situ Combustion Projects Worldwide[J]. J Can Petrol Technol,2007,46(11):8-14.
[4]	Chattopadhyay S K,Binay R,Bhattacharya R N,et al. Enhanced Oil Recovery by in-situ Combustion Process in Santhal Field of Cambay Basin, Mehsana, Gujarat, India-A Case Study[C]//SPE/DOE Symposium on Improved Oil Recovery,17-21 April,Tulsa,Oklahoma,2004.
[5]	Yuan C D,Pu W F,Jin F Y,et al. Characterizing the Fuel Deposition Process of Crude Oil Oxidation in Air Injection[J]. Energy Fuels,2015,29(11):7622-7629.
[6]	Khansari Z.Low Temperature Oxidation of Heavy Crude Oil:Experimental Study and Reaction Modeling[D]. Calgary:University of Calgary,2014.
[7]	Kok M V,Gundogar A S.DSC Study on Combustion and Pyrolysis Behaviors of Turkish Crude Oils[J]. Fuel Process Technol,2013,116(6):110-115.
[8]	Khansari Z,Kapadia P,Mahinpey N,et al. A New Reaction Model for Low Temperature Oxidation of Heavy Oil:Experiments and Numerical Modeling[J]. Energy,2014,64(1):419-428.
[9]	Hussain A.Influence of Chemical Reactions on in Situ Combustion:A Simulation Study[D]. Delft:Delft University of Technology,2011.
[10]	Niu B L,Ren S R,Liu Y H,et al. Low Temperature Oxidation of Oil Components in an Air Injection Process for Improved Oil Recovery[J]. Energy Fuels,2011,25(10):4299-4304.
[11]	Freitag N P.Evidence that Naturally Occurring Inhibitors Affect the Low Temperature Oxidation Kinetics of Heavy Oil[J]. J Can Petrol Technol,2010,49(7):36-41.
[12]	Gui B,Yang Q Y,Wu H J,et al. Study of the Effect of Low Temperature Oxidation on the Chemical Composition of a Light Crude Oil[J]. Energy Fuels,2010,24(2):1139-1145.
[13]	Murugan P,Mahinpey N,Mani T,et al. Effect of Low Temperature Oxidation on the Pyrolysis and Combustion of Whole Oil[J]. Energy,2010,35(5):2317-2322.
[14]	Al-Saffar H B,Hasanin H,Price D,et al. Oxidation Reactions of a Light Crude Oil and Its SARA Fractions in Consolidated Cores[J]. Energy Fuels,2001,15(1):182-188.
[15]	Hu J,Ni J H,Pu W F,et al. New View on the Oxidation Mechanisms of Crude Oil Through Combined Thermal Analysis Methods[J]. J Therm Anal Calorim,2014,118(3):1707-1714.
[16]	Alexandra U,Vladislav Z,Mikhail V,et al. Study of the Radical Chain Mechanism of Hydrocarbon Oxidation for in Situ Combustion Process[J]. J Combust,2017,(2017):1-11.
[17]	Karacan O,Kok M V.Pyrolysis Analysis of Crude Oils and Their Fractions[J]. Energy Fuels,1997,11(2):385-391.
[18]	Castano L C U. Coke Formation During Thermal Cracking of a Heavy Oil[D]. Medellin:Universidad Nacional de Colombia,2015.
[19]	Murugan P,Mani T,Mahinpey N,et al. Pyrolysis Kinetics of Athabasca Bitumen Using a TGA under the Influence of Reservoir Sand[J]. Can J Chem Eng,2012,90(2):315-319.
[20]	Kapadia P R,Kallos M S,Gates I D.A New Kinetic Model for Pyrolysis of Athabasca Bitumen[J]. Can J Chem Eng,2013,91(5):889-901.
[21]	Jia N,Moore R G,Mehta S A,et al. Kinetic Modeling of Thermal Cracking Reactions[J]. Fuel,2009,88(8):1376-1382.
[22]	Kok M V,Gul K G.Thermal Characteristics and Kinetics of Crude Oils and SARA Fractions[J]. Thermochim Acta,2013,569(40):66-70.
[23]	Vyazovkin S,Chrissafis K,Lorenzo M L D,et al. ICTAC Kinetics Committee Recommendations for Collecting Experimental Thermal Analysis Data for Kinetic Computations[J]. Thermochim Acta,2014,590(19):1-23.
[24]	Pu W F,Yuan C D,Jin F Y,et al. Low-Temperature Oxidation and Characterization of Heavy Oil via Thermal Analysis[J]. Energy Fuels,2015,29(2):1151-1159.
[25]	DENG Wen'an,LIU Chenguang,MU Baoquan. Petroleum Chenistry Experiment Handouts[M]. Dongying:China University of Petroleum Press,1999:1-7(in Chinese). 邓文安,刘晨光,沐宝泉. 石油化学实验讲义[M]. 东营:中国石油大学出版社,1999:1-7.
[26]	Karimian M,Schaffie M,Fazaelipoor M H.Determination of Activation Energy as a Function of Conversion for the Oxidation of Heavy and Light Crude Oils in Relation to in Situ Combustion[J]. J Therm Anal Calorim,2016,125(1):301-311.
[27]	Yuan C D,Varfolomeev M A,Emelianov D A,et al. Oxidation Behavior of Light Crude Oil and Its SARA Fractions Characterized by TG and DSC Techniques: Differences and Connections[J]. Energy Fuels,2018,32(1):801-808.
[28]	Barckholtz T A.Modeling the Negative Temperature Coefficient in the Low Temperature Oxidation of Light Alkanes[J]. Prepr Pap-Am Chem Soc,Div Fuel Chem,2003,48(2):518-519.
[29]	ZHU Wenbing.The Experimental Study on Combustion Kinetics and Pyrolysis Thermal Analysis in in-situ combustion[D]. Wuhan:Huazhong University of Science and Technology,2009(in Chinese). 朱文兵. 火烧驱燃烧动力学与裂解热分析实验研究[D]. 武汉:华中科技大学,2009.
[30]	Bozzelli W J,Sheng C. Thermochemistry, Reaction Paths,Kinetics on the Hydroperoxy-Ethyl Radical Reaction with O2:New Chain Branching Reactions in Hydrocarbon Oxidation[J]. J Phys Chem A,2002,106(7):1113-1121.