表面积效应对不同性质原油热力学行为影响研究

doi:10.11949/0438-1157.20201599

摘要/Abstract

摘要：

针对轻、重质油油藏注空气开发机理，选取典型轻、重质油样进行热重实验，采用改进的Ozawa-Flynn-Wall等转化率法对比分析了不同性质原油三种氧化阶段的热行为和动力学特征，同时探讨了表面积效应对轻、重质原油氧化反应的影响。研究表明：①各氧化阶段之间存在过渡区域，转化率的准确选取对动力学参数至关重要。②轻、重质原油不同氧化阶段的氧化特征存在明显差异，轻质油以低温氧化为主，燃料沉积和高温氧化不显著，且低温氧化、燃料沉积、高温氧化阶段的起始温度更低，更易诱发氧化反应；重质油燃料沉积和高温氧化显著，氧化反应速度更快。③表面积效应导致轻质油低温氧化活化能降低15%以上，峰值温度降低7~17℃。重质油燃料沉积和高温氧化显著增强，燃尽温度下降10~17℃。

关键词: 轻、重质原油, 热力学, 动力学, 多孔介质, 空气驱

Abstract:

Focusing on the air injection development mechanism of light and heavy oil reservoirs, typical light and heavy oil samples were selected for thermogravimetric experiments, and the thermal behavior and kinetics characteristics of crude oil at three oxidation stages were comparatively analyzed by the conversion method of Ozawa- Fynn-Wall, and the effect of surface effect on the oxidation reaction of light and heavy crude oil was also discussed. The results showed that: ①There is a transition zone between each oxidation stage, and the accurate selection of conversion rate is very important for kinetic parameters. ②The oxidation characteristics of light and heavy crude oil at different oxidation stages are obviously different. Light crude oil is mainly oxidized at low temperature, while fuel deposition and high temperature oxidation are not significant. Moreover, the initial temperature of low temperature oxidation, fuel deposition and high temperature oxidation stage of light oil is lower, which is more likely to induce oxidation reaction. Fuel deposition and high temperature oxidation of heavy oil are significant, and the oxidation reaction rate is faster. ③The surface area effect causes the low temperature oxidation activation energy of light oil to decrease by more than 15%, and the peak temperature decreases by 7—17℃. The deposition and high temperature oxidation of heavy oil fuels are significantly enhanced, and the burn-out temperature drops by 10—17℃.

Key words: light and heavy oil, thermodynamics, kinetics, porous media, air displacement

中图分类号:

TE 341

陈浩, 刘希良, 谭先红, 田虓丰, 杨胜来, 杨冉, 张超. 表面积效应对不同性质原油热力学行为影响研究[J]. 化工学报, 2021, 72(6): 3338-3348.

CHEN Hao, LIU Xiliang, TAN Xianhong, TIAN Xiaofeng, YANG Shenglai, YANG Ran, ZHANG Chao. Study on the effect of surface area on the thermal behavior of crude oils with different properties[J]. CIESC Journal, 2021, 72(6): 3338-3348.

图/表 12

参考文献 33

14	廖广志, 杨怀军, 蒋有伟, 等. 减氧空气驱适用范围及氧含量界限[J]. 石油勘探与开发, 2018, 45(1): 105-110.
	Liao G Z, Yang H J, Jiang Y W, et al. Applicable scope of oxygen-reduced air flooding and the limit of oxygen content[J]. Petroleum Exploration and Development, 2018, 45(1): 105-110.
15	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 S M, Liu Y H, Yu H M, 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.
16	中国石油天然气总公司. 稠油油藏流体物性分析方法原油黏度测定: [S]. 北京: 石油工业出版社, 1998.
	China National Petroleum Corporation. Analytical approach of fluid physical property for heavy-oil reservoirs: Crude oil viscosity measurements: [S]. Beijing: Petroleum Industry Press, 1998.
17	Saraji S, Kharrat R, Razzaghi S, et al. Kinetic study of crude oil combustion in the presence of carbonate rock[C]//SPE Middle East Oil and Gas Show and Conference, SPE-105112-MS. Manama, Bahrain, 2007.
18	Pu W F, Chen Y F, Li Y B, et al. Comparison of different kinetic models for heavy oil oxidation characteristic evaluation[J]. Energy & Fuels, 2017, 31(11): 12665-12676.
19	Vyazovkin S, Burnham A K, Criado J M, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011, 520(1/2): 1-19.
20	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 J S, Guan W L, Liang J Z, et al. Determination on high-temperature oxidation kinetic parameters of heavy oils with thermogravimetric analyzer[J]. Acta Petrolei Sinica, 2013, 34(4): 775-779.
21	Mothé C G, Miranda I C. Study of kinetic parameters of thermal decomposition of bagasse and sugarcane straw using Friedman and Ozawa-Flynn-Wall isoconversional methods[J]. Journal of Thermal Analysis and Calorimetry, 2013, 113(2): 497-505.
1	张方礼, 赵庆辉, 闫红星, 等. 指纹分析技术在火驱燃烧状态识别中的应用[J]. 特种油气藏, 2015, 22(6): 80-84,144-145.
	Zhang F L, Zhao Q H, Yan H X, et al. Application of signature analysis technique in identification of fire flood combustion state[J]. Special Oil &Gas Reservoirs, 2015, 22(6): 80-84,144-145.
2	田红. 石油焦与油页岩混合燃烧特性及其燃烧动力学[J]. 石油学报(石油加工), 2010, 26(2): 225-230.
	Tian H. Co-combustion characteristics and kinetics of petroleum coke and oil shale[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2010, 26(2): 225-230.
3	蒋有伟, 张义堂, 刘尚奇, 等. 低渗透油藏注空气开发驱油机理[J]. 石油勘探与开发, 2010, 37(4): 471-476.
	Jiang Y W, Zhang Y T, Liu S Q, et al. Displacement mechanisms of air injection in low permeability reservoirs[J]. Petroleum Exploration and Development, 2010, 37(4): 471-476.
4	张斌, 于聪, 崔景伟, 等. 生烃动力学模拟在页岩油原位转化中的应用[J]. 石油勘探与开发, 2019, 46(6): 1212-1219.
	Zhang B, Yu C, Cui J W, et al. Kinetic simulation of hydrocarbon generation and its application to in situ conversion of shale oil[J]. Petroleum Exploration and Development, 2019, 46(6): 1212-1219.
5	江航, 许强辉, 马德胜, 等. 注空气开采过程中稠油结焦量影响因素[J]. 石油学报, 2016, 37(8): 1030-1036.
	Jiang H, Xu Q H, Ma D S, et al. Influence factors of coking amount during recovery of heavy oil by air injection[J]. Acta Petrolei Sinica, 2016, 37(8): 1030-1036.
6	Li Y B, Chen Y F, Pu W F, et al. Low temperature oxidation characteristics analysis of ultra-heavy oil by thermal methods[J]. Journal of Industrial and Engineering Chemistry, 2017, 48: 249-258.
7	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.
8	Kok M V, Gul K G. Thermal characteristics and kinetics of crude oils and SARA fractions[J]. Thermochimica Acta, 2013, 569: 66-70.
9	Zhao R B, Wei Y G, Wang Z M, et al. Kinetics of low-temperature oxidation of light crude oil[J]. Energy & Fuels, 2016, 30(4): 2647-2654.
10	Zheng R N, Pan J J, Cai G, et al. Effects of clay minerals on the low-temperature oxidation of heavy oil[J]. Fuel, 2019, 254: 115597.
11	Varfolomeev M A, Nurgaliev D K, Kok M V. Calorimetric study approach for crude oil combustion in the presence of clay as catalyst[J]. Petroleum Science and Technology, 2016, 34(19): 1624-1630.
12	Yu X C, Qu Z, Kan C B, et al. Effect of different clay minerals on heavy oil oxidation during ignition process[J]. Energy & Fuels, 2017, 31(11): 12839-12847.
13	Kok M V, Gundogar A S. Effect of different clay concentrations on crude oil combustion kinetics by thermogravimetry[J]. Journal of Thermal Analysis and Calorimetry, 2010, 99(3): 779-783.
22	Karger-Kocsis J. Thermal analysis of polymers: fundamentals and applications[J]. Macromolecular Chemistry and Physics, 2009, 210(19): 1661.
23	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: 419-428.
24	Zhao R B, Wei Y G, Wang Z M, et al. Kinetics of low-temperature oxidation of light crude oil[J]. Energy & Fuels, 2016, 30(4): 2647-2654.
25	王正茂, 廖广志, 蒲万芬, 等. 注空气开发中地层原油氧化反应特征[J]. 石油学报, 2018, 39(3): 314-319.
	Wang Z M, Liao G Z, Pu W F, et al. Oxidation reaction features of formation crude oil in air injection development[J]. Acta Petrolei Sinica, 2018, 39(3): 314-319.
26	Ren S R, Greaves M, Rathbone R R. Air injection LTO process: an IOR technique for light-oil reservoirs[J]. SPE Journal, 2002, 7(1): 90-99.
27	王玉婷, 邓君宇, 刘延民, 等. 轻质油藏注空气过程中原油低温氧化反应的O₂-CO₂转换率[J]. 科学技术与工程, 2014, 14(26): 50-54, 71.
	Wang Y T, Deng J Y, Liu Y M, et al. Oxygen-carbon dioxide conversion ratio in air-light oil low temperature oxidation process[J]. Science Technology and Engineering, 2014, 14(26): 50-54, 71.
28	Turta A T, Chattopadhyay S K, Bhattacharya R N, et al. Current status of commercial in situ combustion projects worldwide[J]. Journal of Canadian Petroleum Technology, 2007, 46(11): 7-11.
29	梁金中, 王伯军, 关文龙, 等. 稠油油藏火烧油层吞吐技术与矿场试验[J]. 石油学报, 2017, 38(3): 324-332.
	Liang J Z, Wang B J, Guan W L, et al. Technology and field test of cyclic in situ combustion in heavy oil reservoir[J]. Acta Petrolei Sinica, 2017, 38(3): 324-332.
30	Shah A, Fishwick R, Wood J, et al. A review of novel techniques for heavy oil and bitumen extraction and upgrading[J]. Energy & Environmental Science, 2010, 3(6): 700.
31	Kok M V, Keskin C. Comparative combustion kinetics for in situ combustion process[J]. Thermochimica Acta, 2001, 369(1/2): 143-147.
32	袁士宝, 宁奎, 蒋海岩, 等. 火驱燃烧状态判定试验[J]. 中国石油大学学报(自然科学版), 2012, 36(5): 114-118.
	Yuan S B, Ning K, Jiang H Y, et al. Experiments of judging combustion state of in situ combustion[J]. Journal of China University of Petroleum (Edition of Natural Science), 2012, 36(5): 114-118.
33	Chen H, Liu X L, Jia N H, et al. The impact of the oil character and quartz sands on the thermal behavior and kinetics of crude oil[J]. Energy, 2020, 210: 118573.

转化率α	斜率	活化能E/ (kJ·mol^-1)	相关系数R²
0.1	-4122.4	32.58	0.959
0.2	-4678.9	36.98	0.962
0.3	-5145.4	40.66	0.961
0.4	-5575.2	44.06	0.969
0.5	-6192.5	48.94	0.978
0.6	-6911.9	54.63	0.985
0.7	-7853.7	62.07	0.989
0.8	-9493.2	75.03	0.991
0.9	-11672.1	92.24	0.998
1.0	-19857.0	156.93	0.986

转化率α	斜率	活化能E/ (kJ·mol^-1)	相关系数R²
0.1	-4122.4	32.58	0.959
0.2	-4678.9	36.98	0.962
0.3	-5145.4	40.66	0.961
0.4	-5575.2	44.06	0.969
0.5	-6192.5	48.94	0.978
0.6	-6911.9	54.63	0.985
0.7	-7853.7	62.07	0.989
0.8	-9493.2	75.03	0.991
0.9	-11672.1	92.24	0.998
1.0	-19857.0	156.93	0.986

原油类型	升温速率/ (℃/min)	LTO			FD			HTO			燃尽温度/℃
原油类型	升温速率/ (℃/min)	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	燃尽温度/℃
轻质油	5	25~387	260	86.9	387~481	458	5.8	481~574	526	7.2	574
	10	25~402	298	85	402~505	475	7.6	505~616	544	7.4	616
	15	25~413	310	85.6	413~517	488	6.8	517~633	562	7.6	633
	20	25~434	331	86.1	434~535	498	7	535~653	580	6.6	653
表面积效应+ 轻质油	5	25~416	253	88.3	416~474	468	4.1	474~562	496	7.6	562
	10	25~429	293	88	429~495	489	5.6	495~605	531	5.9	605
	15	25~440	304	87.1	440~510	482	4.9	510~610	549	8.0	610
	20	25~450	314	87.5	450~516	517	4.3	517~632	563	8.1	632

原油类型	升温速率/ (℃/min)	LTO			FD			HTO			燃尽温度/℃
原油类型	升温速率/ (℃/min)	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	燃尽温度/℃
轻质油	5	25~387	260	86.9	387~481	458	5.8	481~574	526	7.2	574
	10	25~402	298	85	402~505	475	7.6	505~616	544	7.4	616
	15	25~413	310	85.6	413~517	488	6.8	517~633	562	7.6	633
	20	25~434	331	86.1	434~535	498	7	535~653	580	6.6	653
表面积效应+ 轻质油	5	25~416	253	88.3	416~474	468	4.1	474~562	496	7.6	562
	10	25~429	293	88	429~495	489	5.6	495~605	531	5.9	605
	15	25~440	304	87.1	440~510	482	4.9	510~610	549	8.0	610
	20	25~450	314	87.5	450~516	517	4.3	517~632	563	8.1	632

原油类型	升温速率/ (℃/min)	LTO			FD			HTO			燃尽温度/℃
原油类型	升温速率/ (℃/min)	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	燃尽温度/℃
重质油	5	25~374	328	49.2	374~466	440	21.0	466~549	509	29.1	549
	10	25~393	348	48.9	393~487	453	22.8	487~590	532	27.2	590
	15	25~400	358	48.1	400~502	475	26.8	502~611	551	25.1	611
	20	25~408	369	47.3	408~521	492	28.5	521~633	574	23.9	633
表面积效应+ 重质油	5	25~357	317	48.3	357~479	432	23.9	479~535	495	26.6	535
	10	25~375	331	47.4	375~495	443	25.1	495~573	509	24.3	573
	15	25~402	343	46.6	402~511	471	28.9	511~601	517	23.8	601
	20	25~405	354	46.1	405~514	490	30.3	514~619	538	22.5	619