稠油低温氧化特性及行为研究

摘要/Abstract

摘要：

针对新疆J区块稠油开展了恒温静态氧化管实验,通过分析氧化后产出气及原油组分的变化来研究温度、压力、石英砂和岩屑对稠油低温氧化特性的影响。实验结果表明：相比70 ℃,稠油在110 ℃条件下的平均耗氧速率增加了1.42 %/d;压力从10 MPa增加至30 MPa时,CO+CO₂生成量增加了2.13 %;石英砂和岩屑均能促进稠油氧化反应进程;与原油相比,加入石英砂和岩屑后耗氧量分别增加了1.71 %和4.08 %;岩屑对稠油低温氧化反应的促进作用主要来自岩屑的催化作用。采用TG-DSC同步热分析仪研究了原油氧化行为,并通过Arrhenius氧化动力学模型计算了活化能。结果表明：稠油在低温氧化阶段具有较低的反应活性,该阶段活化能仅为18.09 kJ/mol,远低于燃料沉积和高温氧化阶段的活化能（84.58 kJ/mol和113.39 kJ/mol）。

关键词: 稠油, 低温氧化, 耗氧速率, 氧化动力学, 活化能

Abstract:

The static isothermal oxidation tube experiments were carried out for heavy crude oil in J block of Xinjiang Oilfield. The effects of temperature, pressure, quartz sand and detritus on the low temperature oxidation（LTO） characteristics of heavy crude oil were investigated by analyzing the alterations in the produced gas and SARA（saturate, aromatic, resin and asphaltene） fractions of oxidized oil. The results showed that the awerage oxygen consumption rate of the crude oil was increased by 1.42 % per day at 110 ℃ relative to that at 70 ℃. When the pressure was increased from 10 MPa to 30 MPa, the production of CO+CO₂ was increased by 2.13 %. Both quartz sand and detritus promoted oxidation reaction on the heavy oil. The oxygen consumption increased by 1.71 % and 4.08 % after the addition of quartz sand and detritus relative to the crude oil. The promotion of detritus on LTO reactions of heavy crude oil mainly derived from the catalytic effect of detritus. The oxidation behavior of the crude oil was studied by the TG-DSC, and the activation energy was calculated by Arrhenius kinetic model. The results indicated that heavy crude oil had poor reactivity in the LTO stage, and the activation energy in the LTO region was only 18.09 kJ/mol, which was much lower than that in the fuel deposition and high temperature oxidation stages（84.58 kJ/mol and 113.39 kJ/mol）.

Key words: heavy crude oil, low temperature oxidation, oxygen consumption rate, oxidation kinetics, activation energy

中图分类号:

TE357

蒲万芬,王亮亮,彭小强,任豪,杨洋,赵帅. 稠油低温氧化特性及行为研究[J]. 油气藏评价与开发, 2019, 9(4): 41-46.

PU Wanfen,WANG Liangliang,PENG Xiaoqiang,REN Hao,YANG Yang,ZHAO Shuai. Study on characteristics and behaviors of low temperature oxidation of heavy crude oil[J]. Reservoir Evaluation and Development, 2019, 9(4): 41-46.

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黏度（40 ^oC）/ （mPa·s）	密度（40 ^oC）/ （g·cm^-3）	四组分,wt%
黏度（40 ^oC）/ （mPa·s）	密度（40 ^oC）/ （g·cm^-3）	饱和烃	芳香烃	胶质	沥青质
17 418	0.943 5	28.09	31.45	32.86	7.60

实验编号	氧化管填充介质	温度/℃	压力/MPa	产出气分析					碳氢比	平均耗氧速率/ （%·d^-1）
实验编号	氧化管填充介质	温度/℃	压力/MPa	O₂,%	N₂,%	CO,%	CO₂,%	C₁—C₆,%	碳氢比	平均耗氧速率/ （%·d^-1）
1	稠油	30	15	19.84	80.16
2	稠油	70	15	18.62	80.91	0.08	0.30	0.09	11.22	0.20
3	稠油	110	15	10.15	84.55	0.27	3.47	1.56	7.67	1.62
4	稠油	150	15	4.27	86.43	0.41	6.41	2.48	6.16	2.60
5	稠油+石英砂	110	15	8.44	85.04	0.31	4.54	1.67	6.53	1.88
6	稠油+岩屑	110	15	6.07	85.98	0.38	5.72	1.85	6.00	2.30
7	稠油+岩屑	110	10	6.85	85.81	0.34	5.37	1.63	6.20	2.16
8	稠油+岩屑	110	20	4.89	85.92	0.41	6.32	2.46	5.85	2.49
9	稠油+岩屑	110	30	3.27	86.39	0.48	7.36	2.50	5.36	2.76

反应条件	饱和烃,wt%	芳香烃,wt%	胶质,wt%	沥青质,wt%
30 ℃	27.89	31.17	33.09	7.85
70 ℃	21.14	26.17	35.97	16.72
110 ℃	18.52	22.47	37.15	21.86
150 ℃	15.20	20.08	35.52	29.20
10 MPa	22.06	28.87	35.13	13.94
15 MPa	19.68	28.86	37.03	14.43
20 MPa	19.21	28.19	37.76	14.84
30 MPa	17.58	26.96	38.89	16.57
稠油+石英砂	22.84	29.08	35.24	12.84
稠油+岩屑	19.68	28.86	37.03	14.43

反应阶段	温度区间/℃	质量损失,%	峰值温度/℃	热焓值/（kJ·g^-1）	峰值热流量/（mW·mg^-1）
低温氧化	37.51 ~ 384.15	33.16	329.83	0.87	1.13
燃料沉积	384.15 ~ 530.61	42.88
高温氧化	530.61 ~ 655.46	19.53	536.61	1.39	5.07

反应阶段	线性拟合斜率	活化能/ （kJ?mol^-1）	阿伦纽斯常数/min^-1	R²
低温氧化	-944.67	18.09	1.26	0.989
燃料沉积	-4 417.26	84.58	1.86×10⁵	0.952
高温氧化	-5 921.94	113.39	2.6310⁶	0.964