模拟内外源协同催化稠油水热裂解研究

doi:10.12422/j.issn.1006-396X.2023.03.002

摘要/Abstract

摘要：

外源催化剂进入油藏后可能与原位无机矿物形成复合物，并发生协同催化水热裂解反应。制备了蒙脱土负载的柠檬酸锌复合物模拟内外源协同催化剂，考察了其对稠油的催化降黏性能，并对反应前后的稠油进行了热重（TGA）、差示扫描量热仪（DSC）、气相色谱（GC）和元素分析（EA）。结果表明，复合催化剂B@Zn(Ⅱ)L使稠油的降黏率（30 ℃）从55.2%升高到65.4%，说明稠油热采中存在内外源协同催化的现象；复合催化剂B@Zn(Ⅱ)L与供氢剂乙醇协同作用后，稠油的降黏率从65.4%升高到80.1%；协同作用后，稠油中的部分高烃类化合物裂解为低烃类化合物，部分重质组分分解为轻质组分。因此，稠油析蜡点降低，N、S质量分数下降，高碳烃类化合物相对含量降低，低碳烃相对含量增加。

关键词: 稠油, 水热裂解, 催化降黏, 复合物

Abstract:

In order to investigate the synergistic catalytic aquathermolysis after external catalyst entering the reservoir and complexation with in?situ inorganic minerals,a simulated internal and external synergistic catalyst of montmorillonite?supported zinc citrate complex was prepared,and its catalytic viscosity reduction performance for heavy oil was investigated.The heavy oil before and after the reaction was analyzed by thermogravimetric analysis(TGA),differential scanning calorimetry(DSC),gas chromatography(GC) and elemental analysis(EA).The results showed that the composite catalyst B@Zn(Ⅱ)L increased the viscosity reduction rate of heavy oil from 55.2% to 65.4% at 30 ℃,which confirmed the phenomenon of internal and external source synergistic catalysis in heavy oil thermal recovery.After synergizing the composite catalyst B@Zn(Ⅱ)L with the hydrogen supply agent ethanol,the viscosity reduction rate of heavy oil increased from 65.4% to 80.1%.After the reaction of heavy oil, some of the high hydrocarbon compounds in the heavy oil were cracked into low hydrocarbon compounds after the reaction,and some heavy components were decomposed into light components.Therefore, the wax precipitation point of heavy oil decreased,the mass fraction of N and S decreased,the content of high hydrocarbons decreased,and the content of low carbon hydrocarbons increased.

Key words: Heavy oil, Aquathermolysis, Catalytic viscosity reduction, Complex

中图分类号:

TQ?9

张舒, 马丽娃, 郭瑞, 李永飞, 陈刚. 模拟内外源协同催化稠油水热裂解研究[J]. 石油化工高等学校学报, 2023, 36(3): 11-16.

Shu Zhang, Liwa Ma, Rui Guo, Yongfei Li, Gang Chen. Study on Aquathermolysis of Heavy Oil Catalyzed by Simulated Internal and External Sources[J]. Journal of Petrochemical Universities, 2023, 36(3): 11-16.

图/表 11

表1 实验用油的主要物性参数

Table 1 The main physical parameters of the experimental oil

凝点/℃	含水率/%	w（饱和烃）/%	w（芳香烃）/%	w（沥青质）/%	w（胶质）/%
25.8	33.30	30.87	25.13	28.90	15.10

图1 Zn(Ⅱ)L的制备过程

Fig.1 Preparation process of Zn(Ⅱ)L

图2 蒙脱土质量分数对稠油黏温性能的影响

Fig.2 Effect of mass fraction of reservoir mineral addition on viscosity?temperature curve of heavy oil

图3 催化剂催化稠油降黏性能评价结果

Fig.3 Evaluation of catalysts for catalyzing the viscosity reduction of heavy oil

图4 供氢剂的助催化效果评价结果

Fig.4 Evaluation of the catalytic effect of hydrogen donors

图5 乙醇助催化水热裂解反应前后稠油的TGA曲线

Fig.5 Thermogravimetric curves before and after ethanol?promoted hydrothermal cracking reaction

图6 乙醇助催化水热裂解反应前后稠油的DSC曲线

Fig.6 DSC curves before and after ethanol?promoted hydrothermal cracking reaction

图7 稠油反应前后饱和烃碳数分布

Fig.7 Carbon number distribution of saturated hydrocarbons before and after heavy oil reaction

表2 不同反应条件下稠油的EA分析结果

Table 2 Elemental analysis results of heavy oil under different reaction conditions

反应条件	w（C）/%	w（H）/%	w（N）/%	w（S）/%	w（H）/w（C）
空白	79.12	10.49	1.47	2.38	0.133
裂解空白	81.12	10.97	1.08	1.73	0.135
油+水+B@Zn(Ⅱ)L	82.40	11.13	0.94	0. 95	0.135
油+水+B@Zn(Ⅱ)L+乙醇	84.42	11.93	0.69	0.84	0.141

图8 稠油反应后水中极性物质的GC?MS

Fig.8 GC?MS of polar substances dissolved in water after heavy oil reaction

图9 外源和内源催化剂的协同催化机理

Fig.9 Catalytic mechanism of exogenous and endogenous catalyst

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