分子氧化及光电催化氧化对石油Pickering乳液的破乳研究进展

doi:10.16085/j.issn.1000-6613.2020-1674

摘要/Abstract

摘要：

石油开采、集输、加工过程中会面临复杂的工况条件，原油中的天然表面活性剂与人工添加乳化剂以及纳微米固体颗粒共同形成石油Pickering乳液，使得油水体系呈稳定的水包油（O/W）、油包水（W/O）或多重乳化状态。油水乳状液作为注水采油的主要产物，其高效破乳是石油工业链条中的普遍需求。目前对于石油Pickering的破乳仍然借鉴普通油水乳液的方法，而对于成因复杂的油水乳状液，以去除成膜乳化剂为目标的氧化破乳法比传统破乳法的效果更佳。为此，本文基于高效的氧化破乳机制，介绍了石油Pickering乳液的特点及危害，与非氧化反应类型的传统化学破乳法进行对比，综述了分子氧化、光催化氧化、电化学氧化三类技术对于不同来源及特征的油水乳状液的破乳进展。通过对每种方法的机理过程、应用实例、优缺点等方面详细分析，总结了分子氧化、光催化氧化、电化学氧化在石油Pickering乳液破乳中的局限性，并对今后如何实现石油Pickering乳液精准破乳提出展望。

关键词: 石油Pickering乳液, 氧化, 天然乳化剂, 表面活性剂, 纳微固体颗粒, 分子氧化, 光催化氧化, 电化学

Abstract:

Complex working conditions is often encountered in petroleum exploitation, gathering and processing. Natural surfactants are mixed with artificial emulsifier and nano-micron solid particles to form petroleum pickering emulsion, which makes the oil-water system in a stable state of O/W, W/O or multiple emulsification. Oil-water emulsion is the main product of water flood recovery, and its efficient demulsification is a common demand in the petroleum industry chain. At present, petroleum industry still adopts the demulsification method for common oil-water emulsion. But for the complex oil-water emulsion, the oxidative demulsification aiming at removing the film-forming emulsifier is better than the traditional demulsification. In view of this, based on the efficient oxidative demulsification mechanism, this paper introduced the characteristics and negative effects of petroleum pickering emulsion. Compared with the traditional chemical demulsification method without oxidation reaction, the demulsification progress of molecular oxidation, photocatalytic oxidation and electrochemical oxidation for oil-water emulsions with different sources and characteristics were reviewed. For each method, the process mechanism, application examples, advantages and disadvantages were analyzed in detail. Finally the limitations of these oxidation methods were summarized and prospected to realize the accurate demulsification of petroleum pickering emulsion in the future.

Key words: petroleum Pickering emulsion, oxidation, natural emulsifier, surfactant, nano-micron solid particle, molecular oxidation, photocatalytic oxidation, electrochemistry

中图分类号:

TE992

苏碧云, 冉良涛, 胡雅和, 张翱, 韩巧巧, 武晋娣, 刘伊婷, 孟祖超. 分子氧化及光电催化氧化对石油Pickering乳液的破乳研究进展[J]. 化工进展, 2021, 40(7): 3995-4002.

SU Biyun, RAN Liangtao, HU Yahe, ZHANG Ao, HAN Qiaoqiao, WU Jindi, LIU Yiting, MENG Zuchao. Research progress on demulsification of petroleum Pickering emulsion by molecular oxidation, photocatalytic oxidation and electrochemical oxidation[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3995-4002.

图/表 5

表1 ClO2氧化破乳除油正交实验表[16]

试验号	因素				除油率/%
试验号	反应时间/h	反应温度/℃	ClO₂浓度/mg·L^-1	初始pH	除油率/%
1	1	45	30	6	67.9
2	1	55	35	7	72.3
3	1	65	40	8	76.6
4	2	45	35	8	88.7
5	2	55	40	6	91.8
6	2	65	30	7	87.6
7	3	45	40	7	89.5
8	3	55	30	8	90.5
9	3	65	35	6	88.4

图1 油水过渡层乳液乳化模型[18]

图2 太阳能对聚合物驱采出水的破乳作用示意图[31]

图3 光催化降解有机污染物示意图[35]

图4 间歇式电化学反应器系统[37]

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