Research progress on highly efficient demulsifiers for complex crude oil emulsions and their applications

doi:10.16085/j.issn.1000-6613.2022-1754

Abstract

Abstract:

In petroleum production, a large number of W/O, O/W or multiple emulsified emulsions are usually produced, resulting in greatly reduced production efficiency and serious environmental problems. The demulsifiers used in production have low demulsification efficiency, high cost, poor universality and insufficient safety. There is still more attention to develop efficient, universal, green and safe demulsifiers. Based on the analysis of the characteristics and stability mechanism of crude oil emulsion, the research progress of demulsifiers for different crude oil lotion were summarized. It mainly included polymer demulsifiers, biomass based demulsifiers, ionic liquid demulsifiers and nano material demulsifiers. Finally, the development of efficient demulsifiers and the future development trend of demulsification technology were put forward. It laid a foundation for the demulsification technology application of W/O, O/W or complex crude oil emulsions.

Key words: complex crude oil emulsion, ionic liquid demulsifier, biomass-based demulsifier, nanogenic material demulsifier, demulsification mechanism

摘要：

石油生产中通常产生大量W/O、O/W或多重乳化的复杂原油乳液，造成生产效率大大降低以及严重的环境问题。目前所使用的破乳剂破乳效率低、普适性差、成本高、安全性不够等，开发高效、普适、绿色、安全破乳剂仍备受关注。本文基于原油乳液的特点及稳定机制分析，综述了不同原油乳液的破乳剂研究进展，主要围绕聚合物破乳剂、生物质基破乳剂、离子液体破乳剂和纳米材料破乳剂的特点、适用范围及其应用效果进行全面总结，对相应破乳剂的破乳机理进行针对性地分析研究，并指出破乳剂机理的研究方法。最后，本文对复杂原油乳液的高效破乳剂开发进行展望，提出破乳技术的未来发展趋势，以期为W/O、O/W或多重乳化的复杂原油乳液的破乳技术应用提供一定借鉴与参考。

关键词: 复杂原油乳液, 离子液体破乳剂, 生物质基破乳剂, 纳米材料破乳剂, 破乳机理

CLC Number:

TE39

WU Ya, ZHAO Dan, FANG Rongmiao, LI Jingyao, CHANG Nana, DU Chunbao, WANG Wenzhen, SHI Jun. Research progress on highly efficient demulsifiers for complex crude oil emulsions and their applications[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4398-4413.

吴亚, 赵丹, 方荣苗, 李婧瑶, 常娜娜, 杜春保, 王文珍, 史俊. 用于复杂原油乳液的高效破乳剂开发及应用研究进展[J]. 化工进展, 2023, 42(8): 4398-4413.

Figures/Tables 16

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破乳剂	适用油水体系类型	DE/%	最佳破乳环境	优点	缺点
BP系列^[25]	胜利油田	90以上	50℃，3h	脱水效果好	对分子量和破乳温度要求高，否则破乳效果不明显，对环境污染较大
AP系列^[23]	渤海油田、东海油田	90	1.25％的水分散体系破乳剂用量25mg/L	对海洋原油具有脱水速度快、油水界面齐、脱出水清
SD破乳剂^[26]	塔河油田重质原油	89	破乳剂用量100mg/L，温度为70℃	—
DS-06/DL11正反破乳剂复配^[27]	呼和浩特炼油厂含油污泥	95	180mg/L，30∶10复配	专一性强，工业应用效果明显
DS-1复配型^[24]	大庆油田北二联合站高机械杂质含量污油	97	4.5h，50℃	—

破乳剂	适用油水体系类型	DE/%	最佳破乳环境	优点	缺点
BP系列^[25]	胜利油田	90以上	50℃，3h	脱水效果好	对分子量和破乳温度要求高，否则破乳效果不明显，对环境污染较大
AP系列^[23]	渤海油田、东海油田	90	1.25％的水分散体系破乳剂用量25mg/L	对海洋原油具有脱水速度快、油水界面齐、脱出水清
SD破乳剂^[26]	塔河油田重质原油	89	破乳剂用量100mg/L，温度为70℃	—
DS-06/DL11正反破乳剂复配^[27]	呼和浩特炼油厂含油污泥	95	180mg/L，30∶10复配	专一性强，工业应用效果明显
DS-1复配型^[24]	大庆油田北二联合站高机械杂质含量污油	97	4.5h，50℃	—

生物质破乳剂原料	生物质破乳剂	适用乳液类型	DE/%	最佳破乳环境	优点	缺点
花青素^[39]	PC9015	渤海油田老化油乳液	84.6	70℃，2h，100mg/L	脱水性能好，实用性较强，适用于海上平台的原油和老化油破乳，以天然多酚为原料，更为经济、绿色油水界面清晰，无挂壁，取代了用于制备常规石油衍生的壬基酚表面活性剂	挂壁严重
表没食子儿茶素没食子酸酯^[41]	EGA603	渤海油田老化原油乳液	94.3	70℃，100min，100mg/L		挂壁较轻
单宁酸^[43]	TAPA9920	南海油田老化油乳液	97.9	70℃，40min，100mg/L		合成困难
腰果酚^[44]	DECA	阿拉伯重质原油	100	60℃，40min，100mg/L		合成困难，尚在实验室阶段
木质素^[49]	木质素和二氧化硅的高效膜	O/W体系	98.6	与滤纸表面完全接触。一旦有色油被完全过滤掉，分离过程就算作结束	效果明显，分离简单	合成困难，尚在实验室阶段
荷叶^[50]	HLLF	长庆油田	88.17	1000mg/L在70℃下持续90min	油水界面清晰，水质清亮	适用范围较窄，DEMLOCS较其他相似产品剂量颇高
稻壳^[51]	RHC	W/O体系	96.99	600mg/L，70℃，80min	具有较宽的pH范围和良好的耐盐性	适用范围较窄，DEMLOCS较其他相似产品剂量颇高
椰子提取物	DEMLOCS	老化油乳液	88	45℃，24h，2000mg/L	温度适宜，水热法合成步骤简单	适用范围较窄，DEMLOCS较其他相似产品剂量颇高

生物质破乳剂原料	生物质破乳剂	适用乳液类型	DE/%	最佳破乳环境	优点	缺点
花青素^[39]	PC9015	渤海油田老化油乳液	84.6	70℃，2h，100mg/L	脱水性能好，实用性较强，适用于海上平台的原油和老化油破乳，以天然多酚为原料，更为经济、绿色油水界面清晰，无挂壁，取代了用于制备常规石油衍生的壬基酚表面活性剂	挂壁严重
表没食子儿茶素没食子酸酯^[41]	EGA603	渤海油田老化原油乳液	94.3	70℃，100min，100mg/L		挂壁较轻
单宁酸^[43]	TAPA9920	南海油田老化油乳液	97.9	70℃，40min，100mg/L		合成困难
腰果酚^[44]	DECA	阿拉伯重质原油	100	60℃，40min，100mg/L		合成困难，尚在实验室阶段
木质素^[49]	木质素和二氧化硅的高效膜	O/W体系	98.6	与滤纸表面完全接触。一旦有色油被完全过滤掉，分离过程就算作结束	效果明显，分离简单	合成困难，尚在实验室阶段
荷叶^[50]	HLLF	长庆油田	88.17	1000mg/L在70℃下持续90min	油水界面清晰，水质清亮	适用范围较窄，DEMLOCS较其他相似产品剂量颇高
稻壳^[51]	RHC	W/O体系	96.99	600mg/L，70℃，80min	具有较宽的pH范围和良好的耐盐性	适用范围较窄，DEMLOCS较其他相似产品剂量颇高
椰子提取物	DEMLOCS	老化油乳液	88	45℃，24h，2000mg/L	温度适宜，水热法合成步骤简单	适用范围较窄，DEMLOCS较其他相似产品剂量颇高

性能	离子液体	传统破乳剂（表面活性剂）
界面张力	表面活性离子液体可以将界面张力降低到10^-2mN/m，有必要提高离子液体的表面活性，并注意界面张力与盐度的协同作用	可以降低IFT达到10^-4~10^-3mN/m，显示了它们在油水分离应用中的有效性
黏度	离子液体的黏度可以通过支化的变化来调节	在水溶液中，它们无法产生更高的黏度
稳定性	离子液体高温下是稳定的，可以长时间储存而不会分解	表面活性剂在高温下不稳定
毒性	离子液体毒性较小且环保	部分烷基酚表面活性剂毒性大，无法达到降解要求
可回收性	回收离子液体的方法有很多种，如液液萃取、蒸馏、吸附、结晶、力场分离和膜分离等^[53]	不可回收