重质油-固体系分离与资源化回收研究进展

doi:10.16085/j.issn.1000-6613.2018-1137

化工进展 ›› 2019, Vol. 38 ›› Issue (01): 649-663.DOI: 10.16085/j.issn.1000-6613.2018-1137

重质油-固体系分离与资源化回收研究进展

王君妍^1,²(),白云^1,²,马国强^1,²,隋红^1,^2,³,李鑫钢^1,^2,³(),何林^1,²()

1. 天津大学化工学院，天津 300072
2. 精馏技术国家工程研究中心，天津 300072
3. 天津化学化工协同创新中心，天津 300072

收稿日期:2018-05-31 修回日期:2018-09-17 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 李鑫钢,何林
作者简介:王君妍（1992—），女，博士研究生，研究方向为非常规石油分离。E-mail：<email>wangjunyan@tju.edu.cn</email>。|李鑫钢，教授，研究方向为精馏分离、非常规石油分离过程、挥发性有机污染资源化、有机污染土壤修复。E-mail：<email>lxg@tju.edu.cn</email>|何林，助理教授，研究方向为非常规石油分离过程、挥发性有机污染资源化、有机污染土壤修复。E-mail：<email>linhe@tju.edu.cn</email>
基金资助:
国家自然科学基金(21506155，41471258);国家自然科学基金（21506155，41471258）。

Recent advances in separation and recovery of oil from heavy oil-solid systems

Junyan WANG^1,²(),Yun BAI^1,²,Guoqiang MA^1,²,Hong SUI^1,^2,³,Xingang LI^1,^2,³(),Lin HE^1,²()

1. School of Chemical Engineering & Techonology, Tianjin University, Tianjin 300072, China
2. National Engineering Research Center for Distillation Technology, Tianjin 300072, China
3. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China

Received:2018-05-31 Revised:2018-09-17 Online:2019-01-05 Published:2019-01-05
Contact: Xingang LI,Lin HE

摘要/Abstract

摘要：

针对异位非常规石油及油泥等重质油固体系分离与资源化利用问题，本文系统介绍了非常规石油资源与油泥的共性分离基础问题，并对几种主要的资源化利用方法进行了综述与展望。重质油固体系在结构上主要由油、矿物和水组成，但其性质则由矿物质理化性质、油组分性质、水分、添加剂（絮凝剂）所决定，从而直接影响油固分离方法的选择及分离效果。基于此，本文从工程化角度出发，重点总结了水洗法、溶剂萃取法和热解法三类重质油-固体系分离工艺研究现状，分别从各工艺基本工作原理、传统工艺流程、新型工艺研究以及发展方向展望4个方面进行了重点讨论。虽然这三类方法的工艺研究相对成熟，但在实际操作过程中，各自仍存在不同的挑战，有待进一步的探索，比如条件及设备优化、添加剂筛选及优化或原料体系改性、能量综合利用等。此外，除了技术本身以外，还需根据工程现场条件、分离经济性等方面对资源化化工艺进行全面分析与优化，确定适用范围，最终实现处理成本的降低。

关键词: 重质油, 界面, 溶剂萃取, 水洗, 热解

Abstract:

In view of the separation and resource utilization of heavy oils such as ectopic unconventional petroleum and sludge, this paper systematically introduces the basic problems of unconventional petroleum resources and sludge separation. Several major resource utilization methods have been summarized and discussed. The heavy oil-solid systems are mainly composed of oil, minerals and water. However, their properties are highly dependent on the physical and chemical properties of the minerals, the properties of the oil components, the moisture, and the additives (flocculants), which further directly affect the selection of oil-solid separation method, as well as the separation efficiency. Accordingly, this paper summarizes the research status of three types of heavy oil-solid separation processes, such as washing, solvent extraction and pyrolysis, from the basic engineering principles, traditional processes and new processes. Although great progress has been made on these processes, there are still different challenges for each method, which needs further exploration, such as condition and equipment optimization, additive screening and optimization, raw material system modification, energy comprehensive utilization, etc. In addition to the technology itself, it is also necessary to conduct a comprehensive analysis of the resource-based process in terms of engineering site conditions and separation economy to reduce the cost.

Key words: heavy petroleum, interface, solvent extraction, water flooding, pyrolysis

中图分类号:

TE99

王君妍, 白云, 马国强, 隋红, 李鑫钢, 何林. 重质油-固体系分离与资源化回收研究进展[J]. 化工进展, 2019, 38(01): 649-663.

Junyan WANG, Yun BAI, Guoqiang MA, Hong SUI, Xingang LI, Lin HE. Recent advances in separation and recovery of oil from heavy oil-solid systems[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 649-663.

图/表 14

图1 油砂资源分布及储量情况[4,11]

图2 重质油固体系及其典型资源化方法[20,24,30,33,35,37,45,70,73,105,107]

图3 微纳固体颗粒稳定油水乳液示意图[45]

图4 水洗法工艺流程示意图

图5 纳米流体促进采油机理示意图[67]

图6 CO2响应开关型表面活性剂转化机理[8]

图7 重质油组分H/C比和溶解度参数分布图[73]

图8 典型的溶剂萃取法工艺流程图

图9 离子液体(ILs)辅助溶剂萃取流程图

图10 CyNMe2萃取油砂沥青工艺流程[83]

表1 重质油热解动力学模型主理论[105]

理论	公式	应用领域
分布活化能（DAEM）法	$l n β T 2 = l n A R E + 0.6075 - E R T$	煤的热解与燃烧领域，适用复杂体系
Flynn-Wall-Ozawa (FWO)法	$l n β = l n A E R G (α) - 2.315 - 0.4567 E R T$	生物质与煤炭热解过程
Coats-Redfern (C-R)法	$l n 1 - (1 - α) 1 - n T 2 (1 - n) = l n A R β E 1 - 2 R T E - E R T$	生物质与煤单独热解和共热解过程

表1 重质油热解动力学模型主理论[105]

理论	公式	应用领域
分布活化能（DAEM）法	$l n β T 2 = l n A R E + 0.6075 - E R T$	煤的热解与燃烧领域，适用复杂体系
Flynn-Wall-Ozawa (FWO)法	$l n β = l n A E R G (α) - 2.315 - 0.4567 E R T$	生物质与煤炭热解过程
Coats-Redfern (C-R)法	$l n 1 - (1 - α) 1 - n T 2 (1 - n) = l n A R β E 1 - 2 R T E - E R T$	生物质与煤单独热解和共热解过程

表2 常用热解技术比较

工艺	优势	限制	参考文献
常压干馏技术	工艺操作及设备要求简单、流程简单、能耗低、易于工业应用	停留时间过长、易发生过度裂解、不凝气产量高、油收率低	[106,107]
氮气吹扫热解	避免过度裂解	加热能耗高、分离难度高、工艺的复杂	[100,108]
加氢热解	油收率和品质高	催化剂易于结焦失活、成本高	[92,97,108]
减压热解	气相产物分压低、停留时间短、油收率高、固体结焦率低、传质传热效率高	装置的密封性及耐高温性能要求高、装置成本高	[40,90]

表3 热解设备对比

设备	优势	限制	参考文献
固定床热解设备	结构简单、操作便捷、易于调整压力及载气	传质传热效果差、热利用率低、难以连续操作	[100,102]
旋转干馏炉	操作简单、收率高、传热效率高，易于加热	装置较为复杂	[109]
流化床干馏炉	传质传热效果好、重质油收率高	装置成本高、不易维护	[110,111]
ATP装置	能量利用率高、油收率高、自动化程度高	设备复杂、维修成本高	[92,112]

表4 重质油-固体系资源化方法比较

设备操作简单，

成本低

分离效率较低，

耗水量大，后处理困难

VOCs

含溶剂尾矿

工艺流程简单，

油收率及分离效率高

溶剂用量大，成本高，

易致二次污染

VOCs

焦炭

分离效率高，

产品油易于精制

能耗大，

设备及操作费用高

[9,41,101,103,114]

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重质油-固体系分离与资源化回收研究进展

Recent advances in separation and recovery of oil from heavy oil-solid systems

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