Research progress on the deacidification technologies of crude oil and various distillates

doi:10.16085/j.issn.1000-6613.2019-1709

Abstract

Abstract:

Petroleum acid is a common corrosive substance in crude oil and its distillates, and the main component of the petroleum acid is naphthenic acid the content of which can be as high as 90%. Naphthanoic acid has all the chemical properties of carboxylic acid, so it often causes serious corrosions that affect the normal operations and service life of crude oil processing equipment and the devices that oil products contact with. With the increasing production of high acid value crude oil in the world in recent years, the corrosions and product quality problems caused by high acid value crude oil and the high acid value distillate are becoming more and more serious, so it is urgent to develop an economical and efficient deacidification technology to process the naphthenic acids. In this paper, various deacidification techniques for crude oil and oil products at home and abroad are reviewed and comprehensively summarized in detail. The analysis shows that there are many deacidification technologies reported at present, among which the hydrodeacidification effect in industrial application is good but the cost is high, while most of the other deacidification methods have many shortcomings. Therefore, it is very necessary to explore a green, environmentally friendly, efficient and universal oil deacidification process. Esterification deacidification process is simple and does not need complex subsequent treatment, and it can almost reduce the acid value of all high acid value crude oil and oil products (light and heavy distillate, residual oil), which will provide conveniences for the further processing of oils. The key point of esterification deacidification process is to develop high efficient catalysts. Although the current catalytic esterification system has a high deacidification rate, there is still a common deficiency of long reaction time. It is believed that after this problem is solved by strengthening the reaction process, the catalytic esterification deacidification process will soon be used to the actual industrial production of crude oil and oil products.

Key words: crude oil, distillate oil, deacdification technologies, esterification

摘要：

石油酸是原油和馏分油中普遍存在的腐蚀性物质，其主要成分为环烷酸并且含量可以高达90%以上。环烷酸具有羧酸的所有化学性质，所以常常造成严重的腐蚀，从而影响原油加工设备及油品使用设备的正常运行和使用寿命。随着近年来世界范围内高酸原油产量的逐渐增加，高原油及各种高酸值馏分油所带来的腐蚀与产品质量问题显得愈发严重，因此迫切需要开发出经济高效的脱酸技术与工艺路线。本文较为全面而详细地总结并评述了国内外原油及油品的各种脱酸技术方法。分析表明：目前所报道的各类脱酸工艺较多，其中工业应用的加氢脱酸效果虽好但是成本较高，而其他大多数脱酸方法都存在较多的缺点或不足，因此探寻一种绿色环保、经济高效并且具有较好普适性的油品脱酸工艺显得非常迫切而必要。酯化法脱酸具有加工工艺简单、不需要复杂的后继处理，几乎可以降低所有的高酸值原油和油品（轻质、重质馏分油以及渣油）的酸值，为原料油的进一步加工提供了方便。酯化脱酸工艺的关键在于高效催化剂的选择，而目前的催化酯化体系虽然脱酸率较高，但仍存在着反应时间较长的不足，相信通过反应过程强化等手段解决该问题以后，催化酯化脱酸工艺会被很快投入到原油及油品的脱酸实际工业生产中去。

关键词: 原油, 馏分油, 脱酸技术, 酯化

CLC Number:

TE65

Bai HE, Xin LIAN, Songshan JIANG, Bo YU, Changguo CHEN, Lin CHEN, Dengli LEI, Mengqing GONG. Research progress on the deacidification technologies of crude oil and various distillates[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3014-3026.

何柏, 连欣, 蒋松山, 余波, 陈昌国, 陈琳, 雷登丽, 龚梦晴. 原油及馏分油脱酸技术进展[J]. 化工进展, 2020, 39(8): 3014-3026.

References

1	毛金成, 王海彬, 李勇明, 等. 稠油开发水热裂解催化剂研究进展[J]. 特种油气藏, 2016, 23(3):1-6.
1	MAO Jincheng, WANG Haibin, LI Yongming, et al. Aquathermolysis catalyst advances in heavy oil production[J]. Special Oil and Gas Reservoirs, 2016, 23(3): 1-6.
2	陈清涛, 朱玉龙, 秦一鸣, 等. 国内外高酸原油脱酸发展现状[J]. 当代化工, 2014, 43(6): 1053-1055.
2	CHEN Qingtao, ZHU Yulong, QIN Yiming, et al. Development status of high acid crude oil deacidification technologies[J]. Contemporatry Chemical Industry, 2014, 43(6): 1053-1055.
3	傅晓钦, 田松柏, 侯栓弟, 等. 高酸原油催化脱酸工艺研究进展[J]. 化工进展, 2005, 24(9): 968-970.
3	FU Xiaoqin, TIAN Songbai, HOU Suandi, et al. Development of catalytic decarboxylation of highly sour crude oil[J]. Chemical Industry and Engineering Progress, 2005, 24(9): 968-970.
4	曹玉亭. 高酸原油的腐蚀研究[J]. 石油化工腐蚀与防护, 2008, 25(2): 1-3.
4	CAO Yuting. Research on corrosion of high TAN crude oil[J]. Corrosion & Protection in Petrochemical Industry, 2008, 25(2):1-3.
5	任晓光, 齐亮, 宋永吉, 等. 苏丹高酸值重质原油脱酸新工艺探索[J]. 过程工程学报, 2004, 4(5): 401-405.
5	REN Xiaoguang, QI Liang, SONG Yongji, et al. Process for separation of naphthenic acids from high TAN heavy crude oil of Sudan[J]. The Chinese Journal of Process Engineering, 2004, 4(5): 401-405.
6	严燕, 贾艳秋, 吴雁, 等. 高酸原油脱酸技术的研究进展[J]. 能源化工, 2010, 31(4): 21-24.
6	YAN Yan, JIA Yanqiu, WU Yan, et al. Research advances in the deacidification technology of highly-contained acid crude oil[J]. Journal of Chemical Industry & Engineering, 2010, 31(4): 21-24.
7	滕天灿. 高酸原油脱酸工艺研究进展[J]. 淮阴工学院学报, 2009, 18(3):77-80.
7	TENG Tiancan. Advances in the deacidification process of highly-contained acid crude oil[J]. Journal of Huaiyin Institute of Technology, 2009, 18(3): 77-80.
8	孙雪莹. 高酸原油酯化脱酸催化剂及工艺研究[D]. 青岛:中国石油大学(华东), 2007.
8	SUN Xueying. Research oil catalyst and process for the removal of naphthenie acids for high acid petroleum by esterificafion[D]. Qingdao: China University of Petroleum (East China), 2007.
9	李江浩, 吴世逵, 戴咏川. 环烷基馏分油萃取脱酸研究[J]. 广东石油化工学院学报, 2015 (4): 34-38.
9	LI Jianghao, WU Shikui, DAI Yongchuan. The deacidification study on naphthenic base distillate through extraction[J]. Journal of Guangdong University of Petrochemical Technology, 2015 (4): 34-38.
10	唐晓东, 李林, 崔盈贤, 等. 糠醛精制变压器油工艺优化研究[J]. 润滑油, 2006, 21(6):24-27
10	TANG Xiaodong, LI lin, CUI Yingxian, et al. Study on optimization of furfural extraction technology for transformer oil[J]. Lubrication Oil, 2006, 21(6): 24-27.
11	吴宝华, 牟宏晶. 超声波辅助溶剂法稠油脱酸工艺研究[J]. 哈尔滨理工大学学报, 2016, 21(1):123-126.
11	WU Baohua, MU Hongjing. The process research of removing acid from heavy oil using solvent method with ultrasonic assisted[J]. Journal of Harbin University of Science and Technology, 2016, 21(1): 123-126.
12	李文深, 刘丹, 刘洁, 等. 减三线脱蜡油糠醛精制脱酸的操作条件研究[J]. 应用化工, 2014, 43(4): 662-665.
12	LI Wenshen, LIU Dan, LIU Jie, et al. Study on operation condition of furfural refining to remove acid from VGO No. 3 dewaxed oil[J]. Applied Chemical Industry, 2014, 43(4): 662-665.
13	SHAH S N, ISMAIL M, MUTALIB M I A, et al. Extraction and recovery of toxic acidic components from highly acidic oil using ionic liquids[J]. Fuel, 2016, 181: 579-586.
14	ISMAIL M, BAKARUDDIN B R, LETHESH K C, et al. Experimental and theoretical study on extraction and recovery of naphthenic acid using dicyanamide-based ionic liquids[J]. Separation and Purification Technology, 2019, 213: 199-212.
15	章群丹, 田松柏, 黄少凯, 等. 环烷酸的分离表征及腐蚀研究[J]. 石油化工腐蚀与防护, 2010, 27(1):12-16.
15	ZHANG Qundan, TIAN Songbai, HUANG Shaokai，et al. Research in separation, characterization and corrosion of naphthenic acid[J]. Corrosion & Protection in Petrochemical Industry, 2010, 27(1): 12-16.
16	NETKE S, PANGARKAR V. Extraction of naphthenic acid from kerosene using porous and nonporous polymeric membranes[J]. Separation Science, 1996, 31(1): 63-76.
17	黄光斗, 张智, 李广, 等. 膜分离环烷酸工艺研究[J]. 化工设计, 2005, 15(5):13-14.
17	HUANG Guangdou, ZHANG Zhi, LI Guang, et al. Study on membrane separation of naphthanoic acid[J]. Chemical Engineering Design, 2005, 15(5): 13-14.
18	毛满意, 夏明桂, 何精平, 等. 中间基润滑油基础油的脱氮与吸附脱酸[J]. 石油炼制与化工, 2008, 38(10): 14-17.
18	MAO Manyi, XIA Minggui, HE Jingpin, et al. Denitrogenation and deacidification ofintermediate base lube base oil[J]. Petroleum Processing and Petrochemicals, 2008, 38(10): 14-17.
19	吴凡, 李春光, 夏明桂, 等. 重质润滑油基础油脱酸[J]. 武汉纺织大学学报, 2011, 24(3): 40-43.
19	WU Fan，LI Chunguan，XIA Minggui，et al. Deacidincation of the heavy lube base oil[J]. Journal of Wuhan Textile University, 2011, 24(3): 40-43.
20	韩恒文, 段庆华. 高酸值润滑油基础油脱酸研究[J]. 石油炼制与化工, 2012, 43(12): 35-38.
20	HAN Hengwen, DUAN Qinghua. Study on the deacidification of high acid value lube base oil[J]. Petroleum Processing and Petrochemicals, 2012, 43(12): 35-38.
21	RONANDER M E. Magnetic nanoparticles for extraction of naphthenic acids from model oil[D]. Trondheim: NTNU, 2015.
22	张鲁. 高酸馏分油酯化脱酸催化剂的研究[D]. 济南: 山东大学, 2007.
22	ZHANG Lu. Study on esterification deacification catalyst for high acid distillate oils[D]. Jinan: Shandong University, 2007.
23	唐晓东, 陈亮, 贾艳秋, 等. 直馏柴油碱洗-吸附分离脱酸技术的实验研究[J]. 炼油技术与工程, 2010, 40(6):15-17.
23	TANG Xiaodong, CHEN Liang, JIA Yanqiu, et al. Experimental stdudy on deacidification of stright-run diesel by caustic washing-adsorption separation[J]. Petroleum Refinery Engineering, 2010, 40(6): 15-17.
24	唐晓东, 李晶晶, 徐卫良, 等. 馏分油脱酸剂技术(Ⅱ型)的工业应用[J]. 炼油技术与工程, 2007, 37(4): 35-37.
24	TANG Xiaodong, LI Jingjing, XU Weiliang, et al. Commercial application of deacidification agent(Ⅱ) for distillate oil[J]. Petroleum Refinery Engineering, 2007, 37(4): 35-37.
25	唐晓东, 王萍萍, 汪芳, 等. 常二线馏分油纤维膜接触器脱酸技术的优化研究[J]. 石油炼制与化工, 2010, 41(4):12-15.
25	TANG Xiaodong, WANG Pingping, WANG Fang, et al. Study on the optimization of fiber membrane contactor technology for deacidification of the 2^nd side cut from atmospheric column[J]. Petroleum Processing and Petrochemicals, 2010, 41(4): 12-15.
26	胡震. 盐法脱除柴油中酸的研究[J]. 四川理工学院学报(自然科学版), 2011, 24(2):231-233.
26	HU Zhen. Study on deprivatin g of naphthenic acid in diesel by salt[J]. Journal of Sichuan University of Science & Engineering(Natural Science Edition), 2011, 24(2): 231-233.
27	HU Zhen, YU Hailian. Removal of naphthenic acid from diesel by complex deacidification agents[J]. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 2016, 38(20): 3042-3047.
28	KUMARA R B, SHINDEB S, GAIKWADC SHASHANK G. Reactive extraction of naphthenic acid by using sodium hydroxide as an extractant[J]. Int. J. Adv. Eng. Tech. , 2014, 5(2): 103-106.
29	安蓉, 唐晓东, 朱波, 等. 直馏柴油微量碱法脱酸技术研究[J]. 炼油技术与工程, 2005, 35(1): 38-41.
29	AN Rong, TANG Xiaodong, ZHU Bo, et al. Study on stright-run diesel deacidification with micro-alkali method[J]. Petroleum Refinery Engineering, 2005, 35(1): 38-41.
30	李林, 唐晓东, 孙贵利, 等. 变压器油脱酸剂技术研究[J]. 石化技术与应用, 2007, 25(3):217-220.
30	LI Lin, TANG Xiaodong, SUN Guili, et al. Study on deacidification-solvent technology for transformer oil[J]. Petrochemical Technology & Application, 2007, 25(3): 217-220.
31	唐晓东, 安蓉, 张海军, 等. 馏分油脱酸剂技术的试验研究与工业试验[J]. 石油炼制与化工, 2005, 36(5): 8-12.
31	TANG Xiaodong, AN Rong, ZHANG Haijun, et al. Progress for removing acid from distillates with an acid removal agent[J]. Petroleum Processing and Petrochemicals, 2005, 36(5): 8-12.
32	杨文倩, 唐晓东, 周郁良, 等. 室温下馏分油聚结过滤脱酸技术的实验研究[J]. 石油炼制与化工, 2008, 39(12):12-15.
32	YANG Wenqian, TANG Xiaodong, ZHOU Yuliang, et al. Laboratory study on the deacidification of distillates under ambient temperature using deacidification agent and coalescer[J]. Petroleum Processing and Petrochemicals, 2008, 39(12): 12-15.
33	唐晓东, 肖黄飞, 崔盈贤, 等. 高酸值原油脱酸剂技术的实验研究[J]. 西南石油大学学报(自然科学版), 2007, 29(3):104-106.
33	TANG Xiaodong, XIAO Huangfei, CUI Yingxian, et al. Lab research on the technology for deacidification solvent of the crude oil with high acid number[J]. Journal of Southwest Petroleum University, 2007, 29(3): 104-106.
34	唐晓东, 杨文倩, 王豪, 等. 直馏柴油绿色脱酸技术的实验研究[J]. 化工学报, 2009, 60(5):1204-1208.
34	TANG Xiaodong, YANG Wenqian, WANG Hao, et al. Experimental study on green deacidification technology of straight-run diesel[J]. CIESC Journal, 2009, 60(5): 1204-1208.
35	唐晓东, 王萍萍, 曹约良, 等. 聚乙烯胺用于直馏柴油脱酸的实验研究[J]. 石油炼制与化工, 2009, 40(10): 39-42.
35	TANG Xiaodong, WANG Pingping, CAO Yueliang. et al. An experimental research of using polyvinylamine in the removal of acid from straight-run diesel fuel[J]. Petroleum Processing and Petrochemicals, 2009, 40(10): 39-42.
36	王延臻, 初照圣, 邱波, 等. 反应-萃取法分离和精制高酸原油中的环烷酸[J]. 炼油技术与工程, 2006, 36(1): 36-38.
36	WANG Yanzhen, CHU Zhaosheng, QIU Bo, et al. Seperation naphthenic acid from high-acidity crudes by reaction-extraction process[J]. Petroleum Refinery Engineering, 2006, 36(1): 36-38.
37	WANG Yanzhen, CHU Zhaosheng, QIU Bo, et al. Removal of naphthenic acids from a vacuum fraction oil with an ammonia solution of ethylene glycol[J]. Fuel, 2006, 85(17): 2489-2493.
38	刘江华, 甄新平, 帕提古丽, 等. 克拉玛依稠油溶剂脱酸工艺研究[J]. 精细石油化工进展, 2010, 11(9):43-47.
38	LIU Jianghua, ZHEN Xingping, PATI Guli, et al. Study on technology of solvent removing naphthenic acid from karamay heavy crude oil[J]. Advances in Fine Petrochemicals, 2010, 11(9): 43-47.
39	余国贤, 潘威, 万昆, 等. 原油的超声辐照-溶剂萃取脱酸工艺研究[J]. 广东化工, 2011, 38(3):77-78.
39	YU Guoxian, PAN Wei, WAN Kun, et al. Study on deacification process of crude oil by solvent extraction under ultrasonic irradiation[J]. Guangdong Chemical Industry, 2011, 38(3): 77-78.
40	李江浩, 戴咏川, 吴世逵. 绥中减二线馏分油氨醇法脱酸研究[J]. 现代化工, 2016, 36(4): 65-67.
40	LI Jianghao, DAI Yongchuan, WU Shikui. Deacidification of Suizhong crude oil from second line vacuum distillate by ammonia-alcohol method[J]. Modern Chemical Industry, 2016, 36(4): 65-67.
41	HU Zhen, YU Hailian. Removal of acid from diesel by tetramethylammonium hydroxide/ethanol[J]. Liquid Fuels Technology, 2016, 34(9): 853-859.
42	YU Hailian, HU Zhen. Deacidification from FCC diesel using 2-methylimidazole and ammonia[J]. Liquid Fuels Technology, 2017, 35(3): 229-234.
43	SHUKRI N M, BAKAR W A W A, JAAFAR J, et al. Removal of naphthenic acids from high acidity Korean crude oil utilizing catalytic deacidification method[J]. Journal of Industrial & Engineering Chemistry, 2015, 28: 110-116.
44	SHOHAIMI N A M, BAKAR W A W A, JAAFAR J. Catalytic neutralization of acidic crude oil utilizing ammonia in ethylene glycol basic solution[J]. Journal of Industrial & Engineering Chemistry, 2014, 20(4): 2086-2094.
45	SHOHAIMI N A M, BAKAR W A W A, JAAFAR J. Catalytic neutralization method for naphthenic acid removal in crude oil by alumina supported Ca and Ba catalysts[J]. Petroleum Science & Technology, 2014, 32(19): 2365-2375.
46	SHOHAIMI N A M, JAAFAR J, BAKAR W A W A. Effect of Cu addition onto CaO/Al₂O₃ catalyst for naphthenic acid removal from crude oil[J]. Advanced Materials Research, 2015, 1107: 79-84.
47	SHOHAIMI N A M, BAKAR W A W A, JAAFAR J. The catalytic deacidification of acidic crude oil using Cu-doped alkaline earth metal oxide catalysts[J]. Petroleum Science & Technology, 2017, 35(11): 1097-1103.
48	陈淳, 吴晶晶, 刘丽芝, 等. 高酸原油润滑油馏分加氢脱酸研究[J]. 工业催化, 2013, 21(4):56-58.
48	CHEN Chun, WU Jingiing, LIU Lizhi, et al. Study on the hydro-deacidification of lube oil distillates from highly acidic crude[J]. Industry Catalysis, 2013, 21(4): 56-58.
49	费亚南, 孙国方, 李孝国, 等. 绥中36-1原油减三线馏分油催化加氢脱酸研究[J]. 石油炼制与化工, 2014(5): 83-86.
49	FEI Yanan, SUN Guofang, LI Xiaoguo, et al. Study on hydro-deacidification of Suizhong 36-1 crude third line vacuum distillate[J]. Petroleum Processing and Petrochemicals, 2014(5): 83-86.
50	ZHANG Aihua, MA Qisheng, WANG Kangshi, et al. Naphthenic acid removal from crude oil through catalytic decarboxylation on magnesium oxide[J]. Applied Catalysis A: General, 2006, 303(1): 103-109.
51	OH H Y, PARK J H, RHEE Y W, et al. Decarboxylation of naphthenic acid using alkaline earth metal oxide[J]. Journal of Industrial & Engineering Chemistry, 2011, 17(4): 788-793.
52	岳鹏, 杨朝合, 胡永庆, 等. 环烷酸在Br?nsted酸位吸附脱酸机理的研究[J]. 石油炼制与化工, 2011, 42(11):36-40.
52	YUE Peng, YANG Chaohe, HU Yongqing, et al. Mechanism study on the deacidification of naphthenic acid over Br?nsted acid sites[J]. Petroleum Processing and Petrochemicals, 2011, 42(11): 36-40.
53	刘洪安, 王延臻, 段红玲, 等. 高酸值馏分油中环烷酸的热分解脱酸反应及机理[J]. 石油学报(石油加工), 2011, 27(6): 999-1003.
53	LIU Hong’an, WANG Yanzhen, DUAN Hongling, et al. Decomposition of naphthenic acids in high acid number distillates and its mechanisms[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2011, 27(6): 999-1003.
54	龙军, 毛安国, 田松柏, 等. 高酸原油直接催化脱酸裂化成套技术开发和工业应用[J]. 石油炼制与化工, 2011, 42(3):1-6.
54	LONG Jun, MAO Anguo, TIAN Songbai, et al. Development and commercial application of packaged techenology for catalytic decarboxylation and cracking of high acid crude oil[J]. Petroleum Processing and Petrochemicals, 2011, 42(3): 1-6.
55	申海平, 王玉章, 李锐. 高酸原油热处理脱酸的研究[J]. 石油炼制与化工, 2004, 35(2):32-35.
55	SHEN Haiping, WANG Yuzhang, LI Rui. Investigation on thermal treatment for decreasing the acidity of sour crude[J]. Petroleum Processing and Petrochemicals, 2004, 35(2): 32-35.
56	代保才, 丁冉峰, 冉国朋, 等. 高酸原油热脱酸实验研究[J]. 炼油与化工, 2008, 19(4): 14-17.
56	DAI Baocai, DING Ranfeng, RAN Guopeng, et al. Experimental research on thermal acid removal of high-acid crude oil[J]. Refining Chemical Industry, 2008, 19(4): 14-17.
57	张同旺, 侯拴弟. 石油酸催化转化过程的研究[J]. 化学工业与工程, 2009, 26(4): 316-320.
57	ZHANG Tongwang, HOU Shuandi. Catalytic conversion of petroleum acid[J]. Chemical Industry and Engineering, 2009, 26(4): 316-320.
58	胡永庆, 刘熠斌, 林伟昌, 等. 环烷酸在不同催化剂上的催化脱酸[J]. 石油学报(石油加工), 2011, 27(3): 355-360.
58	HU Yongqing, LIU Yibin, LIN Weichang, et al. Catalytic deacidification of naphthenic acid over various catalysts[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2011, 27(3): 355-360.
59	WANG Yanzhen, ZHONG Dule, DUAN Hongling, et al. Removal of naphthenic acids from crude oils by catalytic decomposition using Mg-Al hydrotalcite/γ-Al₂O₃ as a catalyst[J]. Fuel, 2014, 134: 499-504.
60	DIAS Heloís P, GONCALVES Gustavo R, FREITAS Jair C C, et al. Catalytic decarboxylation of naphthenic acids in crude oils[J]. Fuel, 2015, 158: 113-121.
61	郭莎莎, 许海龙, 张海洪, 等. 绥中36-1常二线馏分油脱酸工艺分析[J]. 长春工程学院学报(自然科学版), 2016, 17(2): 126-128.
61	GUO Shasha, XU Hailong, ZHANG Haihong, et al. The deacidification process analysis to suizhong 36-1 regular second line distillate[J]. Journal of Changchun Institute of Technology (Natural Science Edition), 2016, 17(2): 126-128.
62	ELSAMANI I A Q, MUSTAFA M A. Reduction of naphthenic acids in high TAN crude oil using a fluid catalytic cracking catalyst[J]. Petroleum Science & Technology, 2018, 36(1): 1-6.
63	FU Xiaoqin, DAI Zhenyu, TIAN Songbai, et al. Catalytic decarboxylation of petroleum acids from high acid crude oils over solid acid catalysts[J]. Energy & Fuels, 2008, 22(3): 1923-1929.
64	黄明福, 刘振志, 李萍, 等. 微波辐射润滑油脱酸精制方法的研究[J]. 润滑油, 2003, 18(2):18-21.
64	HUANG Mingfu, LIU Zhenzhi, LI Ping, et al. Study on the removal of acid from lubricating oil using microwave radiation[J]. Lubricating Oil, 2003, 18(2): 18-21.
65	颜曦明, 李晓鸥, 李东胜, 等. 润滑油馏分脱酸技术研究进展[J]. 化学与粘合, 2011, 33(2): 61-65.
65	YAN Ximing, LI Xiaoou, LI Dongsheng, et al. The progress in research on deacidification technology for lubricating oil distillate[J]. Chemistry and Adhesion, 2011, 33(2): 61-65.
66	李雪辉, 李榕, 陈学伟, 等. 碱性离子液体的研究进展[J]. 工业催化, 2007, 15(5):1-5.
66	LI Xuehui, LI Rong, CHEN Xuewei, et al. Latest researches in basic ionic liquids[J]. Industrial Catalysis, 2007, 15(5): 1-5.
67	王丁, 黄风林, 黎小辉, 等. 润滑油基础油脱酸技术研究进展[J]. 石油化工应用, 2019, 38(5): 11-14.
67	WANG Ding, HUANG Fenglin, LI Xiaohui, et al. Recent advances in deacidfication of lube base oil[J]. Petrochemical Industry Application, 2019, 38(5): 11-14.
68	于英豪. 环烷酸类离子液体的合成、表征及应用研究[D]. 北京: 中国科学院过程工程研究所, 2009.
68	YU Yinghao. Synthesis, characterization and application of naphthenic acid ionic liquids[D]. Beijing: Institute of Process Engineering, Chinese Academy of Sciences, 2009.
69	SHAH S N, MUTALIB M I A, PILUS R B M, et al. Separation of naphthenic acid using hydroxide based ionic liquids[J]. Applied Mechanics & Materials, 2014, 625: 570-573.
70	ANDERSON K, ATKINS M P, GOODRICH P, et al. Naphthenic acid extraction and speciation from Doba crude oil using carbonate-based ionic liquids[J]. Fuel, 2015, 146: 60-68.
71	SHAH S N, MUTALIB M I A, PILUS R B M, et al. Extraction of naphthenic acid from highly acidic oil using hydroxide-based ionic liquids[J]. Energy & Fuels, 2016, 29(1): 106-111.
72	SHAH S N, CHELLAPPAN L K, GONFA G, et al. Extraction of naphthenic acid from highly acidic oil using phenolate based ionic liquids[J]. Chemical Engineering Journal, 2015, 29(4): 106-111.
73	NAJMUDDIN R A, MUTALIB M I A, SHAH S N, et al. Liquid-liquid extraction of naphthenic acid using thiocyanate based ionic liquids[J]. Procedia Engineering, 2016, 148: 662-670.
74	WU Chongchong, DE Visscher A, GATES I D. Molecular interactions between 1-butyl-3-methylimidazolium tetrafluoroborate and model naphthenic acids: a DFT study[J]. Journal of Molecular Liquids, 2017, 243: 462-471.
75	SUN Yu, LI Shi. Basic ionic liquids with imidazole anion: new reagents to remove naphthenic acids from crude oil with high total acid number[J]. Fuel, 2012, 99(9): 83-87.
76	SHI Lijuan, SHEN Benxian, WANG Gongqun. Removal of naphthenic acids from Beijiang crude oil by forming ionic liquids[J]. Energy & Fuels, 2008, 22(6): 4177-4181.
77	师丽娟, 沈本贤, 汪恭群. 基于离子液体的高酸原油脱酸效果研究[J]. 石油炼制与化工, 2008, 39(12):16-20.
77	SHI Lijuan, SHEN Benxian, WANG Gongqun. Study on removing naphthenic acids from highly acidic crude oil by forming ionic liquids[J]. Petroleum Processing and Petrochemicals, 2008, 39(12): 16-20.
78	李静. 离子液体脱除酸性油品中环烷酸的研究[D]. 上海: 华东理工大学, 2011.
78	LI Jing. Study on removal of naphthenic acid from acidic oils[D]. Shanghai: East China University of Science and Technology, 2011.
79	王婷, 蔡文静, 刘熠斌, 等. 固体酸催化制备生物柴油研究进展[J]. 化工进展, 2016, 35(9): 2783-2789.
79	WANG Ting, CAI Wenjing, LIU Yibin, et al. Research progress in preparation of biodiesel with solid acid catalyst[J]. Chemical Industry and Engineering Progress, 2016, 35(9): 2783-2789.
80	李工, 徐小军, 徐恒, 等. 新型离子液体型固体酸的合成及其在酯化反应中的应用[J]. 石油化工, 2012, 41(6): 641-646.
80	LI Gong, XU Xiaojun, XU Heng, et al. Synthesis of novel ionic liquid-based solid acids and their catalytic performances in esterifications[J]. Petrochemical Technology, 2012, 41(6): 641-646.
81	廖洋, 赵仕林. SO₄^2-/M_xO_y类固体酸催化剂研究进展[J]. 四川师范大学学报(自然科学版), 2017, 40(5): 577-584.
81	LIAO Yang, ZHAO Shilin. Review of SO₄^2-/M_xO_y solid acid catalysts[J]. Journal of Sichuan Normal University（Natural Science）, 2017, 40(5): 577-584.
82	WANG Yanzhen, LI Jinyun, SUN Xueying, et al. Removal of naphthenic acids from crude oils by fixed-bed catalytic esterification[J]. Fuel, 2014, 116: 723-728.
83	梁金强, 王延臻, 钟读乐. 新型催化剂酯化高酸原油脱酸的研究[J]. 现代化工, 2011, 31(2): 40-42.
83	LIANG Jinqiang, WANG Yanzhen, ZHONG Dule. Study on new deacidification catalyst for crude oil with high acid value[J]. Modern Chemical Industry, 2011, 31(2): 40-42.
84	何柏, 汪建康, 游晓兰, 等. 减压馏分油催化酯化脱酸的研究[J]. 石油化工, 2013, 42(11):1282-1285.
84	HE Bai, WANG Jiankang, YOU Xiaolan, et al. Deacidification of vacuum gas oil by catalytic esterification[J]. Petrochemical Technology, 2013, 42(11): 1282-1285.
85	何柏, 刘世成, 陈昌国, 等. 减四线馏分油的酯化脱酸反应[J]. 精细化工, 2018, 35(8):1408-1413.
85	HE Bai, LIU Shicheng, CHEN Changguo, et al. Deacidification of 4^th vacuum gas oil by catalytic esterification[J]. Fine Chemicals, 2018, 35(8): 1408-1413.
86	HE Bai, FU Xue, LIAN Xin, et al. Catalytic deacidification of vacuum gas oil by ZnO/Al₂O₃ and its modificatio