直馏柴油氨精制脱酸新技术研究
|
摘要
碱洗电精制-硫酸中和法间歇工艺是国内外精制直馏柴油的经典方法，该法虽然能够生产出合格的柴油产品和环烷酸副产品，但仍存在使用强酸、强碱，且不能再生，设备腐蚀严重，操作能耗与操作费用高，有废水排放等问题。氨法精制直馏柴油是国内外近十几年来开发的热点，采用的溶剂为氨-低分子醇(如甲醇、乙醇和异丙醇)-水体系，又称为醇氨法，低分子醇主要起防乳化和破乳作用。该法克服了碱洗电精制的缺点，具有取消高压电场，不使用强酸、强碱，无或大大减少“三废”排放，溶剂循环使用，连续操作，可同时得到精制柴油和环烷酸产品的优点，是一种具有发展前景的油品精制方法。氨法多采用乙醇破乳剂，但仍存在剂油体积比高、溶剂中乙醇用量高、溶剂再生能耗高及溶剂损耗大等问题。为此，本文采用SW系列破乳剂替代乙醇，对兰州石化分公司生产的3种直馏柴油进行脱酸研究，主要完成了SW系列破乳剂评选，以直馏柴油(混合)为原料，对直馏柴油氨精制工艺的实验室操作条件(包括溶剂组成、反应温度、反应时间、相分离温度与时间、油剂比、溶剂引入含水量、聚结过滤等参数)进行了详细的优选研究，在最佳操作条件下对直馏柴油(青海)和直馏柴油(长庆)的适应性进行了考察，并对皂相与环烷酸的回收进行了系统的研究。分析了精制柴油与环烷酸质量，建立了全套的直馏柴油氨精制工艺的质量控制指标与分析方法，获得了直馏柴油氨精制的原则工艺流程、实验室操作条件。实验结果表明，评选出的SW-1、SW-2破乳剂完全能满足氨法精制直馏柴油的防乳化要求，开发的柴油脱酸新技术具有剂油体积比小、溶剂能循环使用、连续操作、能耗低、无“三废”排放等优点，精制柴油酸度＜10mgKOH／100ml，不含残余溶剂，完全满足柴油质量标准。
Alkali washing and electricity refining is the classic method used in the world for processing the straight-run diesel. Though qualified diesel and naphthenic acids can be obtained through this process, there are lots of problems, such as the use of strong acids, strong alkali that can not be recoveried, the charge for operation is high and severe corrosion in equipment The study of ammonia process for refining straight-run diesel is active in recent years at home and abroad. The solution that contains low molecular weight alcohol, ammonia and water is adopted in the process called as alcohol-ammonia method. This process resolves problems in the alkali washing and electricity refining process. There are many advantages. For example, the use of high voltage field and the strong acids and alkali is canceled, in addition, the process can be operated continuously and the solution can be recoveried without "three-waste". Therefore, this process is a promising method for refining oils. However, there are many pro
blems in the ammonia method in which ethanol is used as demulsifing agent, such as the high volume ratio of the solution and oil, the high dosage of the ethanol, the high consume of energy and the high wastage of solution. To solve those said problems, complex solution method in which series of SW-demulsifier qualify to demulsification is adopted to substitute for alcohol-ammonia method in this paper. Accordingly, this paper mainly has an laboratorial research on deacidification of three kinds of straight-run diesel produced by Lanzhou Petroleum-chemical corporation. A lot of work has been done, for example, having selected the kind of demulsifier; having studied about operating parameters for refining diesel (Hunhe) including the solution makeup, react temperature and time, phase separation temperature and time, volume ratio of oil and solution, extraneous water and gathering filtration; having examined the adaptability of the best operating parameters of the diesel (Hunhe) for refining the diesel (Qingh
ai) and diesel (Changqing); having studied about recovering the soap and naphthenic acid; to analyse the quality of treated oil and naphthenic acid; having established series of control objectives and analysis method of ammonia method for refining diesel; having obtained the schedule drawing and laboratorial operating parameters. It shows that the two kinds of SW-1 and SW-2 demulsifier qualify to demulsification in the ammonia process for refining diesel. In addition, Experiment shows the new deacidification technology has many advantages, for instance, the ratio of the solution and the oil is low, the solution can be recoveried, the process can be operated continuously without "three-waste" and the consume of energy is low. What's more, the treated oil having acid number lower than 10mgKOH/100ml remains no solution and meets the standards of the diesel.
Alkali washing and electricity refining is the classic method used in the world for processing the straight-run diesel. Though qualified diesel and naphthenic acids can be obtained through this process, there are lots of problems, such as the use of strong acids, strong alkali that can not be recoveried, the charge for operation is high and severe corrosion in equipment The study of ammonia process for refining straight-run diesel is active in recent years at home and abroad. The solution that contains low molecular weight alcohol, ammonia and water is adopted in the process called as alcohol-ammonia method. This process resolves problems in the alkali washing and electricity refining process. There are many advantages. For example, the use of high voltage field and the strong acids and alkali is canceled, in addition, the process can be operated continuously and the solution can be recoveried without "three-waste". Therefore, this process is a promising method for refining oils. However, there are many pro
blems in the ammonia method in which ethanol is used as demulsifing agent, such as the high volume ratio of the solution and oil, the high dosage of the ethanol, the high consume of energy and the high wastage of solution. To solve those said problems, complex solution method in which series of SW-demulsifier qualify to demulsification is adopted to substitute for alcohol-ammonia method in this paper. Accordingly, this paper mainly has an laboratorial research on deacidification of three kinds of straight-run diesel produced by Lanzhou Petroleum-chemical corporation. A lot of work has been done, for example, having selected the kind of demulsifier; having studied about operating parameters for refining diesel (Hunhe) including the solution makeup, react temperature and time, phase separation temperature and time, volume ratio of oil and solution, extraneous water and gathering filtration; having examined the adaptability of the best operating parameters of the diesel (Hunhe) for refining the diesel (Qingh
ai) and diesel (Changqing); having studied about recovering the soap and naphthenic acid; to analyse the quality of treated oil and naphthenic acid; having established series of control objectives and analysis method of ammonia method for refining diesel; having obtained the schedule drawing and laboratorial operating parameters. It shows that the two kinds of SW-1 and SW-2 demulsifier qualify to demulsification in the ammonia process for refining diesel. In addition, Experiment shows the new deacidification technology has many advantages, for instance, the ratio of the solution and the oil is low, the solution can be recoveried, the process can be operated continuously without "three-waste" and the consume of energy is low. What's more, the treated oil having acid number lower than 10mgKOH/100ml remains no solution and meets the standards of the diesel.
引文
[1] 李淑贞．杨俊杰．环烷酸与石油磺酸镁．第一版．北京：石油工业出版社，1982：1～10页．
[2] 李成武，苏桂荣．石油产品分析．第一版．哈尔滨：哈尔滨船舶工程学院出版社，1989．97～120页．
[3] 张丕烈，田宗秀等．辽河原油的腐蚀规律及防护问题．炼油设计，1991(1)：46～64
[4] 郑浩．含酸原油的加工．炼油设计，1994，24(2)：1～9
[5] 任凭飞．我国环烷酸精制工艺及应用进展．精细石油化工，2000，(6)：29～31
[6] 徐永强等．用有机溶剂抽提直馏柴油中的环烷酸．石油大学学报，1997，21(5)：64～66
[7] 李恪．克拉玛依九区重质原油中环烷酸分离方案的研究．西安石油学院学报，1991(2)：23～25
[8] Danzik.PROCESS FOR REMOVING NAPHTHENIC ACIDS FROM PETROLEUM DISTILLATES.U.S, 4634519.Jan.6, 1987
[9] Sartori.METAL COMPOUNDS AS ACCELERATORS FOR PETROLEUM ACID ESTERIFICATION.U.S, 5948238.Sep.7, 1999
[10] 阮济之等．石油环烷酸的精制方法．中国，94103538．7．1996年5月15日
[11] 徐岳峰等．从原油中脱除石油酸的方法．中国，90107685．6．1991年2月20日
[12] 宋平等．碳化法处理碱渣技术及其应用．河南石油，2001，15(4)：49～50
[13] 钱建华等．氧化亚锡催化合成环烷酸酯的研究．精细石油化工，1994，(3)：8～10．
[14] 罗来龙．SnO催化合成环烷酸乙二醇酯增塑剂的研究．精细石油化工，1994，(5)：56～63
[15] 李子叔．环烷酸提纯方法探讨．新疆石油科技，1997，7(1)：70～74
[16] 安久玉．直馏柴油碱渣甲醇稀秆法脱油脱脂肪酸钠．石油炼制，1991，(6)：67～68
[17] 田原宇．络合萃取法精制直馏柴油的研究．现代化工，2000，20(10)：41～43
[18] 吕效平．重质高酸值原油及其油品脱环烷酸工艺研究进展．化工进展，1999，(4)：54～56
[19] 澄宇．加工新疆高含酸原油的对策．石油炼制与化工，1982，(4)：45～47
[20] 范维玉．柴油无污染脱酸精制工艺研究．石油炼制与化工．1997，21(1)：43～46
[21] 徐心茹．高酸度稠油的脱盐脱酸．华东理工大学学报，1999，25(4)：357～359
[22] 徐永强．直馏柴油溶剂抽提精制．石油炼制与化工，1997，28(9)：81～85
[23] 范维玉．用溶剂萃取法精制粗环烷酸．石油大学学报，1996，20(3)：105～108
[24] 周世烈．石油加工中的环烷酸分离．陕西化工，1990．(1)：48～50
[25] 吴明清．石油酸钠的水溶性规律探讨．石油学报．1998，14(1)：12～15
[26] 徐心茹．高酸度柴油碱洗防乳化的研究．炼油设计，1993，23(5)：26～28
[27] 吴明清．石油酸钠对馏分油的增溶研究．炼油设计，1999，15(4)：33～36
[28] 王连成．电破乳的机理．石油炼制，1994，(7)：55～58
[29] 张明耀．常压直馏柴油碱洗乳化原因分析．天然气与石油，2001，19(2)：17～19
[30] 宫文爱．消除柴油乳化的精制流程．石油炼制，(2)：37～39
[31] 徐心茹．不同酸度的柴油碱洗防乳化研究．华东理工大学学报，1998，24(1)：54～58
[32] 吴明清．石油酸钠的表面活性研究．石油学报，1999，15(3)：1～4
[33] 唐晓东，周建军．乙醇-氨法化学萃取精制直馏柴油研究．燃料化学学报，2002，30(6)：500～504
[34] 唐晓东，高纯林．直馏柴油氨精制工艺研究进展．炼油设计，2001，31(2)：8～11
[35] 北京大学数学力学系概率统计组编．正交设计法．第一版．北京：石油化学工业出版社，1976．1～15页
[2] 李成武，苏桂荣．石油产品分析．第一版．哈尔滨：哈尔滨船舶工程学院出版社，1989．97～120页．
[3] 张丕烈，田宗秀等．辽河原油的腐蚀规律及防护问题．炼油设计，1991(1)：46～64
[4] 郑浩．含酸原油的加工．炼油设计，1994，24(2)：1～9
[5] 任凭飞．我国环烷酸精制工艺及应用进展．精细石油化工，2000，(6)：29～31
[6] 徐永强等．用有机溶剂抽提直馏柴油中的环烷酸．石油大学学报，1997，21(5)：64～66
[7] 李恪．克拉玛依九区重质原油中环烷酸分离方案的研究．西安石油学院学报，1991(2)：23～25
[8] Danzik.PROCESS FOR REMOVING NAPHTHENIC ACIDS FROM PETROLEUM DISTILLATES.U.S, 4634519.Jan.6, 1987
[9] Sartori.METAL COMPOUNDS AS ACCELERATORS FOR PETROLEUM ACID ESTERIFICATION.U.S, 5948238.Sep.7, 1999
[10] 阮济之等．石油环烷酸的精制方法．中国，94103538．7．1996年5月15日
[11] 徐岳峰等．从原油中脱除石油酸的方法．中国，90107685．6．1991年2月20日
[12] 宋平等．碳化法处理碱渣技术及其应用．河南石油，2001，15(4)：49～50
[13] 钱建华等．氧化亚锡催化合成环烷酸酯的研究．精细石油化工，1994，(3)：8～10．
[14] 罗来龙．SnO催化合成环烷酸乙二醇酯增塑剂的研究．精细石油化工，1994，(5)：56～63
[15] 李子叔．环烷酸提纯方法探讨．新疆石油科技，1997，7(1)：70～74
[16] 安久玉．直馏柴油碱渣甲醇稀秆法脱油脱脂肪酸钠．石油炼制，1991，(6)：67～68
[17] 田原宇．络合萃取法精制直馏柴油的研究．现代化工，2000，20(10)：41～43
[18] 吕效平．重质高酸值原油及其油品脱环烷酸工艺研究进展．化工进展，1999，(4)：54～56
[19] 澄宇．加工新疆高含酸原油的对策．石油炼制与化工，1982，(4)：45～47
[20] 范维玉．柴油无污染脱酸精制工艺研究．石油炼制与化工．1997，21(1)：43～46
[21] 徐心茹．高酸度稠油的脱盐脱酸．华东理工大学学报，1999，25(4)：357～359
[22] 徐永强．直馏柴油溶剂抽提精制．石油炼制与化工，1997，28(9)：81～85
[23] 范维玉．用溶剂萃取法精制粗环烷酸．石油大学学报，1996，20(3)：105～108
[24] 周世烈．石油加工中的环烷酸分离．陕西化工，1990．(1)：48～50
[25] 吴明清．石油酸钠的水溶性规律探讨．石油学报．1998，14(1)：12～15
[26] 徐心茹．高酸度柴油碱洗防乳化的研究．炼油设计，1993，23(5)：26～28
[27] 吴明清．石油酸钠对馏分油的增溶研究．炼油设计，1999，15(4)：33～36
[28] 王连成．电破乳的机理．石油炼制，1994，(7)：55～58
[29] 张明耀．常压直馏柴油碱洗乳化原因分析．天然气与石油，2001，19(2)：17～19
[30] 宫文爱．消除柴油乳化的精制流程．石油炼制，(2)：37～39
[31] 徐心茹．不同酸度的柴油碱洗防乳化研究．华东理工大学学报，1998，24(1)：54～58
[32] 吴明清．石油酸钠的表面活性研究．石油学报，1999，15(3)：1～4
[33] 唐晓东，周建军．乙醇-氨法化学萃取精制直馏柴油研究．燃料化学学报，2002，30(6)：500～504
[34] 唐晓东，高纯林．直馏柴油氨精制工艺研究进展．炼油设计，2001，31(2)：8～11
[35] 北京大学数学力学系概率统计组编．正交设计法．第一版．北京：石油化学工业出版社，1976．1～15页