胡发亭,毛学锋,李军芳,赵鹏,刘敏
HU Fating,MAO Xuefeng,LI Junfang,ZHAO Peng,LIU Min

• 1:煤炭科学技术研究院有限公司煤化工分院
• 2:煤炭资源开采与洁净利用国家重点实验室
• 3:国家能源煤炭高效利用与节能减排技术装备重点实验室

摘要(Abstract)：

2-甲基萘是一种重要的有机化工原料，用途广泛，随着我国精细化工行业的迅速发展，从洗油中分离精制2-甲基萘受到重视。基于洗油加工，论述了从煤焦油中分离精制2-甲基萘的技术特点，介绍了国内外生产2-甲基萘的工业化现状及工艺，并对2-甲基萘分离精制技术研究、产业化发展方向进行了展望。洗油中多种组分相互间可形成多种共沸物和共熔物，很难利用单一的分离精制工艺方法从洗油中得到高纯度2-甲基萘。目前2-甲基萘的分离精制技术是精馏法、共沸精馏法、烷基化法、酸碱洗涤法、异构化法、溶剂重结晶法、溶剂萃取法、冷冻结晶法等单一分离方法的组合。洗涤精馏结晶法成熟可靠，是工业上使用最广泛的2-甲基萘生产技术，但酸碱洗涤存在环境污染、设备腐蚀等问题。洗涤和多级精馏相结合的方法工艺流程简单、生产效率高，但产品纯度有待提高。精馏和共沸精馏相结合的方法绿色环保、成本低，产品中吲哚含量低，是未来分离精制2-甲基萘的发展方向。化学反应和精馏结晶相结合分离精制2-甲基萘的收率高，产品纯度高，但化学反应所需的特殊反应器和催化剂增加了生产成本。国内生产2-甲基萘的企业与国外相比，在产品种类和纯度、能耗、环保等方面存在差距，绿色环保和高效节能是洗油加工企业未来的发展趋势。加强新技术、新工艺的开发，提高产品收率和纯度，解决2-甲基萘分离精制中的产业化、规模化的技术问题，是提高煤化工企业经济和社会效益的有效手段。开发洗油加工中2-甲基萘的绿色分离过程工艺，提高各种分离精制方法的耦合水平，既符合化工生产过程中“节能低碳”的环保要求，也是未来洗油深加工技术的发展方向。
2-Methylanaphthalene is an important organic chemical raw material with a wide application range. With the rapid development of fine chemical industry, separating 2-methyl naphthalene from washing oil has received attention. From the perspective of oil washing processing, the technical characteristics of various separation and purification 2-methylnaphthalene techniques from wash oil were discussed. The industrial status and technological characteristics of 2-methylnaphthalene production at home and abroad were introduced, and the development direction of 2-methylnaphthalene separation and purification technologies and industrialization were prospected. Wash oil′s components form many azeotrope and eutectic mixture. It is difficult to separate and refine 2-methylnaphthalene products with high purity from wash oil by a single process of separating and refining method. At present, the separation and purification techniques of 2-methylnaphthalene are the combination of distillation, azeotropic distillation, alkylation, acid-alkaline washing, isomerization, solvent recrystallization, solvent extraction, freezing crystallization and so on. The washing-distillation-crystallization method is mature and reliable, which is the most widely used 2-methylnaphthalene production technology in industry. However, acid and alkali washing has environmental pollution, equipment corrosion and other problems. The process of washing and multistage distillation is simple and the production efficiency is high, but the purity of the product needs to be improved. The combination of distillation and azeotropic distillation is green, low cost and low indole content. It is the development direction of separating and refining 2-methyl naphthalene in the future. The method of combining chemical reaction with distillation crystallization is high in yield and purity, but the special reactor and catalyst needed for chemical reaction increase the production cost. Compared with similar enterprises abroad, domestic enterprises producing 2-methylnaphthalene have gaps in product type and purity, energy consumption, environmental protection and so on. Green environmental protection and high efficiency energy saving are the future development trends of oil washing processing enterprises. It is an effective means to improve the economic and social benefits of coal chemical enterprises to strengthen the development of new technologies and new processes, improve the product yield and purity, and solve the technical problems of industrialization and scale in 2-methyl naphthalene separation and refining. The development of the green separation process of 2-methyl naphthalene in oil washing processing to improve the coupling level of various separation and refining methods will not only meet the environmental protection requirements of "energy saving and low carbon" in the chemical production process, but also is the development direction of the future oil washing deep processing technology.

关键词(KeyWords)： 洗油;煤焦油;分离精制;2-甲基萘;精馏;洗涤;结晶
wash oil;coal tar;separation and purification;2-methylnaphthalene;rectification;washing;crystallization

Abstract:

Keywords:

基金项目(Foundation): 天地科技股份有限公司科技创新创业资金专项资助项目(2020-TD-MS004)

作者(Author): 胡发亭,毛学锋,李军芳,赵鹏,刘敏
HU Fating,MAO Xuefeng,LI Junfang,ZHAO Peng,LIU Min

DOI: 10.13226/j.issn.1006-6772.20092202

参考文献(References)：

• [1] 李军芳，谷小会，杜淑凤.煤焦油及馏分油的分析方法及其评价[J].煤质技术，2019,34(1):5-10.LI Junfang,GU Xiaohui,DU Shufeng.Analysis method and evaluation of coal tar and distillate oil[J].Coal Quality Technology,2019,34(1):5-10.
• [2] 雷明.降膜结晶法提纯β-甲基萘的研究[D].兰州：兰州大学，2012.
• [3] 韩宇开，杨培，李兵.洗油馏分及其初步分离工艺[J].煤炭与化工，2014,37(5):52-54,138.HAN Yukai,YANG Pei,LI Bing.Wash oil fractions and their preliminary separation technologies[J].Coal and Chemical Industry,2014,37(5):52-54,138.
• [4] 马利军.洗油深加工产品的提取及应用前景[J].化学工业，2011,29(4):25-28.MA Lijun.Extractionand application of deep oil washing product[J].Chemical Industry,2011,29(4):25-28.
• [5] 唐文秀.10万吨苯加氢工艺及分离甲基萘前景展望[J].广东化工，2018,45(20):191-192.TANG Wenxiu.Prospect of 100 000 ton benzene hydrogenation process and separation of methylnaphthalene [J].Guangdong Chemical Industry,2018,45(20):191-192.
• [6] 杨硕，李群生，常秋连.洗油深加工技术的研究与开发[J].煤炭与化工，2018,41(9):133-136,144.YANG Shuo,LI Qunsheng,CHANG Qiulian.Research and development of deep processing technology for washing oil[J].Coal and Chemical Industry,2018,41(9):133-136,144.
• [7] 罗义文，王明亮，龙云，等.从洗油中分离精制β-甲基萘新工艺[C]//2004中国金属学会青年学术年会.福州：福州大学，2004.
• [8] 程志宇，沈和平，熊柱松，等.高温煤焦油洗油馏分的新加工方案探讨[J].煤化工，2016,44(2):20-24.CHENG Zhiyu,SHEN Heping,XIONG Zhusong,et al.Study on a new process scheme of washing oil distillate from high temperature coal tar[J].Coal Chemical Industry,2016,44(2):20-24.
• [9] 王凤武.煤焦油洗油组分提取及其在精细化工中的应用[J].煤化工，2004(2):26-28.WANG Fengwu.Extraction of washing oil distillate from tar and its application in fine chemical industry[J].Coal Chemical Industry,2004(2):26-28.
• [10] 何庆香，程红，王国平，等.浅析洗油深加工工艺[J].包钢科技，2002,28(6):9-11.HE Qingxiang,CHENG Hong,WANG Guoping,et al.Brief analysis on washing oil deep production process[J].Science & Technology of Baotou Steel Corporation,2002,28(6):9-11.
• [11] 罗义文.双炉双塔洗油馏分加工工艺设计[J].四川冶金，2007,29(2):36-39.LUO Yiwen.Process design of washing oil industrial separation with twin furnaces and twin column[J].Sichuan Metallurgy,2007,29(2):36-39.
• [12] FELDMAN J,ORCHIN M.Separation of 1- and 2-methylnaphthalenes by azeotropic distillation[J].Industrial & Engineering Chemistry,1952,44(12):107-110.
• [13] 奥井信之.共沸蒸馏法分离精制1-甲基萘和2-甲基萘[J].化学经济，1988(12):76-81.
• [14] 洪汉贵，郭金海，魏运秩.从煤焦油粗甲基萘精制β-甲基萘的方法：CN1172096A[P].1998-02-04.
• [15] 腾占才，毕红梅，夏远亮，等.高纯度β-甲基萘的工艺研究[J].黑龙江八一农垦大学学报，2002,14(2):100-102.TENG Zhancai,BI Hongmei,XIA Yuanliang,et al.The study of highly pure β-methylnaphthalene′s preparation techniques[J].Journal of Heilongjiang Bayi Agricultural University,2002,14(2):100-102.
• [16] 张俊峰，陈启文，薛永强，等.不同共沸剂对洗油中β-甲基萘分离的影响[J].山西化工，2006,26(1):31-32.ZHANG Junfeng,CHEN Qiwen,XUE Yongqiang,et al.Effect of different azeotrope formers on separation of β-methylnaphthal-ene in washing oil[J].Shanxi Chemical Industry,2006,26(1):31-32.
• [17] 邱广德.焦化洗油深加工工艺系统的优化和开发研究[D].大连：大连理工大学，2005.
• [18] 魏庆开.从工业甲基萘中提取β-甲基萘[J].燃料与化工，2001,32(4):205-206.WEI Qingkai.Extracted β-methylnaphthalene from industrial methyl naphthalene[J].Fuel & Chemical Processes,2001,32(4):205-206.
• [19] 腾占才，毕洪梅，高金玲，等.β-甲基萘的精制[J].佳木斯大学学报(自然科学版),2004,22(4):502-507.TENG Zhancai,BI Hongmei,GAO Jinling,et al.The β-methylnaphthalene′s refine techniques[J].Journal of Jiamusi University (Natural Science Edition),2004,22(4):502-507.
• [20] 张振华.洗油的分离与应用研究[D].兰州：兰州大学，2012.
• [21] 齐国栋，白仲兰，李素坤，等.2-甲基萘从洗油中分离提纯的研究[J].洁净煤技术，2010,16(3):116-119.QI Guodong,BAI Zhonglan,LI Sukun,et al.Separation and purification of 2-methylnaphthalene from wash oil[J].Clean Coal Technology,2010,16(3):116-119.
• [22] 何锡财.从洗油中分离精制β-甲基萘[J].四川冶金，2007,29(2):40-44.HE Xicai.Purification of β-methylnaphthalene from wash oil[J].Sichuan Metallurgy,2007,29(2):40-44.
• [23] 鄂永胜，鄢景森，代文双，等.一种焦化洗油深加工工艺：CN102268273A[P].2011-07-18.
• [24] 李艳芳，曹祖宾，李丹东，等.萃取-精馏法从乙烯焦油中提取β-甲基萘[J].化工进展，2010,29(11):2049-2052.LI Yanfang,CAO Zubin,LI Dandong,et al.Isolation of β-methylnaphthalene from ethylene tar through extraction-rectification[J].Chemical Industry and Engineering Progress,2010,29(11):2049-2052.
• [25] 杨红霞，栾丽杰.洗油中分离和精制β-甲基萘的工艺优化[J].广东化工，2011,38(10):50-51.YANG Hongxia,LUAN Lijie.Process optimization of separation and purification β-methylnaphthalene in wash oil[J].Guangdong Chemical Industry,2011,38(10):50-51.
• [26] 汪旭，顾镇钧，袁康入，等.从煤焦油中同时提取高纯度β-甲基萘和吲哚的方法：CN101774879A[P].2010-07-14.
• [27] 张春婷.洗油中β-甲基萘和苊的提取[D].太原：太原理工大学，2007.
• [28] 姚润生，薛永强，王志忠.从洗油中分离和精制β-甲基萘的新工艺[J].煤炭转化，2009,32(2):25-27.YAO Runsheng,XUE Yongqiang,WANG Zhizhong.A new progress of separating and refining β-methylnaphthalene from gas absorber oil[J].Coal Conversion,2009,32(2):25-27.
• [29] 李健，张德敬，姚君，等.一种采用连续共沸精馏工艺生产β-甲基萘的方法：CN106146245A[P].2016-11-23.
• [30] 齐大彬.一种β-甲基萘提纯系统：CN209537346A[P].2019-10-25.
• [31] 张曾，刘锋，李崇，等.从焦油中提取1-甲基萘和2-甲基萘的方法：CN1721380A[P].2016-01-18.
• [32] 谈勇，谈俊，江晓龙，等.一种从洗油中有效分离提纯2-甲基萘的方法：CN109293464A[P].2019-02-01.
• [33] 谈勇，谈俊，江晓龙.一种基于超临界和超声波的β-甲基萘的分离和精制方法：CN108586184A[P].2018-09-28.
• [34] 熊道陵，陈玉娟，王庚亮.洗油分离精制应用技术[M].北京：冶金工业出版社，2013.
• [35] 刘晟铭，张金涛，薛璋，等.一种β-甲基萘脱除吲哚的方法及装置：CN102935292A[P].2013-02-20.
• [36] 闫建康.气相色谱法测定煤焦油重萘和甲基萘的含量[J].化工技术与开发，2019,48(6):44-45.YAN Jiankang.Determination of naphthalene and methylnaphthalene in coal tar by gas chromatography[J].Technology & Development of Chemical Industry,2019,48(6):44-45.
• [37] 朱政.熔融结晶法提纯β-甲基萘研究[D].天津：天津大学，2007.
• [38] 李军.β-甲基萘的净制方法：CN107459440A[P].2017-12-12.
• [39] 杨云.洗油初蒸馏塔的新工艺流程模拟研究[J].煤化工，2014(2):61-64.YANG Yun.Simulation study of the new process of the wash oil pre-distillation column[J].Coal Chemical Industry,2014(2):61-64.
• [40] 于锦军.从煤焦油洗油中提取高纯度β-甲基萘的方法：CN103992199A[P].2014-08-20.
• [41] 李铁鲁.煤焦油超临界甲醇抽提的研究[D].武汉：武汉科技大学，2011.
• [42] 赵鹏程，姚婷，杨宏伟，等.煤焦油的加工工艺及研究现状[J].广州化工，2013,41(1):26-29.ZHAO Pengcheng,YAO Ting,YANG Hongwei,et al.Research status and processing technology of coal tar[J].Guangzhou Chemical Industry,2013,41(1):26-29.
• [43] 张雄文，闫宏福.新日化公司洗油加工技术简介[J].燃料与化工，2002,33(4):212-213.ZHANG Xiongwen,YAN Hongfu.Brief introduction to wash oil processing technology of the chemical Co.,Nippon Steel Corporation[J].Fuel & Chemical Process,2002,33(4):212-213.
• [44] 何选明，张连斌，潘琛，等.洗油精细加工现状与绿色分离过程开发[J].广东化工，2011,38(5):40-41,56.HE Xuanming,ZHANG Lianbin,PAN Chen,et al.Production process and development of green separation of fine chemicals in wash oil[J].Guangdong Chemical Industry,2011,38(5):40-41,56.