|本期目录/Table of Contents|

[1]沈磊,何伟,方正,等.1,2-环己二醇的连续合成工艺研究[J].南京工业大学学报(自然科学版),2017,39(01):51-56.[doi:10.3969/j.issn.1671-7627.2017.01.009]
 SHEN Lei,HE Wei,FANG Zheng,et al.Continuous synthesis of cyclohexanediol in the micro-flow system[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2017,39(01):51-56.[doi:10.3969/j.issn.1671-7627.2017.01.009]
点击复制

1,2-环己二醇的连续合成工艺研究()
分享到:

《南京工业大学学报(自然科学版)》[ISSN:1671-7627/CN:32-1670/N]

卷:
39
期数:
2017年01期
页码:
51-56
栏目:
出版日期:
2017-01-21

文章信息/Info

Title:
Continuous synthesis of cyclohexanediol in the micro-flow system
文章编号:
1671-7627(2017)01-0051-06
作者:
沈磊何伟方正田启涛郭凯
南京工业大学 生物与制药工程学院 材料化学工程国家重点实验室,江苏 南京 210009
Author(s):
SHEN LeiHE WeiFANG ZhengTIAN QitaoGUO Kai
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering,Nanjing Tech University,Nanjing 210009,China
关键词:
环己烯 12-环己二醇 微反应器 连续合成
Keywords:
cyclohexene 12-cyclohexanediol microreactor continuous synthesis
分类号:
624
DOI:
10.3969/j.issn.1671-7627.2017.01.009
文献标志码:
A
摘要:
以环己烯为原料,在微反应器中将环氧化反应与水解反应串联制备1,2-环己二醇。实验发现,环氧化反应采用双氧水/甲酸体系,而皂化反应采用NaOH催化开环产物水解。在环氧化反应中,当选用HCOOH作为载氧体,n(环己烯):n(双氧水):n(HCOOH)=1:2:8,40 ℃下在微反应器中反应5 min; 在皂化反应中,n(环己烯):n(NaOH)为1:1.5,70 ℃下反应10 min,所得到的1,2-环己二醇的产率高达98.1%。
Abstract:
1,2-cyclohexanediol was synthesized by mixing epoxidation and hydrolysis reaction in the micro-flow system using cyclohexene as the raw material.Hydrogen peroxide/formic acid system was used in the epoxidation reaction,while sodium hydroxide was used as a catalyst in the hydrolysis reaction.With formic acid as oxygen carrier,the optimal results were obtained in the conditions:ratio of cyclohexene to hydrogen peroxide of 1:2,ratio of hydrogen peroxide to formic acid of 1:4,temperature of 40 ℃,residence time of 5 min,and the best results(98.1%)were observed when the mixture in the epoxidation was treated with 1.5 times the equivalent of sodium hydroxide in 70 ℃ for 10 min.

参考文献/References:

[1] EIPERT M,MAICHLE-MÖSSMER C,MAIER M E.Use of epoxidation and epoxide opening reactions for the synthesis of highly functionalized 1-oxaspiro[4.5] decan-2-ones and related compounds[J].Tetrahedron,2003,59(40):7949.
[2] GROOHTOOM N,NYOKONG T.Iron perchlorophthalocyanine and tetrasulfophthalocyanine catalyzed oxidation of cyclohexane using hydrogen peroxide,chloroperoxybenzoic acid and tert-butylhydroperoxide as oxidants[J].Journal of molecular cataylsis A:chemical,2002,179(1/2):113.
[3] TAKATSU H,TAKEUEHI K,TAMURA Y.Cyclohexenederivatives:EP,02331091[P].1989-09-06.
[4] TAKATSU H,TAKEUEHI K,SASKAI M.Physical properties of novel fluorinated ethers and ether mixtures of actively addressed twisted nematic liquid displays[J].Molecular crystals and liquid crystals,1991,206:159.
[5] STYTSENKO V D,DYAKONOV A Y,EIGENSON I A,et al.Kinetics and mechanisms of the reaction of l,2-cyclohexanediol on Ni-Sn ctalysts.Ⅱ.modeling and kinetic description of the dehydrogenation and hydrogenolysis proeesses[J].Kinetics and catalysis,1989,29(4):724.
[6] STYTSENKO V D,DYAKONOV A Y,EIGENSONI A,et al.Kinetics and mechanisms of the reaction of 1,2-cyclohexanediol on Ni-Sn catalysts Ⅰ.basic reaction principles[J].Kinetics and catalysis,1988,29(3):531.
[7] 于剑峰,吴通好.邻苯二酚与对苯二酚的生产与研究现状[J].精细石油化工,1997,11(6):28.
[8] LEE D G.Oxidation in organic chem[M].New York:Academic Press,1982.
[9] 王小光,杨月云.由环己烯合成1,2-环己二醇的研究进展[J].化工中间体,2009(6):5.
[10] 李小爽,徐建东,徐斌,等.偏钛酸催化水解环氧环己烷制备反-1,2-环己二醇[J].南京工业大学学报(自然科学版),2014,36(3):111.
[11] 周华,石晓华,周彩茉,等.固体超强酸催化水解1,2-环氧环己烷制备反式1,2-环己二醇[J].精细与专用化学品,2007,15(1):17.
[12] HASWELL S J,MIDDLETON R J,O’SULLIVAN B,et al.The application of microreactors to synthetic chemistry[J].Chemical communications,2001(5):391.
[13] ROBERGE D M,DUCRY L,BIELER N,et al.Microreactor technology:a revolution for the fine chemical and pharmaceutical industries[J].Chemical engineering & technology,2005,28(3):318.
[14] FORTT R,WOOTTON R C R,DE MELLO A J.Continuous-flow generation of anhydrous diazonium species:monolithic microfluidic reactors for the chemistry of unstable intermediates[J].Organic process research & development,2003,7(5):762.
[15] CHEN Y Z,ZHAO Y C,HAN M,et al.Safe,efficient and selective synthesis of dinitroherbicides via a multifunctional continuous-flow microreactor:one-step dinitration with nitric acid as agent[J].Green chemistry,2013,15:91.
[16] KNAPKIEWICZ P,SKOWERSKI K,JASKOLSKA D E,et al.Nitration under continuous flow conditions:convenient synthesis of 2-isopropoxy-5-nitrobenzaldehyde,an important building block in the preparation of nitro-substituted hoveyda-grubbs metathesis catalyst[J].Organic process research & development,2012,16:1430.
[17] EBRAHIMI F,KOLEHMAINEN E,OINAS P,et al.Production of unstable percarboxylic acids in a microstructured reactor[J].Chemical engineering journal,2011,167:713.
[18] ILLG T,HESSEL V,LOB P,et al.Novel process window for the safe and continuous synthesis of tert-butyl peroxy pivalate in a microreactor[J].Chemical engineering & technology,2011,167(2/3):504.
  
[19] MUNÑOZ MOLINA J,ALCÁZAR J,HOZ AYUSO A,et al.Preparation of amides mediated by isopropylmagnesium bromide under continuous flow conditions[J].Green chemistry,2012,14:1335.
[20] HE W,FANG Z,JI D,et al.Organic process research & development[J].Organic process research & development,2013,17:1137.
[21] 何伟,方正,万志东,等.微反应器在合成化学中的应用[J].应用化学,30(12):1375.
[22] GUNAWARDENA D A,FERNANDO S D.Deoxygenation of methanol over ZSM-5 in a high-pressure catalytic pyroprobe[J].Chemical engineering & technology,2011,167:713.
[23] COZZOLINO M,SERIO M D,TESSER R,et al.Grafting of titanium alkoxides on high-surface SiO2 support:an advanced technique for the preparation of nanostructured TiO2/SiO2 catalysts[J].Applied catalysis A-general,2007,325:256.
[24] RIOS L A,WECKES P,SCHUSTER H,et al.Mesoporous and amorphous Ti-silicas on the epoxidation of vegetable oils[J].Journal of catalysis,2005,232:19.
[25] TATSUMI T,KOYANO K A.Synthesis of titanium-containing mesoporous molecular sieves with a cubic structure[J].Chemical communications,1996(2):145.

相似文献/References:

[1]狄清林,陈长林.Cu/ZnO-Pd/WO3/ZrO2催化甘油氢解制取1,2-丙二醇[J].南京工业大学学报(自然科学版),2012,34(04):50.[doi:10.3969/j.issn.1671-7627.2012.04.010]
 DI Qinglin,CHEN Changlin.Cu/ZnO-Pd/WO3/ZrO2 catalyst for glycerol hydrogenolysis to 1,2-propanediol[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2012,34(01):50.[doi:10.3969/j.issn.1671-7627.2012.04.010]
[2]诸晓东,陈长林.Pt/Nd2O3-WO3/ZrO2催化甘油氢解制1,3-丙二醇[J].南京工业大学学报(自然科学版),2013,35(01):1.[doi:10.3969/j.issn.1671-7627.2013.01.005]
 ZHU Xiaodong,CHEN Changlin.Hydrogenolysis of glycerol over Pt/Nd2O3-WO3/ZrO2 catalysts for 1,3-propanediol[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2013,35(01):1.[doi:10.3969/j.issn.1671-7627.2013.01.005]
[3]陈英,陈长林.还原压力及水对Pt/WO3/ZrO2催化甘油氢解性能的影响[J].南京工业大学学报(自然科学版),2013,35(03):41.[doi:10.3969/j.issn.1671-7627.2013.03.009]
 CHEN Ying,CHEN Changlin.Influences of reduction pressure and water on catalytic performances of Pt/WO3/ZrO2 catalysts for glycerol hydrogenolysis[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2013,35(01):41.[doi:10.3969/j.issn.1671-7627.2013.03.009]
[4]殷文豹,陈长林.WO3/ZrO2-Cu/ZnO催化剂催化甘油氢解性能[J].南京工业大学学报(自然科学版),2013,35(06):52.[doi:10.3969/j.issn.1671-7627.2013.06.011]
 YIN Wenbao,CHEN Changlin.Catalytic performance of Cu/ZnO-WO3/ZrO2 catalysts for hydrogenolysis of glycerol[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2013,35(01):52.[doi:10.3969/j.issn.1671-7627.2013.06.011]
[5]顾正荣,郑英莪,张联科,等.用鼓泡平衡釜测定高温汽液平衡数据及对总压测定的探讨[J].南京工业大学学报(自然科学版),1989,11(02):65.
 Gu Zhengrong Zheng Yinge Zhang Lianke Xu Kezhong (Department of Chemical Engineering).MEASUREMENT OF VAPOR-LIQUID EQUILIBRIUM AT HIGH TEMPERATURE WITH A BUBBLE-EQUILIBRIUM STILL AND THE DISCUSSION OF DETERMINATION OF THE TOTAL PRESSURE[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),1989,11(01):65.
[6]任国卿,张宏科,陈晓蓉,等.Ru/Al2O3催化对苯二甲酸二甲酯合成1,4-环己烷二甲酸二甲酯[J].南京工业大学学报(自然科学版),2015,37(04):1.[doi:10.3969/j.issn.1671-7627.2015.04.001]
 REN Guoqing,ZHANG Hongke,CHEN Xiaorong,et al.Catalytic hydrogenation of dimethyl terephthalate to dimethyl 1,4-cyclohexanedicarboxylate over Ru/Al2O3 catalyst[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2015,37(01):1.[doi:10.3969/j.issn.1671-7627.2015.04.001]
[7]杨玲,康伟杰,陈长林,等.Na2SiO3对Pt/WO3/ZrO2催化剂催化甘油氢解制1,3-丙二醇的影响[J].南京工业大学学报(自然科学版),2016,38(06):9.[doi:10.3969/j.issn.1671-7627.2016.06.002]
 YANG Ling,KANG Weijie,CHEN Changlin,et al.Effects of Na2SiO3 on Pt/WO3/ZrO2 catalyst for glycerol hydrogenolysis to 1, 3-propanediol[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2016,38(01):9.[doi:10.3969/j.issn.1671-7627.2016.06.002]
[8]宫能锋,陈长林.介孔钨铝复合氧化物载铂催化剂催化甘油氢解反应[J].南京工业大学学报(自然科学版),2018,40(01):28.[doi:10.3969/j.issn.1671-7627.2018.01.005]
 GONG Nengfeng,CHEN Changlin.Hydrogenolysis of glycerol over mesoporous tungsten-aluminum mixed oxides supported platinum catalyst[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2018,40(01):28.[doi:10.3969/j.issn.1671-7627.2018.01.005]

备注/Memo

备注/Memo:
收稿日期:2015-05-04
基金项目:国家自然科学基金(U1463201); 江苏省自然科学基金(BK20130913); 江苏高校优势学科建设工程
作者简介:沈磊(1988—),男,江苏盐城人,硕士,主要研究方向为微流场反应技术; 郭凯(联系人),教授,E-mail:guok@njtech.edu.cn.
引用本文:沈磊,何伟,方正,等.1,2-环己二醇的连续合成工艺研究[J].南京工业大学学报(自然科学版),2017,39(1):51-56..
更新日期/Last Update: 2017-01-15