|Table of Contents|

Optimization of cyclodehydration of diethylene glycol in nearcritical water with additives


Research Field:
Publishing date:


Optimization of cyclodehydration of diethylene glycol in nearcritical water with additives
Yang YanShi XinyuWang JinshouHu ShengZhou Hongyan
School of Chemistry and Environmental Engineering,Hubei University for Nationalities,Enshi 445000,China
diethylene glycolcyclodehydrationadditivesnearcritical wateroptimization
A study of the cyclodehydration of diethylene glycol(DEG)is performed in nearcritical water(NCW)to research the effect of parameters on experimental results.An L25(65)orthogonal array design(OAD)with six factors at five levels using statistical analysis is firstly employed to optimize the experimental condition for target product(1,4-dioxane)in which the interactions between the variables are temporarily neglected.The six factors are temperature,time,reactant/water ratio(g·g-1),additive/reactant ratio(g·g-1),additives and reaction pressure.The effects of these parameters are investigated using the analysis of Analysis of Variance(ANOVA)to determine the conversion of DEG and the yield of 1,4-dioxane.The results show:additives have a significant influence on the conversion of DEG and the yield of 1,4-dioxane;the maximum yield of 1,4-dioxane can reach as high as 56.58% and the conversion of DEG is 92.45% under the optimum condition.


[1]Park Y M,Pyo H,Park S J,et al.Development of the analytical method for 1,4-dioxane in water by liquidliquid extraction[J].Analytica Chimica Acta,2005,548(1/2):109-115.
[2]郭登峰,刘红,刘准,等.固体碱催化剂KF/Al2O3催化合成乙二醇丁醚[J].南京理工大学学报,2011,35(1):122-126. Guo Dengfeng,Liu Hong,Liu Huai,et al.Synthesis of ethylene glycol monobutyl ether with KF/Al2O3 solid base catalyst[J].Journal of Nanjing University of Science and Technology,2011,35(1):122-126.
[3]Yoshie K,Masahiro K.Shape selectivity of sepiolite for catalytic cyclodehydration of diethylene glycol to dioxane[J].Chemistry Express,1990,5(8):545-548.
[4]Liu Junfeng,Liu Yuan,Yi Pinggui.Synthesis of diethylene glycol ethyl ether with diethylene glycol and ethanol by the catalysis of heteropoly acid[J].Applied Catalysis A:General,2004,227(1/2):167-171.
[5]Wali A,Pillai S M,Unnikrishnan S,et al.HZSM-5 catalyzed cyclodehydration of diethylene glycol and its derivatives[J].Journal of Molecular Catalysis A:Chemical,1996,109(2):149-155.
[6]Tanaka K.Solventfree organic synthesis[J].Chemical Review,2000,100(2):1025-1074.
[7]Anastas P T,Williamson T C.Green chemistry:Theory and practice[M].London:Oxford Science Publications,2000:99-102.
[8]Azadi P,Otomo J,Hatano H,et al.Hydrogen production by catalytic nearcritical water gasification and steam reforming of glucose[J].International Journal of Hydrogen Energy,2010,35(8):3406-3414.
[9]Ibarra I A,Bayliss P A,Pérez E,et al.Nearcritical water,a cleaner solvent for the synthesis of a metalorganic framework[J].Green Chemistry,2012,14(1):117-122.
[10]Savage P E.Organic chemical reactions in supercritical water[J].Chemical Review,1999,99(2):603-621.
[11]杨艳,吴良春,戴立益.近临界水体系中添加物促进的二甘醇脱水环化研究[J].高校化学工程学报,2008,22(4):591-596. Yang Yan,Wu Liangchun,Dai Liyi.Research on the catalytic cyclodehydration of diethylene glycol assisted withadditive in nearcritical water[J].Journal of Chemical Engineering of Chinese Universities,2008,22(4):591-596.
[12]Sharma P,Verma A,Sidhu P K,et al.Process parameter selection for strontium ferrite sintered magnets using Taguchi L9 orthogonal design[J].Journal of Materials Processing Technology,2005,168(1):147-151.
[13]Tauguchi G.System of Experimental Design:Engineering Methods to Optimize Quality and Minimize Costs[M].New York,NY:Kraus International Publications,1987:83-86.
[14]Zhang J Z,Chen J C,Kirby E D,Surface roughness optimization in an endmilling operation using the Taguchi design method[J].Journal of Materials Processing Technology,2007,184(1-3):233-239.
[15]Zhu Guanghua,Ju Huangxian.Determination of naproxen with solid substrate room temperature phosphorimetry based on an orthogonal array design[J].Analytica Chimica Acta,2004,506(2):177-181.
[16]Duan Peigao,Wang Yuanyuan,Yang Yan,et al.Optimization of adiponitrile hydrolysis in subcritical water using an orthogonal arrary design[J].Journal of Solution Chemistry,2009,38(2):241-258.
[17]Gabriel C,Gabriel S,Grant E H,et al.Dielectric parameters relevant to microwave dielectric heating[J].Chemical Society Reviews,1998,27(3):213-224.
[18]Marshall W L,Franck E U.Ion product of water substance,0-1000 ℃,1-10.000 bars new international formulation and its background[J].Journal of Physical and Chemical Reference Data,1981,10(2):295-304.
[19]高滋.沸石分子筛催化与吸附分离[M].北京:中国石化出版社,1999:478-502. Gao Zi.Technology of zeolit catalysis and separation[M].Beijing:SinoPec,Publiction,1999:478-502.
[20]蒋培华,陈金龙,郑长麟,等.高纯度1,4-二氧六环的合成研究[J].精细石油化工进展,2000,1(1):8-10. Jiang Peihua,Chen Jinlong,Zheng Changlin,et al.Preparation of high purity 1,4-dioxane[J].Advances in Fine Petrochemicals,2000,1(1):8-10.
[21]杨艳.近临界水中少量助剂促进的二醇脱水反应及其动力学研究[D].上海:华东师范大学化学系,2009. Yang Yan.The process and kinetics research on dehydration of glycols assisted with additives in nearcritical water[D].Shanghai,China:Department of Chemistry,East China Normal University,2009.
[22]刘俊峰,易平贵,戚蕴石.杂多酸对二甘醇脱水环化反应的催化作用[J].分子催化,1999,13(6):419-423. Liu Junfeng,Yi Pinggui,Qi Yunshi.Cyclization of diethylene glycol on heteropoly acid[J].Journal of Molecular Catalysis,1999,13(6):419-423.


Last Update: 2013-02-15