TOME环化反应热力学分析及反应动力学研究

刘宏晓; 孙伟振; 赵玲

doi:10.11949/0438-1157.20191485

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TOME环化反应热力学分析及反应动力学研究

热力学 | 更新时间：2026-07-24

- TOME环化反应热力学分析及反应动力学研究
- Thermodynamic analysis and kinetics of cyclization of TOME
- 化工学报 2020年71卷第2期页码：500-506
- 作者机构：
  
  1. 华东理工大学化学工程联合国家重点实验室, 上海 200237
  2. 新疆大学化学化工学院, 新疆, 乌鲁木齐 830046
- 作者简介：
  
  刘宏晓（1994—），男，硕士研究生， liuhongxiao1994@163.com
  孙伟振（1976—），男，博士，教授， sunwz@ecust.edu.cn
- 基金信息：
  
  国家自然科学基金项目(91434108)
- DOI：10.11949/0438-1157.20191485
  中图分类号： TQ 013.1;TQ 013.2
- 收稿：2019-12-06，
  
  修回：2019-12-30，
  
  网络首发：2020-08-14，
  
  纸质出版：2020-02-05
- 稿件说明：
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刘宏晓, 孙伟振, 赵玲. TOME环化反应热力学分析及反应动力学研究[J]. 化工学报, 2020, 71(2): 500-506

LIU Hongxiao, SUN Weizhen, ZHAO Ling. Thermodynamic analysis and kinetics of cyclization of TOME[J]. CIESC Journal, 2020, 71(2): 500-506
刘宏晓, 孙伟振, 赵玲. TOME环化反应热力学分析及反应动力学研究[J]. 化工学报, 2020, 71(2): 500-506 DOI： 10.11949/0438-1157.20191485.

LIU Hongxiao, SUN Weizhen, ZHAO Ling. Thermodynamic analysis and kinetics of cyclization of TOME[J]. CIESC Journal, 2020, 71(2): 500-506 DOI： 10.11949/0438-1157.20191485.

摘要

采用基团贡献法对四甲基-酮-癸烯酸甲酯（TOME）环化反应进行了热力学分析。结果表明，标准压力下该反应为吸热反应，温度高于403 K范围内反应为自发过程；反应的Gibbs自由能变随温度的升高而减小，升温有利于反应正向进行。通过间歇实验研究了非催化条件、常压、463~493 K温度范围内TOME环化反应动力学。动力学拟合结果表明，该反应为一级反应，升温能明显加快反应速率，在所研究温度范围内反应活化能为143.72 kJ•mol

-1

。

Abstract

Thermodynamic analysis of the cyclization reaction of tetramethyl-keto-methyl cenoate (TOME) was performed using the group contribution method. The results indicate that under standard pressure

the reaction is endothermic and it is spontaneous when the temperature is greater than 403 K. The Gibbs free energy decrease with the increase of temperature

indicating that the reaction occurs more easily at higher temperatures. The cyclization kinetics of TOME at atmospheric pressure and temperature range of 463—493 K was studied by batch experiments. The kinetic fitting results show that the reaction is a first-order reaction

and the increase of temperature can significantly accelerate the reaction rate. The activation energy of the reaction is estimated to be 143.72 kJ•mol

-1

in t

he studied temperature range.

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references

Antypenko L M , Solodovnyk V A . Determination of рiroctone olamine (octopirox) in bulk by UV spectrophotometric method [J ] . Dhaka University Journal of Pharmaceutical Sciences , 2017 , 16 ( 1 ): 37 - 42 .

Kelkheim T , Hofheim T . Process for the preparation of 1-hydroxy-pyridones : US 3972888 [P ] . 1976-8-3 .

Reuschling D , Grobel B T . Process for the preparation of 1-hydroxy-2 -pyridones : US 4916228 [P ] . 1990-4-10 .

Horace G , Stephen R . Fungicide comprising 4-methyl-6-pentyl-2H-pyran-2-one: W9904633 [P ] . 1999-2-4 .

Chattapadhyay T K , Dureja P . Antifungal activity of 4-methyl-6-alkyl-2 H -pyran-2-ones [J ] . Journal of Agricultural and Food Chemistry , 2006 , 54 ( 6 ): 2129 - 2133 .

Pittet A O , Klaiber E M . Synthesis and flavor properties of some alkyl-substituted alpha-pyrone derivatives [J ] . Journal of Agricultural and Food Chemistry , 1975 , 23 ( 6 ): 1189 - 1195 .

张继龙 , 赵志仝 , 乔燕 , 等 . 酯交换制油酸甲酯的基团贡献法热力学分析 [J ] . 化工学报 , 2012 , 63 ( 6 ): 1684 - 1690 .

Zhang J L , Zhao Z T , Qiao Y , et al . Thermodynamic analysis on preparation of methyl oleate via transesterification by group-contribution method [J ] . CIESC Journal , 2012 , 63 ( 6 ): 1684 - 1690 .

王晨晔 , 李会泉 , 曹妍 , 等 . 苯胺与甲醛合成 4, 4-二氨基二苯甲烷反应体系的热力学分析 [J ] . 化工学报 , 2012 , 63 ( 8 ): 2348 - 2355 .

Wang C Y , Li H Q , Cao Y , et al . Thermodynamic analysis on synthesis of 4, 4-methylenedianiline by reaction of aniline and formaldehyde [J ] . CIESC Journal , 2012 , 63 ( 8 ): 2348 - 2355 .

王琳琳 , 陈建云 , 梁杰珍 , 等 . 枞酸与甲醇酯化反应的基团贡献法热力学分析 [J ] . 化工学报 , 2013 , 64 ( 6 ): 1900 - 1906 .

Wang L L , Chen J Y , Liang J Z , et al . Thermodynamic analysis for esterification of abietic acid with methanol by group-contribution method [J ] . CIESC Journal , 2013 , 64 ( 6 ): 1900 - 1906 .

杨浩 , 王建红 , 乔聪震 . 柠檬酸与正丁醇合成柠檬酸三丁酯的热力学分析 [J ] . 石油化工 , 2011 , 40 ( 2 ): 171 - 174 .

Yang H , Wang J H , Qiao C Z . Thermodynamic analysis for synthesis of tributyl citrate from citric acid and n -butanol [J ] . Petrochemical Technology , 2011 , 40 ( 2 ): 171 - 174 .

孙伟振 , 黄欢 , 顾晓吴 , 等 . 基于自由基反应机理的芳烃液相氧化动力学模型 [J ] . 化工学报 , 2010 , 61 ( 7 ): 1796 - 1802 .

Sun W Z , Huang H , Gu X W , et al . Modeling of liquid phase oxidation kinetics of aromatic hydrocarbon based on free radical chain reaction mechanism [J ] . CIESC Journal , 2010 , 61 ( 7 ): 1796 - 1802 .

Sun W , Shi Y , Chen J , et al . Alkylation kinetics of isobutane by C 4 olefins using sulfuric acid as catalyst [J ] . Industrial & Engineering Chemistry Research , 2013 , 52 ( 44 ): 15262 - 15269 .

李迪 , 孙伟振 , 奚桢浩 , 等 . 混合丁烯/异丁烷硫酸烷基化反应动力学 [J ] . 化工学报 , 2015 , 66 ( 2 ): 584 - 590 .

Li D , Sun W Z , Xi Z H , et al . Alkylation kinetics of mixed butenes/isobutane by sulfuric acid [J ] . CIESC Journal , 2015 , 66 ( 2 ): 584 - 590 .

刘明鑫 , 许志美 , 孙伟振 , 等 . 非催化条件下异丙苯液相过氧化反应动力学 [J ] . 化工学报 , 2015 , 66 ( 5 ): 1710 - 1715 .

Liu M X , Xu Z M , Sun W Z , et al . Reaction kinetics of non-catalytic peroxidation of liquid phase isopropyl benzene [J ] . CIESC Journal , 2015 , 66 ( 5 ): 1710 - 1715 .

Sun W , Sun J , Xu Z , et al . Experimental study and modeling of homogenous catalytic oxidation of m -xylene to isophthalic acid [J ] . Industrial & Engineering Chemistry Research , 2015 , 54 ( 13 ): 3293 - 3298 .

马沛生 . 有机化合物实验物性数据手册: 含碳、氢、氧、卤部分 [M ] . 北京 : 化学工业出版社 , 2006 : 498 .

Ma P S . Experimental Handbook of Physical Properties of Organic Compounds—Carbon, Hydrogen, Oxygen, Halogen Section [M ] . Beijing : Chemical Industry Press , 2006 : 498 .

张宇英 , 张克武 . 分子热力学性质手册: 计算方法与最新实验数据 [M ] . 北京 : 化学工业出版社 , 2009 : 239 .

Zhang Y Y , Zhang K W . Handbook of Molecular Thermodynamic Properties: Calculation Methods and Latest Experimental Data [M ] . Beijing : Chemical Industry Press , 2009 : 239 .

刘光启 , 马连湘 , 刘杰 . 化学化工物性数据手册: 有机卷 [J ] . 北京 : 化学工业出版社 , 2002 : 600 .

Liu G Q , Ma L X , Liu J . Chemical Property Data Book: Organic Vol [M ] . Beijing : Chemical Industry Press , 2002 : 600 .

Yaws C L . Chemical Properties Handbook [M ] . New York : McGraw-Hill , 1999 : 33 .

田克胜 , 王保伟 , 许根慧 . 草酸二乙酯气相加氢热力学计算与分析 [J ] . 天然气化工 , 2007 , 32 ( 1 ): 48 - 51 .

Tian K S , Wang B W , Xu G H . The thermodynamics of gas phase hydrogenation of diethyl oxalate [J ] . Natural Gas Chemical Industry , 2007 , 32 ( 1 ): 48 - 51 .

张巧玲 , 郑会敏 , 李思意 , 等 . 重氮盐水解制备对苯二酚的热力学分析 [J ] . 化学工程 , 2013 , 41 ( 8 ): 34 - 37 .

Zhang Q L , Zheng H M , Li S Y , et al . Thermodynamic analysis for preparation of hydroquinone by hydrolysis of diazonium salts [J ] . Chemical Engineering (China) , 2013 , 41 ( 8 ): 34 - 37 .

付丽丽 , 蒋登高 . 棕榈酸异丙酯合成反应的热力学分析 [J ] . 高校化学工程学报 , 2016 , 30 ( 2 ): 398 - 403 .

Fu L L , Jiang D G . Thermodynamic analysis of isopropyl palmitate synthesis [J ] . Journal of Chemical Engineering of Chinese Universities , 2016 , 30 ( 2 ): 398 - 403 .

Poling B E , Prausnitz J M , O’connell J P . The Properties of Gases and Liquids [M ] . 4th ed . New York: McGraw-Hill , 1987 : 150 .

董新法 . 物性估算原理及计算机计算 [M ] . 北京 : 化学工业出版社 , 2006 : 182 .

Dong X F . Principle of Physical Property Estimation and Computer Calculation [M ] . Beijing : Chemical Industry Press , 2006 : 182 .

Yoneda Y . An estimation of the thermodynamic properties of organic compounds in the ideal gas state(Ⅰ): Acyclic compounds and cyclic compounds with a ring of cyclopentane, cyclohexane, benzene, or naphthalene [J ] . Bulletin of the Chemical Society of Japan , 1979 , 52 ( 5 ): 1297 - 1314 .

Viswanath D S , Kuloor N R . On a generalized Watson s relation for latent heat of vaporisation [J ] . The Canadian Journal of Chemical Engineering , 1967 , 45 ( 1 ): 29 - 31 .

王福安 , 江登高 . 化工数据导引 [M ] . 北京 : 化学工业出版社 , 1995 : 119 .

Wang F A , Jiang D G . Chemical Data Guidance [M ] . Beijing : Chemical Industry Press , 1995 : 119 .

Ma P S , Zhao X M . Modified group contribution method for predicting the entropy of vaporization at the normal boiling point [J ] . Industrial & Engineering Chemistry Research , 1993 , 32 ( 12 ): 3180 - 3183 .

Joback K G , Reid R C . Estimation of pure-component properties from group-contributions [J ] . Chemical Engineering Communications , 1987 , 57 ( 1-6 ): 233 - 243 .

Stein S E , Brown R L . Estimation of normal boiling points from group contributions [J ] . Journal of Chemical Information and Computer Sciences , 1994 , 34 ( 3 ): 581 - 587 .

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