欢迎访问过程工程学报, 今天是
过程与工艺

1,2,4-丁三醇稀溶液缩醛反应的热力学和动力学特征

  • 李敏 李英波 罗海燕 咸漠 梁向峰 刘会洲
展开
  • 1. 中国科学院过程工程研究所绿色过程工程重点实验室,北京 100190;2. 中国科学院大学化学化工学院,北京 100049; 3. 中国科学院青岛生物能源与过程研究所,山东 青岛 266101

收稿日期: 2017-03-31

  修回日期: 2017-04-18

  网络出版日期: 2017-12-05

Acetalization of 1,2,4-Butanetriol with Aldehydes in Dilute Aqueous Solutions: Thermodynamic and Kinetic Characteristic

  • Min LI Yingbo LI Haiyan LUO Mo XIAN Xiangfeng LIANG Huizhou LIU
Expand
  • 1. Key Laboratory of Green Process and Engineering, Institute of Process Engineering, CAS, Beijing 100190, China; 2. School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China; 3. Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, Shandong 266101, China

Received date: 2017-03-31

  Revised date: 2017-04-18

  Online published: 2017-12-05

摘要

以正丁醛、正戊醛和正己醛为反应底物,研究了催化剂用量、醛醇比、反应温度等对1,2,4-丁三醇缩醛反应的影响,通过热力学平衡研究,获得了热力学平衡常数、反应焓变、反应熵变、反应吉布斯自由能变化等热力学参数,建立了该反应的动力学模型,利用线性自由能关系定量分析了醛的烷基链长度对缩醛反应的影响. 结果表明,在298?323 K温度范围内,该反应为放热反应,明显受热力学限制. 所建模型能很好地描述缩醛反应过程,反应的表观活化能为51.1?52.3 kJ/mol. 缩醛反应的平衡常数和反应速率均与极性效应常数(?*)有良好的线性关系.

本文引用格式

李敏 李英波 罗海燕 咸漠 梁向峰 刘会洲 . 1,2,4-丁三醇稀溶液缩醛反应的热力学和动力学特征[J]. 过程工程学报, 2017 , 17(6) : 1265 -1273 . DOI: 10.12034/j.issn.1009-606X.217202

Abstract

The acetalization reaction between 1,2,4-butanetriol and aldehydes (butyaldehyde, valeraldehyde and hexaldehyde) to produce butanetriol acetals (AC) was investigated with different catalyst amounts, molar ratios and temperatures. Through the study of the reaction thermodynamic equilibrium, the value of the equilibrium constant as a function of temperature and the corresponding thermodynamic parameters ?rH0298K, ?rS0298K, and ?rG0298K were obtained. The results showed that the reaction in the temperature range of 298?323 K was exothermic and significantly thermodynamic limitations. A simple kinetic model well describing the reaction process was presented. The activation energy of the overall acetalization reaction was 51.1?52.3 kJ/mol. Furthermore, the effect of alkyl of various aldehydes on acetalization was quantitatively analyzed using LFER and it demonstrated that excellent correlation between reaction equilibrium and rate constants and polar effect parameter (?*) was found.

参考文献

[1] Frost J W, Niu W. Microbial synthesis of D-1,2,4-butanetriol: KR20097002093 [P]. 2009-01-30.
[2] Li X H, Cai Z, Li Y, et al. Design and construction of a non-natural malate to 1,2,4-Butanetriol pathway creates possibility to produce 1,2,4-Butanetriol from glucose[J]. Sci. Rep., 2014,4(1): 5541-5542.
[3] Cao Y J, Niu W, Guo J T, et al. Biotechnological production of 1,2,4-butanetriol: An efficient process to synthesize energetic material precursor from renewable biomass[J]. Sci. Rep., 2015,5(1): 18149-18150.
[4] Sun L, Yang F, Sun H B, et al. Synthetic pathway optimization for improved 1,2,4?butanetriol production[J]. J. Ind. Microbiol. Biotechnol., 2016,43(1): 67-78.
[5] Gouranlou F, Kohsary I. Synthesis and characterization of 1,2,4-butanetrioltrinitrate[J]. Asian J. Chem., 2010, 22(6): 4221-4228.
[6] Niu W, Molefe M N , Frost J W. Microbial synthesis of the energetic material precursor 1,2,4-butanetriol [J]. J. Am. Chem. Soc., 2013,125(43): 12998-12999.
[7] Zingaro K A, Papoutsakis E T. GroESL over imparts Escherichia coli tolerance to i-, n-, and 2-butanol, 1,2,4-butanetriol and ethanol with complex and unpredictable patterns [J]. Metab. Eng., 2013, 15(1): 196-205.
[8] Tandon V K, Leusen A M V, Wynberg H. Synthesis of enantiomerically pure (S)-(+)-3-hydroxytetrahydrofuran, and its (R)-enantiomer, from malic or tartaric acid [J]. J. Org. Chem., 1983, 48(1): 2767-2769.
[9] Adkins H, Billica H R. The hydrogenation of esters to alcohols at 25-150 oC [J]. J. Am. Chem. Soc., 1948, 70(9): 3121-3125.
[10] Valdehuesa K N G, Liu H W. Ramos K R M, et al. Direct bioconversion of D-xylose to 1,2,4-butanetriol in an engineered Escherichia coli [J]. Proc. Biochem., 2014, 49(1): 25-32.
[11] Zhang Y M, Luo J, Zhao X B, et al. A novel strategy for 1,3-propanediol recovery from fermentation broth and control of product colority using scraped thin-film evaporation for desalination [J]. RSC Adv., 2015 ,5(60): 48269-48270.
[12] Qureshi N, Meagher M M, Hutkins R W. Recovery of 2,3-butanediol by vacuum membrane distillation [J]. Sep. Sci. Technol., 1994,29(13): 1733-1748.
[13] Malinowski J J. Evaluation of liquid extraction potentials for downstream separation of 1,3-propanediol [J]. Biotechnol. Tech., 1999, 13(2): 127-130.
[14] Malinowski J J. Reactive extraction for downstream separation of 1,3-propanediol, Biotechnol [J]. Prog., 2000, 16(1): 76-79.
[15] Li Y J, Wu Y Y, Zhu J W, et al. Separation of 2,3-butanediol from fermentation broth by reactive extraction using acetaldehyde-cyclohexane system [J]. Biotechnol. Biopro. Eng., 2012, 17(2): 337-345.
[16] Hao J, Liu H J, Liu D H. Novel route of reactive exraction to recover 1,3-propanediol from a dilute aqueous solution [J]. Ind. Eng. Chem. Res., 2005, 44(12): 4380-4385.
[17] Dai J Y, Sun Y Q, Sun L H, et al. Research progress of bio-based chemical 2,3-Butanediol [J]. Chin. J. Process Eng., 2010, 10(1): 200-208.
[18] Nanda M R, Yuan Z S, Qin W S, et al. Thermodynamic and kinetic studies of a catalytic process to convert glycerol into solketal as an oxygenated fuel additive [J]. Fuel, 2014, 117(1): 470-477.
[19] Chopade S P, Sharma M M. Acetalization of ethylene glycol with formaldehyde using cation-exchange resins as catalysts: batch versus reactive distillation [J]. React. Funct. Polym., 1997, 34(1): 37-45.
[20] Agirre I, García I, Requies J, et al. Glycerol acetals, kinetic study of the reaction between glycerol and formaldehyde [J]. Biomass Bioenerg., 2011, 35(8): 3636-3642.
[21] Agirre I, Güemez M B, Ugarte A, et al. Glycerol acetals as diesel additives: Kinetic study of the reaction between glycerol and acetaldehyde [J]. Fuel Proc. Technol., 2013, 116(12): 182-188.
[22] Silva P H R, Gon?alves V L C, Mota C J A. Glycerol acetals as anti-freezing additives for biodiesel [J].Bioresour. Technol., 2010, 101(15): 6225-6229.
[23] Rahaman M, Gra?a N S, Pereira C S M, et al. Thermodynamic and kinetic studies for synthesis of the acetal (1,1-diethoxybutane) catalyzed by Amberlyst 47 ion-exchange resin [J]. Chem. Eng. J., 2015, 264(15): 258-267.
[24] Silva V M T M, Rodrigues A E. Synthesis of diethylacetal: thermodynamic and kinetic studies [J]. Chem. Eng. Sci., 2001, 56(4): 1255-1263.
[25] Chen B. Hydrolytic stabilities of halogenated disinfection byproducts: review and rate constant quantitative structure-property relationship analysis [J]. Environ. Eng. Sci., 2011, 28(6): 385-394.
[26] Kreevoy M K, Taft R W. The evaluation of inductive and resonance effects on reactivity. I. hydrolysis rates of acetals of non-conjugated aldehydes and ketones [J]. J. Am. Chem. Soc., 1955, 77(21): 5590-5595.
[27] Taft R W. The general nature of the proportionality of polar effects of substituent groups in organic chemistry [J]. J. Am. Chem. Soc., 1953, 75(17): 4231-4238.
[28] Neuvonen K, Neuvonen H, Koch A, et al. Taft equation in the light of NBO computations. Introduction of a novel polar computational substituent constant scale for sigma(q)* alkyl groups [J]. Comput. Theor. Chem., 2012, 981(1): 52-58.
[29] Neuvonen K, Neuvonen H, Koch A, et al. Nature of the steric ΩS, ER and source substituent constants. Comparison with the aid of NBO and STERIC analysis [J]. Comput. Theor. Chem., 2013, 1015(4): 34-43.
文章导航

/