辛酸甲酯合成新工艺的研究

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南京大学学报(自然科学版) ›› 2018, Vol. 54 ›› Issue (3) : 612-621.

辛酸甲酯合成新工艺的研究

刘承智1，杨高东2，周政3*，张志炳4

作者信息 +

Study on a new method of n-caprylic acid esterification’s synthesis

Liu Chengzhi1, Yang Gaodong2, Zhou Zheng3*, Zhang Zhibing4

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摘要

辛酸甲酯是一种重要的精细化工产品，具有良好的反应活性，在合成化妆品及药物中间体等诸多领域具有特殊的应用价值。而传统工艺一般采用浓硫酸为催化剂，但该工艺存在很多严重的问题，如对实验装置有很强的腐蚀性、催化剂很难回收、污染环境等，这不符合当前绿色、经济、可持续发展的大环境。而强酸性大孔阳离子交换树脂由于有高催化活性、高选择性、化学稳定性好、不腐蚀设备、无“三废”产生、易分离等优异特性，故采用了这种催化剂。通过催化剂的用量、反应原料配比、反应温度、强化反应器中的循环流量、催化剂的重复使用次数等小试条件的优化，以及在酯化过程热力学和动力学方面的探索研究，可以看出计算值与实验值几乎吻合，这对工业上合成辛酸甲酯起到强有力的指导作用。

Abstract

n-Caprylic acid esterification, with good reaction activity, is an important fine chemical products and has special application value in many fields such as synthetic cosmetics and pharmaceutical intermediates. The traditional process generally uses concentrated sulfuric acid as a catalyst, but there are many serious problems in the process, such as strong corrosiveness to the experimental apparatus, difficult recovery of the catalyst, environmental pollution, etc. Not in line with the current green, economical and sustainable development environment. But the strong acid macroporous cation exchange resin has many excellent features including high catalytic activity, high selectivity, good chemical stability, non-corrosiveness to equipment, no "three wastes" produce, and easy separation, so this article uses this catalyst. Through the amount of catalyst, the ratio of the reaction raw materials, the reaction temperature, the circulating flow in the intensified reactor, the number of catalyst re-use and other small test conditional optimization, as well as the thermodynamic and kinetic aspects of the esterification process, the research can be seen that the calculated value and experimental value is almost consistent. Thus on the industrial synthesis of n-caprylic acid esterification process has played a strong guiding role.

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刘承智1，杨高东2，周政3*，张志炳4. 辛酸甲酯合成新工艺的研究[J]. 南京大学学报(自然科学版), 2018, 54(3): 612-621

Liu Chengzhi1, Yang Gaodong2, Zhou Zheng3*, Zhang Zhibing4. Study on a new method of n-caprylic acid esterification’s synthesis[J]. Journal of Nanjing University(Natural Sciences), 2018, 54(3): 612-621

参考文献

[1] Kayapan S D. Composition useful e.g. for treating acne, dandruff, and dry skin and wound healing, comprises e.g. methyl pelargonate, methyl caprate, methyl azelaaldehydate, dimethyl suberate, methyl 6,6-dimethoxy octanoate, and dimethyl azelate. IN, 201741008643-A, 2017-05-19. [2] Togbé C, Dayma G, Mzé-Ahmed A, et al. Experimental and modeling study of the kinetics of oxidation of simple biodiesel?biobutanol surrogates: Methyl octanoate?butanol mixtures. Energy & Fuels, 2010, 24(7): 3906-3916. [3] Chen K K, Du H, Zhang J W, et al. Catalytic synthesis of methyl caprylate using multi-SO3H functionalized Brønsted acidic ionic liquid as catalyst. Green Processing and Synthesis, 2015, 4(1): 31-36. [4] Han X X, Du H, Hung C T, et al. Syntheses of novel halogen-free Brønsted-Lewis acidic ionic liquid catalysts and their applications for synthesis of methyl caprylate. Green Chemistry, 2014, 17(1): 499-508. [5] Liu Y J, Lotero E, Goodwin Jr J G. Effect of water on sulfuric acid catalyzed esterification. Journal of Molecular Catalysis A: Chemical, 2006, 245(1-2): 132-140. [6] Rothen S A, Sauer M, Sonnleitner B, et al. Biotransformation of octane by E. coli HB101[pGEc47] on defined medium: Octanoate production and product inhibition. Biotechnology and Bioengineering, 1998, 58(4): 356-365. [7] 王明慧, 吴坚平, 杨立荣. 离子液体及其在生物催化中的应用. 有机化学, 2005, 25(4): 364-374. (Wang M H, Wu J P, Yang L R. Ionic liquid and its application in biocatalytic reaction. Chinese Journal of Organic Chemistry, 2005, 25(4): 364-374.) [8] Asefa T, MacLachlan M J, Coombs N, et al. Periodic mesoporous organosilicas with organic groups inside the channel walls. Nature, 1999, 402(6764): 867-871. [9] 周海峰. 固体酸催化酯化反应的研究进展. 精细与专用化学品, 2004, 12(23): 1-6. (Zhou H F. Research progress on esterification catalyzed by solid acids. Fine and Specialty Chemicals, 2004, 12(23): 1-6.) [10] 田部浩三. 新固体酸和碱及其催化作用. 郑禄彬译. 北京: 化学工业出版社, 1992, 399. (Tian B H S. New solid acids and bases their catalytic properties. Zheng L B. Beijing: Chemical Industry Press, 1992, 399.) [11] Xie W L, Hu L B. Mesoporous SBA-15 silica-supported diisopropylguanidine: An efficient solid catalyst for interesterification of soybean oil with methyl octanoate or methyl decanoate. Journal of Oleo Science, 2016, 65(10): 803-813. [12] Ma L L, Han Y, Sun K A, et al. Kinetic and thermodynamic studies of the esterification of acidified oil catalyzed by sulfonated cation exchange resin. Journal of Energy Chemistry, 2015, 24(4): 456-462. [13] Sharma M, Toor A P, Wanchoo R K. Kinetics of the esterification reaction between pentanoic acid and methanol catalyzed by noncorrosive cation exchange resin. Chemical and Biochemical Engineering Quarterly, 2014, 28(1): 79-85. [14] Zhang M, Zhu W S, Li H M, et al. Esterification of salicylic acid using Ce4+ modified cation-exchange resin as catalyst. Journal of the Chilean Chemical Society, 2012, 57(4): 1477-1481. [15] 赵志刚, 邵太丽, 秦国正等. H-732阳离子交换树脂催化酯化反应. 化工进展, 2012, 31(7): 1592-1596. (Zhao Z G, Shao T L, Qin G Z, et al. Ability of cation exchange resin H-732 as cataiyst for esterification. Chemical Industry and Engineering Progress, 2012, 31(7): 1592-1596.) [16] 杨英杰, 赵玉娥, 王玉香. 肉桂酸酯食用香料合成方法研究(Ⅱ)——强酸性离子交换树脂催化肉桂酸酯化反应. 吉林化工学院学报, 1992(2): 40-45. (Yang Y J, Zhao Y E, Wang Y X. Studies of synthetic method on cinnamic acid ester food flavor (Ⅱ)——catalytic esterification of cinnamic acid with strong acidity cation—exchange resins. Journal of Jilin Institute of Chemical Technology, 1992(2): 40-45.) [17] Harada M, Okada T. Hydration of counterions in cation exchange resins studied by X-ray absorption fine structure. Chemical Communications, 2008(41): 5182-5184. [18] 王毅, 周明, 许春建. NKC-9离子交换树脂细粉催化异丁烯水合反应动力学. 石油化工, 2003, 32(9): 775-778. (Wang Y, Zhou M, Xu C J. Kinetics of isobutylene hydration reaction catalyzed by fine powder of NKC-9 ion exchange resin. Petrochemical Technology, 2003, 32(9): 775-778.) [19] Talwalkar S, Kumbhar P, Mahajani S. Hydration of dicyclopentadiene in the presence of cation exchange resin. Industrial & Engineering Chemistry Research, 2006, 45(24): 8024-8028. [20] Ihm S K, Chung M J, Park K Y. Activity difference between the internal and external sulfonic groups of macroreticular ion-exchange resin catalysts in isobutylene hydration. Industrial & Engineering Chemistry Research, 1988, 27(1): 41-45. [21] Tang L R, Huang B, Ou W, et al. Manufacture of cellulose nanocrystals by cation exchange resin-catalyzed hydrolysis of cellulose. Bioresource Technology, 2011, 102(23): 10973-10977. [22] Dassy S, Wiame H, Thyrion F C. Kinetics of the liquid phase synthesis and hydrolysis of butyl lactate catalysed by cation exchange resin. Journal of Chemical Technology and Biotechnology, 1994, 59(2): 149-156. [23] Delgado P, Sanz M T, Beltrán S. Kinetic study for esterification of lactic acid with ethanol and hydrolysis of ethyl lactate using an ion-exchange resin catalyst. Chemical Engineering Journal, 2007, 126(2-3): 111-118. [24] 董新法, 方利国, 陈砺. 物性估算原理及计算机计算. 北京: 化学工业出版社, 2006， 352. (Dong X F, Fang L G, Chen L. Physical property estimation principle and computer calculation[M]. Beijing: Chemical Industry Press, 2006，352.) [25] Levenspiel O. Chemical reaction engineering. The 3rd Edition. New York: John Wiley & Sons, 1999. [26] Zhang Y, Ma L, Yang J C. Kinetics of esterification of lactic acid with ethanol catalyzed by cation-exchange resins. Reactive and Functional Polymers, 2004, 61(1): 101-114. [27] Weisz P B, Hicks J S. The behaviour of porous catalyst particles in view of internal mass and heat diffusion effects. Chemical Engineering Science, 1995, 50(24): 3951-3958. [28] Wilke C R, Chang P. Correlation of diffusion coefficients in dilute solutions. AIChE Journal, 1955, 1(2): 264-270. [29] Sanz M T, Murga R, Beltrán S, et al. Autocatalyzed and ion-exchange-resin-catalyzed esterification kinetics of lactic acid with methanol. Industrial & Engineering Chemistry Research, 2002, 41(3): 512-517. [30] Bringué R, Iborra M, Tejero J, et al. Thermally stable ion-exchange resins as catalysts for the liquid-phase dehydration of 1-pentanol to di-n-pentyl ether (DNPE). Journal of Catalysis, 2006, 244(1): 33-42. [31] Liu W T, Tan C S. Liquid-phase esterification of propionic acid with n-butanol. Industrial & Engineering Chemistry Research, 2001, 40(15): 3281-3286. [32] Alt?okka M R, Ç?tak A. Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst. Applied Catalysis A: General, 2003, 239(1-2): 141-148. [33] Gangadwala J, Mankar S, Mahajani S, et al. Esterification of acetic acid with butanol in the presence of ion-exchange resins as catalysts. Industrial & Engineering Chemistry Research, 2003, 42(10): 2146-2155. [34] Lee M J, Chiu J Y, Lin H M. Kinetics of catalytic esterification of propionic acid and n-butanol over amberlyst 35. Industrial & Engineering Chemistry Research, 2002, 41(12): 2882-2887. [35] Lee M J, Wu H T, Lin H M. Kinetics of catalytic esterification of acetic acid and amyl alcohol over dowex. Industrial & Engineering Chemistry Research, 2000, 39(11): 4094-4099.