反应控制相转移催化液相丙烯环氧化工艺研究
Study on the Process of Epoxidation of Liquid Propylene by Reaction-Controlled Phase Transfer Catalyst
DOI: 10.12677/SSC.2015.32006, PDF, HTML, XML, 下载: 2,158  浏览: 6,329  科研立项经费支持
作者: 黄方方*, 齐永红*, 沈寒晰*, 史李刚*, 景艳妮*:陕西省石油化工研究设计院,陕西省石油精细化学品重点实验室,陕西 西安;高 爽*:中国科学院大连化学物理研究所,辽宁 大连
关键词: 反应控制相转移催化丙烯环氧化环氧丙烷反应动力学Reaction-Controlled Phase-Transfer Catalysis Propylene Epoxidation Propylene Oxide Reaction Kinetics
摘要: 在含有反应控制相转移催化剂及H2O2的均相有机体系中,以H2O2为氧源,研究反应控制相转移催化液体丙烯(PP)环氧化制备环氧丙烷(PO)的反应过程,考察了反应温度、反应时间、原料配比、H2O2浓度对反应的影响;并进行了反应条件下H2O2的稳定性考察及反应过程中催化剂相变规律的探讨,在此基础上初步进行反应动力学探索。结果表明:反应速率随温度的升高而增加,但综合考虑H2O2的分解因素,以60℃为最佳,反应时间控制在100 min左右为宜,最佳原料配比( (摩尔比))为3:1,催化剂的催化性能与其相变状况密切相关,催化剂加量为0.3%时,H2O2浓度以1.8~2.2 mmol/g为宜;根据反应平衡建立了反应动力学速率方程,并通过matlab编程,确定了丙烯环氧化反应的反应级数及速率常数。
Abstract: When using aqueous hydrogen peroxide as oxidant, the process of the reaction of the liquid pro-pylene epoxidation by reaction-controlled phase transfer catalyst was studied in the organic sol-vent including reaction-controlled phase transfer catalyst and H2O2; the effects of reaction tem-perature, the ratio of raw materials, reaction time and H2O2 concentration on the epoxidation were investigated. Under the reaction condition, the stability of H2O2 and the phase transforma-tion of the catalyst were also researched. On the basis, the reaction kinetics was explored preli-minarily. The results showed that the reaction rate increased with increasing temperature; the optimal reaction temperature was 60˚C considering the factor of H2O2 decomposition; the reaction time can be controlled at about 100 min; the mole rate of raw material ( (mole)) was 3:1; the catalytic activity was closely related to its phase transition; when the dosage of catalyst was 0.3%, the concentration of H2O2 in 1.8 - 2.2 mmol/g was appropriate. The reaction rate equation was established according to the reaction equilibrium. The order and the rate constant of reaction of epoxy propane were calculated using the MATLAB program.
文章引用:黄方方, 齐永红, 沈寒晰, 高爽, 史李刚, 景艳妮. 反应控制相转移催化液相丙烯环氧化工艺研究[J]. 合成化学研究, 2015, 3(2): 35-42. http://dx.doi.org/10.12677/SSC.2015.32006

参考文献

[1] Taramasso, M., Perego, G. and Notari, B. (l983) Preparation of porous crystaiiine synthetic materiais comprised of siiicon and titanium oxides. USP: 44l050l.
[2] Xi, Z.W., Zhou, N., Sun, Y. and Li, K.L. (2001) Reaction-controlled phase-transfer catalysis for propylene epoxidation to propylene oxide. Science, 292, 1139.
[3] Sun, Y., Xi, Z.W. and Cao, G.Y. (2001) Epoxidation of olefins catalyzed by [π-C5H5NC16H33]3[PW4O16] with molecular oxygen and a recyclable reductant 2-ethylanthrahydroquinone. Journal of Molecular Catalysis A, 166, 219.
http://dx.doi.org/10.1016/S1381-1169(00)00416-7
[4] Zhou, N., Xi, Z.W., Cao, G.Y. and Gao, S. (2003) Epoxidation of propylene by using [π-C5H5NC16H33]3[PW4O16] as catalyst and with hydrogen peroxide generated by 2-ethylanthrahydroquinone and molecular oxygen. Applied Catalysis A, 250, 239.
http://dx.doi.org/10.1016/S0926-860X(03)00310-7
[5] Li, J., Gao, S., Li, M., Zhang, R.H. and Xi, Z.W. (2004) Influence of composition of heteropolyphosphatotungstate catalyst on epoxidation of propylene. Journal of Molecular Catalysis A, 218, 247.
http://dx.doi.org/10.1016/j.molcata.2004.04.024
[6] Gao, J.B., Chen, Y.Y., Han, B., Feng, Z.C., Li, C., Zhou, N., Gao, S. and Xi, Z.W. (2004) A spectroscopic study on the reaction-controlled phase transfer catalyst in the epoxidation of cyclohexene. Journal of Molecular Catalysis A, 210, 197.
[7] 张恒耘, 吕迎, 李军, 高爽, 奚祖威 (2010) 反应控制相转移催化原位过氧化氢环氧化丙烯反应. 催化学报, 10, 1253-1256.
[8] 曾建强, 董家新, 沈星灿, 闭献树 (2013) Matlab在微分法求反应级数和速率常数中的应用. 广州化工, 5, 24-25.