氢氧化钙羰基化合成甲酸钙反应动力学

摘要

以半连续进料方式在高压搅拌釜中对氢氧化钙羰基化反应进行了系统的研究。采用XRD对反应产物进行了定性分析,证明反应生成物为甲酸钙和极少量的碳酸钙。与生成甲酸钙的主反应相比,生产碳酸钙的副反应速率较小可以忽略。考察了反应工艺条件对反应的影响,结果表明,转速达到1 000 r/min时,可以消除外扩散的影响。在反应温度423~453 K、压力2.0~3.5 MPa、不同氢氧化钙初始浓度下对反应进行考察,使用幂函数形式的动力学模型对实验数据进行拟合,结果表明,该反应对CO为一级反应,反应活化能为54.7 kJ·mol^-1。通过模型计算结果与实验数据的比较,证明该模型具有较好的实用性。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	侯志源
	吕静
	李振花

关键词：氢氧化钙羰基化甲酸钙动力学

Abstract：

The synthesis of calcium formate by Ca(OH)₂ carbonylation was studied in a stirred tank reactor in a semi-batch way. The products obtained from the carbonylation reaction were analyzed by XRD. It was found that the products of the reaction were calcium formate and a little calcium carbonate, hence the side reaction could be neglected since its rate was lower than the main reaction rate. The influence of reaction conditions on the formation of calcium formate were investigated, which illustrated that the gaseous diffusion resistance could be eliminated at the stirring speed up to 1 000 r/min. The reaction was carried out at temperature between 423 K and 453 K, pressure from 2.0 MPa to 3.5 MPa and different initial concentration of calcium hydroxide, and the kinetics was simulated using power function. The reaction order with respect to CO is 1 and the activation energy is 54.7 kJ·mol^-1. The effectiveness of the established model could be validated by the comparison between the calculated and experimental data.

Keywords： calcium hydroxide； carbonylation； calcium formate； kinetics

Received 2014-03-12;

Fund:

国家高技术研究发展计划(863计划)支持(2012AA06A113):钙基工业固废制备脱硫剂及脱硝固废再生技术与示范。

Corresponding Authors: 李振花,E-mail:zhenhua@tju.edu.cn。 Email: zhenhua@tju.edu.cn

About author: 侯志源(1988-),女,硕士研究生,从事绿色化工方向研究。

引用本文:

侯志源, 吕静, 李振花.氢氧化钙羰基化合成甲酸钙反应动力学[J]. 化学工业与工程, 2016,33(2): 23-29

Hou Zhiyuan, Lv Jing, Li Zhenhua.Kinetics for the Synthesis of Calcium Formate by Calcium Hydroxide Carbonylation[J]. Chemcial Industry and Engineering, 2016,33(2): 23-29

[1] 王九思, 马思基. 甲酸钙的合成及应用研究[J]. 甘肃化工, 1993, (3): 14-15 Wang Jiusi, Ma Siji. The synthesis and application of calcium formate[J]. GanSu Chemical, 1993, (3): 14-15(in Chinese)
[2] Reed R J. Novel method for the production of hydrogen and hydrogen-carbon monoxide mixtures: US, 4087373[P]. 1978-05-02
[3] 褚森泉. 黄磷尾气的综合利用[J]. 化肥工业, 1997, 24(3): 55-57 Zhe Senquan. Comprehensive utilization of phosphorus furnace tail gas[J]. Jounal of Chemical Fertilizer Industry, 1997, 24(3): 55-57(in Chinese)
[4] 武红杰, 李振花, 马新宾. 氢氧化钙羰基化合成甲酸钙工艺研究[J]. 化学反应工程与工艺, 2007, 23(2): 168-172 Wu Hongjie, Li Zhenhua, Ma Xinbin. Study on synthesis of calcium formate by calcium hydroxide carbonylation[J]. Chemical Reaction Engineering and Technology, 2007, 23(2): 168-172(in Chinese)
[5] 聂颖, 肖明. 季戊四醇的生产技术进展及市场分析[J]. 化工文摘, 2009, (6): 21-24 Nie Ying, Xiao Ming. Production technology advance and market analysis of pentaerythritol[J]. China Chemical, 2009, (6): 21-24(in Chinese)
[6] 张健伟, 赫广田. 单,双季戊四醇的合成工艺研究[J]. 天然气化工: C1 化学与化工, 2007, 32(5): 40-42 Zhang Jianwei, Hao Guangtian. Study on the synthesis of pentaerythritol an dipentaerythritol[J]. Nature Gas Chemical Industry, 2007, 32(5): 40-42(in Chinese)
[7] 贺楚华, 李珊, 肖志海, 等. 单,双,三季戊四醇的合成[J].化工时刊, 2005, 19(1): 11-13 He Chuhua, Li Shan, Xiao Zhihai, et al. Synthesis of mono-, di-and tri-pentaerythritol[J]. Chemical Industry Times, 2005, 19(1): 11-13(in Chinese)
[8] 钟国清. 饲料添加剂甲酸钙的合成研究与应用[J]. 粮油食品科技, 2002, 10(1): 23-24 Zhong Guoqing. Synthesis and application of calcium formate used as feed additive[J]. Science and Technology of Cereals, Oils and Foods, 2002, 10(1): 23-24(in Chinese)
[9] 李国庭, 潘福星, 冯树波. 流沙状甲酸钙的生产[J]. 饲料工业, 2005, 26(4): 45-46 Li Guoting, Pan Fuxing, Feng Shubo. The production of quick sand-like calcium formate[J]. Feed Industry, 2005, 26(4): 45-46(in Chinese)
[10] 罗宗恬. 甲酸钙的合成[J]. 磷酸盐工业, 2000, (2): 24-26 Luo Zongtian. The synthesis of calcium formate[J]. Phosphate Industry, 2000, (2): 24-26(in Chinese)
[11] Duderstadt U, Trageser M, Werle P. Process for the production of calcium formate: US, 5248818A[P]. 1993-09-28
[12] 薛强, 陈金芳, 陈启明, 等. 渗析法合成甲酸钙[J]. 武汉工程大学学报, 2009, 31(1): 10-12 Xue Qiang, Chen Jinfang, Chen Qiming, et al. Study on synthesis process of calcium formate by dialysis[J]. Journal of Wuhan Institute of Technology, 2009, 31(1): 10-12(in Chinese)
[13] Yu Y, Liu X, Zhang W, et al. Electrosynthesis of dimethyl carbonate from methanol and carbon monoxide under mild conditions[J]. Ind Eng Chem Res, 2013, 52(21): 6 901-6 907
[14] Beller M. Catalytic carbonylation reactions[M]: Springer: Springer Berlin Heidelberg, 2006
[15] Zhang S, Yuan J. A new craftwork for producing sodium formate by carbon monoxide in the synthetic ammonia virgin gas: CN, 101033183A[P]. 2007-09-12
[16] Iwata M. Reaction rate of formation of sodium formate under low pressure (2~7 kg/cm²)[J]. Nagaoka Kogyo Tanki Daigaku Koto Semmon Gakko Kenkyu Kiyo, 1968, 4(4): 307-313
[17] Pohorecki R, Moniuk W, Kumur A, et al. Kinetics of sodium formate synthesis[J]. Inz Chem Procesowa, 1987, 8(3): 391-406
[18] 曹正祥, 曹勇. 一氧化碳与氢氧化钙连续羰基化制备甲酸钙装置: CN, 200820214570.0[P]. 2009-10-14
[19] 曾舟华, 黄春保, 陈年友, 等. 单级循环或多级串联式生产甲酸钙的装置: CN, 200920228830.4[P]. 2010-06-30
[20] 许风玉, 赵靖宇. 一种利用一氧化碳和氢氧化钙制备甲酸钙的方法: CN, 201010212519.8[P]. 2010-11-10