Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate

doi:10.1016/j.cjche.2014.12.008

Chinese Journal of Chemical Engineering ›› 2015, Vol. 23 ›› Issue (5): 775-779.DOI: 10.1016/j.cjche.2014.12.008

• 催化、动力学与反应工程 • 上一篇下一篇

Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate

Yan Cao, Huiquan Li, Ningbo Qin, Ganyu Zhu

National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

收稿日期:2014-01-20 修回日期:2014-06-05 出版日期:2015-05-28 发布日期:2015-06-26
通讯作者: Huiquan Li
基金资助:
Supported by the National Key Technology R&D Program (2013BAC11B03), the Knowledge Innovation Fund of Chinese Academy of Science (KGCX2-YW-215-2) and the National Natural Science Foundation of China (21476244).

Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate

Yan Cao, Huiquan Li, Ningbo Qin, Ganyu Zhu

National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2014-01-20 Revised:2014-06-05 Online:2015-05-28 Published:2015-06-26
Contact: Huiquan Li
Supported by:
Supported by the National Key Technology R&D Program (2013BAC11B03), the Knowledge Innovation Fund of Chinese Academy of Science (KGCX2-YW-215-2) and the National Natural Science Foundation of China (21476244).

摘要/Abstract

摘要： The kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate was studied. A consecutive reaction model was established and the reaction orders for the two steps were confirmed to be 1 and 1.3 by the integral test method and the numerical differential method, respectively. The activation energies of the two steps were (56.94±5.90) kJ·mol^-1 and (72.07±3.47) kJ·mol^-1 with the frequency factors exp(12.53±1.42) min^-1 and (14.254±0.84) mol-0.33·L0.33·min^-1, respectively. Based on the kinetic model obtained, the progress of the reaction can be calculated under given conditions.

关键词: Kinetics, 1, 6-Hexamethylene diisocyanate, Decomposition, Dimethylhexane-1, 6-dicarbamate

Abstract: The kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate was studied. A consecutive reaction model was established and the reaction orders for the two steps were confirmed to be 1 and 1.3 by the integral test method and the numerical differential method, respectively. The activation energies of the two steps were (56.94±5.90) kJ·mol^-1 and (72.07±3.47) kJ·mol^-1 with the frequency factors exp(12.53±1.42) min^-1 and (14.254±0.84) mol-0.33·L0.33·min^-1, respectively. Based on the kinetic model obtained, the progress of the reaction can be calculated under given conditions.

Key words: Kinetics, 1,6-Hexamethylene diisocyanate, Decomposition, Dimethylhexane-1,6-dicarbamate

Yan Cao, Huiquan Li, Ningbo Qin, Ganyu Zhu. Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate[J]. Chinese Journal of Chemical Engineering, 2015, 23(5): 775-779.

Yan Cao, Huiquan Li, Ningbo Qin, Ganyu Zhu. Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate[J]. Chin.J.Chem.Eng., 2015, 23(5): 775-779.

参考文献

[1] R.G. Deleon, A. Kobayashi, T. Yamauchi, J. Ooishi, T. Baba, M. Sasaki, F. Hiarata, Catalytic methoxycarbonylation of 1, 6-hexanediamine with dimethyl carbonate to dimethylhexane-1, 6-dicarbamate using Bi(NO₃)₃, Appl. Catal. A Gen. 225 (2002) 43-49.

[2] H.C. Zhou, F. Shi, X. Tian, Q.H. Zhang, Y.Q. Deng, Synthesis of carbamates from aliphatic amines and dimethyl carbonate catalyzed by acid functional ionic liquids, J. Mol. Catal. A Chem. 271 (2007) 89-92.

[3] T. Baba,M. Fujiwara, A. Oosaku,A.Kobayashi,R.G.Deleon,Y. Ono, Catalytic synthesis of N-alkyl carbamatesbymethoxycarbonylation of alkylamines with dimethylcarbonate using Pb(NO₃)₂, Appl. Catal. A Gen. 227 (2002) 1-6.

[4] M. Toatsu, Chemicals Inc, Process for Preparing Hexamethylenediisocyanate, 1987. DE3540863.

[5] B. Aktiengesellscharft, Process for the production of diisocyanates. Patent DE 4412327 (1994).

[6] B. Han, T.W. Hu, X.Y. Qin, B. Liu, S.S.Wu, P.C. Lian,W.B. Zhao, Research in the synthesis of dialkyl hexamethylene-1,6-diyldicarbamate, Chem. Ind. Eng. Prog. 32 (2013) 1081-1085.

[7] Y. Zhou, J. Cheng, J. Yao, Y.Wang, G.Y.Wang, The synthesis of hexamethylene-1, 6-diisocyanate, Polyurethane Ind. 21 (2006) 44-46.

[8] D.L. Sun, S.J. Xie, J.R. Deng, Z.S. Chao, Progress in clean synthesis of hexamethylene-1,6-diisocyanate, Chem. Ind. Eng. 27 (2010) 271-277.

[9] S.C. Miranda, C.C. Cabrero, E.F. Gutierrez, P.S. Camero, M.S. Queralt, P.U. Sola, “Isocyanate production procedure”, US: 6639101B2 (2003).

[10] G.B. Delamater, E.C. Herrick, B. Milligan, “Isocyanates from urethanes”, US: 3870739 (1975).

[11] H.D. Shen, J.L. Wang, Liquid-phase catalytic decomposition reaction of 1,6-hexamethylenedimethylurethane, Hebei Chem. Ind. 33 (2010) 28-68.

[12] L. Chen, J.R. Deng,M.L. Fan, T.T. Shan, B. Lei, H.B.Wang, Investigation on the newcatalyst for preparing 1,6-hexamethylene diisocyanate from thermal decomposition of hexamethylene di-n-Butylur ethane, Fine Chem. Intermed. 37 (2007) 44-47.

[13] W. Wu, T. Zhai, H.S. Tian, Synthesis of hexamethylene diisocyanate by nonphosgene method, GD Chem. 36 (2009) 36-71.

[14] N.B. Qin, H.Q. Li, Y. Cao, K.L. Huang, X.T. Li, D.K. Liao, Preparation of 1,6-hexamethylene diisocyanate by catalytic thermal decomposition with low-boiling solvent under pressure, Petrochem. Technol. 42 (2013) 1141-1146.

[15] G.Z. Tong, J.F. Zhang, F.F. Li, Gas chromatography analysis of freemonomers in biuret of HDI, Shanghai Coat. 13 (1997) 77-81.

[16] M. Moller, H.U. Moritz, Kinetic investigations of trimethylolpropane—diisocyanate reactions, Appl. Polym. Sci. 101 (2006) 4090-4097.

[17] G. Anitescu, Z.H. Zhang, L.L. Tavlarides, A kinetic study of methanol oxidation in supercritical water, Ind. Eng. Chem. Res. 38 (1999) 2231-2237.

[18] D. Kim, B.K. Kim, Y. Cho, Kinetics of polycarbonatemethanolysis by a consecutive reaction mode, Ind. Eng. Chem. Res. 48 (2009) 6591-6599.

Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate

Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Jiahao Lu, Zhimeng Wang, Qi Zhang, Cheng Sun, Yanyan Zhou, Sijia Wang, Xiangyun Qiu, Shoudong Xu, Rentian Chen, Tao Wei. The effects of amino groups and open metal sites of MOFs on polymer-based electrolytes for all-solid-state lithium metal batteries[J]. 中国化学工程学报, 2023, 60(8): 80-89.
[2]	Xiaolin Guo, Zhaoyang Zhang, Pengfei Xing, Shuai Wang, Yibing Guo, Yanxin Zhuang. Kinetic mechanism of copper extraction from methylchlorosilane slurry residue using hydrogen peroxide as oxidant[J]. 中国化学工程学报, 2023, 60(8): 228-234.
[3]	Xun Tao, Fan Zhou, Xinlei Yu, Songling Guo, Yunfei Gao, Lu Ding, Guangsuo Yu, Zhenghua Dai, Fuchen Wang. Effect of carbon dioxide on oxy-fuel combustion of hydrogen sulfide: An experimental and kinetic modeling[J]. 中国化学工程学报, 2023, 59(7): 105-117.
[4]	Chaoyi Yin, Jingyuan Ma, Jian Qiu, Ruifang Liu, Long Ba. Mass-producible low-cost flexible electronic fabrics for azo dye wastewater treatment by electrocoagulation[J]. 中国化学工程学报, 2023, 59(7): 222-230.
[5]	Junyang Liu, Luming Wang, Yuhang Bian, Chunshan Li, Zengxi Li, Jie Li. Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies[J]. 中国化学工程学报, 2023, 58(6): 1-10.
[6]	Wei Wang, Romain Lemaire, Ammar Bensakhria, Denis Luart. Thermogravimetric analysis and kinetic modeling of the co-pyrolysis of a bituminous coal and poplar wood[J]. 中国化学工程学报, 2023, 58(6): 53-68.
[7]	Bing Liu, Yingjiao Li, Moses Arowo, Guangwen Chu, Yong Luo, Liangliang Zhang, Haikui Zou, Baochang Sun. Sulfonation of 1, 4-diaminoanthraquinone leuco by chlorosulfonic acid: Kinetics and process intensification[J]. 中国化学工程学报, 2023, 58(6): 163-169.
[8]	Yun-Zhang Liu, Lu-Yao Zhang, Dan He, Li-Zhen Chen, Zi-Shuai Xu, Jian-Long Wang. Solubility measurement, correlation and thermodynamic properties of 2, 3, 4-trichloro-1, 5-dinitrobenzene in fifteen mono-solvents at temperatures from 278.15 to 323.15 K[J]. 中国化学工程学报, 2023, 58(6): 224-233.
[9]	Xinyu Liu, Hongliang Sheng, Song He, Chunhua Du, Yuansheng Ma, Chichi Ruan, Chunxiang He, Huaming Dai, Yajun Huang, Yuelei Pan. Insight into pyrolysis of hydrophobic silica aerogels: Kinetics, reaction mechanism and effect on the aerogels[J]. 中国化学工程学报, 2023, 58(6): 266-281.
[10]	Guangyuan Chen, Tong Zhou, Meng Zhang, Zhongxiang Ding, Zhikun Zhou, Yuanhui Ji, Haiying Tang, Changsong Wang. Effects of heavy metal ions Cu²⁺/Pb²⁺/Zn²⁺ on kinetic rate constants of struvite crystallization[J]. 中国化学工程学报, 2023, 57(5): 10-16.
[11]	Linlin Su, Meijun Chen, Li Gong, Hua Yang, Chao Chen, Jun Wu, Ling Luo, Gang Yang, Lulu Long. Boost activation of peroxymonosulfate by iron doped K_2-xMn₈O₁₆: Mechanism and properties[J]. 中国化学工程学报, 2023, 57(5): 88-97.
[12]	Hu Chen, Ying Wang, Puyu Wang, Yongkang Lv. Assessing quinoline removal performances of an aerobic continuous moving bed biofilm reactor (MBBR) bioaugmented with Pseudomonas citronellolis LV1[J]. 中国化学工程学报, 2023, 57(5): 132-140.
[13]	Shujun Peng, Song Lei, Sisi Wen, Jian Xue, Haihui Wang. A Ruddlesden–Popper oxide as a carbon dioxide tolerant cathode for solid oxide fuel cells that operate at intermediate temperatures[J]. 中国化学工程学报, 2023, 56(4): 25-32.
[14]	Shiyong Xing, Yan Cui, Tiefeng Wang, Jinwei He, Minghan Han. Elucidating the effect of oxides on the zeolite catalyzed alkylation of benzene with 1-dodecene[J]. 中国化学工程学报, 2023, 56(4): 126-135.
[15]	Peiyin Chen, Yanxiong Fang, Kaihong Xie, Yao Chen, Yang Liu, Hongliang Zuo, Weijian Lu, Baoyu Liu. Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene[J]. 中国化学工程学报, 2023, 56(4): 152-159.