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[1]梁伟,崔咪芬,汤吉海,等.高氢胺比下苯胺催化加氢制备环己胺和二环己胺的本征动力学[J].南京工业大学学报(自然科学版),2014,36(02):89-94.[doi:10.3969/j.issn.1671-7627.2014.02.015]
 LIANG Wei,CUI Mifen,TANG Jihai,et al.Kinetics of hydrogenation of aniline to cyclohexylamine and dicyclohexylamine on high molar ratio of H2 to aniline[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2014,36(02):89-94.[doi:10.3969/j.issn.1671-7627.2014.02.015]
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高氢胺比下苯胺催化加氢制备环己胺和二环己胺的本征动力学()
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《南京工业大学学报(自然科学版)》[ISSN:1671-7627/CN:32-1670/N]

卷:
36
期数:
2014年02期
页码:
89-94
栏目:
出版日期:
2014-03-30

文章信息/Info

Title:
Kinetics of hydrogenation of aniline to cyclohexylamine and dicyclohexylamine on high molar ratio of H2 to aniline
文章编号:
1671-7627(2014)02-0089-06
作者:
梁伟1崔咪芬1汤吉海1陈献1乔旭12
1.南京工业大学 化学化工学院 江苏省工业节水减排重点实验室,江苏 南京 210009; 2.南京工业大学 材料化学工程国家重点实验室,江苏 南京 210009
Author(s):
LIANG Wei1CUI Mifen1TANG Jihai1CHEN Xian1QIAO Xu12
1.Jiangsu Key Laboratory of Industrial Water-Conservation & Emission Reduction,College of Chemistry and Chemical Engineering,Nanjing Tech University,Nanjing 210009,China; 2.State Key Laboratory of Materials-Oriented Chemical Engineering,Nanjing Tech U
关键词:
苯胺加氢 环己胺 二环己胺 动力学
Keywords:
aniline hydrogenation cyclohexylamine dicyclohexylamine kinetics
分类号:
TQ03-39
DOI:
10.3969/j.issn.1671-7627.2014.02.015
文献标志码:
A
摘要:
采用非贵金属催化剂进行苯胺加氢制备环己胺和高比例的二环己胺,在固定床反应器中进行苯胺连续加氢和缩合反应。在消除了催化剂内、外扩散阻力的情况下,考察进料氢胺摩尔比、反应温度对苯胺加氢制备环己胺和二环己胺的影响,提出了苯胺催化加氢的反应网络; 通过对反应网络的合理简化,建立高氢胺摩尔比下苯胺催化加氢连串反应的本征动力学模型。以苯胺的转化率和二环己胺的收率计算值与实验值的残差平方和最小值建立目标函数,利用Matlab软件对实验数据进行拟合,估算出连串反应的本征动力学模型中的各个参数,并对模型的显著性进行了检验。结果表明:在实验条件范围内,本征动力学模型对苯胺加氢制备环己胺和二环己胺是高度适定的。
Abstract:
The non-noble metal catalyst was used for the hydrogenation of aniline to synthesize cyclohexylamine and high proportion dicyclohexylamine.The continuous hydrogenation of aniline and the condensation reaction were carried out in a fixed bed reactor.Under the conditions of eliminating the external film and internal diffusion resistance of the catalyst,effects of the feed hydrogen/aniline molar ratio,temperature of aniline hydrogenation on the synthesis of cyclohexylamine and dicyclohexylamine were investigated.The intrinsic kinetics model for catalytic hydrogenation of aniline with a series of reactions on the high hydrogen/aniline molar ratio was established.Minimum of the sum of squared residuals of the experimental values of the conversion of aniline,yield of dicyclohexylamine and the calculated values of the model was considered as objective function.Using nonlinear least square method in Matlab software to fit the experimental data,a series of parameters in the intrinsic kinetics model were estimated and the significance of the model was tested.Results showed that, in the range of experimental conditions,the intrinsic kinetics model of hydrogenation of aniline to cyclohexylamine and dicyclohexylamine was highly appropriate.

参考文献/References:

[1] 章文.苯胺市场竞争日趋激烈[J].精细化工原料及中间体,2008(5):40-41.
[2] 齐秀玲.苯胺产能急剧增加结构调整尚需时日[J].精细与专用化学品,2012,20(5):13-16.
[3] Robinson R M.Preparation of cyclohexylamine by hydrogenation of aniline using a rhodium catalyst:US,3196179[P].1965-07-20.
[4] Gobron G,Brum C,Bezons M.Continuous liquid phase hydrogenation process using excess hydrogen:US,3565921[P].1971-02-23.
[5] Helmut L M,Gene R W.Production of cyclohexylamine:EP,0067058[P].1982-12-15.
  
[6] Helmut L M,Gene R W.Hydrogenation of aniline to cyclohexylamine with platinum metal catalysts:US,4384142[P].1983-05-17.
[7] Immel O,Schwarz H H.Process for its preparation and process for the preparation of a mixture of cyclohexylamine and dicyclohexylamine using the ruthenium catalyst:US,4952549[P].1990-08-28.
[8] Immel O,Schwarz H H,Thiel R.Supported ruthenium catalyst,tis preparation and its use in the preparation of optionally substituted cyclohexylamine and optinally substituted dicylohexylamine:US,4943549[P].1990-07-24.
[9] Immel O,Schwarz H H,Thiel R.Ruthenium supported catalyst,its preparation and its use in the preparation of substituted or unsubstituted cyclohexylamine and substituted or unsubstituted dicyclohexylamine:US,5023226[P].1991-06-11.
[10] Darsow G,Immel O,Petruck G M,et al.Process for the preparation of a mixture of cyclohexylamine and dicyclohexylamine using a supported noble metal catalyst:US,5322965,[P].1994-06-21.
[11] Buysch H J,Darsow G,Immel O.Process for the preparation of a mixture of cyclohexylamine and dicyclohexylamine:US,5371294[P].1994-12-06.
[12] Darsow G,Immel O,Petruck G M,et al.Palladiun catalyst and its use in the preparation of a mixture of optionally substituted cyclohexylamine and oprionally substituted dicyclohexylamine:US,5386060[P].1995-01-31.
[13] Langer R,Petruck G M.Process for preparing variable mixtures of cyclohexylamine and dicyclohexylamine:US,6043395[P].2000-05-28.
[14] Darsow G,Langer R.Method for producing variable mixtures cyclohexylamine and dicyclohexylamine:US,6335470[P].2002-01-01.
[15] Chatterjee M,Szto M,Kawanami H.Hydrogenation of aniline to cyclohexylamine in supercritical carbon dioxide:significance of phase behaviour[J].Appl Catal A:General 2011,396:186-193.
[16] Greenfield H.Hydrogenation of aniline to cyclohexylamine with platinum metal catalysts[J].J Org Chem,1964,29:3082-3084.

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备注/Memo

备注/Memo:
收稿日期:2013-05-08
作者简介:梁伟(1988—),男,江苏宜兴人,硕士,主要研究方向为绿色化工; 崔咪芬(联系人),教授, E-mail:mfcui@njtech.edu.cn..
更新日期/Last Update: 2014-03-20