李颖,安华良,赵新强,王延吉

• 1:河北工业大学绿色化工与高效节能河北省重点实验室

摘要(Abstract)：

苯氨基甲酸甲酯(MPC)是非光气法合成二苯甲烷二异氰酸酯的重要中间体。以苯胺、CO2和甲醇为原料催化合成MPC是一条绿色的工艺路线。为此重点研究了制备条件对Cu-Fe/Zr O2-Si O2催化性能的影响以及反应条件对MPC合成反应的影响。结果表明,采用机械混合法制备的金属负载量为10%(按氧化物计)的Cu-Fe/Zr O2-Si O2对MPC合成反应具有较好的催化效果。对不同方法制备的催化剂进行了H2-TPR实验测定,发现催化剂表面的金属活性位越多,金属与载体之间的作用越强,催化剂的活性越好。适宜的MPC合成反应条件为:溶剂乙腈/苯胺体积比为2:1,甲醇/苯胺摩尔比为1.2:1,催化剂用量为13%(wt),CO2初压为2.0 MPa,反应温度为180℃和反应时间为11 h。在此条件下,苯胺的转化率为14.0%,MPC的收率及其选择性分别为9.2%及65.7%,远高于目前文献值。

关键词(KeyWords)： 苯胺;CO2;甲醇;负载型双金属催化剂;苯氨基甲酸甲酯

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金重点项目(21476058,21236001);; 天津市自然科学基金(12JCYBJC12800);; 河北省应用基础研究计划重点基础研究(12965642D)

作者(Author): 李颖,安华良,赵新强,王延吉

参考文献(References)：

• [1]Shinsuke F,Masazumi C,Masashi K.A novel catalytic synthesis of carbamates by oxidative alkoxycarbonylation of amines in the presence of palladium and iodide[J].J Chem Soc Chem Commun,1984,14(6):399-400.
• [2]Alessio E,Mestroni G.Catalytic reductive carbonylation of aromatic nitro compounds to urethanes promoted by supported palladium activated with 1,10-phenanthroline derivatives[J].Journal of Organometallic Chemistry,1985,291(1):117-127.
• [3]Hwang K-Y,Chen Y-Z,Chu C-C,et al.Process for preparing carbonate compounds:EP,0 709 363 A1[P].1996-05-01.
• [4]Heitkamper P,Koenig K,Findeisen K,et al.Process for the preparation of N,O-disubstituted urethanes useful for the preparation of isocyanates:USP,4 430 505[P].1984-02-07.
• [5]DOU Ling-yun(窦凌云),AN Hua-liang(安华良),LI Qun(李群),et al.One-step synthesis of methyl n-phenyl carbamate from anline,urea and methanol over?-Al2O3(?-Al2O3催化苯胺、尿素和甲醇一步合成苯氨基甲酸甲酯反应)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2013,27(6):1004-1011.
• [6]Zhao X Q,Wang Y J,Wang S F,et al.Synthesis of MDI from dimethyl carbonate over solid catalysts[J].Ind Eng Chem Res,2002,41(21):5139-5144.
• [7]Baba T,Kobayashi A,Kawanami Y,et al.Characteristics of methoxycarbonylation of aromatic diamine with dimethyl carbonate to dicarbamate using a zinc acetate catalyst[J].Green Chem,2005,7(3):159-165.
• [8]Honda M,Sonehara S,Yasuda H,et al.Heterogeneous Ce O2 catalyst for the one-pot synthesis of organic carbamates from amines,CO2 and alcohols[J].Green Chem,2011,13(12):3406-3413.
• [9]Zhao B,Yao S J,An H L,et al.One-pot synthesis of methyl n-phenyl carbamate from aniline,carbon dioxide and methanol[J].Journal of Chemical Technology and Biotechnology,2014,89(10):1553-1558.
• [10]Zhong S H,Li H S,Wang J W,et al.Study on Cu-Ni/Zr O2-Si O2 catalyst for direct synthesis of DMC from CO2 and CH3OH[J].Chinese Journal of Catalysis,2000,21(2):117-120.
• [11]Zhong S H,Li H S,Wang J W,et al.Cu-Ni/V2O5-Si O2 catalyst for the direct synthesis of dimethyl carbonate from carbon dioxide and methanol[J].Acta Physico-Chimica Sinica,2000,16(3):226-231.
• [12]Bian J,Xiao M,Wang S J,et al.Highly effective synthesis of dimethyl carbonate from methanol and carbon dioxide using a novel copper-nickel/graphite bimetallic nanocomposite catalyst[J].Chemical Engineering Journal,2009,147(2-3):287-296.
• [13]Bian J,Xiao M,Wang S J,et al.Direct synthesis of DMC from CH3OH and CO2 over V-doped Cu-Ni/AC catalysts[J].Catalysis Communications,2009,1(8):1142-1145.
• [14]Bian J,Xiao M,Wang S J,et al.Carbon nanotubes supported Cu-Ni bimetallic catalysts and their properties for the direct synthesis of dimethyl carbonate from methanol and carbon dioxide[J].Applied Surface Science,2009,255(16):7188-7196.
• [15]Bian J,Wei X W,Wang L,et al.Graphene nanosheet as support of catalytically active metal particles in DMC synthesis[J].Chinese Chemical Letters,2011,22(1):57-60.
• [16]An H L,Zhang L L,Zhao X Q,et al.Effect of preparation conditions on the catalytic performance of Cu-Fe/Zr O2 for the synthesis of DPU from aniline and CO2[J].Chemical Engineering Journal,2014,255:266-273.
• [17]An H L,Zhang L L,Yuan B G,et al.Influence of solvent on reaction path to synthesis of methyl n-phenyl carbamate from aniline,CO2 and methanol[J].Chinese Journal of Chemical Engineering,2014,22(5):607-610.
• [18]Guo Q,Mao D,Yu J,et al.Effects of different supports on the catalytic performance of supported Cu-Fe catalyst for CO hydrogenation[J].Journal of Fuel Chemistry and Technology,2012,40(9):1103-1109.
• [19]ZHANG Min(张敏),JIN Zhen-sheng(金振声),ZHANG Zhi-jun(张治军),et al.Strong metal-support interaction and its effect on heterogeneous catalyst reaction(金属-载体强相互作用及其对多相催化反应的影响)[J].Journal of Henan University(Natural Science)(河南大学学报(自然科学版)),2005,35(4):21-26.
• [20]YAO Su-jie(姚素杰),ZHAO Xin-qiang(赵新强),AN Hua-liang(安华良),et al.Acidic ionic liuid-catalyzed synthesis of1,3-diphenyl urea from aniline and carbon dioxide(酸性离子液体催化苯胺、CO2合成二苯脲)[J].Journal of Chemical Industry and Engineering(化工学报),2012,63(3):812-818.
• [21]ZHANG Li-li(张丽丽),YAO Su-jie(姚素杰),AN Hua-liang(安华良),et al.Recovery of propionic acid from residual liquid of acetic acid production(苯胺、CO2和甲醇合成苯氨基甲酸甲酯的热力学分析)[J].Natural Gas Chemical Industry(天然气化工(C1化学与化工)),2013,38(2):42-45.
• [22]FU Jie(傅杰),REN Hao-ming(任浩明),LüXiu-yang(吕秀阳).Effect of carbon dioxide on phenylacetonitrile hydrolysis in high temperature liquid water(CO2对高温液态水中苯乙腈水解方应的影响)[J].Fine Chemicals(精细化工),2012,29(1):86-90.