杨洋,刘晓勤,刘定华,姚虎卿

• 1:南京工业大学化学化工学院
• 2:南京工业大学化学化工学院
• 3:南京工业大学化学化工学院
• 4:南京工业大学化学化工学院 江苏南京210009

摘要(Abstract)：

开发了甲醇液相羰基化法合成碳酸二甲酯的新型CuBr3L2络合催化剂。实验结果表明,该催化剂在反应温度373~383K、压力3.0~3.5MPa、催化剂质量浓度0.15~0.20g·mL-1、反应时间4~6h的条件下,甲醇的转化率可达23%~25%,碳酸二甲酯选择性为96%~98%。且该催化剂性能稳定,可反复使用。XPS等表征发现配位剂四丁基溴化铵(简称L)的添加有助于表面活性物种Cu(I)的形成,推导了可能的反应机理。对该催化体系进行动力学研究,推导出合适的动力学方程以及相关的动力学参数。该反应是一近似二级反应,反应表观速率常数Kp与催化剂质量浓度和反应温度有关,且Kp与催化剂质量浓度的平方成正比;高温高压不利于主反应的进行,导致目的产物选择性的下降。

关键词(KeyWords)： 碳酸二甲酯;甲醇;氧化羰化;液相;动力学

Abstract:

Keywords:

基金项目(Foundation):

作者(Author): 杨洋,刘晓勤,刘定华,姚虎卿

参考文献(References)：

• [1]Delledonne D,Rivetti F,Romano U.Developments in the production and application of dimethyl carbonate[J].Appl Catal,A,2001,221:241-251.
• [2]FANG Ding-ye(房鼎业),CAO Fa-hai(曹发海),LIU Dian-hua(刘殿华)et al.Reaction kinetics of methanol oxidation and carbonylation in vapor phase for DMC production catalyzed by CuCl2/C(CuCl2/C催化剂上甲醇氧化羰化合成碳酸二甲酯的本征动力学)[J].J Chem Eng of Chinese Univ(高校化学工程学报),1997,11(2):212-216.
• [3]SU Yue-hua(苏跃华),WU Xiao-hua(吴晓华),JIANG Xuan-zhen(姜玄珍).Oxidative carbonylation synthesis of DMC from methanol in vapor phase(甲醇气相氧化羰基化合成碳酸二甲酯)[J].J Chem Eng of Chinese Univ(高校化学工程学报),1999,13(6):564-567.
• [4]Romano U,Tesel R,Maurl M M et al.Synthesis of dimethyl carbonate from methanol,carbon monoxide,and oxygen catalyzed by copper compounds[J].Ind Eng Chem Prod Res Dev,1980,19:396-403.
• [5]HUANG Tao(黄涛),YAO Jie(姚洁),WANG Gong-ying(王公应).Study of the copper-based catalysts for oxidative carbonylation of methanol to dimethyl carbonate(甲醇氧化羰化合成DMC铜系催化剂的研究)[J].Journal of Natural Gas Chemistry(天然气化工),1998,23(1):26-29.
• [6]Sato Y,Kagotani M,Yamamoto T et al.Novel effective poly(2,2'-bipyridine-5,5'-diyl)-CuCl2catalyst for synthesis of DMC by oxidative carbonylation of methanol[J].Appl Catal,A,1999,185:219-226.
• [7]Hu J C,Cao Y,Yang P et al.A novel homogeneous catalyst made of poly(N-vinyl-2-pyrrolidone)-CuCl2complex for the oxidative carbonylation of methanol to dimethyl carbonate[J].Journal of Molecular Catalysis A:Chemical,2002,185:1-9.
• [8]LIU Ding-hua(刘定华),ZHAO Xian-guang(赵贤广),WANG Hai-shan(王海善)et al.Dimethyl carbonate synthesis by oxidative carbonylation with MXnLm catalyst(MXnLm体系催化合成碳酸二甲酯)[J].Journal of Chemical Industry&Engineering(化学工业与工程技术),1998,19(2):6-8.
• [9]YANG Yang(杨洋),LIU Xiao-qin(刘晓勤),LIU Ding-hua(刘定华)et al.Reaction progress study of dimethyl carbonate synthesis by oxidative carbonylation with a new Cu-based complex catalyst(新型铜络合催化剂用于羰基合成碳酸二甲酯的工艺过程研究)[J].Journal of Nanjing University of Technology(Natural Science Edition)(南京工业大学学报(自然科学版)),2006,28(1):75-79.
• [10]NIST(National Institute of Standards and Technology)Online Databases:NIST X-ray Photoelectron Spectroscopy Database[DB/OL].http://srdata.nist.gov/gateway/gateway.
• [11]Yang P,Cao Y,Hu J C et al.Mesoporous bimetallic PdCl2-CuCl2catalysts for dimethyl carbonate synthesis by vapor phase oxidative carbonylation of methanol[J].Appl Catal,A,2003,241:363-373.
• [12]WANG Zheng-lie(王正烈),ZHOU Ya-ping(周亚平),LI Song-lin(李松林)et al.Physical Chemistry(物理化学)[M].Beijing(北京):High Education Press(高等教育出版社),2001.
• [13]MO Wan-lin(莫婉玲),XIONG Hui(熊辉),LI Guang-xing(李光兴)et al.Kinetics of the oxidative carbonization of MeOH to dimethyl carbonate by CuCl/Schiff base complexes system(甲醇液相氧化羰化合成碳酸二甲酯动力学研究)[J].J Huazhong Univ of Sci&Tech(Nature Science Edition)(华中科技大学学报(自然科学版)),2002,30(6):111-113.
• [14]MA Zheng-fei(马正飞),YIN Xiang(殷翔).Engineering Application of Mathematical Calculation Methods and Software(数学计算方法与软件的工程应用)[M].Beijing(北京):Chemical Industry Press(化学工业出版社),2002.