[1]倪嵩波,黄凯,傅淑霞.Mn/W催化剂上甲烷氧化偶联反应机理的Monte Carlo模拟[J].东南大学学报(自然科学版),2011,41(1):134-139.[doi:10.3969/j.issn.1001-0505.2011.01.026]
 Ni Songbo,Huang Kai,Fu Shuxia.Reaction mechanism of oxidative coupling of methane over Mn/W catalyst based on Monte Carlo simulations[J].Journal of Southeast University (Natural Science Edition),2011,41(1):134-139.[doi:10.3969/j.issn.1001-0505.2011.01.026]
点击复制

Mn/W催化剂上甲烷氧化偶联反应机理的Monte Carlo模拟()
分享到:

《东南大学学报(自然科学版)》[ISSN:1001-0505/CN:32-1178/N]

卷:
41
期数:
2011年第1期
页码:
134-139
栏目:
化学化工
出版日期:
2011-01-20

文章信息/Info

Title:
Reaction mechanism of oxidative coupling of methane over Mn/W catalyst based on Monte Carlo simulations
作者:
倪嵩波1黄凯12傅淑霞3
(1东南大学化学化工学院,南京 211189)
(2东南大学常州研究院,常州 213164)(3东南大学电工电子实验中心,南京 211189)
Author(s):
Ni Songbo1Huang Kai12Fu Shuxia3
(1School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China)
(2Changzhou Institute, Southeast University, Changzhou 213164, China)
(3Laboratory of Electrotechnics and Electronics, Southeast Uni
关键词:
甲烷氧化偶联Monte Carlo模拟Mn/W催化剂反应机理
Keywords:
methane oxidative coupling Monte Carlo simulation Mn/W catalyst reaction mechanism
分类号:
TQ015.9
DOI:
10.3969/j.issn.1001-0505.2011.01.026
摘要:
通过对Mn-Na2WO4/SiO2催化剂的甲烷氧化偶联反应机理进行初步研究,以Mn/W双金属活性中心为基础,分析了CH4和O2共进料氧化偶联制C2烃的反应模型,并采用Monte Carlo方法对该反应的微观过程进行模拟,在与实验相近的条件下,得到了较准确的模拟结果.在模拟实验中,考察了活性位规模和原料气组成对反应结果的影响以及反应过程中表面吸附物种的变化规律.结果表明:活性位规模增大将减缓表面反应的速度,而不同进料烷氧比将对甲烷转化率以及C2烃收率产生影响; 同时在对表面吸附物种的考察中发现,反应末期催化剂催化活性不高与晶格氧的补充不足有关,而C2H6和C2H4的反应更多地发生在气相主体.
Abstract:
The mechanism of oxidative coupling of methane over Mn-Na2WO4/SiO2 catalyst is studied. Base on the double-activity-site Mn / W catalytic centers, the reaction model of methane and oxygen co-feeding to product C2 hydrocarbon was simulated by means of Monte Carlo approach. The computer simulation results are in good agreement with experiment under similar conditions, which indicate that the complex surface model presented is reasonable. The influence of grid size and feeding ratio of methane to oxygen are also taken into account. Further analysis of the surface coverage with virtual reaction time is also discussed in the paper. The results show that the surface reaction is restrained by enlargement of grid size; feeding ratio of NCH4/NO2 has significant effect on the conversion of methane and selectivity of C2 hydrocarbon. Base on the research of the surface coverage with virtual reaction time, short of lattice oxygen supplement results in low activity of the catalyst; most of the oxidative reaction of ethane and ethylene occur in the gas-phase.

参考文献/References:

[1] Ziff R M,Gulari E,Barshad Y.Kinetic phase transition in an irreversible surface reaction model [J].Phys Rev Lett,1986,56(24):2553-2556.
[2] Chakarova R.Monte Carlo simulation of hysteresis behaviour of CO oxidation on surfaces [J].Surface Science,1997,389(1/2/3):234-240.
[3] Zhdanov V P.Monte Carlo simulation of oscillation,chaos and pattern formation in heterogeneous catalytic reactions [J].Surface Science Reports,2002,45(7/8):231-236.
[4] Luque J J.CO plus NO surface reaction model by Monte Carlo simulation [J].Physica A,2004,331(3/4):505-516.
[5] Ahmad W,Hussain A.Water gas shift reaction:a Monte Carlo simulation [J].Chinese Physics Letters,2006,23(9):2602-2605.
[6] Ren X B,Li H Y,Guo X Y.Monte Carlo simulation of the oscillatory behavior in partial oxidation of methane on nickel catalyst [J].Surface Science, 2008,602(1):300-306.
[7] 王远洋,高荫本.V/Sb催化剂上丙烷氨氧化反应机理的Monte Carlo模拟 [J].分子催化,1995(6):417-423.
  Wang Yuanyang,Gao Yinben.Monte Carlo simulation to mechanism of propane ammoxidation over V/Sb catalyst[J].Journal of Molecular Catalysis(China),1995(6):417-423.(in Chinese)
[8] 汪洋.丙烯_氨_氧化催化剂表面反应的原位漫反射红外光谱和Monte Carlo模拟研究[D].杭州:浙江大学材料与化工学院,2007.
[9] 季生福,李树本,许传芝,等.Na-W-Mn/SiO2催化剂活化甲烷的研究:Ⅰ.活性中心的结构 [J].分子催化,2000(1):1-5.
  Ji Shengfu,Li Shuben,Xu Chuanzhi,et al.Study on methane activation over Na-W-Mn/SiO2 catalysts:Ⅰ.structure of the active center[J].Journal of Molecular Catalysis(China),2000(1):1-5.(in Chinese)
[10] Ji S F,Coleman K,Green M,et al.The relationship between the structure and the performance of Na-W-Mn/SiO2 catalysts for the oxidative coupling of methane [J].Applied Catalyst A,2002,225(1):271-284.
[11] Kou Y,Zhang B,Niu J Z,et al.Amorphous features of working catalysts:XAFS and XPS characterization of Na-W-Mn/SiO2 as used for the oxidative coupling of methane [J].Journal of Catalysis,1998,173(2):399-408.
[12] Chua Y T,Mohamed A R,Bhatia S.Oxidative coupling of methane for the production of ethylene over sodium-tungsten-manganese-supported-silica catalyst (Na-W-Mn/SiO2) [J].Applied Catalysis A:General,2008,343(1/2):142-148.
[13] 季生福,李树本,许传芝,等.Na-W-Mn/SiO2催化剂表面甲烷脉冲反应:Ⅱ.多组分Na,W,Mn/SiO2催化剂 [J].分子催化,2002 (6):205-208.
  Ji Shengfu,Li Shuben,Xu Chuanzhi,et al.Methane pulse reaction over Na-W-Mn/SiO2 Catalysts:Ⅱ.multicomponent Na,W,and Mn SiO2-supported catalysts[J].Journal of Molecular Catalysis(China),2002(6):205-208.(in Chinese)
[14] 龚华,蒋致诚,褚衍来.Mn2O3-Na2WO4/SiO2催化剂中钨锰间的电子传递作用 [J].催化学报,1997,9(5):378-383.
  Gong Hua,Jiang Zhicheng,Chu Yanlai.Electron transfer between W and Mn ions in Mn2O3-Na2WO4/SiO2 catalyst [J].Chinese Journal of Catalysis,1997,9(5):378-383.(in Chinese)
[15] Ahari J S,Ahmadi R,Mikami H,et al.Application of a simple kinetic model for the oxidative coupling of methane to the design of effective catalysts [J].Catalysis Today,2009,145(1/2):45-54.
[16] Shahri S M K,Alavi S M.Kinetic studies of the oxidative coupling of methane over the Mn/Na2WO4/SiO2 catalyst [J].Journal of Natural Gas Chemistry, 2009,18(1):25-34.
[17] Farooji N R,Vatani A,Mokhtari S.Kinetic simulation of oxidative coupling of methane over perovskite catalyst by genetic algorithm:Mechanistic aspects [J].Journal of Natural Gas Chemistry,2010,19(4):385-392.
[18] Sun J J,Thybaut J W,Marin G B.Microkinetics of methane oxidative coupling [J].Catalysis Today,2008,137(1):90-102.
[19] Salehouna V,Khodadadib A,Mortazavib Y,et al.Dynamics of Mn/Na2WO4/SiO2 catalyst in oxidative coupling of methane [J].Chemical Engineering Science,2008,63(20):4910-4916.
[20] Sinev M Y,Fattakhova Z T,Lomonosov V I,et al.Kinetics of oxidative coupling of methane:bridging the gap between comprehension and description [J].Journal of Natural Gas Chemistry,2009,18(3):273-287.
[21] Mokhtari S,Vatani A,Farooji N R.Comparative study of kinetic modeling for the oxidative coupling of methane by genetic and Marquardt algorithms [J].Journal of Natural Gas Chemistry, 2010,19(3):293-299.
[22] Daneshpayeh M,Khodadadi A,Mostoufi N,et al.Kinetic modeling of oxidative coupling of methane over Mn/Na2WO4SiO2 catalyst [J].Fuel Processing Technology,2009,90(3):403-410.
[23] 倪嵩波.W/Mn催化剂上甲烷氧化偶联反应机理的Monte Carlo模拟 [D].南京:东南大学化学化工学院,2010.
[24] 方学平,李树本,林景治.甲烷在W-Mn体系催化剂上氧化偶联制乙烯[J].分子催化,1992(6):427-433.
  Fang Xueping,Li Shuben,Lin Jingzhi.Oxidative coupling of methane on W-Mn catalysts[J].Journal of Molecular Catalysis (China),1992(6):427-433.(in Chinese)
[25] 王嘉欣,丑凌军,张兵,等.甲烷氧化偶联Na2WO4-Mn/SiO2催化剂热效应的研究[J].分子催化,2006(4):306-310.
  Wang Jiaxin,Chou Lingjun,Zhang Bing,et al.Thermal effects during the oxidative coupling of methane over Na2WO4-Mn/SiO2 catalyst[J].Journal of Molecular Catalysis (China),2006(4):306-310.(in Chinese)

备注/Memo

备注/Memo:
作者简介:倪嵩波(1985—),男,硕士生;黄凯(联系人),男,博士,副教授,huangk@seu.edu.cn.
基金项目:江苏省自然科学基金资助项目(BK2010198)、常州市社会发展科技计划资助项目 (CS20100004)、浙江工业大学绿色化学合成技术国家重点实验室开放基金资助项目 (GCTKF 2010013)、东南大学自然科学基金预研资助项目 (XJ0619245).
引文格式: 倪嵩波,黄凯,傅淑霞.Mn/W催化剂上甲烷氧化偶联反应机理的Monte Carlo模拟[J].东南大学学报:自然科学版,2010,41(1):0134-139.[doi:10.3969/j.issn.1001-0505.2011.01.026]
更新日期/Last Update: 2011-01-20