Catalytic Pathways Identification for Partial Oxidation of Methanol on Copper-Zinc Catalysts: CH3OH + 1/2O2 CO2 + 2H2

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• 作者：Yu-Chuan Lin ; L. T. Fan ; Shahram Shafie ; Keith L. Hohn ; Botond Bertó ; k ; Ferenc Friedler
• 刊名：Industrial & Engineering Chemistry Research
• 出版年：2008
• 出版时间：April 16, 2008
• 年：2008
• 卷：47
• 期：8
• 页码：2523 - 2527
• 全文大小：140K
• 年卷期：v.47,no.8(April 16, 2008)
• ISSN：1520-5045

文摘

Much effort has been spent to investigate catalytic generation of hydrogen from methanol partial oxidation(MPO) in light of its practical and theoretical importance. Nevertheless, relatively little has been done to gainin-depth understanding of the catalytic mechanisms or pathways of MPO. The exploration of pathways ofany catalytic reaction can be greatly facilitated by exhaustively generating at the outset stoichiometricallyfeasible and independent catalytic mechanisms or pathways (IP_i's) from a set of plausible elementary reactionsby means of our graph-theoretic method based on P-graphs (process graphs). The method is implemented byresorting to the combinatorial algorithms derived from the two sets of rigorously stated axioms on the basisof the mass-conservation law and stoichiometric principle. In the current work, a set of 13 plausible elementaryreactions has been proposed for MPO from which six IP_i's have been generated in less than 1 s with a PC(Pentium 4, CPU 3.06 GHz, and 1 GB RAM). Subsequently, the rate equations of these six IP_i's have beenderived according to the Langmuir-Hinshelwood-Hougen-Watson (LHHW) formalism. The kinetic constants of the resultant rate equations have been estimated through nonlinear regression of the equations withexperimental data. In light of the least-square criterion, IP₂ and IP₆ are deemed potentially dominant pathways.