High-throughput screening of HZSM-5 supported metal-oxides catalysts for the coupling of methane with CO to benzene and naphthalene

High-throughput screening of HZSM-5 supported metal-oxides catalysts were carried out for the coupling reaction of methane with CO to aromatics in a multi-stream reactor system. Zn/HZSM-5 and Mo/HZSM-5 were observed to be rather effective for the catalytic formation of aromatics from the coupling reaction of methane with CO. Temperature-programmed reaction has further proven the efficiency of the coupling of methane and CO over Zn/HZSM-5 catalyst. The results were also validated in a conventional fixed-bed reactor coupled with GC. The results propose that the coupling methane with CO toward benzene and naphthalene can be catalyzed by Zn/HZSM-5 at 500 ° C. Both methane and CO are needed for the formation of reactive coke on the catalyst, and the reactive coke may be the initial product in the producing of hydrocarbons. © 2005 Elsevier B.V. All rights reserved.

A facile and effective method for the distribution of Mo/HZSM-5 catalyst active centers

Post-steaming treatment of Mo/HZSM-5 catalysts results in more molybdenum species migrating into and residing in the HZSM-5 zeolite channels. This is confirmed by XRF and XPS measurements. H-1 MAS NMR and Si-29 MAS NMR also demonstrate that the number of free Bronsted acid sites decreases in the Mo/HZSM-5 catalysts that underwent post-steaming treatment, compared to untreated Mo/HZSM-5 catalysts. As a result, the deactivation rate constant (kd) on the Mo/HZSM-5 catalyst after post-steaming treatment for 0.5 h is much smaller, and the catalyst therefore shows remarkable stability in the probe reaction of methane dehydro-aromatization. The results suggest that a more beneficial bi-functional balance between active Mo species for methane activation and acid sites for the following aromatization is developed over those Mo/HZSM-5 catalysts that have experienced post-steaming treatment for 0.5 h, in comparison with the untreated Mo/HZSM-5 catalysts.

Effect of addition of Zn on the catalytic activity of a Co/HZSM-5 catalyst for the SCR of NOx with CH4

The selective catalytic reduction (SCR) of NOx by methane in the presence of excess oxygen was studied on a Zn-Co/HZSM-5 catalyst. It was found that the addition of Zn could improve effectively the selectivity of methane towards NOx reduction. When prepared by a coimpregnation method, the Zn-Co/HZSM-5 catalyst showed much higher catalytic activity than the two catalysts of a Zn/Co/HZSM-5 and Co/Zn/HZSM-5 prepared by the successive impregnation method. It is considered that there exists a cooperative effect among the Zn, Co and zeolite, which enhances the reduction of NO to NO2 reaction and the activation of methane. (C) 2002 Elsevier Science B.V. All rights reserved.

On the induction period of methane aromatization over Mo-based catalysts

The behavior of different species during the temperature-programmed surface reaction (TPSR) of methane over various catalysts is traced by an online mass spectrometer, It is demonstrated that the transformation of MoO3 to molybdenum carbide hinders the activation of methane as well as the succeeding aromatization in the TPSR, If this transformation process is done before the reaction, the temperature needed for methane activation and benzene formation will be greatly lowered (760 and 847 K, respectively). On the basis of comparison of the catalytic behavior of molybdenum supported on different zeolites, it is suggested that the initial activation of methane is the rate-determining step of this reaction. For the cobalt catalysts supported on HMCM-22 or Mo catalysts supported on TiO2, no benzene formation could be observed during the TPSR, However, the prohibition of benzene formation is different in nature over these two catalysts: the former lacks the special properties exhibited by molybdenum carbide, which can continuously activate methane even when multiple layers of carbonaceous species are formed on its surface, while the latter cannot accomplish the aromatization reaction since there are no Bronsted acid sites to which the activated intermediates can migrate, although the activation of methane can be achieved on it. Only for the catalysts that possess both of these properties, together with the special channel structure of zeolite, can efficient methane aromatization be accomplished. (C) 2000 Academic Press.