Mo／MCM－49催化剂上甲烷的脱氢芳构化反应

In recent years, the catalytic dehydroaromatization of methane to benzene has been a challenging and intriguing research subject in heterogeneous catalysis and natural gas chemical industry. Since the first report on non-oxidative conversion of methane to benzene on Mo/HZSM-5[1], many attractive studies regarding the development of new catalyst, the catalyst characterization[2～4], the reaction mechanism and the bifunctional role of Mo carbide and HZSM-5 have been reported. However, Mo/HZSM-5 catalyst was thought to have the best catalytic performance for CH4 dehydroaromatization to benzene. Recently, another kind of zeolite, MCM-22, was found to be a promising catalyst support for formation of benzene from methane[5]. Xu et al[6] studied the catalytic performance of MoO3/MCM-49 for this reaction without accounting for coke formation. In this paper, we present MCM-49 as a support, and the catalyst Mo/MCM-49 shows high ratio of benzene to aromatics in selective dehydroaromatization of methane.     

In改性Mo/HZSM-S催化剂上的甲烷芳构化反应性能

Dehydrogenation and aromatization of methane over Mo/HZSM-5 catalyst without adding oxygen were widely studied［1～3］. However, the existing problem of this route is the low yield of aromatics, owing to the high stability of methane. Recently, the introduction of the second metal species was believed to be a promising route to improve non-oxidative transformation of methane over Mo/HZSM-5 catalyst[4-7].     

Hydrogen Effect on Coke Removal and Catalytic Performance in Pre-Carburization and Methane Dehydro-Aromatization Reaction on Mo/HZSM-5

1. Introduction As an effective utilization of methane, the methane dehydro-aromatization was focused in the last decade [1-28]. Over the Mo/HZSM-5 bi- functional catalyst at high reaction temperature, methane can be converted into light aromatics (ben- zene and naphthalene) and hydrogen. Mo active species can activate the C—H bond of methane; and HZSM-5 supplies the acid sites for the oligomeriza- tion and cyclization of hydrocarbons to form aromat- ics, and suppresses the deeper condens…     

METHANE DIRECT CONVERSION TO ETHENE OVER Mo/SAPO-34 CATALYSTS

We have studied the methane activation in non-oxidative condition[1,2],and have shown the possibility of direct methane conversion to aromaticsover Mo/HZSM-5.Ethene is regarded as the initial product of the reaction.We thus pay attention to the selective production of ethene and low hydro-carbons from methane directly.The molecular sieve HSAPO-34(SP) waschosen as catalyst support,which has the framework topology of naturalchabazite,and has been shown to convert methanol selectively to Cl~ C3 hy-drocarbons[3].The framework Of SP contains a three-dimensional channel     

A 13CO isotopic study on the CO promotion effect in methane dehydroaromatization reaction over a Mo/HMCM-49 catalyst

The promotion effect of CO in methane dehydroaromatization was investigated using 13CO probe molecules. By alternative injection of 13CO to the methane feed,the distribution of 13CxC6-xH6(x=0-3)products changed significantly,confirming the participation of13CO in the reaction network.The addition of 13CO did not change the conversion of CH4 but improved slightly the durability of the methane dehydroaromatization(MDA)reaction,which might be caused by the interaction of the dissociated oxygen species and the ...     

Methane dehydroaromatization with periodic CH4-H2 switch:A promising process for aromatics and hydrogen

Long-term stability test of Mo/HZSM-5-N catalysts(HZSM-5-N stands for nano-sized HZSM-5) in methane dehydroaromatization(MDA)reaction has been performed with periodic CH4-H2 switch at 1033-1073 K for more than 1000 h.During this test,methane conversion ranges from 13% to 16%,and mean yield to aromatics(i.e.benzene and naphthalene) exceeds 10%.N2-physisorption,XRD,NMR and TPO measurements were performed for the used Mo/HZSM-5 catalysts and coke deposition,and the results revealed that the periodic hydrogenation can effectively suppress coke deposition by removing the inert aromatic-type coke,thus ensuring Mo/HZSM-5 partly maintained its activity even in the presence of large amount of coke deposition.The effect of zeolite particle size on the catalytic activity was also explored,and the results showed that the nano-sized zeolite with low diffusion resistance performed better.It is recognized that the size effect was enhanced by reaction time,and it became more remarkable in a long-term MDA reaction even at a low space velocity.     

Comparison of the activities of binder-added and binder-free Mo/HZSM-5 catalysts in methane dehydroaromatization at 1073 K in periodic CH4-H2 switch operation mode

Three industry-supplied,well-shaped Mo/HZSM-5 catalysts,two binder-added and one binder-free,were tested for the first time in methane dehydroaromatization to benzene at 1073 K and 10000 mL/(g h)in periodic CH4-H2 switch operation mode,and their catalytic performances were compared with those of three self-prepared,binder-free powder Mo/HZSM-5 catalysts.XRD,27Al NMR,SEM,BET and NH3-TPD characterizations of all the catalysts show that the zeolites in the two binder-added catalysts are comparable to those in the three binder-free powder catalysts in crystallinity,crystal size,micropore volume and Brnsted acidity.The test results,on the other hand,show that the catalytic performances of the two binder-added catalysts are worse than those of the four binder-free catalysts on both catalyst mass and zeolite mass bases.Then,TPO and BET measurements of all spent samples were conducted to get a deep insight into the negative effects of binder addition, and the results suggest that the binder additives functioned mainly to enhance the polyaromatization of formed aromatics to coke on their external surfaces and consequently lower the benzene formation activity and selectivity of the catalyst.     

Partial Oxidation of Methane to Formaldehyde over Superfine Mo／ZrO2 Catalysts

Superfine Mo/ZrO2 catalysts were prepared for partial oxidation of methane to HCHO and characterized by BET,XRD,LRS,H2-TPR and XPS,Mo existed mainly in the form of Zr(MoO4)2,and the catalytic performance and physicochemical properties of the Mo/ZrO2 catalysts were closely related to this species.     

Partial Oxidation of Methane to Formaldehyde over Superfine Mo/ZrO_2 Catalysts

Superfine Mo/ZrO_2 catalysts were prepared for partial oxidation of methane to HCHO and characterized by BET, XRD, LRS, H2-TPR and XPS. Mo existed mainly in the form of Zr(MoO4)2, and the catalytic performance and physicochemical properties of the Mo/ZrO2 catalysts were closely related to this species.     

Ni催化剂上甲烷部分氧化制合成气反应性能与碳物种的关系

In the partial oxidation of methane (POM) to syngas, carbon deposition on the catalyst causing catalyst deactivation or reactor plugging was reported[1～3]. Our previous work showed that methane dissociation on metallic sites to H2 and NixC is an initial step of POM over Ni/Al2O3[4]. If NixC can not be consumed immediately after its formation, it has a tendency to dissolve into the nickel crystal to form carbon whiskers. The bulk carbon and carbon whiskers are more difficult to be oxidized than NixC. Therefore, prohibiting the transformation of NixC to bulk carbon and carbon whiskers can depress the formation of carbon deposition effectively.     

乙烷添加对 Mo/HZSM-5 催化剂上甲烷芳构化反应的影响

 研究了乙烷添加对 Mo/HZSM-5 催化剂上甲烷芳构化反应性能的影响. 在所考察的反应条件下, 未观察到乙烷添加对甲烷转化的促进作用, 乙烷本身反而生成甲烷, 同时导致更高的积炭生成速率, 使 Mo/HZSM-5 催化剂更快地失活. 但添加乙烷加速了钼活性中心的形成, 缩短了芳构化反应的诱导期, 使苯的生成提前.     

Effect of the conditions of thermal pretreatment on the properties of Mo/ZSM-5 catalyst of the nonoxidative conversion of methane

Mo-containing zeolite catalysts for the nonoxidative conversion of methane are produced via solid-phase synthesis, followed by thermal treatment at different temperatures. The state of nanosized Mo powders is investigated by means of X-ray diffraction and thermal analysis. The effect the temperature of Мо/ZSM-5 catalyst annealing has on its acidic characteristics and activity in the process of methane dehydroaromatization is established.     

A new phenomenon in the induction period of the methane dehydroaromatization reaction

The induction period of dehydroaromatization of methane to benzene over Mo/HZSM-5 had been investigated in real-time by the resonant-enhanced two-photon ionization (RE2PI) technique; it is remarkable that there is a small amount of benzene formed in the early stage of the induction period; we suggest that the trace amount of benzene was caused by the reduction of the original Mo6+ ion during the induction period and the Mo6+ species has a slight catalytic activity for methane-benzene conversion.     

Confined Carbon Mediating Dehydroaromatization of Methane over Mo/ZSM‐5

Non‐oxidative dehydroaromatization of methane (MDA) is a promising catalytic process for direct valorization of natural gas to liquid hydrocarbons. The application of this reaction in practical technology is hindered by a lack of understanding about the mechanism and nature of the active sites in benchmark zeolite‐based Mo/ZSM‐5 catalysts, which precludes the solution of problems such as rapid catalyst deactivation. By applying spectroscopy and microscopy, it is shown that the active centers in Mo/ZSM‐5 are partially reduced single‐atom Mo sites stabilized by the zeolite framework. By combining a pulse reaction technique with isotope labeling of methane, MDA is shown to be governed by a hydrocarbon pool mechanism in which benzene is derived from secondary reactions of confined polyaromatic carbon species with the initial products of methane activation.     

Comparison of 6Mo/MCM-22 and 6Mo/ZSM-5 in the MDA process

A comparison of methane dehydroaromatization (MDA) on 6Mo/MCM-22 and 6Mo/ZSM-5 was carried out using a gas mixture of 90%CH₄, 2%CO₂ and 8%Ar as the feed. The results indicate that the stability of 6Mo/MCM-22 is better than that of 6Mo/ZSM-5. A detailed study reveals that the ability for coke accommodation and the retention of the shape selectivity for aromatics formation is responsible for the stability of a MDA catalyst. This revised version was published online in August 2006 with corrections to the Cover Date.     

Recent progress in methane dehydroaromatization: From laboratory curiosities to promising technology

Direct conversion of methane to benzene or other valuable chemicals is a very promising process for the efficient application of natural gas. Compared with conversion processes that require oxidants, non-oxidative direct conversion is more attractive due to high selectivity to the target product. In this paper, an alternative route for methane dehydrogenation and selective conversion to benzene and hydrogen without the participation of oxygen is discussed. A brief review of the catalysts used in methane dehydroaromatization (MDA) is first given, followed by our current understanding of the location and the active phase of Mo species, the reaction mechanism, the mechanism of carbonaceous deposit and the deactivation of Mo/zeolite catalysts are systematically discussed. Ways to improve the catalytic activity and stability are described in detail based on catalyst and reaction as well as reactor design. Future prospects for methane dehydroaromatization process are also presented.     

Quantitative measurement of the Brönsted acid sites in solid acids: toward a single-site design of Mo-modified ZSM-5 zeolite

On the basis of our previous H/D exchange studies devoted to the quantification of the number of Br?nsted acid sites in solid acids, we report here an innovative approach to determine both the amount and the localization of Mo atoms inside the Mo/ZSM-5 catalyst, commonly used for the methane dehydroaromatization reaction. The influence of Mo introduction in the MFI framework was studied by means of BET, X-ray diffraction, 27Al magic angle spinning NMR, NH3 temperature-programmed desorption, and H/D isotopic exchange techniques. A dependence was found between the decrease of acidic OH groups and the Mo content. Depending on the Si/Al ratio of the zeolite, i.e., the proximity of two Br?nsted acid sites, the Mo atoms substitute a different number of OH groups. Consequently, a chemical structure was proposed to describe the geometry of the Mo complex in the channels of the ZSM-5 zeolite.     

用于甲烷芳构化的Mo/HZSM-5催化剂的活化（英文）

The effect of Mo/HZSM-5 pretreatment at 973 K in inert(He), oxidizing(artificial air), and carburizing(CH4/He mixture) atmospheres on its performance in non-oxidative methane dehydroaromatization(MDA) was investigated. The effect of post-synthesis silylation on deactivation of external acid sites was also studied. Precarburization resulted in increased aromatic selectivity and improved catalyst stability. The benzene selectivity was the highest for the silylated Mo/HZSM-5 catalyst(benzene + naphthalene selectivity after 1 h on stream was close to 100%). The deactivation of precarburized zeolites was less pronounced than that of zeolites heated in air or He. During heating in air or He, larger fractions of the molybdenum oxide species diffused into the micropores than during heating in methane. Carburization of the molybdenum oxide species in the micropores during MDA resulted in the formation of molybdenum carbide particles, and these contributed to pore blocking, making the Brnsted acid sites inaccessible. The formation of molybdenum carbides during heating in methane resulted in a less mobile Mo phase. It is argued that the presence of molybdenum carbide particles in the micropores contributes to rapid catalyst deactivation, in addition to the formation of hard coke on the external surface.     

Methane dehydroaromatization with periodic CH_4-H_2 switch:A promising process for aromatics and hydrogen

Long-term stability test of Mo/HZSM-5-N catalysts(HZSM-5-N stands for nano-sized HZSM-5) in methane dehydroaromatization(MDA)reaction has been performed with periodic CH4-H2 switch at 1033-1073 K for more than 1000 h.During this test,methane conversion ranges from 13% to 16%,and mean yield to aromatics(i.e.benzene and naphthalene) exceeds 10%.N2-physisorption,XRD,NMR and TPO measurements were performed for the used Mo/HZSM-5 catalysts and coke deposition,and the results revealed that the periodic hydrogenation can effectively suppress coke deposition by removing the inert aromatic-type coke,thus ensuring Mo/HZSM-5 partly maintained its activity even in the presence of large amount of coke deposition.The effect of zeolite particle size on the catalytic activity was also explored,and the results showed that the nano-sized zeolite with low diffusion resistance performed better.It is recognized that the size effect was enhanced by reaction time,and it became more remarkable in a long-term MDA reaction even at a low space velocity.     

多级孔IM-5分子筛的简易制备及其在甲烷芳构化中的催化性能

采用一步水热晶化法、不添加第二模板剂、仅通过控制合成条件,制备了具有多级孔道结构的IM-5-H分子筛。多级孔IM-5-H材料展现了与常规IM-5-C分子筛不同的形貌、结构和酸性质。由于IM-5-H分子筛载体介孔结构的促进作用,钼基Mo-IM-5-H催化剂在甲烷无氧芳构化反应中表现出较高的甲烷转化率（13.1%）、芳烃产率（7.5%）和稳定性。该研究为合成多级孔IM-5材料提供了一种简便的方法,同时扩展了微孔-介孔复合材料在甲烷芳构化反应中的应用。