Basic zeolite and zeolite-type catalysts for the oxidative methylation of toluene with methane

The oxidative methylation of toluene with methane is used as a test reaction for determining the activity, selectivity and yield of C₈ hydrocarbons (ethylbenzene and styrene) over different zeolite and zeolite-type catalysts, viz., X, Y, mordenite, ZSM-5, silicalite and AlPO₄-5. Selectivity and basicity increase with decreasing Si/Al atomic ratio within the series of the same structural type. The basicity, surface structure and structural integrity are characterized by TPD of CO₂, XPS and IRS, respectively. This revised version was published online in June 2006 with corrections to the Cover Date.     

Methane activation over zeolite catalysts: The methylation of benzene

The methylation of benzene with methane over ZSM-5 zeolite catalysts in a high pressure static reactor is shown to require oxygen as a reactant, implicating methanol as a key intermediate species. In the case of zeolite H-beta, methyl aromatics can be formed in the absence of oxygen, consistent with an earlier report that these products are formed from cracking of benzene over the acid zeolite.     

Effect of structural analogy between ZSM-5 and silicalite catalysts on the oxidative methylation of toluene with methane

Summary With ZSM-5 and silicalite (both initial and BaO modified) the yield of styrene, the most desirable reaction product, was highly represented when BaO modified silicalite was used as catalyst for the reaction. The catalytic results fitted the basicity, surface area and structural crystallinity.     

Spectral study of catalysts for the oxidative condensation of methane

Methods for preparing catalysts for the oxidative condensation of methane based on a metal support (FeCrAl foil) containing Al₂O₃ and SiO₂ and active ingredients (Na₂WO₄, Mn₂O₃, and PbO) are developed. The prepared catalysts are studied by XRD, XPS, and EM.     

The mechanism of phenol methylation on acid and basic zeolite catalysts

The alkylation of phenol with methanol on HY and CsY/CsOH catalysts was studied in situ under static conditions by ¹³C NMR spectroscopy. Attention was largely given to the identification of intermediate compounds and mechanisms of anisole, cresol, and xylenol formation. The mechanisms of phenol methylation were found to be different on acid and basic catalysts. The primary process on acid catalysts was the dehydration of methanol to dimethyl ether and methoxy groups. This resulted in the formation of anisole and dimethyl ether, the ratio between which depended on the reagent ratio, which was evidence of similar mechanisms of their formation. Subsequent reactions with phenol gave cresols and anisoles. Cresols formed at higher temperatures both in the direct alkylation of phenol and in the rearrangement of anisole. The main alkylation product on basic catalysts was anisole formed in the interaction of phenolate anions with methanol; no cresol formation was observed. The deactivation of acid catalysts was caused by the formation of condensed aromatic hydrocarbons that blocked zeolite pores. The deactivation of basic catalysts resulted from the condensation of phenol and formaldehyde with the formation of phenol-formaldehyde resins.     

New approach to the preparation of catalysts for the oxidative coupling of methane

A new approach to the preparation of systems that exhibit catalytic activity in the oxidative coupling of methane (OCM) is considered. With the use of ferrospheres separated from power-generation ashes from different sources as an example, it was demonstrated that OCM catalysts can be prepared by the crystallization/solidification of oxide melts with the formation of microspherical particles. The dependence of activity and selectivity for the oxidative reforming of methane on the ferrospheres containing from 36.2 to 92.5 wt % Fe₂O₃ into the products of deep oxidation and OCM was studied. It was found that deep oxidation reactions on ferrospheres with Fe₂O₃ contents higher than 85% were suppressed, and the main reaction path of CH₄ conversion was its oxidative coupling with the formation of C₂ products (with selectivity to 60% at 750°C); moreover, the selectivity for C₂ formation in this region was proportional to the concentration of Fe₂O₃. Phases responsible for the catalytic conversion of methane into CO _x and OCM products were considered, and it was shown that the catalytic activity and selectivity of the oxidative transformation of CH₄ on ferrospheres is determined by the position of the point that corresponds to their composition on a phase diagram of CaO-Fe₂O₃-SiO₂.     

Selective oxidation of benzene to phenol with molecular oxygen on rhenium/zeolite catalysts

Zeolite-supported rhenium catalysts are active for selective oxidation of benzene with molecular oxygen, where coexisting ammonia is prerequisite to the direct phenol synthesis.     

Catalytic reforming of methane by carbon dioxide over nickel-exchanged zeolite catalysts

A series of nickel-exchanged catalysts based on ZSM-5, USY, and Mordenite zeolites has been prepared by the ionic exchange method. The NiZeol catalysts have been characterized by XRD and BET. The exchange levels and nickel contents of the catalysts have been determined by chemical analysis. The acidity of the zeolite supports has been investigated using NH₃ adsorption microcalorimetry. The number of acidic sites was found to decrease according to the following sequence: HUSY > HZSM-5 > HMOR. The temperature programmed reduction studies showed that the most reducible catalyst is NiZSM-5. The Ni-exchanged zeolites presented good catalytic performance in the methane reforming by CO₂. At a temperature of 650°C, CH₄ conversions of 71 and 54% were achieved on NiUSY and NiZSM-5 respectively. At 400°C, CO₂ FTIR adsorption has shown that CO₂ decomposes into CO and oxygen on NiZSM-5 which explains its reactivity at such a low temperature, while no decomposition of this probe molecule was observed on the NiUSY catalyst. The catalytic performance was found to vary in the following sequence at 650°C: NiUSY > NiZSM-5 > NiMOR. Moreover, the catalytic performances were found to depend strongly on the CO₂/CH₄ ratio in the feed and were markedly improved for CO₂/CH₄ greater than 1.     

Hydrogen production by conversion of methane over nickel-supported USY-type zeolite catalysts

Hydrogen production by conversion of methane over Ni-supported zeolite catalysts was investigated, and Ni-supported USY-type zeolite (Si/Al₂ = 14.0, 360) was found to have longer catalytic lifetime than Ni-supported silica (Cab-O-Sil) catalyst, which had been reported to have the longest catalytic lifetime for this reaction.     

Alkylation of benzene by olefins on zeolite catalysts in the presence of CO2

Conclusions The yields of the products obtained in the alkylation of benzene with ethylene and propylene on zeolites CaY, CoY, SrY, NdCaNaY and dealuminized zeolite CaY' should increase by 2–4 times when CO₂ is added to the reaction mixture, in which connection the effect of the CO₂ depends on the nature of the catalyst.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1138–1140, May, 1973.     

Finned Zn-MFI zeolite encapsulated noble metal nanoparticle catalysts for the oxidative dehydrogenation of propane with carbon dioxide

Oxidative dehydrogenation of propane with carbon dioxide(CO₂-ODP) characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO₂ to valuable CO.However, the existing catalyst is limited due to the poor activity and stability, which hinders its industrialization. Herein, we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI) for CO₂-ODP. Characterization...     

Physicochemical properties and activity of Mo-containing zeolite catalysts of nonoxidative conversion of methane

High-silica zeolites of ZSM-5 structural type were synthesized using various structure-forming additives and without them. Mo-containing catalytic systems were prepared on the basis of these zeolites. Their physicochemical properties and activity in the course of the nonoxidative conversion of methane were studied. The Mo/ZSM-5 catalyst obtained on the basis of zeolite synthesized with hexamethylenediamine showed high aromatizing activity and stability.     

Selective conversion of methane to aromatic hydrocarbons on large crystallite zeolite catalysts with mesoporous structure

Large crystallite mesoporous MFI (ZSM-5) zeolite was synthesized by using carbon nano-powder as a secondary template. The surface properties, morphological and phase composition of the synthesized material and of the commercial ZSM-5 (Zeolyst) zeolite were studied by nitrogen porosimetry, XRD and scanning electron microscopy. The results showed that the volume of mesopores volume increases with development of a secondary mesoporosity in the structure of zeolite. The obtained zeolite supports were used to prepare molybdenum-containing catalysts for the methane aromatization by solid phase preparation technique. Based on the XPS data, molybdenum particles in these catalysts are characterized by more uniform size distribution. The formation of a secondary pore structure restrains the carbon deposit formation as well as increases the methane conversion and the yield of the aromatic compounds.     

Natural calcium minerals as catalysts of oxidative conversion of methane

The studies of the influence of the kind of natural calcium mineral and the kind and amount of sodium promoter on the conversion degree of methane and oxygen, selectivity and yield of the oxidative conversion of methane have shown the usability of limestone as a basic component of the catalyst for this process.     

Regiocontrolled aerobic oxidative coupling of indoles and benzene using Pd catalysts with 4,5-diazafluorene ligands

Palladium-catalyzed aerobic oxidative cross-couplings of indoles and benzene have been achieved by using 4,5-diazafluorene derivatives as ancillary ligands. Proper choice of the neutral and anionic ligands enables control over the reaction regioselectivity.     

Role of phase boundary in heterogeneous oxide catalysts for oxidative coupling of methane

Bi₂EO₅ (E=Si, Ge) catalysts in a metastable state have been found to possess a high activity for oxidative coupling of methane. It has been assumed that the intergrowth boundaries for the Bi₂EO₅ decomposition products, on which active catalytic sites may be located, play a specific role on the catalytic performance of the oxides.