The effect of alkali promoters in oxidative coupling of methane with Mn-oxide catalysts

The catalytic oxidalive coupling of metnane to ethylene and ethane with manganese oxide catalysts promoted with alkali metal and alkali metallic-chloride has been studied at atmospheric pressure in a fixed bed flow reactor. The main studies of reaction were carried out over maganese oxide catalysts promoted with sodium chloride and the structure and surface morphology of these catalysts was characterized by an X-ray diffraction and a scanning electron microscope. The powdered MnO₂ was changed into Mn₂O₃, and MnO₂ containing alkali metallic-chlorides was not changed to new ternary oxides but changed into Mn₃O₄ and/or Mn₂O₃ at higher calcination temperature(above 780°C). The optimum content of NaCl promoted was 10–20wt%, an in over 10wt%, the conversion and the selectivity were kept constant. The main factor on deactivation of catalysts was the loss of thepromoter(NaCl). The addition of alkali metal salts to manganese oxide catalyst has enhanced C₂(C₂H₄ + C₂H₆) selectivity due to neutralizing acid sites more than the electronic factor. It was confirmed that chlorine in alkali metallicchloride has enhanced the formation of C₂H₄, resulting in a good C₂-yield (up to 25.7%).     

Characterization of Ti/Si binary oxides prepared by the sol-gel method and their photocatalytic properties: The hydrogenation and hydrogenolysis of CH3CCH with H2O

Titanium-silicon (Ti/Si) binary oxides having different Ti content were prepared by the sol-gel method and utilized as photocatalysts for the hydrogenation and hydrogenolysis of CH₂CCH with H₂O. The photocatalytic reactivity and selectivity of these catalysts were investigated as a function of the Ti content and it was found that the hydrogenolysis reaction (C₂H₆ formation) was predominant in regions of low Ti content, while the hydrogenation reaction (C₃H₆ formation) proceeded in regions of high Ti content. The in situ photoluminescence, diffuse reflectance absorption, FT-IR, XAFS (XANES and EXAFS), and XPS spectroscopic investigations of these Ti/Si binary oxides indicated that the titanium oxide species are highly dispersed in the SiO₂ matrices and exist in a tetrahedral coordination exhibiting a characteristic photoluminescence spectrum. The charge transfer excited state of the tetrahedrally coordinated titanium oxide species plays a significant role in the efficient photoreaction with a high selectivity for the hydrogenolysis of CH₃CCH to produces mainly C₂H₆ and CH₄, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity for the hydrogenation of CH₃CCH to produce C₃H₆, being similar to reactions of the powdered TiO₂ catalysts. The good parallel relationship between the yield of the photoluminescence and the specific photocatalytic reactivity of the Ti/Si binary oxides as a function of the Ti content clearly indicates that the high photocatalytic reactivity of the Ti/Si binary oxides having low Ti content is associated with the high reactivity of the charge transfer excited state of the isolated titanium oxide species in tetrahedral coordination, [Ti³⁺-O⁻]*.     

Oxidative coupling of methane by carbon dioxide: a highly C2 selective La2O3/ZnO catalyst

In the oxidative coupling of methane by carbon dioxide, La₂O₃/ZnO catalysts were found to have high C₂ selectivity and good stability. The coupling selectivity on La₂O₃/ZnO is about 90%, which is much higher than that on pure La₂O₃ or ZnO. The consumption ratio of carbon dioxide to methane is approximately one. X-ray diffraction analysis reveals that the structural forms of the oxides are unchanged during the reaction. The reaction mechanism for C₂ formation is discussed.     

Activities of γ-Al2O3-Supported Metal Oxide Catalysts in Propane Oxidative Dehydrogenation

The activities of metal oxide catalysts in propane oxidative dehydrogenation to propene have been studied. The catalysts are M/-Al₂O₃ (where M is an oxide of Cr, Mn, Zr, Ni, Ba, Y, Dy, Tb, Yb, Ce, Tm, Ho or Pr). Both transition metal oxides (TMO) and rare-earth metal oxides (REO) are found to catalyze the reaction at 350-450 °C, 1 atm and a feed rate of 75 cm³/min of a mixture of C₃H₈, O₂ and He in a molar ratio of 4:1:10. Among the catalysts, Cr-Al-O is found to exhibit the best performance. The selectivity to propene is 41.1% at 350 °C while it is 54.1% at 450 °C. Dy-Al-O has the highest C₃H₆ selectivity among the REO. At 450 °C, the other catalysts show C₃H₆ selectivity ranging from 16.2 to 37.7%. In general TMO show higher C₃H₆ selectivity than REO, which, however, show higher C₂H₄ selectivity. An attempt is made to correlate propane conversion and selectivity to C₃H₆ with metal-oxygen bond strength in the catalysts. For the TMO a linear correlation is found between the standard aqueous reduction potential of the metal cation of the respective catalyst and its selectivity to propane at 11% conversion. No such correlation has been found in the case of REO. Analyses of the product distributions suggest that for TMO propane activation the redox mechanism seems to prevail while the REO activate it by adsorbed oxygen.     

Catalysis of Methane Coupling with Carbon Dioxide Over Binary Oxides

Binary oxides of Ca-Ce, Ca-Cr, and Ca-Mn exhibit good performance and similar kinetic behavior in the conversion of CH₄ to C₂ hydrocarbons with CO₂, whereas the corresponding Sr- and Ba-containing catalysts show lower activity in C₂ formation except for Sr-Mn and Ba-Mn oxides. The Sr-Mn oxide provides even higher C₂ yield than the Ca-containing catalysts. Characterization reveals that solid solution and composite oxides comprising Ca²⁺ species and the redox component (Ce, Cr, or Mn) exist at a steady state of reaction and probably account for the synergy in C₂ formation over the Ca-containing catalysts. On the other hand, Sr and Ba carbonates are formed along with Ce, Cr, or Mn oxides during the reactions over Sr- and Ba-containing oxides. The carbonates, however, can react with MnO to form SrMnO_2.5 and BaMnO_2.5, the probable active species for CH₄ activation over the Sr-Mn and Ba-Mn catalysts.     

Oxidation of ketones over metal oxide catalysts: I. Catalytic synthesis of biacetyl from methyl ethyl ketone

The gas-phase oxidation of methyl ethyl ketone was studied on metal oxide catalysts in the presence of water vapor. Two types of competitive partial oxidations, i.e., biacetyl formation and oxidative scission reaction leading to acetaldehyde and acetic acid, took place on every oxide studied at 400–500 K. An approximate linear relationship was observed between the selectivity of each reaction and the acid-base property of the oxides; the former reaction was accelerated on the basic oxides such as Co₃O₄, while the latter reaction became predominant on the acidic oxides. As Co₃O₄ was the most effective biacetyl former of single-component oxides, modification of Co₃O₄ was examined to develop more effective catalysts for biacetyl synthesis. Scission reaction took the place of biacetyl formation over a catalyst where Co²⁺ ions were located in Y zeolite by an ion-exchanged method. Scission reaction was suppressed when Co oxide was supported on basic oxides such as MgO or CaO; however, the selectivity to biacetyl was slightly decreased due to the occurrence of a new reaction, acetone formation. The addition of Na₂O or Li₂O to Co₃O₄ was found to improve the selectivity to biacetyl without loss of catalytic activity. The maximum efficiency (13%) in biacetyl formation was attained at a Li content of ca. 7 at.%.     

Role of defect structure of active oxides in oxidative coupling of methane

A new approach to the choice of catalysts for oxidative coupling of methane based on the determination of the defect degree is suggested. For the most active catalysts (oxides of rare earth elements (REE), alkaline earth metals (AEM), manganese, lead), it is shown that oxygen defectness is of great importance in this process.Based on the structural approach Bi₂O₃-containing catalytic systems have been suggested. They have C₂-hydrocarbon formation activity and selectivity to be comparable with those ones for most active catalysts as REE oxides.     

Total Oxidation of Methane and Chlorinated Hydrocarbons on Zirconia Supported A1–xSrxMnO3 Catalysts

The catalytic behavior of ZrO₂ and ZrO₂ containing 8 mol‐% Y₂O₃ supported A_1–xSr_xMnO₃ (A = La, didymium) perovskites was studied in the total oxidation of methane, chloromethane and dichloromethane considering catalyst deactivation and byproduct formation. The perovskites are dispersed on the support surface; clusters with a perovskite‐like structure were formed. The supported catalysts are characterized by higher specific surface areas compared with the unsupported ones. Partial substitution of A‐site cations by Sr leads to an enhancement of the catalytic activity in the total oxidation of methane, but not in the total oxidation of chlorinated hydrocarbons (CHC). The catalytic activity of supported and unsupported catalysts is comparable in the total oxidation of methane in spite of the significantly lower perovskite content of the supported catalysts. In the CHC conversion the catalytic activity of the supported catalysts is higher than that of the unsupported ones.     

Propane ammoxidation on bulk, diluted and supported VSb oxides

VSb oxides diluted with Mg, Al and Zr displayed substantially higher selectivity for propane ammoxidation to acrylonitrile than their bulk and supported analogues. Diluted catalysts were found to consist of oxide compounds of antimony with diluent element, such as AlSbO₄ or MgSb₂O₆, and small amounts of individual oxides of antimony and diluent element. No VSbO₄ phase was detected in their body in contrast with bulk and supported catalysts. It appears that better isolation of vanadium and antimony entities in the structure of diluted oxides was responsible for their enhanced catalytic behavior. Tungsten loaded to the surface of diluted catalysts further improved their selectivity through tuning the surface acidity.     

Low-temperature catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

MnO_x–CeO₂ mixed oxide catalysts prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of chlorinated aromatic volatile organic compounds (CVOCs). MnO_x–CeO₂ catalysts with the different ratio of Mn/Ce + Mn were found to possess high catalytic activity for catalytic combustion of CB, and MnO_x(0.86)–CeO₂ was the most active catalyst, on which the complete combustion temperature (T_90%) of chlorobenzene was 236 °C. The stability of MnO_x–CeO₂ catalysts in the CB combustion was investigated. MnO_x–CeO₂ catalysts with high Mn/Ce + Mn ratios present high stable activity, which is related to their high ability to remove Cl species adsorbed and a large amount of active surface oxygen.     

Total Oxidation of Chlorinated Hydrocarbons on A1–xSrxMnO3 Perovskite‐Type Oxide Catalysts – Part II: Catalytic Activity

The influence of the kind of A‐site cation in A_1–xSr_xMnO₃ perovskites (A = La, Pr, Nd, Di [didymium]) on the catalytic activity in the total oxidation of methane, chloromethane, dichloromethane, and trichloroethylene has been studied. In contrast to methane, the total oxidation of chlorinated hydrocarbons (CHC) is connected with a reversible catalyst deactivation and the formation of byproducts at low reaction temperatures. For the catalysts calcined at 600 and 800 °C, resp., the catalytic activity is determined mainly by specific surface area, amount of oxide admixtures and crystallinity of the perovskite. DiMnO₃ showed the highest and PrMnO₃ catalysts the lowest catalytic activity in the total oxidation of methane and CHC. Partial substitution of A by Sr leads to an enhancement of the catalytic activity in the total oxidation of methane, but not in the total oxidation of CHC.     

Lowering methane and raising distillates yields in Fischer–Tropsch synthesis by using promoted and unpromoted cobalt catalysts in a dual bed reactor

Fischer–Tropsch synthesis was studied by using a combination of promoted and unpromoted cobalt catalysts in a dual bed reactor. An alkali-promoted catalyst was used in the first bed of a fixed-bed reactor followed by an unpromoted catalyst in the second bed. The activity and product selectivity of the system were assessed and compared with those using a mixture of both catalysts in a single bed. The methane selectivity in the dual bed reactor was about 17% less compared to that of the single bed reactor. The C₅₊ selectivity for the dual bed reactor was 12.3% higher than that of the single bed reactor.     

MnOx/CeO2 catalysts for the low-temperature selective catalytic reduction of NO with NH3

CeO₂–nanorod support was synthesized by hydrothermal method and different manganese oxides (MnO, MnO_2, and Mn₂O₃) were impregnated over support by the wet-impregnation forming MnO/CeO₂-NR, MnO₂/CeO₂-NRm and Mn₂O₃/CeO₂-NR. The physico-chemical properties of the as-prepared catalysts were analyzed using x-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area, x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope–energy-dispersive x-ray spectroscopy (SEM–EDX), hydrogen-temperature-programmed reduction (H₂-TPR), and Raman spectroscopy. These catalysts were further analyzed for NO reduction using NH₃ as a reducing gas in the temperature range of 50 to 450°C. The results confirmed that MnO₂/CeO₂-NR gave the maximum NO conversion (65%) and N₂ selectivity (89%) among all catalysts. Further, MnO₂/CeO₂-NR catalyst was studied for the effect of MnO₂ loading and more than 90% NO conversion and N₂ selectivity were obtained in the temperature range of 250 to 300°C.     

Screening of doped MnOx–CeO2 catalysts for low-temperature NO-SCR

The effect of different dopants including niobium, iron, tungsten and zirconium oxide on the low-temperature activity of MnO_x–CeO₂ catalysts for the selective catalytic reduction (SCR) of NO_x with ammonia has been studied with coated cordierite monoliths in model gas experiments. A clearly higher activity and particularly superior nitrogen selectivity was obtained with the niobium-doped catalyst in comparison with the MnO_x–CeO₂ reference system. At 200 °C, the DeNO_x was 80% while the N₂ selectivity reached more than 96%. In contrast, a decrease of the SCR activity was observed when iron, zirconium or tungsten oxides were added to MnO_x–CeO₂. However, the addition of niobium oxide did not improve the resistance of the catalyst against SO₂ poisoning. A strong and irreversible deactivation occurred after exposure to SO₂.     

Oxidation of o-Xylene to Phthalic Anhydride on Sb-V/ZrO2 Catalysts

Zirconia-supported and bulk-mixed vanadiumantimonium oxide catalysts were used for the oxidation of o-xylene to phthalic anhydride. X-ray diffraction, Raman spectroscopy and photoelectron spectroscopy were used for characterization. It was found that vanadium promotes the transition of tetragonal to monoclinic zirconia. The simultaneous presence of Sb and V on zirconia at low coverage led to a preferential interaction of individual V and Sb oxides with the zirconia surface rather than the formation of a binary Sb-V oxide, while at higher Sb-V contents the formation of SbVO₄ took place. Sb-V/ZrO₂ catalysts showed high activity for o-xylene conversion and better selectivity to phthalic anhydride as compared to V/ZrO₂ catalysts. However, their selectivity to phthalic anhydride was poor in comparison to a V/TiO₂ commercial catalyst. The improved selectivity of the Sb-containing catalysts is attributed to the blocking of non-effective surface sites of ZrO₂, the decrease of the total amount of acid sites and the formation of surface V-O-Sb-O-V structures.     

Unterschiede in der Totaloxidation organischer Verbindungen an heterogenen Platin- und Palladiumkatalysatoren

Differences in the Total Oxidation of Organic Compounds on Heterogeneous Pt- and Pd-Catalysts The catalytic oxidation of selected organic compounds was studied on supported Pd and Pt catalysts and on massive wires. Unfunctionalized (Decane), unsaturated (dodecene, benzene), oxygen containing (1-octanol, formaldehyde, acetone, n-butylacetate, formic acid), nitrogen containing (aniline, pyridine), sulfur containing (thiophene) and chlorinated (1,2-dichloroethane) hydrocarbons were used as model compounds. The relative activity of the metals for oxidation of the various compounds was determined from the turnover frequencies. While platinum is more active for the oxidation of the unfunctionalized, aromatic and chlorinated compounds, palladium is more active for nitrogen and sulfur containing compounds and for formic acid. No specificity is found for alkenes and compounds with a lower oxygen content. In the presence of octane, the unreactive pyridine is much more effectively oxidized than pyridine alone. There are distinct differences for the oxidation of octane/pyridine mixtures on bimetallic, mixed and pure Pt- and Pd-catalysts. The bimetallic catalyst and the pure Pt-catalyst dominate with respect to conversion and selectivity. The oxidation of linear alkanes on Pt correlates with the boiling point. Pd catalyzes the oxidation of lower hydrocarbons (< C₅) better, while higher hydrocarbons ( > C₅) are better oxidized by Pt.     

Dehydrochlorination of Intermediates in the Production of Vinyl Chloride over Lanthanum Oxide-Based Catalysts

Lanthanum oxide-based catalysts are active in the elimination of HCl from C₂H₅Cl, 1,2-C₂H₄Cl₂ and 1,1,2-C₂H₃Cl₃ leading to the formation of their respective chlorinated ethenes. An oxygen-rich catalytic surface may form CO, CO₂ and C₂HCl as side products, whereas with chlorine-rich catalytic surfaces a stable product distribution is achieved with 100% selectivity towards the formation of ethenes, such as the valuable C₂H₃Cl intermediate.     

Preparation of manganese oxide–polyethylene oxide hybrid nanofibers through in situ electrospinning

Manganese oxide nanoparticles–polyethylene oxide nanofibers as organic–inorganic hybrid were prepared via in situ electrospinning. Thus, electrospinning of polyethylene oxide solution with different manganese chloride concentration was carried out in gaseous ammonia atmosphere containing oxygen. The reaction of manganese chloride with ammonia produces manganese hydroxide, and then oxygen in the reaction media reacts with manganese hydroxide to yield manganese oxide. These two reactions occur during fiber formation. Transmission electron microscopy and scanning electron microscopy showed that manganese oxide (MnO₂) nanoparticles were formed on the produced nanofibers of 100–600 nm in diameter. The existence of the formed MnO₂ was also proved by X‐ray diffraction analysis, and it showed that the λ‐MnO₂ nanoparticles were produced. Differential scanning calorimetry (DSC) analysis was used to determine the melting point and to calculate the crystallinity of the produced hybrid nanofibers. The DSC and thermogravimetric analysis results of the obtained nanofibers were compared with those of the nanofibers produced in electrospinning of pure polyethylene oxide solution. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The catalytic conversion of CO2 to hydrocarbons over Fe–K supported on Al2O3–MgO mixed oxides

Al₂O₃–MgO mixed oxides prepared by a co-precipitation method have been used as supports for potassium-promoted iron catalysts for CO₂ hydrogenation to hydrocarbons. The catalysts have been characterized by XRD, BET surface area, CO₂ chemisorption, TPR and TPDC techniques. The CO₂ conversion, the total hydrocarbon selectivity, the selectivities of C₂–C₄ olefins and C₅₊ hydrocarbons are found to increase with increase in MgO content upto 20 wt% in Fe–K/Al₂O₃–MgO catalysts and to decrease above this MgO content. The TPR profiles of the catalysts containing pure Al₂O₃ and higher (above 20 wt%) MgO content are observed to contain only two peaks, corresponding to the reduction of Fe₂O₃ to Fe⁰ through Fe₃O₄. However, the TPR profile of 20 wt% MgO catalyst exhibits three peaks, which indicate the formation of iron phase through FeO phase. The TPDC profiles show the formation of three types of carbide species on the catalysts during the reaction. These profiles are shifted towards high temperatures with increasing MgO content in the catalyst. The activities of the catalysts are correlated with physico-chemical characteristics of the catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Control of Metal Dispersion and Structure by Changes in the Solid-State Chemistry of Supported Cobalt Fischer–Tropsch Catalysts

Controlling preparation variables in supported cobalt Fischer–Tropsch catalysts has a dramatic effect on the dispersion and distribution of cobalt, and determines how active and selective the resulting catalyst will be. We detail specific examples of catalyst synthesis strategies for modifying interactions between the support and the cobalt precursor, promoting reduction, stabilizing catalysts to high-temperature treatments, minimizing deleterious support metal interactions, and controlling the distribution of cobalt on large support particles. It is important to optimize the support and precursor interaction strength, so that it is strong enough to obtain good dispersion but not too strong to prevent low temperature reduction. We show examples in which formation of surface complexes and epitaxial matching of precursor and support structures improves dispersion dramatically. Reduction promoters can help in those cases where support–precursor interactions are too strong. We show how substitutions of silicon into a titania lattice stabilizes surface area and retards formation at high oxidation temperatures of cobalt ternary oxides that reduce only at very high temperatures—an important consideration if oxidative coke removal is necessary. In addition, surface treatment of TiO₂ with an irreducible oxide like ZrO₂ can inhibit deleterious support interactions that can block surface cobalt sites. Selectivity can also be dramatically altered by catalyst synthesis. We illustrate a case of large (2 mm) SiO₂ particles onto which cobalt can be added either uniformly or in discrete eggshells, with the eggshell catalysts having substantially higher C₅₊ selectivity. These approaches can lead to optimal Fischer–Tropsch catalysts with high activity and C₅₊ selectivity, good physical integrity, and a long life.