Methane Reforming with Carbon Dioxide on the Co/α-Al2O3 Catalyst: The Formation, State, and Transformations of Surface Carbon

The interactions of oxidized and reduced Co/-Al₂O₃ (4 wt % CoO) with H₂, CH₄, CO₂, and O₂ and their mixtures are studied in flow and pulse regimes using a setup involving a DSC-111 differential scanning calorimeter and a system for chromatographic analyses. It is shown that treatment with hydrogen at 700°C results in the partial reduction of cobalt oxide to Co. Methane poorly reacts with the oxidized catalyst but readily reacts with the reduced catalyst to form H₂ and surface carbon. The initial surface carbon transforms into other forms, which block the cobalt surface to different extents and differ in the heats of reaction with CO₂. Carbon dioxide may react with the surface carbon to form CO (rapidly) and with metallic Co to form CO and CoO (slowly). Thus, the main route of methane reforming with carbon dioxide on Co/-Al₂O₃ is the dissociative adsorption of CH₄ to form surface carbon and H₂ and the reaction of surface carbon with CO₂ to form CO via the reverse Boudouard reaction.     

Tungsten Promoted Ni／Al2O3 Catalysts for Carbon Dioxide Reforming of Methane to Synthesis Gas

A series of tungsten promoted alumina supported nickel catalysts has been prepared for the carbon diox-ide reforming of methane to synthesis gas. The catalysts have been characterized by means of XRD, TEM,and Laser Raman spectroscopy. It is shown that the addition of tungsten to the nickel catalyst can stabilize the catalyst and increase the resistance to carbon deposition. Adding a suitable amount of tungsten can also increase the catalyst activity to be close to that of supported noble metal catalysts. The carburisation of the tungsten modified nickel catalyst decreases the catalyst activity at lower reaction temperatures (＜1123K),but has no effect on the catalyst performance at higher reaction temperatures. The alumina supported nickel catalyst modified by 0. 67% (mass fraction) WO3 has the equivalent equilibrium constant of the dry reforming reaction to that of alumina supported 5% (mass fraction) Ru at 873 K, and also has a lower activation energy for dry reforming than the latter.     

Autothermal Reforming of Methane over Ni Catalysts Supported on CuO-ZrO2-CeO2-Al2O3

Ni catalysts supported on various mixed oxides of Al2O3 with rare earth oxide and transitional metal oxides were synthesized. The studies focused on the measurement of the autothermal reforming of methane to hydrogen over Ni catalysts supported on the mixed oxide ZrxCe30-xAl70Oδ (x=5, 10, 15). The catalytic performance of Ni/Zr10Ce20Al70Oδ was better than that of other catalysts. XRD results showed that the addition of Zr to Ni/Ce30Al70Oδ prevented the formation of NiAl2O4 and facilitated the dispersion of NiO. Effects of CuO addition to Zr10Ce20Al70Oδ were also investigated. The activity of Ni catalyst supported on CuO-ZrO2-CeO2-Al2O3 was somewhat affected and the Ni/Cu5Zr10Ce20Al65Oδ showed the best catalytic performance with the highest CH4 conversion, yield of H2, selectivity for H2 and H2/CO production ratio in operation temperatures ranging from 650 to 750℃.     

Syngas Production by Methane Reforming with Carbon Dioxide on Noble Metal Catalysts

A series of noble metal catalysts (Ru, Rh, Ir, Pt, and Pd) supported on alumina-stabilized magnesia (Spinel) were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.     

Study on the Reaction Mechanism for Carbon Dioxide Reforming of Methane over supported Nickel Catalyst

The adsorption and dissociation of methane and carbon dioxide for reforming on nickel catalyst were extensively investigated by TPSR and TPD experiments. It showed that the decomposition of methane results in the formation of at least three kinds of surface carbon species on supported nickel catalyst, while CO2 adsorbed on the catalyst weakly and only existed in one kind of adsorption state. Then the mechanism of interaction between the species dissociated from CH4 and CO2 during reforming was proposed.     

Formation of the Ni–CrOx/MgO and Ni/MgO Catalysts for Carbon Dioxide Reforming of Methane

Temperature-programmed reduction by hydrogen, temperature-programmed desorption of O₂, local X-ray spectral analysis, and scanning electron microscopy are used to study redox processes occurring on the Ni–Cr₂O₃/MgO and Ni/MgO catalysts for carbon dioxide reforming of methane. The reduction of Ni/MgO leads to the formation of nickel clusters distributed over the surface of MgO. During the reduction of NiO–Cr₂O₃/MgO, chromates are transformed into chromites, and then nickel is formed by the reduction of spinel NiCr₂O₄. Reoxidation leads to the oxidized structures NiO, NiCr₂O₄, and NiCrO₄.     

Methane Decomposition over Ni/α-Al2O3 Promoted by La2O3 and CeO2

The decomposition of methane on Ni/a-Al2O3 modified by La2O3 and CeO2 with differ-ent contents has been investigated and the ralationship between methane decomposition and removal of carbon by CO2 over these catalyst has also been studied by pulse-chromatography. The catalysts were characterized by TPR and XRD. It was shown that Ni/a-Al2O3 could be promoted by adding La2O3, and the carbon species produced over this catalyst was activated and eliminated by CO2. But CeO2 would suppress the decomposition of methane over Ni crystallite. Both La2O3 and CeO2 can inhibit aggregation of the Ni particles. Decomposition of methane over the Ni-based catalysts is structure sensitive to a certain extent.     

Carbon Dioxide/Methane Separation by Adsorption on Sepiolite

In this work,the use of sepiolite for the removal of carbon dioxide from a carbon diox- ide/methane mixture by a pressure swing adsorption(PSA)process has been researched.Adsorption equilibrium and kinetics have been measured in a fixed-bed,and the adsorption equilibrium parameters of carbon dioxide and methane on sepiolite have been obtained.A model based on the LDF approxima- tion has been employed to simulate the fixed-bed kinetics,using the Langmuir equation to describe the adsorption equilibrium isotherm.The functioning of a PSA cycle for separating carbon dioxide/methane mixtures using sepiolite as adsorbent has also been studied.The experimental results were compared with the ones predicted by the model adapted to a PSA system.Methane with purity higher than 97% can be obtained from feeds containing carbon dioxide with concentrations ranging from 34% to 56% with the proposed PSA cycle.These results suggest that sepiolite is an adsorbent with good properties for its employment in a PSA cycle for carbon dioxide removal from landfill gases.     

The Carbonylations of Cyclohexene with Carbon Dioxide

Carb0ndi0xide,anaturalandinexpensivesourceoffunctionalcarbonunits,showspotentialabilitiesf0rthefunctionalization0f0rganicsubstrate.ThehighstabilityofCO=,however,andthelack0freliablemeth0ds0factivation,considerablyrestrictitsappIications'.Inrecentyearstransiti0nmetalcatalyzedreacti0ns0fcarb0ndi0xideaimedattheutilizationofCO2asbuildingblockinorganicsynthesishaveattractedc0nsiderableattentions,becausecarbondi0xideisthebiggestcarbonsourceonearchandthebasisofallbiochemicalorganicsynthesispr0cesse…     

Kinetics of Carbon Deposition on Hexaaluminate LaNiAl11O19 Catalyst During CO2 Reforming of Methane

In this paper, the properties of carbon deposited on hexaaluminate LaNiAl11O19 catalyst were characterized by X-ray photoelectron spectroscopy (XPS), and in the meantime, the amount of carbon deposited on the catalyst, after both CH4 decomposition and CO2 reforming of CH4, was determined by means of thermogravimetric analysis (TGA), respectively. The rates of carbon deposited on the catalyst were also investigated and the apparent kinetic equation of CO2 reforming of CH4: vc = kp0.72(CH4).p-0.55(CO2), was established by analyzing the relation between the rates of deposited carbon and the pressure ratio of CH4 and CO2.     

Study of The Pd-B/ γ-Al2O3 Amorphous Alloy Catalyst

The Pd-B/γ-Al2O3 amorphous alloy catalyst and Pd/γ-Al2O3 crystalline metal catalyst were prepared by KBH4 reduction and routine impregnation,respectively.Pd-B/γ-Al2O3 and Pd/γ-Al2O3 catalysts were characterized by XRD and SEM.It was found that the catalytic activity of the Pd-B/γ-Al2O3 amorphous alloy catalyst was higher than that of the Pd/γ-Al2O3 crystalline metal catalyst in the anthraquinone hydrogenation.     

Combination of Partial Oxidation and CO2 Reforming of Methane over Monolithic Ni／CeO2-ZrO2／γ-Al2O3 Catalyst

A new monolithic Ni/CeO2-ZrO2/γ-Al2O3 catalyst for combined partial oxidation and CO2 reforming of methane was prepared. The result shows that the addition of O2 to the feed can improve the activity of the catalyst and adjust the H2/CO ratio of the productive gases.     

Nickel Supported on Alkaline Earth Metal–Doped γ-Al2O3–La2O3 as Catalysts for Dry Reforming of Methane

Russian Journal of Applied Chemistry - Nickel catalysts supported on γ–Al2O3 doped with La2O3 and alkaline earth oxides (MgO, CaO, and SrO) were investigated in the dry reforming of...     

Repair of Pd/α-Al2O3 composite membrane with defects

A palladium composite membrane with a large number of defects was repaired using the electroless plating combined with the technique of osmosis. The loose structure of palladium film prepared by the conventional electroless plating was densified. Defects were repaired. Hydrogen selectivity was thus significantly increased without significantly increasing palladium film thickness and reducing hydrogen permeability. Project supported by the Chinese Academy of Sciences (Grant No. KJ951-A1-508) and the National Natural Science Foundation of China (Grant No. 29392003).     

TG Study of the Dispersion Threshold of Mn2O3 on γ-Al2O3

Mn₂O₃/-Al₂O₃ catalysts were prepared by the impregnation method, and the maximum monolayer dispersion capacity or dispersion threshold value of Mn₂O₃ on the surface of -Al₂O₃ was determined to be 13.08% from the decomposition mass loss of supported Mn(NO₃)₂ in the monolayer state. This was compared with the values estimated from a close-packed monolayer model and an interaction model. It was confirmed that the high activities and selectivities of the catalysts for benzoic acid hydrogenation to benzaldehyde are due to the monolayer dispersion of the Mn₂O₃ on the surface of -Al₂O₃.This revised version was published online in November 2005 with corrections to the Cover Date.     

Preparation of Carbon Nanotubes from Methane on Ni/Cu/Al Catalyst

1. Introduction With the discovery of carbon nanotubes, much attention [1-3] now has been paid to their potential application in various fields, due to their many attrac- tive physical and chemical properties. They are also being used as an important material. For instance, the large cavities of carbon nanotubes can be used as an encouraging microscopic catalytic reactor [4- 5], capable of tunnel selecting molecules in different sizes. So it is important to synthesize carbon nan- otubes with t…     

Carbon Deposits Formed on the Surface of Ru–Ni Catalysts During the Mixed Reforming of Methane Process

Monometallic nickel and bimetallic ruthenium–nickel catalysts supported onto aluminum oxide without additives and aluminum oxide modified with MgO and CaO were prepared by an impregnation method. The catalysts were tested in the process of the mixed reforming of methane, and their properties were characterized by thermogravimetry, scanning electron microscopy, and X-ray diffractometry. The total organic carbon content of the catalysts was also measured. The promoting effect of ruthenium and structural promoters on the catalytic activity of Ni/Al₂O₃ was confirmed. The Ru–Ni/MgO–Al₂O₃ catalyst exhibited the highest stability and activity; this fact can be explained by the increased adsorption of methane on the surface of ruthenium–nickel clusters.     

Studies on the Adsorption and Dissociation of Methane and Carbon Dioxide on Nickel Catalysts

The adsorption and dissociation of methane and carbon dioxide for reforming on nickel catalysts were extensively investigated by TPSR, TPD, XPS and pulse reaction methods. These studies showed that the decomposition of methane results in the formation of at least three kinds of surface carbon species on supported nickel catalysts. Carbidic Cα, carbonaceous Cβ and carbidic clusters C-γ surface carbon species formed by the decomposition of methane demonstrated different surface mobility, thermal stability and reactivity. Carbidic Cα is a very active and important intermediate in carbon dioxide reforming with methane, and the carbidic clusters Cγ species might be the precursor of surface carbon deposition. The partially dehydrogenated Cβ species can react with H2 or CO2 to form CH4 or CO. On the other hand, it was proven that CO2 can be weakly adsorbed on supported nickel catalysts, and only one kind of CO2 adsorption state is formed. The interaction mechanism between the species dissociated from CH4     

Surface Acidity/Basicity and Catalytic Reactivity of CeO2/7-Al2O3 Catalysts for the Oxidative Dehydrogenation of Ethane with Carbon Dioxide to Ethylene

Dehydrogenation of ethane to ethylene in CO2 was investigated over CeO2/γ-Al2O3 catalysts at 700℃ in a conventional flow reactor operating at atmospheric pressure. XRD, BET and microcalori-metric adsorption techniques were used to characterize the structure and surface acidity/basicity of the CeO2/γ-Al2O3 catalysts. The results show that the surface acidity decreased while the surface basicity increased after the addition of CeO2 to γ-A12O3. Accordingly, the activity of the hydrogenation reaction of CO2 increased, which might be responsible for the enhanced conversion in the dehydrogenation of ethane to ethylene. The highest ethane conversion obtained was about 15% for the 25%CeO2/γ-Al2O3. The selectivity to ethylene was high for all the CeO2,γ-A12O3 and CeO2/γ-Al2O3 catalysts.