CO removal from reformed fuel over Cu/ZnO/Al2O3 catalysts prepared by impregnation and coprecipitation methods

A composition of Cu/ZnO/Al₂O₃ catalysts prepared by the impregnation method was optimized for water gas shift reaction (WGSR) coupled with CO oxidation in the reformed gas. The optimum composition of the impregnated catalyst for high WGSR activity was 5 wt.% Cu/5 wt.% ZnO/Al₂O₃. The optimum loading amounts of Cu and ZnO in the impregnated catalyst were smaller than those in the coprecipitated catalyst. Its catalytic activity above 200 °C was comparable to that of the conventional coprecipitated Cu/ZnO/Al₂O₃ catalyst. However, the activity of the impregnated Cu/ZnO/Al₂O₃ catalysts was significantly lowered at 150 °C, whereas no deactivation was observed for the coprecipitated catalyst at the same temperature. It was found that deactivation occurred over impregnated catalysts with H₂O and/or O₂ in the reaction gas; it prevented CO adsorption on the surface.     

Solvent free synthesis of chalcone and flavanone over zinc oxide supported metal oxide catalysts

Liquid phase Claisen–Schmidt condensation between 2′-hydroxyacetophenone and benzaldehyde to form 2′-hydroxychalcone, followed by intramolecular cyclisation to form flavanone was carried out over zinc oxide supported metal oxide catalysts under solvent free condition. The reaction was carried out over ZnO supported MgO, BaO, K₂O and Na₂O catalysts with 0.2 g of each catalyst at 140 °C for 3 h. Magnesium oxide impregnated zinc oxide was observed to offer higher conversion of 2′-hydroxyacetophenone than other catalysts. Further MgO impregnated with various other supports such as HZSM-5, Al₂O₃ and SiO₂ were also used for the reaction to assess the suitability of the support. The order of activity of the support is ZnO > SiO₂ > Al₂O₃ > HZSM-5. Various weight percentage of MgO was loaded on ZnO to optimize maximum efficiency of the catalyst system. The impregnation of MgO (wt%) in ZnO was optimized for better conversion of 2′-hydroxyacetophenone. The effect of temperature and catalyst loading was studied for the reaction.     

A new method of low-temperature methanol synthesis on Cu/ZnO/Al2O3 catalysts from CO/CO2/H2

A new synthesis method of low-temperature methanol proceeded on Cu/ZnO/Al₂O₃ catalysts from CO/CO₂/H₂ using 2-butanol as promoters. The Cu/ZnO/Al₂O₃ catalysts were prepared by co-impregnation of r-Al₂O₃ with an aqueous solution of copper nitrate and zinc nitrate. The total carbon turnover frequency (TOF), the yield and selectivity of methanol were the highest by using the Cu/ZnO/Al₂O₃ catalyst with copper loading of 5% and the Zn/Cu molar ratio of 1/1, which precursor were not calcined, and reduced at 493 K. The activity of the catalysts increased due to the presence of the CuO/ZnO phase in the oxidized form of impregnation Cu/ZnO/Al₂O₃ catalysts. The active sites of the Cu/ZnO/Al₂O₃ catalyst for methanol synthesis are not only metallic Cu but also special sites such as the Cu–Zn site, i.e. metallic Cu and the Cu–Zn site work cooperatively to catalyze the methanol synthesis reaction.     

A novel glass fiber catalyst for the catalytic combustion of ethyl acetate

Supported CuO catalysts were prepared by wet impregnation into novel glass fiber corrugated honeycomb supports, and the catalytic combustion of ethyl acetate and the effect of copper loading were examined. Among the catalysts tested, Cu10/Al₂O₃-M showed the highest activity. For the catalyst, 100% conversion of ethyl acetate was achieved at 300 °C, feed concentration of 1802 mg/m³ and the space velocity of 5000 h^− 1. To reveal these phenomena, the supports and catalysts were characterized by SEM, BET, XRD, H₂-TPR and ethyl acetate-TPD. The catalyst activity was strongly related to the amount of highly dispersed CuO species and suitable porosity.     

The development of a fully integrated micro-channel fuel processor using low temperature co-fired ceramic (LTCC)

A fully integrated micro-channel fuel processor system consisting of vaporizer, steam reformer, heat exchanger and preferential CO oxidation (PROX) was developed using low temperature co-fired ceramic (LTCC). To fabricate a compact all-in-one system, each substrate was stacked to build a multilayered type fuel processor. A CuO/ZnO/Al₂O₃ catalyst and Pt-based catalyst prepared by wet impregnation were deposited inside the micro-channel of steam reformer and PROX, respectively. The performance of the fully integrated micro-channel reformer was measured at various conditions such as the ratio of the feed flow rate, the ratio of H₂O/CH₃OH and the operating temperature of the reactor. In parallel with the experiments, 3-D fluid dynamics simulation (Fluent) was conducted to verify the micro-reformer performance. The fully integrated micro-channel reformer has the dimensions of W: 130 mm × D: 50 mm × H: 3 mm. The fuel processor produced the gas composition of 71% H₂ and 25% CO₂, and more than 93% of methanol conversion was achieved at 300 °C and 2 cm³/h of the feed flow rate when CO concentration was maintained below 100 ppm by PROX.     

High performance Cu–ZnO/Pd-β catalysts for syngas to LPG

The catalytic performance of Cu–ZnO/Pd-β catalyst for syngas to LPG (Liquefied Petroleum Gas) has been investigated in this paper. The kind of zeolite, SiO₂/Al₂O₃ ratio in Pd-β, Pd-β particle size, Pd content in Pd-β, and reaction conditions, have been optimized. The results showed that the suitable reaction conditions for syngas to LPG over Cu–ZnO/Pd-β are: 325–350 °C, 2.1–3.6 MPa, 4.5–9 g h/mol gas velocity (W/F), and 37–75 ratio of SiO₂/Al₂O₃. At the optimal conditions, Cu–ZnO/Pd-β could exhibit an excellent catalytic performance for syngas to LPG: 72.2% CO conversion, 45.3% hydrocarbon yield and 78.0% LPG selectivity in hydrocarbons could be achieved.     

Characteristics of integrated micro packed bed reactor-heat exchanger configurations in the direct synthesis of dimethyl ether

The performance of three integrated micro packed bed reactor-heat exchangers (IMPBRHEs) for direct DME synthesis over physical mixtures of CuO–ZnO–Al₂O₃ and γ-Al₂O₃ catalysts was experimentally investigated. Systematic variations in reactor and slit dimensions and configuration were analyzed in terms of thermal behaviour, mass transfer, pressure drop and residence time distribution (RTD). The pressure drop was always small (<0.12 bar) relative to the total pressure (50 bar), and linear dependence with GHSV confirms the predicted laminar flow for Re = 0.1–2. A narrow RTD was estimated by the dispersion analysis. Careful temperature measurements confirmed that the reaction temperature is mainly controlled by the oil heat exchange to give a practically uniform temperature profile for set inlet oil temperatures of 220–320 °C. The micro packed beds were found free of the internal as well as external mass transfer limitations, as showed by no significant change in the CO conversion and DME yield for different catalyst particle sizes, no effect of varying the linear gas velocity, and no effect of manipulating reactant diffusion coefficient. Packed bed microstructured reactors hence provide an isobaric and isothermal environment free from transport limitations for the direct DME synthesis, in the kinetic regime as well as at equilibrium conversion.     

Method of catalyst coating in micro-reactors for methanol steam reforming

Micro-channels of silicon-based micro-reactors were successfully coated with deionized (DI) water-based Cu–ZnO–Al₂O₃ catalyst slurry by a fill-and-dry coating method, applicable to pre-assembled micro-reactors, for steam reforming of methanol. The 10–20 μm thick catalyst layers could be formed on the inner walls of the micro-channels after the micro-channels were fully filled with catalyst slurry, because the catalyst particles in the slurry cohered to the walls of micro-channels by surface tension during drying and calcinations. The adhesion between the catalyst layer and silicon surface was improved by pre-coating the micro-channels with an alumina adhesion layer. The addition of polyvinyl alcohol (PVA) in the alumina sol resulted in better adhesion of the alumina layer at the corners of the channels. The critical minimum thickness of the alumina layer for catalyst coating was 0.15 μm. The highest catalytic activity without loss of intrinsic catalytic activity was obtained using 1:5 (catalyst to solvent) DI water-based catalyst layers coated by fill-and-dry coating. The maximum H₂ production rate was 85 ccm with 1650 ppm of CO measured at 300 °C using a methanol feed rate of 9 ml/h.     

Effect of impregnation sequence on performance of SiO2 supported Cu-Fe catalysts for higher alcohols synthesis from syngas

The effects of different impregnation sequences of copper and iron on the performance of Cu-Fe/SiO₂ catalysts for higher alcohols synthesis from syngas were investigated by N₂ adsorption, XRD, H₂-TPR, CO-IR, XPS, and CO hydrogenation reaction. The results indicate that the catalyst prepared by impregnation of support first with Fe and then with Cu exhibits the highest selectivity (36.1%) and space time yield (153.3 g·kg_cat^− 1·h^− 1) of alcohols. The CO conversion and alcohol selectivity of the catalysts was closely related to the content of surface Cu, and the ratio of surface contents of Cu to Fe, respectively.     

Zirconia: Selective oxidation catalyst for removal of tar and ammonia from biomass gasification gas

Catalysts containing zirconia and alumina were tested for their activity in the selective oxidation of tar and ammonia in biomass gasification gas. Their performance was compared with that of nickel and dolomite catalysts. Synthetic gasification gas with toluene as tar model compound was used as feed. In the presence of oxygen, zirconia and alumina-doped zirconia gave high toluene and ammonia conversions even below 600 °C. They were the most active catalysts for toluene oxidation below 700 °C and for ammonia oxidation below 650 °C. At higher temperatures than these, the impregnated ZrO₂/Al₂O₃ catalysts performed better: oxidation selectivity was improved and toluene and ammonia conversions were higher. The presence of both zirconia and alumina in the catalyst promoted toluene and ammonia conversions at low temperatures: zirconia enhanced the oxidation activity, while alumina improved the oxidation selectivity. The presence of H₂S had little effect on the activity of alumina-doped zirconia.     

Hydrogen production from glycerol steam reforming over molybdena–alumina catalysts

The glycerol steam reforming was investigated on alumina supported molybdena catalysts (with 2, 5 and 12 wt.%) prepared by the sol–gel method and gel combustion. The catalysts were characterized by XRD, BET, UV–VIS, DRIFT, SEM and TEM. The catalytic performances were studied at 400–500 °C, steam to glycerol molar ratio between 9:1 and 20:1 and feed flow rate 0.04–0.08 ml/min. The conversion is directly proportional to molybdena loading, while the hydrogen selectivity has reached greater value on catalyst with 2% MoO₃. The optimum ratio steam to glycerol for reforming is 15:1 and for decomposition in syngas 9:1 and the ratio 20:1 favors water gas shift reaction.     

Characterization and application of a Pt/ZSM-5/SSMF catalyst for hydrocracking of paraffin wax

The microstructured Pt/ZSM-5/SSMF catalysts, for hydrocracking of paraffin wax, have been developed by impregnation method to place Pt onto thin-sheet ZSM-5/SSMF composites obtained by direct growth of ZSM-5 on the sinter-locked stainless steel microfibers (SSMF). The best catalyst is the one with ZSM-5 having a SiO₂/Al₂O₃ weight ratio of 200, delivering ~ 95% conversion with 77.5% selectivity to liquid products or 64.4% selectivity to naphtha at 280 °C. This new approach is capable of increasing the naphtha selectivity with high activity maintenance in comparison with the literature catalysts.     

Direct synthesis of iso-paraffins from syngas with slurry phase reaction

The direct synthesis of gasoline-range iso-paraffins from synthesis gas (CO + H₂, syngas) via modified Fischer–Tropsch (FT) reaction was investigated in the slurry phase reaction system, the contact state of hybrid catalyst components and the composition of hybrid catalyst were optimized in this reaction system. The results show that the FT reaction and the in situ hydroconversion of its products occurred over hybrid catalysts containing Co/SiO₂, very high selectivity of gasoline-range iso-paraffins could be achieved.     

Effect of calcination and reaction conditions on the catalytic performance of Co–Ni/Al2O3 catalyst for CO hydrogenation

The Co–Ni/Al₂O₃ catalysts prepared using impregnation procedure, were used for the Fischer–Tropsch synthesis. The effect of calcination conditions of the catalyst as well as reactor situation was studied. It was found that the catalyst calcined at 550 °C for 6 h in air atmosphere has shown the best catalytic performance for CO hydrogenation. The best operational conditions were obtained as following: T = 350 °C, P = 1 atm and H₂/CO = 2/1.     

Effect of preparation method on catalytic performance,structure and surface reaction rates of MgO supported Fe–Co–Mn catalyst for CO hydrogenation

The MgO supported Fe–Co–Mn catalyst was prepared using different preparation methods including co-precipitation, sol–gel, incipient wetness impregnation and dry impregnation. All of these catalysts were tested for Fischer–Tropsch synthesis under the same operational conditions of T = 300 °C, P = 1 bar, H₂/CO = 2/1 and GHSV = 4500 h^?1. It was found that the co-precipitated catalyst has shown the better catalytic performance for CO hydrogenation. The effect of the preparation method on different surface reaction rates was also investigated and it was found that the preparation methods can influenced the rates of different surface reaction rates. Catalyst characterization was carried out using XRD, SEM, BET, TPR, TGA and DSC.     

Selective gas-phase conversion of maleic anhydride to propionic acid on Pt-based catalysts

Pt-based catalysts, supported on Al₂O₃, SiO₂ and SiO₂–Al₂O₃, were prepared by incipient wetness impregnation and tested in the gas phase hydrogenation of maleic anhydride at atmospheric pressure and 240 °C. In these conditions, the hydrogenolytic activity pattern was: Pt/SiO₂ > Pt/Al₂O₃ > Pt/SiO₂–Al₂O₃, which is just the opposite of the support acidity trend. These metal Pt-based catalysts showed high selectivity to propionic acid, which was always higher than 80%. The selectivity pattern to this product was: Pt/Al₂O₃ > Pt/SiO₂ > Pt/SiO₂–Al₂O₃. Both activity and selectivity patterns may be explained on the basis of metal-support interaction and support acidity.     

Mesoporous CuO/TixZr1 − xO2 catalysts for low-temperature CO oxidation

Mesoporous CuO/Ti_xZr_1 − xO₂ catalysts were prepared by a surfactant-assisted method, and characterized by N₂ adsorption/desorption, TEM, XPS, in-situ FTIR and H₂-TPR. The catalysts exhibited high specific surface area (S_BET = 241 m²/g) and uniform pore size distribution. XPS and in-situ FTIR displayed that Cu⁺ and Cu²⁺ species coexisted in the catalysts. The CuO/Ti_xZr_1 − xO₂ catalysts presented obviously higher activity in CO oxidation reaction than the CuO/TiO₂ and CuO/ZrO₂ catalysts. Effect of molar ratios of Ti to Zr and calcination temperature on catalytic activity was investigated. The CuO/Ti_0.6Zr_0.4O₂ catalyst calcined at 400 °C exhibited excellent activity with 100% CO conversion at 140 °C.     

Preparation of a highly dispersed Ni2P/Al2O3 catalyst using Ni–Al–CO32 − layered double hydroxide as a nickel precursor

We now report a novel method for the synthesis of a Ni₂P/Al₂O₃-LW catalyst using Ni–Al–CO₃^2 − layered double hydroxide (Ni–Al–CO₃^2 −-LDH) as a nickel precursor and ammonium dihydrogen phosphate as a phosphorous precursor under microwave–hydrothermal (MWH) treatment for 20 min at 363 K. The catalysts were characterized by XRD, TPR, BET, CO uptake and XPS. MWH treatment can promote the formation of smaller and highly dispersed Ni₂P particles and a higher surface area of the catalyst. The Ni₂P/Al₂O₃-LW shows hydrodesulfurization activity of 99.3%, which was much higher than that found for the Ni₂P/Al₂O₃ catalyst obtained via an impregnation method.     

Effect of component interaction on the activity of Co/CuZnO for CO hydrogenation

Co/CuZnO is known as a base metal catalyst active for C₂₊ oxygenate synthesis. This study probed the interactions of the different components of Co/CuZnO catalysts on CO hydrogenation using Fischer–Tropsch synthesis (250 °C, H₂/CO = 2) and SSITKA. Only combination of all three metal components produced a catalyst with relatively high C₂₊ oxygenate selectivity, but with much lower activity compared to that for Co/Al₂O₃. In situ reaction characterizations, albeit at somewhat different conditions than alcohol synthesis, helped explain interaction of the components. SSITKA, under methanation conditions, indicated that the most striking feature for the combination of Co with ZnO and/or Cu was a much decreased amount of reaction intermediates. Ethane hydrogenolysis results suggested that the different components for these catalysts were in close contact and few or no large ensembles (n ? 12) of Co atoms existed, confirming that ZnO and/or Cu covered/blocked a substantial number of active sites on Co for CO hydrogenation.     

Preparation of nanostructure CuO/ZnO mixed oxide by sol–gel thermal decomposition of a CuCO3 and ZnCO3: TG,DTG, XRD,FESEM and DRS investigations

Nanostructure CuO/ZnO mixed oxide was systematically prepared via the sol–gel route using zinc and copper carbonates as precursors (molar ratio of 2:1) under thermal decomposition. The zinc and copper carbonates precursors have been synthesized by a simple chemical reaction in high yield and characterized by its melting point, FT-IR and thermal analysis (TG/DTG). The TG/DTG analysis proved that the thermal decomposition of zinc and copper carbonates precursors at 255 °C and 289 °C respectively. Thermo-gravimetric analysis (TG-DTG), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and diffuse reflectance spectroscopy (DRS) studies were undertaken to investigate the thermal properties and electronic structure of the CuO/ZnO mixed oxide catalysts. XRD data of the samples proved the formation of the nano-crystalline CuO/ZnO mixed oxide. Scanning electron microscopy (SEM) showed that the spherical-like particles have a diameter in the range 35–45 nm. Optical spectra of the nanostructure show a band peaked at 1.35 eV which is associated to near band gap transitions of CuO and a band centered at about 3.00 eV related to band gap transitions of ZnO nanostructures.