Effect of combining metallic and acid functions in CZA/HZSM-5 desilicated zeolite catalysts on the DME steam reforming in a fluidized bed

A study has been carried out on the effect of combining the metallic (CuO–ZnO–Al₂O₃) and acid (HZSM-5 zeolite treated with NaOH) functions, and of their mass ratio, on the kinetic performance in the steam reforming of dimethyl ether (SRD). The runs have been conducted in a fluidized bed reactor in the 225–325 °C range, and the reaction indices (dimethyl ether and methanol conversions, and H₂ and CO yields) have been explained based on the physico-chemical properties of the catalyst.     

Dimethyl ether (DME) synthesis from CO2 and H2 through ethanol-assisted methanol synthesis and methanol dehydration

Two steps of dimethyl ether (DME) synthesis from CO₂ and H₂ in a batch reactor were studied, including CO₂ hydrogenation to methanol through ethanol-assisted method and methanol dehydration to DME. Additions of 10 wt% ZrO₂, Al₂O₃ and ZrO₂–Al₂O₃ into Cu/ZnO were investigated in low-temperature methanol synthesis using ethanol as catalytic solvent. Suitable zeolite (ZSM-5 and ferrierite) for methanol dehydration was also determined. Ethanol-assisted method offered high methanol yield and Cu/ZnO/ZrO₂ catalyst provided the highest CO₂ conversion (82.1%) and methanol yield (60.8%) at 150 °C and 50 bar since ZrO₂ decreased CuO crystallite sizes and increased surface areas of the catalyst. For methanol dehydration to DME, zeolite's strong acidity related to DME formation. The Cu/ZnO/ZrO₂ - Ferrierite provided the highest DME productivity at 0.44 mmol_DME/g_cat. In addition, DME synthesis from CO₂ and H₂ through ethanol-assisted methanol synthesis and methanol dehydration can be a potential method to simultaneously produce DME and ethylene. Under the operating conditions, ethylene was produced as a valued by-product of 5.65 mmol_Ethylene/g_cat from dehydration of ethanol. In this study, rather high methanol yield was obtained from ethanol-assisted method. However, DME yield can be further improved by increasing synthesis temperature.     

Effect of metal additives on the catalytic performance of Ni/Al2O3 catalyst in thermocatalytic decomposition of methane

Thermocatalytic decomposition of methane is proposed to be an economical and green method to produce CO_x-free hydrogen and carbon nanomaterial. In present work, 60 wt% Ni/Al₂O₃ catalysts with different additives (Cu, Mn, Pd, Co, Zn, Fe, Mg) were prepared by co-impregnation method to investigate promotional effects of these metal additives on the activity and stability of 60 wt% Ni/Al₂O₃ and find out a really effective promoter for decomposition of methane. The catalyst was characterized by N₂ adsorption/desorption, X-ray diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometer and hydrogen temperature programmed reduction. While metal additives (5 wt%) were added into 60 wt% Ni/Al₂O₃, the activity stability of 60 wt% Ni/Al₂O₃ was improved and the CH₄ conversion of 60 wt% Ni/Al₂O₃ was also improved except Zn addition. Mn addition was found to improve the catalytic activity of 60 wt% Ni/Al₂O₃ significantly and the CH₄ conversion of 5 wt% Mn-60 wt% Ni/Al₂O₃ was ∼80%. Cu addition was found to remarkably improve the catalytic stability of 60 wt% Ni/Al₂O₃ and the CH₄ conversion of 5 wt% Cu-60 wt% Ni/Al₂O₃ decreased from 61% to 45% after 250 min of reaction time. Carbon nanomaterials formed in the thermocatalytic decomposition process were characterized by X-ray diffraction, scanning electron microscopy, thermal gravimetric analyzer and Raman spectroscopy. Carbon deposits consist of amorphous carbon and carbon nanofibers.     

Characterization and activity test of commercial Ni/Al2O3, Cu/ZnO/Al2O3 and prepared Ni–Cu/Al2O3 catalysts for hydrogen production from methane and methanol fuels

In this study, methane and methanol steam reforming reactions over commercial Ni/Al₂O₃, commercial Cu/ZnO/Al₂O₃ and prepared Ni–Cu/Al₂O₃ catalysts were investigated. Methane and methanol steam reforming reactions catalysts were characterized using various techniques. The results of characterization showed that Cu particles increase the active particle size of Ni (19.3 nm) in Ni–Cu/Al₂O₃ catalyst with respect to the commercial Ni/Al₂O₃ (17.9). On the other hand, Ni improves Cu dispersion in the same catalyst (1.74%) in comparison with commercial Cu/ZnO/Al₂O₃ (0.21%). A comprehensive comparison between these two fuels is established in terms of reaction conditions, fuel conversion, H₂ selectivity, CO₂ and CO selectivity. The prepared catalyst showed low selectivity for CO in both fuels and it was more selective to H₂, with H₂ selectivities of 99% in methane and 89% in methanol reforming reactions. A significant objective is to develop catalysts which can operate at lower temperatures and resist deactivation. Methanol steam reforming is carried out at a much lower temperature than methane steam reforming in prepared and commercial catalyst (275–325 °C). However, methane steam reforming can be carried out at a relatively low temperature on Ni–Cu catalyst (600–650 °C) and at higher temperature in commercial methane reforming catalyst (700–800 °C). Commercial Ni/Al₂O₃ catalyst resulted in high coke formation (28.3% loss in mass) compared to prepared Ni–Cu/Al₂O₃ (8.9%) and commercial Cu/ZnO/Al₂O₃ catalysts (3.5%).     

Hydrogen production by steam reforming of dimethyl ether and CO-PrOx in a metal foam micro-reactor

A bi-function catalyst containing CuZnAlCr and HZSM-5 was used to generate hydrogen by stream reforming of dimethyl ether (SRD) in a metal foam micro-reactor and a fix-bed reactor. Dimethyl ether conversion of 99% and hydrogen yield of >95% was reached with HZSM-5/CuZnAlCr (mass ratio of 1:1) in the micro-reactor. A suitable balance between the dimethyl ether hydrolysis and methanol reforming steps requires the proper acidity and the metal sites. The CuZnAlCr/HZSM-5 properties, effect of CuZnAlCr to HZSM-5 mass ratio were investigated in the metal foam micro-reactor. Moreover, CO was removed from hydrogen-rich gas by preferential oxidation reaction (CO-PrOx) with PtFe/γ-Al₂O₃ catalyst in a similar metal foam micro-reactor follows the SRD stage. With the optimized O₂/CO ratio and reaction temperature, the CO concentration dropped to <10 ppm and hydrogen yield of ∼90% were achieved in the new-type SRD-COPrOx system. The SRD-COPrOx system provide a constant hydrogen production with CO concentration lower than 10 ppm during 20 h. The results indicate that metal foam micro-reactor has the great potential in the DME steam reforming to supply hydrogen for low-temperature fuel cells.     

Improving the hydrothermal stability and hydrogen selectivity of Ni-Cu based catalysts for the aqueous-phase reforming of methanol

Non-precious metal catalysts suitable for hydrogen production via aqueous phase reforming (APR) of methanol show important technical and commercial value in the development of distributed, small/micro-scale on-site hydrogen production systems. They still face the challenges of reduced activity and stability due to sintering and oxidation of active metal nanoparticles, change of the surface state and collapse of the pore structure of used supports under hydrothermal conditions. To solve these problems, a series of ZnO/Ni-xCu/Al₂O₃ (x = 0, 2, 4, 6, 8, 10) catalysts were prepared by a simple impregnation method in this work. The addition of Cu improved the reducibility of NiO, and promoted the formation of smaller and more dispersed metal particles on the surface of Al₂O₃, facilitating hydrogen production and hindering methane formation. Among them, the highest average hydrogen production rate (362.1 μmol‧min⁻¹‧gcat⁻¹) and the highest hydrogen selectivity (99%) were reached using ZnO/Ni-8Cu/Al₂O₃ catalyst, which were 1.6 times and 20.7% higher than those obtained on the mono-metallic ZnO/Ni/Al₂O₃ catalyst, respectively. On the other hand, the modification of Ni-8Cu/Al₂O₃ with ZnO prevented effectively the reaction of surface water with Al₂O₃ and inhibited the formation of boehmite phase, leading to dramatical improvement of its stability during APR of methanol with a prolonged lifetime (72 h) by 6 times. This new developed ZnO/Ni-xCu/Al₂O₃ catalysts offer great potential for the development of commercial catalysts to produce hydrogen from APR of methanol.     

Hydrogen production by steam reforming of dimethyl ether over ZnO–Al2O3 bi-functional catalyst

A series of ZnO–Al₂O₃ catalysts with various ZnO/(ZnO + Al₂O₃) molar ratios have been developed for hydrogen production by dimethyl ether (DME) steam reforming within microchannel reactor. The catalysts were characterized by N₂ adsorption-desorption, X-ray diffraction and temperature programmed desorption of NH₃. It was found that the catalytic activity was strongly dependent on the catalyst composition. The overall DME reforming rate was maximized over the catalyst with ZnO/(ZnO + Al₂O₃) molar ratio of 0.4, and the highest H₂ space time yield was 315 mol h⁻¹·kg_cat⁻¹ at 460 °C. A bi-functional mechanism involving catalytic active site coupling has been proposed to account for the phenomena observed. An optimized bi-functional DME reforming catalyst should accommodate the acid sites and methanol steam reforming sites with a proper balance to promote DME steam reforming, whereas all undesired reactions should be impeded without sacrificing activity. This work suggests that an appropriate catalyst composition is mandatory for preparing good-performance and inexpensive ZnO–Al₂O₃ catalysts for the sustainable conversion of DME into H₂-rich reformate.     

Hydrogen generation characteristics of reduced DME steam reforming catalysts according to heating methods

The purpose of this study is to investigate the hydrogen generation characteristics of H₂-reduced dimethyl ether (DME) steam reforming (SR) catalysts using different heating processes. The effects of the H₂ reduction temperature and space velocity were investigated to identify an optimal reaction environment. Both the resistive and induction heating methods were used. The catalysts were prepared by impregnating copper over a γ-Al₂O₃ support. The Cu/Al₂O₃ catalysts with different loading amounts of 5–15 wt% Cu exhibited different characteristics when subjected to hydrogen reduction. The variation in acidity had a dominant effect on the DME-SR activity, and 15Cu/Al₂O₃ that underwent hydrogen reduction treatment at 500 °C attained improved performance at low temperatures and low formation of by-products, allowing for the achievement of its highest H₂ concentration of 74.08% at 375 °C. The induction heating reactor had an energy consumption that was about 25% lower than that of the resistive heating reactor.     

Synthesis and regeneration of mesoporous Ni–Cu/Al2O4 catalyst in sub-kilogram-scale for methanol steam reforming reaction

A green template-free method is proposed for the synthesis of mesoporous Ni–Cu/Al₂O₄ catalyst in sub-kilogram scale. In the convenient synthetic method, an intermediate is formed via electrostatic forces and hydrogen bonding interactions between the aluminate ions and the metal ions and/or metal hydroxides under suitable pH conditions. The desired Ni–Cu/Al₂O₄ composites, with Ni/Cu molar ratios of 10%, 20% and 30% of Cu at Cu/Al molar ratio of 10.0%, respectively, are then obtained from calcination. The nitrogen adsorption-desorption isotherms show that the Ni–Cu/Al₂O₄ composites have specific surface areas of 136–170 m²g^-1. The Ni–Cu/Al₂O₄ products are used as catalyst materials in the methanol steam reforming (MSR) of hydrogen and are shown to have a high conversion efficiency (>99%), a low methane concentration, good stability, and a high hydrogen yield (H₂/methanol molar ratio ≈ 3.0) at low reaction temperatures in the range of 200–300 °C. In addition, the coke formation on the catalyst surface is less than 1.0 wt% even after a reaction time of 30 h. Notably, the Ni–Cu/Al₂O₄ catalyst can be regenerated by calcination at 800 °C and retains a high methanol conversion efficiency of close to >99% when reused in MSR.     

Copper promoted Co/MgO: A stable and efficient catalyst for glycerol steam reforming

Different types of cobalt-based mixed oxide catalysts (20 wt%Co/MgO, 5 wt%Cu-20 wt% Co/MgO, 20 wt%Co/50%MgO–50%Al₂O₃) were synthesized by the co-precipitation method and applied for hydrogen production from glycerol steam reforming. The catalysts were characterized using X-ray diffraction (XRD), H₂-Temperature-programmed reduction (H₂-TPR), CO₂-Temperature Programmed desorption, CO-Chemisorption, and CHN techniques. The H₂-TPR analysis showed the reducibility of cobalt-oxide (5Cu20CM; 5 wt%Cu-20 wt% Co/MgO) was enhanced by the copper, and reduction profiles of cobalt oxide shifted to a lower temperature (<450 °C). Among the catalysts, 5Cu20CM showed a maximum yield of hydrogen (74.6%) with 100% conversion of glycerol to the gaseous phase. The superior catalytic performance of 5Cu20CM for glycerol conversion was attributed to the smaller particle size (7 nm), higher dispersion of cobalt (35.0%), and the higher surface area (56 m²/g) of cobalt metal. Furthermore, Raman spectroscopy of the spent catalysts confirmed that the copper promoted cobalt-magnesium catalyst suppressed the carbon formation, consequently, 5Cu20CM catalyst showed a stable performance up to 30 h.     

Direct conversion of syngas to DME over CuO–ZnO–Al2O3/HZSM‐5 nanocatalyst synthesized via ultrasound‐assisted co‐precipitation method: New insights into the role of gas injection

In this study, direct synthesis of dimethyl ether (DME) is conducted over a bifunctional CuO–ZnO–Al₂O₃/H Zeolite Socony Mobil‐5 (HZSM‐5) nanocatalyst. A hybrid method of ultrasound‐assisted co‐precipitation is used for the synthesis of catalysts, and the effect of gas injection during sonication is investigated. The physicochemical characteristics of the catalysts are analysed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), particle size distribution (PSD), energy dispersive X‐ray (EDX), Brunauer–Emmett–Teller (BET) and Fourier‐transformed infrared (FTIR) methods. In the absence of gas injection, the acetate‐based catalysts have a better morphology and higher surface area than the nitrate‐based catalyst. Gas injection significantly changes the morphology and structural properties of the acetate‐based catalyst. High surface area, narrow PSD and better dispersion of small CuO crystals are obtained in a gas‐injected synthesized sample. DME synthesis experiments showed that the CO conversion and DME selectivity are correlated with surface area, nanocatalyst particle size and its dispersion. The gas‐injected CuO–ZnO–Al₂O₃/HZSM‐5 nanocatalyst that has the highest surface area and the smallest dispersed particles showed more than 70% DME selectivity. The gas‐injected CuO–ZnO–Al₂O₃/HZSM‐5 nanocatalyst exhibited high stability in terms of CO conversion and DME yield over 1440‐min time on a stream test at 275°C, 40 bar and 18 000 cm³ g.h^?1. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrogen production by steam reforming of methanol in a micro-channel reactor coated with Cu/ZnO/ZrO2/Al2O3 catalyst

Hydrogen production by steam reforming of methanol is studied over Cu/Zn-based catalysts (Cu/ZnO, Cu/ZnO/Al₂O₃, Cu/ZnO/ZrO₂/Al₂O₃). Cu/Zn-based catalysts are derived from hydrotalcite-like precursors prepared by a co-precipitation method. The catalysts are characterized by N₂O chemisorption, XRD, and BET surface area measurements. ZrO₂ added to the Cu/Zn-based catalyst enhances copper dispersion on the catalyst surface. Among the catalysts tested, Cu/ZnO/ZrO₂/Al₂O₃ exhibits the highest methanol conversion and the lowest CO concentration in the outlet gas. A micro-channel reactor coated with a Cu/ZnO/ZrO₂/Al₂O₃ catalyst in the presence of an undercoated Al₂O₃ buffer layer exhibits higher methanol conversion and lower CO concentration in the outlet gas than in the absence of an undercoated Al₂O₃ buffer layer. The micro-channel reactor with a undercoated Al₂O₃ buffer layer produces large amounts of hydrogen compared with one without a buffer layer. The undercoated Al₂O₃ buffer layer enhances the adhesion between catalysts and micro-channel walls, which leads to improvement in reactor performance.     

Oxidative steam reforming of methanol over CuO/ZnO/CeO2/ZrO2/Al2O3 catalysts

The composition (CuO/ZnO/Al₂O₃ = 30/60/10) of a commercial catalyst G66B was used as a reference for designing CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts for the oxidative (or combined) steam reforming of methanol (OSRM). The effects of Al₂O₃, CeO₂ and ZrO₂ on the OSRM reaction were clearly identified. CeO₂, ZrO₂ and Al₂O₃ all promoted the dispersions of CuO and ZnO in CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts. Aluminum oxide lowered the reducibility of the catalyst, and weakened the OSRM reaction. Cerium oxide increased the reducibility of the catalyst, but weakened the reaction. Zirconium oxide improved the reducibility of the catalyst, and promoted the reaction. A lower CuO/ZnO ratio of the catalyst was associated with greater promotion of ZrO₂. The critical CuO/ZnO ratio for the promotion of ZrO₂ was approximately 0.75–0.8. Introducing of ZrO₂ into CuO/ZnO/Al₂O₃ also improved the stability of the catalyst. Although Al₂O₃ inhibited the OSRM reaction, a certain amount of it was required to ensure the stability and the mechanical strength of the catalysts.     

Hydrogen production from carbon dioxide reforming of methane over highly active and stable MgO promoted Co–Ni/γ-Al2O3 catalyst

CoNi/Al₂O₃ and MgCoNi/Al₂O₃ catalysts are investigated for hydrogen production from CO₂ reforming of CH₄ reaction at the gas hourly space velocity of 40,000 mL g⁻¹ h⁻¹. The MgO promoted CoNi/Al₂O₃ catalyst shows much higher conversions (97% for CO₂ and 95% for CH₄ at 850 °C) than the CoNi/Al₂O₃ catalyst. In addition, the stability is maintained for 200 h in CO₂ reforming of CH₄. The outstanding catalytic activity and stability of the MgO promoted CoNi/Al₂O₃ catalyst is mainly due to the basic nature of MgO, an intimate interaction between Ni and the support, and rapid decomposition/dissociation of CH₄ and CO₂, resulting in preventing coke formation in CO₂ reforming of CH₄.     

Cu/ZnO/Al2O3 water–gas shift catalysts for practical fuel cell applications: the performance in shut-down/start-up operation

The Cu/ZnO/Al₂O₃ catalysts were prepared by the coprecipitation method, and were evaluated in the water–gas shift (WGS) reaction. The effects of the calcination temperature on the BET surface area and crystallite size were characterized. In WGS reaction, the Cu/ZnO/Al₂O₃ catalysts suffered from continuous deactivation in shut-down/start-up operation – the daily requirement for mobile and residential fuel cell systems. Among them, the Cu/ZnO/Al₂O₃ catalyst prepared at the calcination temperature of 450 °C showed the best activity and stability, with the decrement of the CO conversion of only 12.8% after three shut-down/start-up cycles. Deactivation of the Cu/ZnO/Al₂O₃ catalysts is attributed to the blocking or deterioration of the active sites by Zn₆Al₂(OH)₁₆CO₃·4H₂O resulting from the degeneration of the oxides under cyclic operations. Removal of the hydroxycarbonate species by calcination in air followed by re-reduction could restore the steady-state WGS activity; however, the regenerated catalyst underwent much severe deactivation in subsequent shut-down/start-up operation.     

Plasma-assisted CO2 reforming of methane over Ni-based catalysts: Promoting role of Ag and Sn secondary metals

Carbon dioxide (CO₂) and methane (CH₄) are the primary greenhouse gases (GHGs) that drive global climate change. CO₂ reforming of CH₄ or dry reforming of CH₄ (DRM) is used for the simultaneous conversion of CO₂ and CH₄ into syngas and higher hydrocarbons. In this study, DRM was investigated using Ag–Ni/Al₂O₃ packing and Sn–Ni/Al₂O₃ packing in a parallel plate dielectric barrier discharge (DBD) reactor. The performance of the DBD reactor was significantly enhanced when applying Ag–Ni/Al₂O₃ and Sn–Ni/Al₂O₃ due to the relatively high electrical conductivity of Ag and Sn as well as their anti-coke performances. Using Ag–Ni/Al₂O₃ consisting of 1.5 wt% Ag and 5 wt% Ni/Al₂O₃ as the catalyst in the DBD reactor, 19% CH₄ conversion, 21% CO₂ conversion, 60% H₂ selectivity, 81% CO selectivity, energy efficiency of 7.9% and 0.74% (by mole) coke formation were achieved. In addition, using Sn–Ni/Al₂O₃, consisting of 0.5 wt% Sn and 5 wt% Ni/Al₂O₃, 15% CH₄ conversion, 19% CO₂ conversion, 64% H₂ selectivity, 70% CO selectivity, energy efficiency of 6.0%, and 2.1% (by mole) coke formation were achieved. Sn enhanced the reactant conversions and energy efficiency, and resulted in a reduction in coke formation; these results are comparable to that achieved when using the noble metal Ag. The decrease in the formation of coke could be correlated to the increase in the CO selectivity of the catalyst. Good dispersion of the secondary metals on Ni was found to be an important factor for the observed increases in the catalyst surface area and catalytic activities. Furthermore, the stability of the catalytic reactions was investigated for 1800 min over the 0.5 wt% Ag-5 wt% Ni/Al₂O₃ and 0.5 wt% Sn-5 wt% Ni/Al₂O₃ catalysts. The results showed an increase in the reactant conversions with an increase in the reaction time.     

Simultaneous dehydrogenation of 1,4- butanediol to γ-butyrolactone and hydrogenation of benzaldehyde to benzyl alcohol mediated over competent CeO2–Al2O3 supported Cu as catalyst

Hydrogen being a dynamically impending energy transporter is widely used in hydrogenation reactions for the synthesis of various value added chemicals. It can be obtained from dehydrogenation reactions and the acquired hydrogen molecule can directly be utilized in hydrogenation reactions. This correspondingly avoids external pumping of hydrogen making it an economical process. We have for the first time tried to carryout 1,4-butanediol dehydrogenation and benzaldehyde hydrogenation simultaneously over ceria-alumina supported copper (Cu/CeO₂–Al₂O₃) catalyst. In this concern, 10 wt% of Cu supported on CeO₂–Al₂O₃ (3:1 ratio) was synthesized using wet impregnation method. The synthesized catalyst was then characterized by various analytical methods such as BET, powder XRD, FE-SEM, H₂-TPR, NH₃ and CO₂-TPD, FT-IR and TGA. The catalytic activity towards simultaneous 1,4-butanediol dehydrogenation and benzaldehyde hydrogenation along with their individual reactions was tested for temperature range of 240 °C–300 °C. The physicochemical properties enhanced the catalytic activity as clearly interpreted from the results obtained from the respective characterization data. The best results were obtained with 10 wt% of Cu supported on CeO₂–Al₂O₃ (3:1 ratio) catalyst with benzaldehyde conversion of 34% and 84% selectivity of benzyl alcohol. The conversion of 1,4-butanediol was seen to be 90% with around 95% selectivity of γ-butyrolactone. The catalyst also featured physicochemical properties namely increased surface area, higher dispersion and its highly basic nature, for the simultaneous reaction towards a positive direction. In terms of permanence, the Cu/CeO₂–Al₂O₃ (10CCA) catalyst was quite steady and showed stable activity up to 24 h in time on stream profile.     

A highly active and stable Pt modified molybdenum carbide catalyst for steam reforming of dimethyl ether and the reaction pathway

To improve the stability of molybdenum carbide catalysts in dimethyl ether steam reforming (DSR), the inactivation mechanism and the performance of Pt modified catalyst has been investigated. The Mo₂C oxidation induced by H₂O is verified to be the main reason of catalytic deactivation. After modified with Pt, the H₂ production rate and selectivity are greatly enhanced, reaches 1605 μmol min⁻¹·g_cat⁻¹ at 350 °C, in comparison to that of the Mo₂C/Al₂O₃ catalyst. Moreover, the 2%Pt–Mo₂C/Al₂O₃ catalyst is more stable with only 20% activity loss after 50 h on stream compares to the 73% activity loss in 12 h with Mo₂C/Al₂O₃ catalyst. By means of in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the enhancement brought by Pt is ascribed to the consumption acceleration of intermediate oxygen species on catalyst surface and the decline of onset temperature of DSR reaction. It is expected that these findings can lead us to more practical molybdenum carbide catalysts in DSR.     

Comparison of hydrogen consumption behavior of chromium and manganese promoted copper-based catalysts

CuO/ZnO/Al₂O₃/MgO–Cr and -Mn catalysts are synthesized using nitrate route via co-precipitation method. The precursors are characterized by XRD. The decomposition behavior of the precursors is analyzed by Air-TGA. The catalysts calcined at 250, 300, 350 and 450 °C are characterized by XRD and BET. CuO particle size reduction and surface area of the catalysts are investigated. Increasing the calcination temperature from 350 °C to 450 °C crystallite size increases about 3 nm, and BET surface area decreases about 30 m²/g. The reduction characteristics of the catalysts are analyzed via TPR and H₂-TGA, and H₂ consumption values of Cr and Mn containing catalysts is found as 40% and 60%, respectively. Peak temperatures of Mn containing catalysts (290–325 °C) are lower than peak temperatures of Cr containing catalysts (300–360 °C) as confirmed by H₂-TGA and H₂-DTG. The optimum H₂ consumption value of 52% is obtained with CuO/ZnO/Al₂O₃/MgO–Mn catalyst calcined at 350 °C.     

Preparation and characterization of Ni based catalysts for the catalytic partial oxidation of methane: Effect of support basicity on H2/CO ratio and carbon deposition

The catalytic partial oxidation of methane (CPOM) was studied on Ni based catalysts. Catalysts were prepared by wet impregnation method and characterized by using AAS, BET, XRD, HRTEM, TPR, TPO, Raman Spectroscopy and TPSR techniques. The prepared catalysts showed nearly 95% CH₄ conversion and nearly 96% H₂ selectivity under the flow of 157,500 (L kg⁻¹ h⁻¹) with the ratio of CH₄/O₂ = 2 by using air as an oxidant at 1 atm and 800 °C. Support basicity greatly influenced the H₂/CO ratio and carbon deposition. It was found that the lowest carbon deposition occurred on Ni impregnated MgO catalyst. Considering the results, it was found that Ni/MgO catalyst with 10% Ni content would be the best catalyst amongst Ni/Al₂O₃, Ni/MgO/Al₂O₃, Ni/MgAl₂O₄ and Ni/Sorbacid for the CPOM only under more reductive conditions. Under optimum conditions, Ni/MgO showed poor performance and therefore Ni/Sorbacid would be the ideal catalyst because of its greater carbon resistance than the other catalysts.