Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> xerogel support on hydrogen production by steam reforming of LNG over Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> catalyst

An Al₂O₃-ZrO₂ xerogel (AZ-SG) was prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/AZ-SG catalyst was then prepared by an impregnation method, and was applied to hydrogen production by steam reforming of LNG. A nickel catalyst supported on commercial alumina (A-C) was also prepared (Ni/A-C) for comparison. The hydroxyl-rich surface of the AZ-SG support increased the dispersion of nickel species on the support during the calcination step. The formation of a surface nickel aluminate-like phase in the Ni/AZ-SG catalyst greatly enhanced the reducibility of the Ni/AZ-SG catalyst. The ZrO₂ in the AZ-SG support increased the adsorption of steam onto the support and the subsequent spillover of steam from the support to the active nickel sites in the Ni/AZ-SG catalyst. Both the high surface area and the well-developed mesoporosity of the Ni/AZ-SG catalyst improved the gasification of adsorbed surface hydrocarbons in the reaction. In the steam reforming of LNG, the Ni/AZ-SG catalyst showed a better catalytic performance than the Ni/A-C catalyst. Moreover, the Ni/AZ-SG catalyst showed strong resistance toward catalyst deactivation.     

Doped Ni Catalysts for Methane Reforming with CO<Subscript>2</Subscript>

Pb, Sb, Bi and Te doped Ni catalysts were prepared and used for methane reforming with CO₂ in order to diminish coke deposition. It was found that small amounts of Pb doped Ni catalysts exhibited excellent coke resistance ability with minor loss of the reforming activity. As the added amount of Pb increased from 0 to 0.015 (mole ratio between Pb/Ni), coke formation rate decreased from 166.7 mg-coke/g-cat h (on Ni/SiO₂) to 0, while the reforming activity decreased slightly from 73.2% to 63.3% (conversion of CO₂) at 800 °C, 60,000 ml(STP)/g-cat·h (CH₄ CO₂=1:1, no dilution gas in feed). Higher amounts of Pb and Sb, Bi, Te made Ni catalyst deactivated for methane reforming with CO₂.     

Oxidative reforming of methane on structured Ni-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/cordierite catalysts

The catalytic properties of Ni/Al₂O₃ composites supported on ceramic cordierite honeycomb monoliths in oxidative methane reforming are reported. The prereduced catalyst has been tested in a flow reactor using reaction mixtures of the following compositions: in methane oxidation, 2–6% CH₄, 2–9% O₂, Ar; in carbon dioxide and oxidative carbon dioxide reforming of methane, 2–6% CH₄, 6–12% CO₂, and 0–4% O₂, and Ar. Physicochemical studies include the monitoring of the formation and oxidation of carbon, the strength of the Ni-O bond, and the phase composition of the catalyst. The structured Ni-Al₂O₃ catalysts are much more productive in the carbon dioxide reforming of methane than conventional granular catalysts. The catalysts performance is made more stable by regulating the acid-base properties of their surface via the introduction of alkali metal (Na, K) oxides to retard the coking of the surface. Rare-earth metal oxides with a low redox potential (La₂O₃, CeO₂) enhance the activity and stability of Ni-Al₂O₃/cordierite catalysts in the deep and partial oxidation and carbon dioxide reforming of methane. The carbon dioxide reforming of methane on the (NiO + La₂O₃ + Al₂O₃)/cordierite catalyst can be intensified by adding oxygen to the gas feed. This reduces the temperature necessary to reach a high methane conversion and does not exert any significant effect on the selectivity with respect to H₂.     

Catalytic cracking of isobutane over HZSM-5, FeHZSM-5 and CrHZSM-5 catalysts with different SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratios

Several systems of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts with different ratios of SiO₂/Al₂O₃ (25,38,50,80, and 150) were prepared and they were characterized by means of X-ray diffraction (XRD), UV–Vis, NH₃-TPD and BET techniques. The results indicated that, compared with uncalcined HZSM-5 zeolites, the total acid amounts, acidic site density and acidic strength of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts obviously decreased, while those of weak acid amounts obviously enhanced with the decrease of SiO₂/Al₂O₃ molar ratio. When the ratio of SiO₂/Al₂O₃ is less than 50, the three systems of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolite catalysts with same ratio of SiO₂/Al₂O₃ gave similar and high isobutane conversions. However, when the ratio of SiO₂/Al₂O₃ was equal to or greater than 80, these three systems of catalysts possessed different altering tendencies of isobutane conversions, thus their isobutene conversions were different. High yields of light olefins were obtained over the FeHZSM-5 and CrHZSM-5 zeolite catalysts with high ratio of SiO₂/Al₂O₃ (≥80). The ratio of SiO₂/Al₂O₃ has large effects on the surface area, and acidic characteristics of HZSM-5, FeHZSM-5 and CrHZSM-5 zeolites catalysts, and thus further affect their catalytic performances for isobutane cracking. That is the nature of SiO₂/Al₂O₃ ratio effect on the catalytic performances.     

Synthesis of nickel catalysts supported on Zr-doped ordered mesoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and their catalytic performance for low-temperature CO<Subscript>2</Subscript> reforming of CH<Subscript>4</Subscript>

A series of Zr-doped ordered mesoporous Al₂O₃ with various Zr contents were synthesized by evaporation-induced self-assembly strategy and the Ni-based catalysts supported on these Al₂O₃ materials were prepared by impregnation method. These catalysts with large specific surface area, big pore volume, uniform pore size possess excellent catalytic performance for the low-temperature carbon dioxide reforming of methane. The activities of these catalysts were tested in carbon dioxide reforming of methane reaction with temperature increasing from 500 to 650?°C and the stabilities of these catalysts were evaluated for long time reaction at 650?°C. It was found that when Zr/(Zr?+?Al) molar ratio?=?0.5%, the Ni/0.5ZrO₂–Al₂O₃ catalyst showed the highest activity, and exhibited superior stabilization compared to the Ni-based catalyst supported on traditional ordered mesoporous Al₂O₃. The “confinement effect” from mesoporous channels of alumina matrix is helpful to stabilize the Ni nanoparticles. As a promoter, Zr could stabilize the ordered mesoporous framework by reacting with Al₂O₃ to form ZrO₂–Al₂O₃ solid solution. Since ZrO₂ enhances the dissociation of carbon dioxide, more oxygen intermediates are given to remove the carbon formed during the reaction.     

Combined Steam and Carbon Dioxide Reforming of Methane on Ni/MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: Effect of CeO<Subscript>2</Subscript> Promoter to Catalytic Performance

Abstract  

The catalytic performance during combined steam and carbon dioxide reforming of methane (SCR) was investigated on Ni/MgAl₂O₄ catalyst promoted with CeO₂. The SCR catalyst was prepared by co-impregnation method using nickel and cerium metal precursors on hydrotalcite-like MgAl₂O₄ support. In terms of catalytic activity and stability, CeO₂-promoted Ni/MgAl₂O₄ catalyst is superior to Ni–CeO₂/Al₂O₃ or Ni/MgAl₂O₄ catalysts because of high resistance to coke formation and suppressed aggregation of nickel particles. The role of CeO₂ on Ni/MgAl₂O₄ catalyst was elucidated by carrying out the various characterization methods in the viewpoint of the aggregation of nickel particles and metal-support interactions. The observed superior catalytic performance on CeO₂-promoted Ni/MgAl₂O₄ catalyst at the weight ratio of MgO/Al₂O₃ of 3/7 seems to be closely related to high dispersion and low aggregation of active metals due to their strong interaction with the MgAl₂O₄ support and the adjacent contact of Ni and CeO₂ species. The CeO₂ promoter also plays an important role to suppress particle aggregation by forming an appropriate interaction of NiO–CeO₂ as well as Ni–MgAl₂O₄ with the concomitant enhancement of mobile oxygen content.     

Effects of preparation methods for V<Subscript>2</Subscript>O<Subscript>5</Subscript>-TiO<Subscript>2</Subscript> aerogel catalysts on the selective catalytic reduction of NO with NH<Subscript>3</Subscript>

A series of V₂O₅-TiO₂ aerogel catalysts were prepared by the sol-gel method with subsequent supercritical drying with CO₂. The main variables in the sol-gel method were the amounts of V₂O₅ and when the vanadium precursor was introduced. V₂O₅-TiO₂ xerogel and V₂O₅/TiO₂ (P-25) were also prepared for comparison. The V₂O₅-TiO₂ aerogel catalysts showed much higher surface areas and total pore volumes than V₂O₅-TiO₂ xerogel and impregnated V₂O₅/TiO₂ (P-25) catalysts. The catalysts were characterized by N₂ physisorption, X-ray diffraction (XRD), FT-Raman spectroscopy, temperature-programmed reduction with H₂ (H₂-TPR), and temperature-programmed desorption of ammonia (NH₃-TPD). The selective catalytic reduction of NOx with ammonia in the presence of excess O₂ was studied over these catalysts. Among various V₂O₅-TiO₂ catalysts, V₂O₅ supported on aerogel TiO₂ showed a wide temperature window exhibiting high NOx conversions. This superior catalytic activity is closely related to the large amounts of strong acidic sites as well as the surface vanadium species with characteristics such as easy reducibility and monomeric and polymeric vanadia surface species. This work was presented at the 7 ^th Korea-China Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Stable carbon dioxide reforming of methane over modified Ni/Al2O3 catalysts

CO₂ reforming of methane was studied over modified Ni/Al₂O₃ catalysts. The metal modifiers were Co, Cu, Zr, Mn, Mo, Ti, Ag and Sn. Relative to unmodified Ni/Al₂O₃, catalysts modified with Co, Cu and Zr showed slightly improved activity, while other promoters reduced the activity of CO₂ reforming. Mn-promoted catalyst showed a remarkable reduction in coke deposition, while entailing only a small reduction in catalytic activity compared to unmodified catalyst. The catalysts prepared at high calcination temperatures showed higher activity than those prepared at low calcination temperature. The Mn-promoted catalyst showed very low coke deposition even in the absence of diluent gas and the activity changed only slightly during 100 h operation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Reductive amination of ethanol to ethylamines over Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

Ni(x)/Al₂O₃ (x=wt%) catalysts with Ni loadings of 5–25 wt% were prepared via a wet impregnation method on an γ-Al₂O₃ support and subsequently applied in the reductive amination of ethanol to ethylamines. Among the various catalysts prepared, Ni(10)/Al₂O₃ exhibited the highest metal dispersion and the smallest Ni particle size, resulting in the highest catalytic performance. To reveal the effects of reaction parameters, a reductive amination process was performed by varying the reaction temperature (T), weight hourly space velocity (WHSV), and NH₃ and H₂ partial pressures in the reactions. In addition, on/off experiments for NH₃ and H₂ were also carried out. In the absence of NH₃ in the reactant stream, the ethanol conversion and selectivities towards the different ethylamine products were significantly reduced, while the selectivity to ethylene was dominant due to the dehydration of ethanol. In contrast, in the absence of H₂, the selectivity to acetonitrile significantly increased due to dehydrogenation of the imine intermediate. Although a small amount of catalyst deactivation was observed in the conversion of ethanol up to 10 h on stream due to the formation of nickel nitride, the Ni(10)/Al₂O₃ catalyst exhibited stable catalytic performance over 90 h under the optimized reaction conditions (i.e., T=190 °C, WHSV=0.9 h^?1, and EtOH/NH₃/H₂ molar ratio=1/1/6).     

Maximization of total surface area of Pt-SnO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst by the Taguchi method

The maximization of the total surface area of Pt-SnO₂/Al₂O₃ catalyst was studied by using the Taguchi method of experimental design. The catalysts were prepared by sol-gel method. The effects of HNO₃, H₂O and aluminum nitrate concentrations and the stirring rate on the total surface area were studied at three levels of each. L₉ orthogonal array leading nine experiments was used in the experimental design. The parameter levels that give maximum total surface area were determined and experimentally verified. In the range of conditions studied it was found that, medium levels of HNO₃ and H₂O concentration and lower levels of aluminum nitrate concentration and stirring rate maximize the total surface area.     

Properties of unsupported MoS<Subscript>2</Subscript> species produced in the preparation of MoS<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> using a sonochemical method

Unsupported MoS₂ particles, which were produced in the preparation of MoS₂/Al₂O₃ using a sonochemical method, were successfully separated from the prepared sample catalyst by adding oleylamine as an agent for dispersing the unsupported particles. The fraction of the unsupported MoS₂, which was estimated based on Mo balance, varied between 0.03 and 0.4, independent of the Mo loading levels investigated (6–54 wt% of Mo). The activity of the unsupported MoS₂ for the hydrodesulfurization of dibenzothiophene was nearly the same as that of the Al₂O₃-supported MoS₂, indicating that the activity of the prepared catalyst was not affected by the presence of the unsupported MoS₂ particles.     

Effect of CeO<Subscript>2</Subscript>-addition sequence on the performance of CeO<Subscript>2</Subscript>-modified Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst in autothermal reforming of iso-octane

Two types of CeO₂-modified Ni/Al₂O₃ catalysts were prepared by a consecutive impregnation method with different sequences in the impregnation of Ni and CeO₂, and their performance in autothermal reforming (ATR) of isooctane was investigated. Catalysts prepared by adding CeO₂ prior to the addition of Ni, Ni/CeO₂-Al₂O₃, produced larger amounts of hydrogen than those obtained using catalysts prepared by adding the two components in an opposite sequence, Ni-CeO₂/Al₂O₃. The results of H₂ chemisorption and temperature-programmed reduction revealed that added CeO₂ increased the dispersion of the Ni species on Al₂O₃ and suppressed the formation of NiAl₂O₄ in the catalyst such that large amounts of Ni species were present as NiO, the active species for the ATR. The elemental and thermogravimetric analyses of deactivated catalysts indicated that Ni/CeO₂-Al₂O₃, which showed a longer lifetime than Ni-CeO₂/Al₂O₃, contained lesser amounts and different types of coke on the surface.     

Partial oxidation of methane over Ni/Ce-Zro<Subscript>2</Subscript>/θ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The catalytic behavior of Ni/Ce-ZrO₂/θ-Al₂O₃ has been investigated in the partial oxidation of methane (POM) toward synthesis gas. The catalyst showed high activity and selectivity due to the heat treatment of the support and the promotional effect of Ce-ZrO₂. It is suggested that the support was stabilized through the heat treatment of γ-Al₂O₃ and the precoating of Ce-ZrO₂, on which a protective layer was formed. Moreover, sintering of the catalyst was greatly suppressed for 24 h test. Pulse experiments of CH₄, O₂ and/or CH₄/O₂ with a molar ratio of 2 were systematically performed over fresh, partially reduced and well reduced catalyst. Results indicate that CH₄ can be partially oxidized to CO and H₂ by the reactive oxygen in complex NiO_x species existing over the fresh catalyst. It is demonstrated that POM over Ni/Ce-ZrO₂/θ-Al₂O₃ follows the pyrolysis mechanism, and both the carbonaceous materials from CH₄ decomposition over metallic nickel and the reactive oxygen species present on NiO_x and Ce-ZrO₂ are intermediates for POM.     

Hydrogen Production by Steam Reforming of Commercially Available LPG in UAE

Steam reforming of commercially available LPG using Ru/Al₂O₃ and Ni/Al₂O₃ catalysts has been studied at temperatures between 573 and 773 K. Ru/Al₂O₃ catalyst showed higher rates of reaction and lower activation energies of the three main components of LPG, compared with Ni/Al₂O₃. However, Ni/Al₂O₃ catalyst showed a better H₂:CH₄ selectivity. The activation energy of n-butane was the lowest over Ru/Al₂O₃, whereas over Ni/Al₂O₃, propane had the lowest activation energy. The activation energy of i-butane was always the highest over both catalysts, which suggests that both catalysts performed better with unbranched molecules. A slight increase in activation energy was observed, when each component of the LPG mixture was studied separately as a pure gas, compared with being mixed in LPG. At a constant temperature of 773 K, hydrogen production yield and H₂:CH₄ selectivity were determined using Ru/Al₂O₃ at different steam:carbon (S:C) ratios and LPG flow rates. It was found that the yield and selectivity increased with the increase in S:C ratio and the decrease in the flow rate. The highest yield of 0.64 was achieved using S:C ratio of 6.5 and a LPG flow rate of 50 mL min^?1. The work provides valuable information on steam reforming of pure components of LPG, compared with when they are in the mixture. The comparison is done using conventional steam reforming catalyst, Ni/Al₂O₃, and compared with Ru/Al₂O₃. The observed trends and variations in reaction rates, in pure and mixed gases, indicated that the mechanism of steam reforming of a hydrocarbon mixture depends on its composition.     

Hydrogen Production from Glycerol Over Nickel Catalysts Supported on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Modified by Mg,Zr, Ce or La

Hydrogen production from glycerol reforming in liquid (aqueous phase reforming, APR) and vapor (steam reforming SR) phase over alumina-supported nickel catalysts modified with Ce, Mg, Zr and La was studied. Characterization of catalysts by temperature programmed reduction and XPS analyses revealed important structural effects: (i) the intercalation of Mg between nickel and alumina that inhibited the alumina incorporation to nickel phases, (ii) the close contact between Ni and Zr phases and, (iii) the close surface interaction of La and Ce ions with NiO phases. The catalytic activity of the samples studied in this work clearly indicated the different catalyst functionalities necessary to carry out aqueous-phase and vapor-phase steam reforming of glycerol. For aqueous phase reforming of glycerol, the addition of Ce, La and Zr to Ni/Al₂O₃ improves the initial glycerol conversions obtained over the Ni/Al₂O₃ supported catalyst. It is suggested that the differences in catalytic activities are related with geometric effects caused by the decoration of Ni phases by Ce and La or by the close interaction between Ni and Zr. In spite that nickel catalysts showed high APR activities at initial times on stream, all samples showed, independently of support, important deactivation rates that deactivate the catalysts after few hours under operation. Catalysts characterization after APR showed the oxidation of the active metallic Ni during reaction as the main cause of the observed deactivation. In the case of the glycerol steam reforming in vapor phase, the use of Ce, La, Mg and Zr as promoters of Ni based catalysts increases the hydrogen selectivity. Differences in activity were explained in terms of enhancement in: surface nickel concentration (Mg), capacity to activate steam (Zr) and stability of nickel phases under reaction conditions (Ce and La).     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Catalytic Steam Reforming of Propane over Ni/LaAlO<Subscript>3</Subscript> Catalysts: Influence of Preparation Methods and OSC on Activity and Stability

Abstract  

To develop an efficient catalyst for steam reforming of propane, Ni/LaAlO₃ catalysts were prepared by deposition precipitation, impregnation, and solvo-thermal methods, and characterized by XRD, BET, H₂-TPR, elemental analyses, and TEM. Ni/Al₂O₃ and Ni/CeO₂ catalysts were also synthesized by the solvo-thermal method for comparison. The Ni/LaAlO₃ catalysts exhibited better catalytic performance than both Ni/Al₂O₃ and Ni/CeO₂ catalysts, and activities with Ni/LaAlO₃ were found to be dependent upon the preparation methods. In particular, the Ni/LaAlO₃ catalyst synthesized by the solvo-thermal method exhibited the highest activity presumably because tetrahydrofuran helps distribute generated Ni nanoparticles onto the catalyst surface in a uniform fashion. In addition, the solvo-thermally prepared Ni/LaAlO₃ catalyst was found to be highly stable, with its activity being maintained at least during 100 h. The observed high stability is attributed to the excellent oxygen storage capacity of LaAlO₃, which was first determined by thermogravimetric methods as well as by soot oxidations in the presence of Al₂O₃, CeO₂, and LaAlO₃. Compared to the Ni/Al₂O₃ and Ni/CeO₂ catalysts, Ni/LaAlO₃ exhibited suppressed carbon formation even at lower S/C ratios due to the superior oxygen transport ability of the LaAlO₃ support.     

Characterization of aerogel Ni/Al2O3 catalysts and investigation on their stability for CH4-CO2 reforming in a fluidized bed

The CH₄-CO₂ reforming was investigated in a fluidized bed reactor using nano-sized aerogel Ni/Al₂O₃ catalysts, which were prepared via a sol–gel method combined with a supercritical drying process. The catalysts were characterized with BET, XRD, H₂-TPR and H₂-TPD techniques. Compared with the impregnation catalyst, aerogel catalysts exhibited higher specific surface areas, lower bulk density, smaller Ni particle sizes, stronger metal-support interaction and higher Ni dispersion degrees. All tested aerogel catalysts showed better catalytic activities and stability than the impregnation catalyst. Their catalytic stability tested during 48 h reforming was dependent on their Ni loadings. Characterizations of spent catalysts indicated that only limited graphitic carbon formed on the aerogel catalyst, while massive graphitic carbon with filamentous morphology was observed for the impregnation catalyst, leading to significant catalytic activity degradation. An aerogel catalyst containing 10% Ni showed the best catalytic stability and the lowest rate of carbon deposition among the aerogel catalysts due to its small Ni particle size and strong metal-support interaction.     

Combined XPS and TPR study of sulfur removal from a Pt/BaO/Al2O3 NO x storage reduction catalyst

Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts (1 wt% Pt, 10 wt%BaO) were sulfated under conditions simulating a real NSR catalyst operation. Comparative TPR and XPS studies of sulfur removal from Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts indicate that the sulfur removal from Al₂O₃ surface precedes reductive decomposition of BaSO₄ (250–400 °C). Barium sulfate decomposition started with further increase in desulfation temperature at the point of surface atomic ratio Ba:S = 1 (~450^o). Simultaneously, an intensive formation of sulfide species on the catalyst surface was observed. Thermodynamic analysis of the desulfation process allows us to hypothesize that barium sulfide formation may hinder sulfur removal under reducing conditions.     

Influence of preparation method on performance of Cu(Zn)(Zr)-alumina catalysts for the hydrogen production via steam reforming of methanol

The selective production of hydrogen via steam reforming of methanol (SRM) was performed using prepared catalysts at atmospheric pressure over a temperature range 200–260^∘C. Reverse water gas shift reaction and methanol decomposition reactions also take place simultaneously with the steam reforming reaction producing carbon monoxide which is highly poisonous to the platinum anode of PEM fuel cell, therefore the detailed study of effect of catalyst preparation method and of different promoters on SRM has been carried out for the minimization of carbon monoxide formation and maximization of hydrogen production. Wet impregnation and co-precipitation methods have been comparatively examined for the preparation of precursors to Cu(Zn)(Al₂O₃) and Cu(Zn)(Zr)(Al₂O₃). The catalyst preparation method affected the methanol conversion, hydrogen yield and carbon monoxide formation significantly. Incorporation of zirconia in Cu(Zn)(Al₂O₃) catalyst enhanced the catalytic activity, hydrogen selectivity and also lower the CO formation. Catalyst Cu(Zn)(Zr)(Al₂O₃) with composition Cu/Zn/Zr/Al:12/4/4/80 prepared by co-precipitation method was the most active catalyst giving methanol conversion up to 97% and CO concentration up to 400 ppm. Catalysts were characterized by atomic absorption spectroscopy (AAS), Brunauer-Emett-Teller (BET) surface area, pore volume, pore size and X-ray powder diffraction (XRPD). The XRPD patterns revealed that the addition of zirconia improves the dispersion of copper which resulted in the better catalytic performance of Cu(Zn)(Zr)(Al₂O₃). The time-on-stream (TOS) catalysts stability test was also conducted for which the Cu(Zn)(Zr)(Al₂O₃) catalyst gave the consistent performance for a long time compared to other catalysts.