Improving the Activity of Rh/Al2O3 Catalyst for NO Reduction by Na Addition in the Presences of H2O and O2

The effect of Na addition on the performance of Rh/Al₂O₃ catalyst for NO reduction with CO in the presence of H₂O and O₂ was investigated. The reacted catalysts were analyzed by the FTIR technique to identify the products for further investigation on the possible catalytic reaction mechanisms and the reasons behind the H₂O poisoning. Experimental results show that the removal efficiency of NO by Rh/Al₂O₃ catalyst was 63% at 250 °C but that decreased as the H₂O content increased. Adding Na to modify the Rh/Al₂O₃ catalyst significantly enhanced the conversion of NO to 99% at 250–300 °C even as the H₂O content was 1.6 vol%. The FTIR analyses results reveal that the abundant H₂O in the flue gas can compete with NO to adsorb on the surfaces of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts and further enhance the formation of NO₃ that reacts with H. The effects of H₂O on Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts can be eliminated by increasing the reaction temperature to higher than 300 °C. Rh-Na/Al₂O₃ is a feasible catalyst for NO reduction at such condition with relative high H₂O and O₂ contents.     

Cooperation of Ag/Al2O3 and Sn/Al2O3 Catalysts for the Selective Reduction of NO by Propene

Compared to the Ag/Al₂O₃ catalyst, a two‐stage catalyst composed of an Ag/Al₂O₃ layer followed by a Sn/Al₂O₃ layer shows higher low‐temperature activity and a wider temperature window. Its activity below 350 °C is enhanced in the presence of SO₂. Even in the presence of H₂O and SO₂, the performance of the same catalytic system is still satisfactory.     

Effect of Organic Nickel Precursor on the Reduction Performance and Hydrogenation Activity of Ni/Al2O3 Catalysts

Different nickel precursors, i.e., nickel nitrate, nickel acetate and nickel acetate plus citric acid, were used to prepare supported Ni/γ-Al₂O₃ catalysts for naphthalene hydrogenation to decalin. The catalysts thus prepared were reduced without calcination and after calcination, respectively. The physicochemical characterization and activity testing results show that the catalyst prepared with nickel acetate as precursor and reduced without calcination possesses modest reduction character, higher adsorption and desorption abilities of H₂, and exhibits most excellent catalytic performance for the reaction with 99.1% selectivity of decalin at the naphthalene conversion of 100%.     

Activity Enhancement of Bimetallic Rh-Ag/Al2O3 Catalysts for Selective Catalytic Reduction of NO by C3H6

The catalytic performance of bimetallic rhodium–silver clusters for the selective catalytic reduction of NO by propylene has been examined over 1%(Rh-Ag)/A₂O₃ catalysts of variable Ag content. It was found that substitution of small amounts of Rh by Ag results in a significant increase of the catalytic activity, which goes through a maximum for catalysts with metal compositions of ca. 95%Rh-5%Ag. This behaviour is tentatively attributed to the formation of rhodium-rich phase alloys, which may stabilize Rh in its reduced state at reaction conditions.     

Dynamical Changes in Cu/ZnO/Al2O3 Catalysts

A combination of various transient and steady-state kinetic experiments was used to provide evidence for dynamical changes in a Cu/ZnO/Al₂O₃ catalyst of industrial interest. From these it can be deduced that the reversible structural alterations strongly depend on the reaction conditions as well as on the pretreatment. The pretreatment was found to induce changes in the morphology of the metallic Cu particles to some extent, and surface alloying under more severe reducing conditions.     

Hydrogenolysis of Dimethyl Maleate on Cu/ZnO/Al2O3 Catalysts

The gas‐phase hydrogenolysis of dimethyl maleate at 10 bar and 513 K was investigated over a series of co‐precipitated Cu/ZnO/Al₂O₃ catalysts. High copper surface areas were obtained with a molar Al content of 5 % in the catalysts. Upon variation of composition at fixed alumina content, copper surface areas increased until the molar ratio exceeded Cu/Zn = 2:1. At the given reaction conditions, dimethyl maleate was completely converted to dimethyl succinate, which further reacted to methanol, γ‐butyrolactone, tetrahydrofuran, and water over all catalysts. Initial deactivation of catalysts was mainly caused by a loss of copper surface area. The catalyst with a molar Cu/Zn ratio of 1:2 was found to be most active and stable under reaction conditions.     

The Effect of Preparation Variables on the CO Hydrogenation Activity of Coprecipitated Co/Al2O3 Catalysts

Studies have been conducted on the effect of preparation variables on the activity of coprecipitated cobalt–alumina catalysts to be used for the production of C₁–C₄ hydrocarbons by CO hydrogenation. The preparation parameters considered were the precipitation pH, the precipitation agent, the metal loading, the reduction temperature and the reduction period. It was found that changing pH precipitation with a constant final pH between 11·0 and 12·5 and the use of NaOH together with nitrates as precursors yielded better catalysts with maximal metal surface area. The optimum cobalt loading for the selective production of C₁–C₄ hydrocarbons is around 35 wt%. Optimum activity and selectivity are obtained by applying an 8-h reduction scheme at 648 K under 100 cm³ min⁻¹ hydrogen. Calcination prior to reduction has a detrimental effect on metal surface area and hence on catalytic activity. © 1997 SCI.     

Cu–ZnO and Cu–ZnO/Al2O3 Catalysts for the Reverse Water-Gas Shift Reaction. The Effect of the Cu/Zn Ratio on Precursor Characteristics and on the Activity of the Derived Catalysts

Comparison is made between Cu–ZnO and alumina-supported Cu–ZnO as catalysts for the reverse water-gas shift (RWGS) reaction. For both types of catalyst the Cu/Zn ratio has been varied between Cu-rich and Zn-rich compositions. By applying X-ray diffractometry, X-ray line broadening, optical reflectance spectroscopy and other techniques the effects on the structural and physical properties of the hydroxycarbonate precursors, the calcined products and the ultimately derived catalysts are determined. The presence of alumina decreases the crystallite size of the CuO and ZnO particles produced on calcination and at high Cu/Zn ratios increases the dispersion of copper in the final catalyst. The activities of the catalysts for the RWGS reaction at 513K are compared and the most active are shown to be those which are Cu rich (Cu/Zn > 3) and contain alumina as support. The activities of all the catalysts can be rationalized by referring the activity to unit surface area of copper metal.     

Differences Between Al2O3 and Ag/Al2O3 for Lean Reduction of NO x with Dimethyl Ether

Lean reduction of NO _x with DME occurs with high selectivity to N₂ over Al₂O₃ between 300 °C and 550 °C with a maximum of 47% at 380 °C, and with lower selectivity over Ag/Al₂O₃ between 250 °C and 400 °C due to the catalysts’ sensitivity to gas phase radical reactions and activity for NO _x reduction with methanol.     

Nitrogen Tolerant Hydrodesulfurization Catalysts Based on Rh and Ru Promoted Mo/Al2O3

Rh and Ru promoted Mo/Al₂O₃ catalysts were tested in HDS of thiophene in the presence of different amounts of pyridine and compared with CoMo/Al₂O₃. The Rh and Ru promoted catalysts were more nitrogen tolerant and in the presence of pyridine showed higher HDS activities than CoMo/Al₂O₃. This was explained by higher C–N bond hydrogenolysis activity and high nitrogen tolerance of the free Rh and Ru sulfides in the promoted catalysts.     

载体氧化铝的粒径对对硝基苯酚加氢催化剂Ni/Al2O3的影响

The catalytic hydrogenation ofp-nitrophenol to p-aminophenol was investigated over Ni/Al2O3 catalyst on alumina support with different particle size. It is found that support particle size has significant influences on physiochemical properties and catalytic activity of the resulting Ni/A12O3 catalyst,but little influence on the selectivity. At a comparable amount of Ni loading,the catalytic activity of Ni/Al2O3 prepared with alumina support of smaller particle size is lower. The reduction behavior of the catalyst is a key factor in determining the catalytic activity of Ni/A12O3 catalyst. The supported nickel catalyst 10.3Ni/Al2O3-3 improves the life span of the membrane by reducing fouling on the membrane surface compared to nano-sized nickel.     

The Catalytic Activity of Co/ZrO2 for NO Reduction with Propane in O2 Presence

The selective catalytic reduction (SCR) of NO by propane in the presence of excess oxygen was studied on a Co/ZrO₂ catalyst. This system is present as active for the NO reduction to N₂. It was found that the addition of Co could improve the activity and selectivity of propane towards NO_x reduction. The activity depends strongly on the space velocity (GHSV) when the system works with low oxygen concentration and it is independent of the space velocity when the system operates with excess oxygen. The water vapor present in the feed produces deactivation in the catalyst as well as in the support.     

The CO methanation over NaY-zeolite supported Ni/Co3O4, Ni/ZrO2, Co3O4/ZrO2 and Ni/Co3O4/ZrO2 catalysts

The CO methanation was studied over zeolite NaY supported Ni, Co₃O₄, ZrO₂ catalysts. The XRD, N₂ physisorption and SEM analysis were used in order to characterize the catalysts. Catalytic activities were carried out under a feed composition of 1% CO, 50% H₂ and 49% He between the 125 °C to 375 °C. Except for the Ni/Co₃O₄/NaY catalyst, all catalysts gave high surface area because of the presence of zeolite NaY. Average pore diameter of the catalysts fell into the mesopore diameter range. The highest CO methanation activity was obtained with Ni/ZrO₂/NaY catalyst at which the CO methanation was started after 175 °C and 100% CO conversion was obtained at 275 °C using the same catalyst.     

Effects of space velocity on methanol synthesis from Co2/Co/H2 over Cu/ZnO/Al2O3 catalyst

The space velocity had profound and complicated effects on methanol synthesis from CO₂/CO/H₂ over Cu/ZnO/Al₂O₃ at 523 K and 3.0MPa. At high space velocities, methanol yields as well as the rate of methanol production increased continuously with increasing CO₂ concentration in the feed. Below a certain space velocity, methanol yields and reaction rates showed a maximum at CO₂ concentration of 5–10%. Different coverages of surface reaction intermediates on copper appeared to be responsible for this phenomenon. The space velocity that gave the maximal rate of methanol production also depended on the feed composition. Higher space velocity yielded higher rates for CO₂/ H₂ and the opposite effect was observed for the CO/H₂ feed. For CO₂/CO/H₂ feed, an optimal space velocity existed for obtaining the maximal rate.     

氧化铝载体对镍/氧化铝催化剂性能的影响

氧化铝是化工催化行业广泛应用的催化剂载体。油脂加氢催化剂主要是以氧化铝为载体、镍为主要活性组分的催化剂。在制备镍/氧化铝催化剂的过程中,载体氧化铝使用的最佳条件：载体在共沉淀反应前加入,载体氧化铝比表面积为340.6 m2/g,载体氧化铝加入量为m（镍）∶m（氧化铝）=5∶4,反应的老化时间为45 min。在此条件下,制备的镍/氧化铝催化剂活性最高,应用效果最好。     

Effects of penta-coordinated Al3+ sites and Ni defective sites on Ni/Al2O3 for CO methanation

Engineering sophisticated structure of Al₂O₃ and controlling the structure of counterpart metal active sites remain challenges to achieve a high catalytic-performance in heterogeneous catalysis. Herein, we present a confinement strategy to stabilize homogeneous Ni by penta-coordinated Al³⁺ anchoring sites in Al₂O₃. This approach is involved in using a metal–organic framework as host to load Ni²⁺ ions, by the aim of producing a confined Ni/Al₂O₃ catalyst after a standard calcination. Metal–support interaction between Ni and Al₂O₃ was tailored to be medium to avoid the formation of inactive NiAl₂O₄, which favors the generation of more available Ni active sites accessible to the reactants. The resultant Ni/Al₂O₃ exhibited superior catalytic performance in comparison with the control Ni/Al₂O₃ in CO methanation owing to the presence of defective sites on sufficient Ni⁰ surface. Furthermore, the presence of oxygen vacancies on Al₂O₃ and hydrogen spillover contributed toward excellent coke resistance properties in the reaction.     

The Nature of Active Sites of Co/Al2O3 for the Selective Catalytic Reduction of NO with C2H4

The effects of Co loading and calcination temperatures on the catalytic activity of Co/Al₂O₃ for selective catalytic reduction (SCR) of NO with ethylene in excess oxygen were investigated. Co/Al₂O₃ showed high and low activities when calcined at high (800 °C) and low (350 °C) temperatures, respectively. The formation and dispersion of cobalt species for catalysts calcined at 350 and 800 °C as well as for Al₂O₃ were studied by XRD, UV–vis and FTIR spectra. Combined with DRIFTS results of ad-species and reaction experiments, it allowed us to correlate the catalytic activity with active sites of Co/Al₂O₃, and the catalytic functions of active cobalt species and support were clarified. Co₃O₄ species contributed to the oxidation of NO to various nitrates and of C₂H₄ to reactive formate species, even in the absence of O₂, whereas the side reaction of ethylene combustion occurred simultaneously when excess oxygen was present. Tetrahedral Co²⁺ ions in CoAl₂O₄, which acted as the active sites, were responsible for the reaction between formate and nitrate species to form organic nitro compound.     

Glycerol Hydrogenolysis to 1,2-Propanediol by Cu/ZnO/Al2O3 Catalysts

The effect of preparation methods on the Cu/ZnO/Al₂O₃ catalyst structure and catalytic activity on liquid glycerol hydrogenolysis to 1,2-propanediol has been investigated. The physicochemical properties of the catalysts were characterized by BET, XRD, TG/DTA, NH₃-TPD and TPR. The experimental results showed that the catalyst prepared by an oxalate gel–coprecipitation had the highest activity. At 200 °C and 400 psi hydrogen pressure, the glycerol conversion and 1,2-propanediol selectivity catalyzed by the Cu/ZnO/Al₂O₃ catalyst prepared via oxalate gel–coprecipitation were 92.3 and 94.5 % respectively. It was found that the 1,2-propanediol selectivity was dependent on hydrogen pressure and the un-desired by-products were mainly due to the side reactions caused by the presence of the intermediate acetol.

     

Glycerol Hydrogenolysis to 1,2-Propanediol by Cu/ZnO/Al2O3 Catalysts

The effect of preparation methods on the Cu/ZnO/Al₂O₃ catalyst structure and catalytic activity on liquid glycerol hydrogenolysis to 1,2-propanediol has been investigated. The physicochemical properties of the catalysts were characterized by BET, XRD, TG/DTA, NH₃-TPD and TPR. The experimental results showed that the catalyst prepared by an oxalate gel–coprecipitation had the highest activity. At 200 °C and 400 psi hydrogen pressure, the glycerol conversion and 1,2-propanediol selectivity catalyzed by the Cu/ZnO/Al₂O₃ catalyst prepared via oxalate gel–coprecipitation were 92.3 and 94.5 % respectively. It was found that the 1,2-propanediol selectivity was dependent on hydrogen pressure and the un-desired by-products were mainly due to the side reactions caused by the presence of the intermediate acetol.