Screening of bifunctional water-gas shift catalysts

A large number of different formulations have been recently proposed in the literature as new catalysts for the water-gas shift (WGS) reaction. These formulations typically consist of a metal deposited on a reducible support. As these catalysts have been synthesized and tested by different groups in different operating conditions, a true comparison of their activities is not really possible. The aim of this study is to screen these samples under identical conditions using a model reformate as reaction mixture. A commercial parallel reactor has been used for this task. Comparison of the data obtained for the Pt catalysts from the parallel reactor with those obtained from a single fixed bed reactor showed deviations of 20–30% in the kinetic parameters. Rh and Ru based catalysts produced significant amounts of methane. Pt/CeO₂/Al₂O₃ and Pt/TiO₂ were found to be the most active catalysts for the high temperature water-gas shift while gold and copper catalysts showed promising results for low temperature applications, but they require testing at lower CO partial pressures.     

铜含量对Cu/CeO2水煤气变换催化剂性能的影响

采用共沉淀法制备了不同铜含量的Cu/CeO₂水煤气变换催化剂，考察了铜含量对催化活性的影响。结果表明，Cu/CeO₂催化剂呈现出良好的水煤气变换活性。铜含量对催化活性有显著影响，铜摩尔分数为50%时，催化剂的低温活性最高，在200 ℃时CO转化率达到66.1%。Cu/CeO₂与FBD型铁基高温变换催化剂相比，具有低温活性好、活性温区宽的特点。用XRD、N2吸附法、H₂-TPR和CO-TPD对催化剂进行了表征，结果表明,无定形CuO、纳米颗粒CuO等可能是催化反应的活性物种，晶粒CuO对催化活性影响不大。铜含量的催化剂在不同温度下呈现出不同的活性。     

Chloride poisoning of water-gas shift activity in nickel catalysts during steam reforming

This Letter reports preliminary findings on the role of chloride poisoning during steam reforming of chlorocarbons over nickel catalysts. When conversions of chlorocarbon are very high and thermal pyrolysis absent, the principal effect of chloride is to decrease water-gas shift and CH₄-steam reforming activity. Product carbon dioxide/carbon monoxide ratios are then far from equilibrium and methane remains unconverted when introduced into the feed. These results are linked to previously published surface science studies.     

负载型铁基高温变换催化剂的制备和性能研究

分别以镁铝尖晶石和活性炭作为载体制备了负载型铁基高温变换催化剂，通过XRD、TEM和活性评价测试，考察了催化剂的结构和催化反应性能。以镁铝尖晶石负载γ-Fe₂O₃制得的催化剂，其催化活性明显高于负载α-Fe₂O₃催化剂，当催化剂组成为：Fe₂O₃ 26%，K2O 2%，MgO 0.05%，Cr₂O₃ 0.7%时，400℃下CO转化率为92%，350℃为84%（汽/气=1， 空速=2000 h^-1）；经氧化处理的活性炭作为催化剂载体时，低铬条件下也具有较好的催化活性，当负载量为40%时，相同变换反应条件下CO的转化率在400℃和350℃下分别为88%和80%。两种催化剂在低Cr₂O₃含量时都保持了与传统铁铬系变换催化剂(B117型)相当的催化活性，对于改善环境具有很大意义。     

整体式高温水煤气变换催化剂的初步研制

采用不同方法制备了整体式高温水煤气变换催化剂。利用经酸处理的蜂窝状堇青石作载体制备整体式催化剂，着重研究酸处理对堇青石载体结构、性能及其催化性能的影响。利用改性Al₂O₃涂层浸渍负载活性组分制备整体式催化剂，重点考察化学组成对整体式催化剂性能的影响。研究结果表明，蜂窝状堇青石经酸适当处理及表面改性后，可用作整体式催化剂的载体;K₂O、CuO及稀土氧化物对整体式催化剂的水煤气变换活性有很好的促进作用，而且多组分间存在的某种协同作用更有利于调变整体式催化剂的催化性能     

Low-temperature water-gas shift reaction over Mn-promoted Cu/Al2O3 catalysts

Water-gas-shift reaction was carried our over a series of Mn-promoted Cu/Al₂O₃ catalysts in the temperature range of 448–533 K. The catalysts were characterized suitably by various techniques. The catalyst containing 8.55 wt% Mn was found to be the most active one among five catalysts tested. A maximum CO conversion of 90% was obtained over this catalyst at 513 K with a CO space-time of 5.33 h. The catalysts were found to be structure sensitive for the low-temperature water-gas shift reaction. A detailed kinetic study was performed for the reaction under investigation over the best catalyst. The kinetic data were fitted to two different models and the redox model was found to the better one than the other. From the estimated kinetic constant, the activation energy was determined to be 81 kJ/mol for the water-gas shift reaction in the temperature range of 448–463 K.     

Methanol synthesis and reverse water-gas shift kinetics over clean polycrystalline copper

The kinetics of simultaneous methanol synthesis and reverse water-gas shift from CO₂/H₂ mixtures have been measured at low conversions over a clean polycrystalline Cu foil at pressures of 5 bar. An absolute rate of 1.2 × 10^–3 methanol molecules produced per second per Cu surface atom was observed at 510 K, with an activation energy of 77 ± 10 kJ/mol. The rate of CO production was 0.12 molecules per second per Cu surface atom at this temperature, with an activation energy of 135 ± 5 kJ/mol. The rates, normalized to the metallic Cu surface area, are equal to those measured over real, high-area Cu/ZnO catalysts. The surface after reaction was examined by XPS and TPD. It was covered by almost a full monolayer of adsorbed formate, but no other species like carbon or oxygen in measurable amounts. These results prove that a highly active site for methanol synthesis on real Cu/ZnO catalysts is metallic Cu, and suggest that the rate-determining step in methanol synthesis is one of the several steps in the further hydrogenation of adsorbed formate to methanol.     

Comparison of the dynamics of the high-temperature water-gas shift reaction on oxide catalysts

The dynamics of the high-temperature water-gas shift reaction on iron oxide and Co-Mo-oxide catalysts was studied with transient response experiments performed at 563–673 K at atmospheric pressure in a gradientless spinning basket reactor. At the reaction start-up the step response of CO₂ on the iron oxide catalyst was always faster than the response of H₂, whereas the response of H₂ on the Co-Mo catalyst was faster than the response of CO₂. Water pretreatment retarded the response of H₂ on the iron oxide catalyst, whereas a similar pretreatment accelerated the response of H₂ on the Co-Mo catalyst. Based on the results of the transient response experiments reaction mechanisms were proposed for the water-gas shift reaction on both catalysts. The rate determining steps on the iron oxide catalyst were assumed to be the CO₂ desorption and surface hydroxyl decomposition steps. The rate determining steps on the Co-Mo catalyst were assumed to be the surface reaction and CO₂ desorption steps. The transient responses were modelled with non-steady-state rate equations based on the mechanisms, and the kinetic constants were determined by regression analysis. The kinetic models were able to describe the transient behaviours of the oxide catalysts.     

Superior catalytic behavior of trace Pt-doped Ni/Mg(Al)O in methane reforming under daily start-up and shut-down operation

Doping effects of Pt and Ru on Ni/Mg(Al)O catalysts were compared in daily start-up and shut-down operations of steam reforming of CH₄. Trace Pt-doped catalyst showed better behavior than trace Ru-doped catalyst; the former was self-activated but the latter was not, although both exhibited self-regenerative activity. Moreover, the former exhibited sustainable activity, although the latter was quickly passivated, in the autothermal reforming of CH₄. Formation of Pt–Ni alloy on the surface of fine Ni metal particles on the catalysts was suggested by EXAFS analyses. CH₄ was dissociatively activated to form hydrogen on Pt, assisted by adsorbed O or OH species, leading to the self-activation via Ni reduction by hydrogen spillover from Pt. The self-regeneration of the Pt–Ni/Mg(Al)O catalysts can be achieved by the continuous rebirth of active Ni metal species via reversible reduction–oxidation between Ni⁰ and Ni²⁺ in/on Mg(Ni,Al)O periclase assisted by the hydrogen spillover.     

Mesoporous and nanostructured CeO2 as supports of nano-sized gold catalysts for low-temperature water-gas shift reaction

Mesoporous particles and 1D nanorods of cerium oxides have been prepared by modifying the hydrothermal route of a surfactant-assisted controllable synthesis. Mesoporous cerias were obtained in a sealed glass vessel under continuous stirring, while ceria nanorods were obtained in a Teflon-lined autoclave without stirring. The mesoporous cerias did not show long-range mesoscopic organization, exhibiting a broad mesopore size distribution in the region 8–15 nm. A BET surface area of 100 m²/g with a total pore volume of 0.33 cm³/g is obtained for as-synthesized mesoporous ceria. The ceria nanorods exhibit a cubic crystalline structure after calcination, having the lengths in the range of 150–300 nm and diameters in the range of 10–25 nm. The growth direction of ceria nanorods is along [1 1 0]. A surface area of above 50 m²/g is obtained in the calcined nanorods. These synthesized ceria materials were used as supports of nano-sized gold catalysts, prepared by deposition–precipitation method. Their catalytic activity was evaluated by the low-temperature water-gas shift reaction. The gold/mesoporous ceria catalytic system exhibited higher catalytic activity than gold/ceria nanorods. It is revealed that the mesoporous and nanostructured cerias are of much interest as potential supports for gold-based catalysts that are effective for low-temperature water-gas shift reaction.     

Total oxidation catalysts based on manganese or copper oxides and platinum or palladium II: Activity, hydrothermal stability and sulphur resistance

Deactivation of catalysts based on either manganese oxides, copper oxides, platinum, palladium or combinations of these metal oxides and noble metals supported on γ-alumina was studied. The activity of the catalysts for the oxidation of carbon monoxide, naphthalene and methane, in a mixture resembling the flue gases from wood combustion, was measured before and after exposure of the catalysts either to a temperature of 900°C in the presence of steam or to sulphur dioxide. Most of the mixed catalysts were more resistant to hydrothermal and sulphur treatments than the catalysts with a single active component. After the hydrothermal treatment the activity of the MnO_x catalyst was enhanced. When Pt is combined with MnO_x or CuO_x, the loss of activity of Pt was decreased during the hydrothermal treatment. Also, the hydrotreated mixed MnO_x–Pd and CuO_x–Pd catalysts were more active than the treated Pd catalyst for the oxidation of methane. After sulphur treatment, the activities of the mixed MnO_x–Pt (Pt: 0.05 mol%), MnO_x–Pd and CuO_x–Pd catalysts were improved for the oxidation of carbon monoxide and naphthalene. Among the catalysts studied, the MnO_x–Pt, CuO_x–Pt and CuO_x–Pd catalysts, with a metal oxide and a noble metal loading of 10 and 0.1 mol%/γ-alumina, respectively, had the best combination of activity, thermal stability and resistance to sulphur treatment.     

Identification of valence shifts in Au during the water-gas shift reaction

In situ X-ray absorption spectroscopy (XAS) has been performed to investigate the active site on Au-based catalysts in the water-gas shift (WGS) reaction. The surface area and hence the WGS activity is higher for AuTiO₂ catalysts supported on carbon nanofibres (CNF) than TiO₂. The WGS reaction rate depends on the Au coordination number with an apparent maximum close to eight which corresponds to a particle size of approximately 2.5–3.0 nm. A likely cause for the changes in the electronic structure of Au is the adsorption of CO on the surface, which also creates a small positive charge in the Au atoms. The catalytic activity significantly improves when titania is present compared to Au deposited directly on CNF.     

制备方法对高CuO含量的Cuo/CeO_2催化剂水煤气变换性能的影响

采用机械混合法、固相合成法、水热法、沉积-沉淀法和共沉淀法制备系列CuO/CeO_2水煤气变换催化剂,采用XRD、N_2物理吸附和H_2-TPR等方法对样品进行表征,研究制备方法对CuO/CeO_2催化剂结构的影响以及催化剂结构与其催化性能的关系。结果表明,共沉淀法有利于获得较小的CuO和CeO_2晶粒、较大的比表面积、孔容和孔径以及较好的还原性能,制得的催化剂活性和稳定性较好。     

Total oxidation catalysts based on manganese or copper oxides and platinum or palladium I: Characterisation

Temperature-programmed reduction (TPR), oxidation (TPO), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to characterise catalysts based on manganese oxides, copper oxides or one of them mixed with platinum or palladium-supported on γ-alumina. The catalysts were characterised before and after they had been exposed either to high temperature in the presence of steam or to sulphur dioxide. Raman spectroscopy, XRD, XPS and TPR performed on the fresh samples of MnO_x, mixed MnO_x–Pt and MnO_x–Pd revealed the presence of a mixture of manganese oxides, particularly Mn₂O₃. In the fresh mixed MnO_x–Pd and CuO_x–Pd samples, Pd catalysed the reduction of both MnO_x and CuO_x, whereas Pt only catalysed the reduction of MnO_x. After hydrothermal treatment at 900°C of the MnO_x, mixed MnO_x–Pt and MnO_x–Pd samples, there was a formation of new manganese oxide phase, Mn₃O₄ detected by Raman spectroscopy. TPR revealed increasing interaction between the metal oxides and the noble metals in the hydrothermally treated mixed MnO_x–Pd and CuO_x–Pd samples, and also the appearance of interaction in the treated mixed CuO_x–Pt sample. The sulphur adsorbed in all the MnO_x samples formed sulphate, which was more difficult to reduce than the oxides. Also, the reduction temperature of sulphates was lowered when noble metals are present.     

Comparison of the activity of Au/CeO2 and Au/Fe2O3 catalysts for the CO oxidation and the water-gas shift reactions

We compare the activity and relevant gold species of nanostructured gold–cerium oxide and gold–iron oxide catalysts for the CO oxidation by dioxygen and water. Well dispersed gold nanoparticles in reduced form provide the active sites for the CO oxidation reaction on both oxide supports. On the other hand, oxidized gold species, strongly bound on the support catalyze the water-gas shift reaction. Gold species weakly bound to ceria (doped with lanthana) or iron oxide can be removed by sodium cyanide at pH ≥12. Both parent and leached catalysts were investigated. The activity of the leached gold–iron oxide catalyst in CO oxidation is approximately two orders of magnitude lower than that of the parent material. However, after exposure to H₂ up to 400 °C gold diffuses out and is in reduced form on the surface, a process accompanied by a dramatic enhancement of the CO oxidation activity. Similar results were found with the gold–ceria catalysts. On the other hand, pre-reduction of the calcined leached catalyst samples did not promote their water-gas shift activity. UV–Vis, XANES and XPS were used to probe the oxidation state of the catalysts after various treatments.     

The influence of alkali metals on the activity of supported ruthenium catalysts for the water-gas shift reaction

This paper presents the results of the studies on the influence of alkali metals on the activity of ruthenium catalysts, which were supported on the products of α- and δ-iron oxide-hydroxide calcination. Modification of these supports with alkali metals, in particular potassium, rubidium and cesium, prior to deposition of ruthenium was found to increase the activity of Ru/Fe₂O₃ catalysts in the water-gas shift reaction. It was also established that the activity and stability of catalysts prepared on iron oxide obtained from α-FeOOH increased when the latter was modified with sodium ions. The favourable effect of sodium on the activity of the catalysts was shown to appear at a certain proportion of the base to the active component, i.e. ruthenium. This revised version was published online in July 2006 with corrections to the Cover Date.     

逆水煤气变换耦合乙烷脱氢反应中助剂对Cr/SiO2催化剂性能的影响

分别制备了以Mn、Ce、Cu、Zn、K等为助剂的Cr/SiO2催化剂,考察了助剂在逆水煤气变换耦合乙烷脱氢制乙烯反应中对Cr/SiO2催化剂反应性能的影响。结果表明,高温下Mn的加入有利于催化活性的提高,Cr-Mn/SiO2催化剂显示了较好的催化活性。在740℃、n(CO2)/n(C2H6)=7的条件下,乙烷转化率为47%,乙烯选择性为99%。XRD、XPS、UV-DRS和TPR技术的表征表明催化剂表面存在Cr3+、Cr6+、Mn4+物种,Mn的加入使得催化剂还原性能增强,有助于反应过程中氧化还原循环的进行,提高了反应活性。     

CuO and CuO-ZnO catalysts supported on CeO2 and CeO2-LaO3 for low temperature water-gas shift reaction

This paper describes an investigation on CuO and CuO-ZnO catalysts supported on CeO₂ and CeO₂-La₂O₃ oxides, which were designed for the low temperature water-gas shift reaction (WGSR). Bulk catalysts were prepared by co-precipitation of metal nitrates and characterized by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area (by the BET method), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption near edge structure (XANES). The catalysts' activities were tested in the forward WGSR, and the CuO/CeO₂ catalyst presented the best catalytic performance. The reasons for this are twofold: (1) the presence of Zn inhibits the interaction between Cu and Ce ions, and (2) lanthanum oxide forms a solid solution with cerium oxide, which will cause a decrease in the surface area of the catalysts. Also the CuO/CeO₂ catalyst presented the highest Cu content on the surface, which could influence its catalytic behavior. Additionally, the Cu⁰ and Cu¹⁺ species could influence the catalytic activity via a reduction-oxidation mechanism, corroborating to the best catalytic performance of the Cu/Ce catalyst.