An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO₂ catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO₂ and H₂ on ZnO/SiO₂ catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO₂ and H₂ with Cu/ZnO/SiO₂ catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism.     

Selective catalytic reduction of NOx, by propene over copper-exchanged pillared clays

Copper-exchanged pillared clays were examined as an SCR catalyst for NO_x, removal by propene. Both micropores and mesopores were simultaneously developed by pillaring a bentonite with TiO₂. Therefore, TiO₂-pillared clay has about 8 to 9 times higher surface area and 3 times higher pore volume than the parent unpillared bentonite. The presence of water in the feed gas stream caused a small and reversible inhibition effect on NO removal activity of Cu/Ti-PILC. The water tolerance of Cu/Ti-PILC was higher than copper-exchanged zeolites such as CuHM and Cu/ZSM-5 due to its high hydrophobicity as confirmed by H₂O-TPD experiment. Copper-exchanged PILC was confirmed to be an active catalyst for NO_x, removal by propene. The addition of copper to TiO₂-pillared clay greatly enhanced the catalytic activity for NO removal. Cupric ions on Ti-PILC were active reaction sites for the present reaction system. The state of copper species on the surface of Ti-PILC varied with the content of copper and TiO₂. The catalyst having more easily reducible cupric ions showed maximum NO conversion at relatively lower reaction temperatures. It indicates that the redox behavior of cupric ions is directly related to NO removal mechanism. The redox property of cupric ions depended on the copper content and dehydration temperature of PILC.     

Selective kinetic deactivation model for methanol synthesis from simultaneous reaction of CO2 and CO with H2 on a commercial copper/zinc oxide catalyst

A kinetic model for the deactivation of copper/zinc oxide catalyst during the methanol synthesis has been developed. This model is of the Langmuir-Hinshelwood-Hougen-Watson type and considers two types of active sites for the deactivation of catalyst. One of the site types on copper is allocated for the deactivation of the catalyst due to carbon dioxide while another type is assigned for the deactivation of the catalyst due to carbon monoxide. The parameters of the deactivation rate equations based on the above concept have been determined using the experimental data of Hoffmann (1993). The validity of the deactivation model has been checked by comparing the results predicted by the model with experimental data different than of those used to evaluate the parameters of the model. The good agreement that noticed in this comparison confirmed the idea that CO and CO₂ are responsible at different extent for the deactivation of Cu/ZnO catalyst during methanol synthesis.     

改性Raney Cu催化一乙醇胺脱氢合成甘氨酸

一乙醇胺在氢氧化钠的水溶液中〔w(NaOH)=12%～18%〕,用含有铬和锗等贵金属改性的RaneyCu催化剂脱氢合成甘氨酸。反应温度150～180℃,反应压力0 8～1 2MPa,反应时间2～4h。实验结果表明:改性RaneyCu催化剂比普通RaneyCu有更好的活性和使用寿命,使一乙醇胺的平均转化率从92%提高到97%,有效使用寿命(一乙醇胺的转化率≥90%)从5次延长到15次以上。     

Characterization of Copper Foam as Catalytic Material in Ethanol Dehydrogenation

Copper foam was used as a catalyst in ethanol dehydrogenation to acetaldehyde. Catalyst pretreatment, reaction temperature, liquid feed composition, and catalyst loading all affect ethanol conversion. Copper foam pretreated by oxidation yielded the highest ethanol conversion but deactivated due to copper surface reconstruction. The foam catalyst can be repeatedly reactivated by a short time exposure to air under reaction conditions. Yet, copper foam performance for ethanol dehydrogenation has been inferior in terms of activity and stability to that of supported copper catalysts.     

The role of surface oxygen on copper metal in catalysts for the synthesis of methanol

Discrepancies in experimental measurements of adsorbed oxygen coverage on copper metal surfaces in working Cu/ZnO/Al₂O₃ catalysts are interpreted in terms of two types of adsorbed oxygen. The first, O(a), is identical with that observed in studies of single‐crystal copper surfaces. The second, O^*(a), not seen in single‐crystal studies, is more strongly bonded to the metal surface. It is suggested that the adsorption sites of O^*(a) contain Zn as well as Cu, from surface α‐brass (copper/zinc alloy) formation during catalyst reduction. Earlier experimental results on O(a) coverages on various supported copper catalysts are re‐assessed. Only catalysts containing Zn (or Ga) gave abnormally high coverages: with other supports, basic or acidic, O(a) coverages are less than ∼0.1. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synergistic Solvent Extraction and Transport of Zn(II) and Cu(II) across Polymer Inclusion Membranes with a Mixture of TOPO and Aliquat 336

Separation of zinc(II) and copper(II) ions from aqueous solutions by synergistic extraction and transport through polymer inclusion membranes (PIMs) has been investigated. A mixture of trioctylphosphine oxide (TOPO) and trioctymethylammonium chloride (Aliquat 336) was used as a selective extractant as well as an ion carrier in polymer membranes. The effects of hydrochloric acid concentration in the aqueous phase and extractants concentration in the organic phase on the separation process of zinc(II) and copper(II) ions have been studied. Zn(II) ions were successfully separated from Cu(II) ions in solvent extraction process using 0.025 M TOPO and 0.06 M Aliquat 336 in kerosene. Polymer inclusion membranes (PIMs) containing a mixture of TOPO and Aliquat 336 as the ion carrier have been prepared and the facilitated transport of Zn(II) and Cu(II) ions has been studied. The influence of membrane composition on the transport kinetic of Zn(II) and Cu(II) has been evaluated. Zn(II) ions were preferably transported from the aqueous solutions containing Cu(II) and above 87% of Zn(II) ions were effectively recovered from the 0.5 M HCl solution as the source phase through PIM into 0.5 M H₂SO₄ as the stripping phase.     

Cu/SiO2 catalyst prepared by electroless method

Cu/SiO₂ catalysts prepared by an electroless deposition method were investigated and compared with those by an impregnation method. Copper contents varied from 5% to 15% and SiO₂ was used as support. All catalysts were characterized by BET, DSC, SEM and TPR and tested by an n-butanol dehydrogenation reaction for activities and stabilities. BET analysis showed that the catalysts prepared by the two methods present larger average pore size and less surface area than those of the fresh SiO₂, indicating that smaller pores may get blocked during the course of preparation. This blockage is more severe in the impregnation method. SEM photos showed that the electroless method produces smaller copper crystals than the impregnated method. The reaction activity was found to be in the order of the calcined electroless copper catalyst>the fresh electroless copper catalyst>impregnated copper catalyst. © 1998 Society of Chemical Industry     

Influence of various metal oxides in the bistability observed in the oxidative dehydrogenation of 2 — Propanol over copper catalysts

This article presents new results concerning a bistability phenomenon observed recently in the oxidative dehydrogenation of 2 - propanol over copper catalysts. In this system, an activity hysteresis loop is observed when the partial oxygen pressure is varied. This bistability has been explained by the oxidation of metallic copper when the partial oxygen pressure increases and copper oxide reduction when the partial oxygen pressure decreases. In the experiments reported here, an external second phase (α-Sb₂O₄, SnO₂, Cr₂O₃, CeO₂, Co₃O₄, MoO₃, PbO₂, NiO, Bi₂O₃ and MnO₂) has been mixed with the copper catalysts. This modifies the hysteresis loop. The possible role played by the oxygen spillover at low temperature (150°C) on this modification is discussed.     

Effect of manganese on Cu/SiO2 catalysts for the dehydrogenation of cyclohexanol to cyclohexanone

The effect of the addition of manganese to Cu/SiO₂ catalysts for cyclohexanol dehydrogenation reaction was investigated. At reaction temperature of 250 °C, the conversion and the selectivity to cyclohexanone were both increased with the addition of manganese to Cu/SiO₂ catalyst. However, as the reaction temperature was further increased, higher loading of manganese in Cu/SiO₂ catalyst led to a decrease in the conversion of cyclohexanol. Manganese in Cu/ SiO₂ catalyst decreased the reduction temperature of copper oxide, increased the dispersion of copper metal, and decreased the selectivity to cyclohexene. It was found that the dehydration of cyclohexanol to cyclohexene occurred on the intermediate acid sites of catalyst. At high Mn loading, catalyst surface was more enriched with manganese in used catalyst compared to that in freshly calcined or reduced catalyst, which may account for the sharp decrease of the conversion at high temperature of 390 °C. Upon reduction, copper manganate on silica was decomposed into fine particles of copper metal and manganese oxide (Mn₃O₄).     

Effect of chromium promoter on copper catalysts in ethanol dehydrogenation

A series of chromium-promoted copper catalysts with various Cr to Cu molar ratios were prepared with the co-precipitation method. The promotional effects of chromium on copper catalysts were examined by X-ray powder diffraction (XRD), nitrous oxide decomposition, and the dehydrogenation reaction of ethanol. The dehydrogenation reaction was carried out in a continuous-flow microreactor between 523 and 583 K under atmospheric pressure. The results indicated that the promotional effect was dependent on the Cr/Cu molar ratio, and the predominant decay of catalysts in this study was caused by sintering. The catalyst with the Cr/Cu molar ratio of 4/40 has the highest activity and stability. The surrounded well-dispersed chromia strongly influenced the catalytic properties of copper metal. It also showed that the over-promotation of a catalyst has a disastrous effect on the total make of product. The ethanol dehydrogenation reaction follows a first-order reaction, and the kinetics for deactivation can be described by a second-order expression.     

Characterization and oxidation states of Cu and Pd in Pd–CuO/ZnO/ZrO2 catalysts for hydrogen production by methanol partial oxidation

Copper and zinc oxide based catalysts prepared by coprecipitation were promoted with palladium and ZrO₂, and their activity and selectivity for methanol oxidative reforming was measured and characterized by N₂O decomposition, X-ray absorption spectroscopy, BET, X-ray photoelectron spectroscopy, X-ray diffraction, and temperature programmed reduction. Addition of ZrO₂ increased copper dispersion and surface area, with little effect on activity, while palladium promotion significantly enhanced activity with little change of the catalytic structure. A catalyst promoted with both ZrO₂ and palladium yielded hydrogen below 150 °C. EXAFS results under reaction conditions showed that the oxidation state of copper was influenced by palladium in the catalyst bulk. A palladium promoted catalyst contained 90% Cu⁰, while the copper in an unpromoted catalyst was 100% Cu¹⁺ at the same temperature. Palladium preferentially forms an unstable alloy with copper instead of zinc during reduction, which persists during reaction regardless of copper oxidation state. A 100-h time on stream activity measurement showed growth in copper crystallites and change in copper oxidation state resulting in decreasing activity and selectivity. A kinetic model of the reaction pathway showed that palladium and ZrO₂ promoters lower the activation energy of methanol combustion and steam reforming reactions.     

Photocatalytic Cyanide Oxidation from Aqueous Copper Cyanide Solutions over TiO2 and ZnO

The elimination of cyanide from aqueous copper cyanide solutions by oxidation under UV illumination using titanium oxide (TiO₂) and zinc oxide (ZnO) as catalyst has been investigated. The study has been carried out by determining the yield of cyanide elimination at different irradiation times, initial cyanide concentrations and pH. It has been observed that cyanide is photo-oxidised with higher yields in presence than in absence of copper in solution when TiO₂ is used as photocatalyst, while the opposite behaviour is reported when ZnO is the photocatalyst employed. This fact is related with the feasibility in which copper species are able to react with photogenerated electrons in the conduction band of the TiO₂ particles. Finally, the elimination of cyanide, both free and complexed, from a sample of an electroplating bath has also been studied. The results show that the photocatalytic method is very efficient in the elimination of cyanide in aqueous dilute solutions.     

Biguanide/Pd(OAc)2 immobilized on magnetic nanoparticle as a recyclable catalyst for the heterogeneous Suzuki reaction in aqueous media

Immobilization of Pd(II) ions on magnetite nanoparticle (MNP) has been simply achieved through a surface modification of Fe₃O₄ nanoparticle with a biguanide. This surface-modified nanoparticle was characterized by various techniques such as TEM, XRD, VSM, TGA, elemental analyzer, atomic absorption spectroscopy, N₂ adsorption–desorption (BET and BJH), and FT-IR. This nanosolid exhibits excellent catalytic activity for heterogeneous Suzuki reaction in aqueous media, and could be easily separated by an external magnet and reused for several times. TEM study of the recovered catalyst showed the preservation of the support core–shell structure and the good dispersion of the produced palladium nanoparticles.     

Recovery of Zinc Ions From the Resulting Solution after Copper Cementation with Metallic Zinc

In this study, recovering of zinc ions in the residual solution occurring after copper cementation by zinc metal was investigated. The zinc ions in the solution were recovered by using sodium bicarbonate as precipitation agent. After the precipitated product was separated from the solution, it was dried at 80°C for 5 h in an oven and was subjected to the calcination process to obtain zinc oxide. The XRD and SEM analyses of the precipitated and calcined products were carried out. It was determined that the precipitated solid was Zn₅(CO₃)₂(OH)₆ (hydrozincite) and the calcined product was ZnO.     

Development of New Cu0–ZnII/Al2O3 Catalyst Supported on Copper Metallic Foam for the Production of Hydrogen by Methanol Steam Reforming

Copper metallic foam with thermal conductive properties, manufactured by S.C.P.S., has been investigated as a support for catalysts to improve thermal exchange inside the reactor for the endothermic steam reforming of methanol. Thus, we have developed a procedure for the in situ preparation of a Cu⁰–Zn^II/Al₂O₃ catalyst onto the copper metallic foam. The foam-based Cu⁰–Zn^II/Al₂O₃ catalyst shows an activity three times as high as commercial catalysts for a conversion of 74% of methanol into hydrogen.     

The role of Cl− in a Li+-ZnO-Cl− catalyst on the oxidative coupling of methane and the oxidative dehydrogenation of ethane

The effect of Cl^? ion addition to a Li⁺-ZnO catalyst has been studied with respect to the oxidative coupling of CH₄ and the oxidative dehydrogenation (OXD) of C₂H₆. Increasing the Cl/Li ratio from 0.65 to 0.90 had relatively little effect on the CH₄ conversion, whereas the C₂H₄/C₂H₆ ratio was enhanced significantly as a result of an increase in the OXD reaction rate. Conversely, loss of Cl^? from the catalyst during the reaction had a much more deleterious effect on ethane OXD activity than on methane coupling activity. Addition of Cl^? ions at a Cl/Li ratio of 0.9 caused a decrease both in the number of basic sites and in the basic strength of these sites, as determined by temperature-programmed desorption of CO₂. The similarities between the results obtained over Li⁺-ZnO-Cl^? catalysts and those previously reported for Li⁺-MgO-Cl^? catalysts confirm that basicity of the host oxide plays only a minor role in determining the properties of these chlorided catalysts.     

Steam reforming of methanol using Cu-ZnO catalysts supported on nanoparticle alumina

Methanol steam reforming was studied over several catalysts made by deposition of copper and zinc precursors onto nanoparticle alumina. The results were compared to those of a commercially available copper, zinc oxide and alumina catalyst. Temperature programmed reduction, BET surface area measurements, and N₂O decomposition were used to characterize the catalyst surfaces. XRD was used to study the bulk structure of the catalysts, and XPS was used to determine the chemical states of the surface species. The nanoparticle-supported catalysts achieved similar conversions as the commercial reference catalyst but at slightly higher temperatures. However, the nanoparticle-supported catalysts also exhibited a significantly lower CO selectivity at a given temperature and space time than the reference catalyst. Furthermore, the turnover frequencies of the nanoparticle-supported catalysts were higher than that of the commercial catalyst, which means that the activity of the surface copper is higher. It was determined that high alumina concentrations ultimately decrease catalytic activity as well as promote undesirable CH₂O formation. The lower catalytic activity may be due to strong Cu-Al₂O₃ interactions, which result in Cu species which are not easily reduced. Furthermore, the acidity of the alumina support appears to promote CH₂O formation, which at low Cu concentrations is not reformed to CO₂ and H₂. The CO levels present in this study are above what can be explained by the reverse water-gas-shift (WGS) reaction. While coking is not a significant deactivation pathway, migration of ZnO to the surface of the catalyst (or of Cu to the bulk of the catalyst) does explain the permanent loss of catalytic activity. Cu₂O is present on the spent nanoparticle catalysts and it is likely that the Cu⁺/Cu⁰ ratio is of importance both for the catalytic activity and the CO selectivity.     

Influence of pH on the wet oxidation of phenol with copper catalyst

This work reports the influence of pH on the catalytic wet oxidation (CWO) of phenol performed with a commercial copper-based catalyst. The results obtained show that pH is a critical parameter able to modify the chemical stability of the catalyst, the significance of the oxidation reaction in the liquid phase, the reaction mechanism and, consequently, the oxidation route of phenol. Experiments have been carried out to study the mentioned aspects. Stirred basket and fixed bed reactors (FBRs) have been employed, at 140 °C and at 16 bar of oxygen pressure. Three initial pH values have been used: 6 (the pH of the phenol solution), 3.5 (adjusted by H₂SO₄) and 8 (by addition of Na₂CO₃). Furthermore, some phenol oxidation runs without solid catalyst but with different concentrations of copper in solution have been accomplish at pHo=3.5. At acid pH, important leaching of copper from the catalyst to the solution was achieved, finding this negligible at pH 8. It was found that the major contribution to the phenol conversion reached at acid pH by using the solid catalyst was due to the catalytic activity of the leached copper. Both oxidation mechanisms at acid and basic conditions have been elucidated to explain the differences in the type and distribution of the intermediates obtained. The catalytic phenol oxidation route found at pH=8 comprises intermediates less toxic than phenol while at acid pH the cyclic intermediates formed as first oxidation intermediates are far more toxic than phenol.     

A highly efficient Cu/ZnO/Al2O3 catalyst via gel-coprecipitation of oxalate precursors for low-temperature steam reforming of methanol

The impact of preparation methods on the structure and catalytic behavior of Cu/ZnO/Al₂O₃ catalysts for H₂ production from steam reforming of methanol (SRM) has been reported. The results show that the nanostructured Cu/ZnO/Al₂O₃ catalyst obtained by a novel gel-coprecipitation of oxalate precursors has a high specific surface area and high component dispersion, exhibiting much higher activity in the SRM reaction as compared to the catalysts prepared by conventional coprecipitation techniques. It is suggested that the superior catalytic performance of the oxalate gel-coprecipitation-derived Cu/ZnO/Al₂O₃ catalyst could be attributed to the generation of “catalytically active” copper material with a much higher metallic copper specific surface as well as a stronger Cu–Zn interaction due to an easier incorporation of zinc species into CuC₂O₄ · x H₂O precursors as a consequence of isomorphous substitution between copper and zinc in the oxalate gel-precursors.