Copper-impregnated Al–Ce-pillared clay for selective catalytic reduction of NO by C3H6

The selective catalytic reduction (SCR) of NO by hydrocarbon is an efficient way to remove NO emission from lean-burn gasoline and diesel exhaust. In this paper, a thermally and hydrothermally stable Al–Ce-pillared clay (Al–Ce-PILC) was synthesized and then modified by SO₄²⁻, whose surface area and average pore diameter calcined at 773 K were 161 m²/g and 12.15 nm, respectively. Copper-impregnated Al–Ce-pillared clay catalyst (Cu/SO₄²⁻/Al–Ce-PILC) was applied for the SCR of NO by C₃H₆ in the presence of oxygen. The catalyst 2 wt% Cu/SO₄²⁻/Al–Ce-PILC showed good performance over a broad range of temperature, its maximum conversion of NO was 56% at 623 K and remained as high as 22% at 973 K. Furthermore, the presence of 10% water slightly decreased its activity, and this effect was reversible following the removal of water from the feed. Py-IR results showed SO₄²⁻ modification greatly enhanced the number and strength of Brönsted acidity on the surface of Cu/SO₄²⁻/Al–Ce-PILC, which played a vital role in the improvement of NO conversion. TPR and XPS results indicated that both Cu⁺ and isolated Cu²⁺ species existed on the optimal catalyst, mainly Cu⁺, as Cu content increased to 5 wt%, another species CuO aggregates which facilitated the combustion of C₃H₆ were formed.     

High-throughput synthesis and screening of V–Al–Nb and Cr–Al–Nb oxide libraries for ethane oxidative dehydrogenation to ethylene

High-throughput synthesis and screening of mixed metal oxide libraries for ethane oxidative dehydrogenation to ethylene have been developed. A 144-member catalyst library was prepared on a 3 in. quartz wafer. An apparatus for screening catalytic activity and selectivity of a 144-member catalyst library consists of a reaction chamber, where each member can be heated individually by a CO₂ laser and reactant gases can be delivered locally to each member. The reaction products, ethylene and CO₂, are detected by photothermal deflection spectroscopy and by mass spectrometry. A 144-member catalyst library can be screened in slightly more than 2 h. V–Al–Nb oxide and Cr–Al–Nb oxide libraries are illustrated as examples. V–Al–Nb oxide catalysts are high temperature catalysts and Nb did not affect the catalytic activity of the V–Al oxides in contrast to the effect of Nb found in Mo–V–Nb oxides. However, for the Cr–Al–Nb oxide library, the most active catalyst contains about 4% Nb. These results suggest that a fine composition mapping is necessary for discovery of new heterogeneous catalysts in those ternary systems.     

A novel catalyst fabricated from Al–Cu–Fe quasicrystal for steam reforming of methanol

The optimum preparation condition of Al–Cu–Fe quasicrystalline (QC) catalyst with excellent catalytic performance for steam reforming of methanol (SRM) has been investigated. The QC alloy is superior to the other crystalline Al–Cu–(Fe) alloys (i.e., beta and theta phase) as a catalyst material because of the brittle nature of QC. The wet milling process (in ethanol) for the QC powders is much better than the dry milling process to obtain fine particles with high surface area. The QC powder prepared by the wet process followed by leaching in Na₂CO₃ aq. at 323 K exhibited the highest catalytic performance (activity and stability) in the present study. From these findings, it is clear that the QC catalyst with the excellent catalytic performance could be obtained by controlling the initial grain size of the QC powder and the leaching temperature.     

The difference in the active sites for CO2 and CO hydrogenations on Cu/ZnO-based methanol synthesis catalysts

The effect of Zn in copper catalysts on the activities for both CO₂ and CO hydrogenations has been examined using a physical mixture of Cu/SiO₂+ZnO/SiO₂ and a Zn-containing Cu/SiO₂ catalyst or (Zn)Cu/SiO₂. Reduction of the physical mixture with H₂ at 573–723 K results in an increase in the yield of methanol produced by the CO₂ hydrogenation, while no such a promotion was observed for the CO hydrogenation, indicating that the active site is different for the CO₂ and CO hydrogenations. However, the methanol yield by CO hydrogenation is significantly increased by the oxidation treatment of the (Zn)Cu/SiO₂ catalyst. Thus it is concluded that the Cu–Zn site is active for the CO₂ hydrogenation as previously reported, while the Cu–O–Zn site is active for the CO hydrogenation.     

Development of cobalt–copper nanoparticles as catalysts for higher alcohol synthesis from syngas

The synthesis of higher alcohols from syngas has been studied over different types of Cu-based catalysts. In order to provide control over the catalyst composition at the scale of a few nanometers, we have synthesized two sets of Co–Cu nanoparticles with novel structures by wet chemical methods, namely, (a) cobalt core–copper shell (Co@Cu) and (b) cobalt–copper mixed (synthesized by simultaneous reduction of metal precursors) nanoparticles. These catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The catalysts were tested for CO hydrogenation at temperatures ranging from 230 °C to 300 °C, 20 bar and 18,000 scc/(hr.gcat). It was observed that the Co–Cu mixed nanoparticles with higher Cu concentration exhibit a greater selectivity towards ethanol and C₂₊ oxygenates. The highest ethanol selectivity achieved was 11.4% with corresponding methane selectivity of 17.2% at 270 °C and 20 bar.     

碱金属对CO加氢制备低碳醇Cu-Fe-Co基催化剂的影响

考察了碱金属(Li、Na、K、Cs)对CO加氢制备低碳醇Cu-Fe-Co基催化剂反应性能的影响.研究发现:碱金属的添加能明显降低甲烷化反应,提高催化剂活性,使醇分布向碳链增长方向转移;碱金属Na的添加对催化剂活性的提高影响最大,与未添加碱金属的催化剂相比,液体产物中总醇质量分数提高45.98%,其中C2+醇和C5+醇在总醇中的摩尔分数分别提高了21.88%和22.89%,尾气中CH4摩尔分数下降42.83%.XRD结果表明,碱金属的加入使Cu、Fe、Co三种组分在载体上分散性加强,增加了CO与活性组分的接触位点从而使碳链增长;FE-SEM结果表明,碱金属Na的添加提高了催化剂孔隙结构和活性组分的均匀性和稳定性,同时减轻了催化剂积炭现象,提高了醇收率.     

Pitting corrosion of Al and Al–Cu alloys by ClO4 ions in neutral sulphate solutions

The influence of various concentrations of NaClO₄, as a pitting corrosion agent, on the corrosion behaviour of pure Al, and two Al–Cu alloys, namely (Al + 2.5 wt% Cu) and (Al + 7 wt% Cu) alloys in 1.0 M Na₂SO₄ solution was investigated by potentiodynamic polarization and potentiostatic techniques at 25 °C. Measurements were conducted under the influence of various experimental conditions, complemented by ex situ energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) examinations of the electrode surface. In free perchlorate sulphate solutions, for the three Al samples, the anodic polarization exhibits an active/passive transition. The active dissolution region involves an anodic peak (peak A) which is assigned to the formation of Al₂O₃ passive film on the electrode surface. The passive region extends up to 1500 mV with almost constant current density (j_pass) without exhibiting a critical breakdown potential or showing any evidence of pitting attack. For the three Al samples, addition of ClO₄⁻ ions to the sulphate solution stimulates their active anodic dissolution and tends to induce pitting corrosion within the oxide passive region. Pitting corrosion was confirmed by SEM examination of the electrode surface. The pitting potential decreases with increasing ClO₄⁻ ion concentration indicating a decrease in pitting corrosion resistance. The susceptibility of the three Al samples towards pitting corrosion decreases in the order: Al > (Al + 2.5 wt% Cu) alloy > (Al + 7 wt% Cu) alloy. Potentiostatic measurements showed that the rate of pitting initiation increases with increasing ClO₄⁻ ion concentration and applied step anodic potential, while it decreases with increasing %Cu in the Al samples. The inhibitive effect of SO₄²⁻ ions was also discussed.     

Theoretical studies of CO hydrogenation to methanol over Cu, Pd, and Pt metals

Theoretical studies of CO hydrogenation to methanol over Cu, Pd, and Pt metals have been carried out using a quasi‐relativistic density‐functional method. The metal surface is simulated by a M₁₀ cluster model. Reaction energies for the elementary steps involved are determined. The activation energies are estimated by the analytic BOC‐MP formula. The results support that these metals are active in CO hydrogenation to methanol. The rate‐determining steps are shown to be different for the metals. The highest activation energies of reaction on the metals fall in the order Cu < Pd < Pt, which corresponds to the order of the catalytic activities of the metals in CO hydrogenation. This revised version was published online in July 2006 with corrections to the Cover Date.     

High-performance Cu/MgO–Na catalyst for methanol synthesis via ethyl formate

A novel hybrid catalyst system containing alkali formate and Cu/MgO–Na was developed to synthesize methanol from syngas via ethyl formate in a slurry reactor. The results exhibited that high CO conversion (>80%) and methanol selectivity (90%) with a mass space velocity of 1800 L(STP)/(h kg) were achieved at a low temperature of 433 K and at 5.0 MPa. A synergic function between HCOOM (M = Li, Na, K, Rb and Cs) and Cu/MgO–Na was in existence for promoting the reaction performance, in which sodium formate showed the optimizing synergy with Cu/MgO–Na catalyst. In addition, the nature of the solid copper catalysts also had a remarkable influence on the catalytic activity.     

Au–Cu alloy nanoparticles supported on silica gel as catalyst for CO oxidation: Effects of Au/Cu ratios

Au–Cu bimetallic catalysts with Au/Cu ratios ranging from 3/1 to 20/1 were prepared on silica gel support by a two-step method. The catalysts were characterized by ICP, XRD and TEM. The results showed that, irrespective of Au/Cu ratios, all the bimetallic nanoparticles had significantly reduced particle sizes (3.0–3.6 nm) in comparison with monometallic gold catalysts (5.7 nm). Both CO oxidation and PROX reactions were employed to evaluate the catalytic activities of Au–Cu bimetallic catalysts. For CO oxidation, the alloy catalysts show non-monotonic temperature dependence showing a valley in the intermediate temperature range. The catalyst with Au/Cu ratio of 20/1 gave the highest activity at room temperature, but its activity showed the deepest valley with increasing the reaction temperature. On the other hand, the catalyst with Au/Cu ratio of 3/1 exhibited the best performance for PROX reaction. For the Au/Cu ratios investigated, the bimetallic catalysts showed superior performance to monometallic gold catalysts, demonstrating the synergy between gold and copper.     

Ethylene hydroformylation and carbon monoxide hydrogenation over modified and unmodified silica supported rhodium catalysts

Ethylene hydroformylation and carbon monoxide hydrogenation (leading to methanol and C₂-oxygenates) over Rh/SiO₂ catalysts share several important common mechanistic features, namely, CO insertion and metal–carbon (acyl or alkyl) bond hydrogenation. However, these processes are differentiated in that the CO hydrogenation also requires an initial CO dissociation before catalysis can proceed. In this study, the catalytic response to changes in particle size and to the addition of metal additives was studied to elucidate the differences in the two processes. In the hydroformylation process, both hydroformylation and hydrogenation of ethylene occurred concurrently. The desirable hydroformylation was enhanced over fine Rh particles with maximum activity observed at a particle diameter of 3.5 nm and hydrogenation was favored over large particles. CO hydrogenation was favored by larger particles. These results suggest that hydroformylation occurs at the edge and corner Rh sites, but that the key step in CO hydrogenation is different from that in hydroformylation and occurs on the surface. The addition of group II–VIII metal oxides, such as MoO₃, Sc₂O₃, TiO₂, V₂O₅, and Mn₂O₃, which are expected to enhance CO dissociation, leads to increased rates in CO hydrogenation, but only served to slow the hydroformylation process slightly without any effect on the selectivity. Similar comparisons using basic metals, such as the alkali and alkaline earths, which should enhance selectivity for insertion of CO over hydrogenation, increased the selectivity for the hydroformylation over hydrogenation as expected, although catalytic activity was reduced. Similarly, the selectivity toward organic oxygenates (a reflection of the degree of CO insertion) in CO hydrogenation was also increased.     

Cu/Zn/Al/Zr纳米纤维催化剂上的CO2加氢合成甲醇过程

A highly active Cu/Zn/Al/Zr fibrous catalyst was developed for methanol synthesis from CO₂ hydrogenation.Various factors that affect the activity of the catalyst,including the reaction temperature,pressure and space velocity,were investigated.The kinetic parameters in Graaf’s kinetic model for methanol synthesis were obtained.A quasistable economical process for CO₂ hydrogenation through CO circulation was simulated and higher methanol yield was obtained.     

THE PROMOTER EFFECT OF ALKALI METAL TO SUPPORTED IRON CATALYST IN CARBON MONOXIDE HYDROGENATION, THE INFLUENCE OF ALKALI ON CARBON DEPOSITIONS

The promoter effect of alkali metals on CO hydrogenation was studied on a series of silica supported iron catalysts. Mossbauer spectra of the catalysts show that iron is well dispersed on the silica support. The decrease in chemisorption of carbon monoxide on addition of promoters reveals that alkali covers part of the iron metal surface. The production of olefins, carbon dioxide and long chain hydrocarbons increases with decreasing ionization potentials of the alkali metals added. Hydrogenative decarbidation of catalysts after CO/H₂ reaction show that the hydrogenation of the carbon depositions on iron catalysts can be well explained by a series reaction model. The relative reactivity of carbon depositions on well dispersed iron catalysts are strongly affected under the influences of alkali. Addition of alkali metals to iron catalyst may depress the hydrogenation ability of the catalysts.     

Abatement of volatile organic compounds: oxidation of ethanal over niobium oxide-supported palladium-based catalysts

Niobium-supported palladium-based catalysts (Pd, Pd–Cu and Pd–Au) were employed in the oxidation of ethanal. The catalysts were prepared according to original methods by either multi-steps (anchoring of complexes, calcination and reduction) or one-step (photoassisted reduction) procedures. The oxidation of ethanal was carried out in gas phase in a dynamic-differential reactor at 300 °C at atmospheric pressure. The activity/selectivity of the catalysts depend on (i) the catalyst preparation; (ii) the presence of a second metal. Addition of Au or Cu decreases the catalysts deactivation and the best performance in total oxidation was obtained with Pd–Au/Nb₂O₅ prepared by photoassisted reduction. As shown by in situ IR spectroscopy of adsorbed CO, this peculiarity may be ascribed to Au→Pd electron donation, which prevents the surface oxidation of palladium particles.     

K2O影响Cu/ZnO催化剂CO2加氢反应性能的原因分析

运用活性评价、XRD、TPR、CO2-TPD、CO-TPD等手段,分析了K₂O影响Cu/ZnO催化剂CO₂加氢反应性能的原因。试验结果表明,甲醇收率大幅度降低的原因是CuO-ZnO催化剂经K₂O改性后,催化剂还原难度增加;提高了金属Cu的电子密度,促进了CO的歧化反应;催化剂还原后,对CO₂的吸附量大为减少。     

New insight in the solid state characteristics, in the possible intermediates and on the reactivity of Pd–Cu and Pd–Sn catalysts, used in denitratation of drinking water

Bimetallic palladium-based supported catalysts were tested in the liquid phase hydrogenation of nitrates. They were characterised by XPS, CO chemisorption, TPD–TPR and DRIFT. The effect of the preparation method, the support, the precursors, the relative amount of active metals and their role in the formation of intermediates and products are tentatively discussed. The catalytic activity and the formation of intermediate nitrite depend on the Pd–Cu ratio. Catalysts presenting a Pd/Cu atomic ratio >1 display the highest activity and the lowest intermediate nitrite than those presenting a Pd/Cu atomic ratio <1. Sol–gel method gives catalysts with a high activity and a low nitrite formation. The Pd–Cu-based catalyst supported on zirconia is more active and selective in N₂ compared to the corresponding Pd–Sn catalyst. An enrichment of the surface by Pd is responsible for a low intermediate nitrite formation and high selectivity in N₂. The reduction of NO is activated on Pd–Cu catalysts, contrary to Pd–Sn catalysts. Sn promotes the formation of ammonia.     

Hydrogenation of Sunflower Oil over M/SiO2 and M/Al2O3 (M = Ni,Pd, Pt,Co, Cu) Catalysts

This work is aimed at evaluating the performance of several catalysts in the partial hydrogenation of sunflower oil. The catalysts are composed of noble (Pd and Pt) and base metals (Ni, Co and Cu), supported on both silica and alumina. The following order can be proposed for the effect of the metal on the hydrogenation activity: Pd > Pt > Ni > Co > Cu. At a target iodine value of 70 (a typical value for oleomargarine), the production of trans isomers is minimum for supported nickel catalysts (25.7–32.4 %, depending on the operating conditions). Regarding the effect of the support, Al₂O₃ allows for more active catalysts based on noble metals (Pd and Pt) and Co, the effect being much more pronounced for Pt. Binary mixtures of catalysts have been studied, in order to strike a balance between catalyst activity and product distribution. The results evidence that Pd/Al₂O₃–Co/SiO₂ mixture has a good balance between activity and selectivity, and leads to a very low production of trans isomers (11.8 %) and a moderate amount of saturated stearic acid (13.5 %). Consequently, the utilization of cobalt‐based catalysts (or the addition of cobalt to other metallic catalysts) could be considered a promising alternative for the hydrogenation of edible oil.     

Nano-structured CeO2 supported Cu-Pd bimetallic catalysts for the oxygen-assisted water–gas-shift reaction

The present work focuses on the development of novel Cu-Pd bimetallic catalysts supported on nano-sized high-surface-area CeO₂ for the oxygen-assisted water–gas-shift (OWGS) reaction. High-surface-area CeO₂ was synthesized by urea gelation (UG) and template-assisted (TA) methods. The UG method offered CeO₂ with a BET surface area of about 215 m²/g, significantly higher than that of commercially available CeO₂. Cu and Pd were supported on CeO₂ synthesized by the UG and TA methods and their catalytic performance in the OWGS reaction was investigated systematically. Catalysts with about 30 wt% Cu and 1 wt% Pd were found to exhibit a maximum CO conversion close to 100%. The effect of metal loading method and the influence of CeO₂ support on the catalytic performance were also investigated. The results indicated that Cu and Pd loaded by incipient wetness impregnation (IWI) exhibited better performance than that prepared by deposition–precipitation (DP) method. The difference in the catalytic activity was related to the lower Cu surface concentration, better Cu–Ce and Pd–Ce interactions and improved reducibility of Cu and Pd in the IWI catalyst as determined by the X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) studies. A direct relation between BET surface area of the CeO₂ support and CO conversion was also observed. The Cu-Pd bimetallic catalysts supported on high-surface-area CeO₂ synthesized by UG method exhibited at least two-fold higher CO conversion than the commercial CeO₂ or that obtained by TA method. The catalyst retains about 100% CO conversion even under extremely high H₂ concentration.     

CO and CO2 hydrogenation study on supported cobalt Fischer–Tropsch synthesis catalysts

The conversion of CO/H₂, CO₂/H₂ and (CO+CO₂)/H₂ mixtures using cobalt catalysts under typical Fischer–Tropsch synthesis conditions has been carried out. The results show that in the presence of CO, CO₂ hydrogenation is slow. For the cases of only CO or only CO₂ hydrogenation, similar catalytic activities were obtained but the selectivities were very different. For CO hydrogenation, normal Fischer–Tropsch synthesis product distributions were observed with an of about 0.80; in contrast, the CO₂ hydrogenation products contained about 70% or more of methane. Thus, CO₂ and CO hydrogenation appears to follow different reaction pathways. The catalyst deactivates more rapidly for the conversion of CO than for CO₂ even though the H₂O/H₂ ratio is at least two times larger for the conversion of CO₂. Since the catalyst ages more slowly in the presence of the higher H₂O/H₂ conditions, it is concluded that water alone does not account for the deactivation and that there is a deactivation pathway that involves the assistance of CO.     

Gas phase hydrogenation of ortho-chloronitrobenzene (O-CNB) to ortho-chloroaniline (O-CAN) over unpromoted and alkali metal promoted-alumina supported palladium catalysts

A series of alkali metals (Li, Na, K and Cs) promoted alumina-supported palladium catalysts were prepared by a wet impregnation method and characterized by X-ray diffraction (XRD) and CO chemisorption measurements. The samples were tested for the gas phase hydrogenation of ortho-chloronitrobenzene (O-CNB) to ortho-chloroaniline (O-CAN) in a fixed-bed micro reactor at 250 °C under normal atmospheric pressure. The promoted-Pd/Al₂O₃ catalysts show higher conversion for O-CNB and the hydrogenation activity of O-CNB per site decreases with the increasing ionic radius of the alkali metal promoter ions. However, the selectivity for O-CAN remains more or less the same in both unpromoted and promoted catalysts and also irrespective of the nature of the alkali metal promoter ions used for promotion of alumina support. Despite, similar activity and selectivity observed between Li- and Na-promoted Pd/Al₂O₃ catalysts, the Na-promoted showed higher resistance for coke formation than a Li-promoted catalyst. The increase in the intrinsic activity of palladium site on alkali promotion has been attributed to the increase in hydrogenation activity over promoted catalysts.