A Pd–Fe/α-Al2O3/cordierite monolithic catalyst for CO coupling to oxalate

A novel Pd–Fe/α-Al₂O₃/cordierite monolithic catalyst was prepared for the synthesis of diethyl oxalate from CO and ethyl nitrite. The palladium-based monolithic catalyst with an optimal thickness (15 μm) of Al₂O₃ washcoat showed excellent catalytic activity and selectivity in a continuous flow, fixed-bed microreactor. The physicochemical properties of catalyst were studied by a variety of characterization techniques. Catalytic performances of Pd–Fe/α-Al₂O₃/cordierite monolithic catalysts were dependent on particle size of alumina-sol, thickness of Al₂O₃ washcoat, pore structure, surface acidity of carrier, and distribution of active metal component on the Al₂O₃ washcoat. Under the mild reaction conditions, CO conversion was 32% and the space–time yield of diethyl oxalate was 429 g/(L h). Pd efficiency (DEO(g)/Pd(g)/h) of the monolithic catalyst (274 h⁻¹) was much higher than that of a reference pellet catalyst (46 h⁻¹), probably due to high dispersion of the Pd nanoparticles on the surface of the monolithic catalyst.     

Effect of method of preparation on activity of Pd/Al2O3 monolith catalysts

Pd/Al₂O₃ monolithic catalyst of different washcoat thicknesses were prepared by two methods and tested for the activity of hydrogenation of α‐methyl styrene. These catalysts were prepared by two methods; either the palladium was impregnated on γ‐alumina and this Pd/Al₂O₃ powder was used to prepare the slurry for washcoating (Cat 1) or γ‐alumina washcoating was followed by impregnation of palladium (Cat 2). The effect of slurry concentration, pH of the slurry, and addition of binders on the catalyst properties was investigated. The monolithic catalysts were characterised by determination of metal dispersion, surface area, scanning electron microscopy, and weight loss of washcoat during ultrasonication. Well‐adhered washcoats were obtained with slurry prepared using milled γ‐alumina, whereas the adhesion of the washcoat prepared using Pd/Al₂O₃ powders was very poor. Addition of binders significantly improved the adhesion of the washcoats prepared from Pd/Al₂O₃. Metal dispersion for Cat 2 decreased with washcoat loading but did not change with loading for Cat 1. The activity tests were conducted at different washcoat loadings and the productivity of the monolithic catalyst prepared in both methods has been compared.     

Partial oxidation of ethanol over Pd/CeO2 and Pd/Y2O3 catalysts

The effect of the support nature on the performance of Pd catalysts during partial oxidation of ethanol was studied. H₂, CO₂ and acetaldehyde formation was favored on Pd/CeO₂, whereas CO production was facilitated over Pd/Y₂O₃ catalyst. According to the reaction mechanism, determined by DRIFTS analyses, some reaction pathways are favored depending on the support nature, which can explain the differences observed on products distribution. On Pd/Y₂O₃ catalyst, the production of acetate species was promoted, which explain the higher CO formation, since acetate species can be decomposed to CH₄ and CO at high temperatures. On Pd/CeO₂ catalyst, the acetaldehyde preferentially desorbs and/or decomposes to H₂, CH₄ and CO. The CO formed is further oxidized to CO₂, which seems to be promoted on Pd/CeO₂ catalyst.     

Effect of additives on Pd/Al2O3 for CO and propylene oxidation at oxygen-deficient conditions

The effects of additives, CeO₂ and K₂O, on Pd Al₂O₃ for CO and C₃H₆ oxidation under oxygen-deficient conditions were investigated. The unpromoted Pd Al₂O₃ exhibits the highest C₃H₆ conversion among the Pd catalysts, but its CO conversion is very low and even negative at the higher temperature . Nevertheless, the CO conversion on Pd Al₂O₃ can be significantly promoted by the addition of CeO₂ and K₂O. When water participates in the reaction, the CO conversions on the promoted Pd Al₂O₃ catalysts can be further increased. The promotional extent of CO conversion on the Pd catalysts is in the order: Pd-K₂O- - - . Moreover, Pd-K₂O-CeO₂ Al₂O₃ exhibits the highest CO conversion among the Pd catalysts. In addition, the test results of the monolithic catalysts also reveal that the CO conversion on PdRh K₂O Al₂O₃-CeO₂ is quite close to that on PtRh Al₂O₃-CeO₂ under the simulative gases and the ECE-40 mode driving cycle test. However, PdRh K₂O Al₂O₃-CeO₂ exhibits lower HC conversion due to the lower activity for alkane oxidation.     

Direct H2-to-H2O2 Oxidation in Aqueous Acidic Medium Containing Br Promoter Over Pd/Al2O3 and Pd/C Catalysts Thermally Pretreated Under Different Conditions

Influence of thermal pretreatments (under N₂, air or H₂ gas atmosphere at 500 °C or 700 °C) has been investigated for the Pd/Al₂O₃ and Pd/Carbon catalysts in terms of its effect on their Pd particle size and performance in the H₂-to-H₂O₂ oxidation and H₂O₂ destruction (by decomposition and/or hydrogenation) reactions in aqueous acidic medium containing Br promoter. The influence on the net H₂O₂ formation is found to depend strongly upon the catalyst support due to support–Pd cluster interactions. For both the catalysts, the thermal treatments (except in air) caused a large increase in their Pd particle size. The increase in Pd particle size caused an increase in the H₂O₂ formation activity of Pd/Al₂O₃ but a decrease in the H₂O₂ formation activity of Pd/C.     

Co–Pd/γ‐Al2O3 catalyst for heavy oil upgrading: Desorption kinetics,reducibility and catalytic activity

The influence of Pd on a Co–Pd/γ‐Al₂O₃ heavy oil upgrading catalyst is investigated using different physicochemical and reactive Characterization techniques. Nitrogen adsorption isotherm analysis shows that the specific surface area and porosity of the support alumina is significantly decreased due to the blockage of the pores by the loaded cobalt species. The estimated activation energy of NH₃ desorption is found to be less for Co–Pd/γ‐Al₂O₃ sample, which confirms improved acidity due to Pd. TPR experiments show that the reducibility of the catalyst is significantly improved with the presence of Pd. Higher metal dispersion and hydrogen spillover effects are the main reasons for the enhanced reducibility of the Pd promoted catalyst as revealed by the H₂‐pulse chemisorptions study. When evaluated using VGO as feed stock, the Co–Pd/γ‐Al₂O₃ displayed superiority both in hydrodesulphurisation (HDS) and hydrocracking (HC) activities as compared to the unpromoted Co/γ‐Al₂O₃ catalyst. The coke deposition on the spent catalyst is also found to be low due to the Pd promotional effects. This is an encouraging result, given that higher hydrogenation activity of the catalyst can be achieved without compromising the cracking activity and sustained activity of the catalyst.     

Steady State Isotopic Transient Kinetic Analysis of Flameless Methane Combustion over Pd/Al2O3 and Pt/Al2O3 Catalysts

The SSITKA measurements were performed in the steady state of complete methane oxidation on the Pd/Al₂O₃ and Pt/Al₂O₃ catalysts. It was found that the number of intermediates and their average life-time on the catalyst surface changes with the increase of reaction temperature. On the Pd/Al₂O₃ catalyst there is larger number of active centres than on Pt/Al₂O₃ catalyst which permits the course of methane oxidation at lower temperatures.     

Catalytic activity of Pd/Al2O3 toward the combustion of methane

This work focuses on the improving of the activities and stabilities of Pd/Al₂O₃ catalysts for lean methane catalytic combustion. The influence of preparation conditions on performance of Pd/Al₂O₃ catalyst has been studied. Results showed that excellent performance of the catalyst was attributed to high hydrothermal stability at the support calcination temperature of 1100 °C. In addition, the catalytic activity was enhanced due to high dispersion of active species at lower catalyst calcination temperature. The catalysts were studied by XPS analysis. Results showed that the active phase of Pd/Al₂O₃ was Pd or Pd/PdO mixture. And the state transformation of Pd species resulted in the deactivation of Pd/Al₂O₃.     

Fabrication of supported Pd–Ir/Al2O3 bimetallic catalysts for 2‐ethylanthraquinone hydrogenation

A series of χ wt % Pd‐(1‐χ) wt % Ir (χ = 0.75, 0.50, and 0.25) catalysts supported on γ‐Al₂O₃ have been prepared by co‐impregnation and calcination‐reduction, and subsequently employed in the hydrogenation of 2‐ethylanthraquinone—a key step in the manufacture of hydrogen peroxide. Detailed studies showed that the size and structure of the bimetallic Pd–Ir particles vary as a function of Pd/Ir ratio. By virtue of its small metal particle size and the strong interaction between Pd and Ir, the 0.75 wt % Pd–0.25 wt % Ir/Al₂O₃ catalyst afforded the highest yield of H₂O₂, some 25.4% higher than that obtained with the monometallic 1 wt % Pd catalyst. Moreover, the concentration of the undesired byproduct 2‐ethyl‐5,6,7,8‐tetrahydroanthraquinone (H₄eAQ) formed using the Pd–Ir bimetallic catalysts was much lower than that observed with the pure Pd catalyst, which can be assigned to the geometric and electronic effects caused by the introduction of Ir. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3955–3965, 2017     

Decomposition and oxidation of CH3 13CH2OH on A12O3, Pd/Al2O3, and PdO/Al2O3 catalysts

Temperature-programmed desorption (TPD) and oxidation (TPO) were used to investigate the decomposition and oxidation of ethanol on Al₂O₃, Pd/Al₂O₃, and PdO/Al₂O₃. Ethyl--¹³C alcohol (CH₃ ¹³CH₂OH) was adsorbed on the catalysts so that reaction pathways of the two carbons could be distinguished. Alumina was mainly a dehydration catalyst, but dehydrogenation was also observed and some carbon remained on the surface. In the presence of O₂, A1₂O₃ oxidized the decomposition products and the-carbon was oxidized faster. Ethanol, which was adsorbed on A1₂O₃, decomposed much faster on Pd/A1₂O₃ by diffusing to Pd and undergoing CO elimination to form CH₄,¹³CO, H₂, and surface carbon. On PdO/A1₂O₃, the decomposition was slower than on Pd/A1₂O₃ until lattice oxygen was extracted above 450 K; the decomposition products were oxidized by lattice oxygen. In the presence of gas phase O₂, Pd/Al₂O₃ was an active oxidation catalyst at low temperature, but lattice oxygen had to be extracted from PdO/A1₂O₃ before it had significant oxidation activity.     

Hydrogen Production from Partial Oxidation and Steam Reforming of N‐octane Over Alumina‐supported Ni and Ni‐Pd Catalysts

Hydrogen production by partial oxidation and steam reforming (POSR) of n‐octane was investigated over alumina‐supported Ni and Ni‐Pd catalysts. It showed that Ni‐Pd/Al₂O₃ had higher activity and hydrogen selectivity than the nickel catalyst under the experimental conditions, which indicated Ni‐Pd/Al₂O₃ could be an effective catalyst for the production of hydrogen from hydrocarbons.     

CO/FTIR Spectroscopic Characterization of Pd/ZnO/Al2O3 Catalysts for Methanol Steam Reforming

An as-synthesized 8.8wt% Pd/ZnO/Al₂O₃ catalyst was either pretreated under O₂ at 773 K followed by H₂ at 293 K or under H₂ at 773 K to obtain, respectively, a supported metallic Pd° catalyst (Pd°/ZnO/Al₂O₃) or a supported PdZn alloy catalyst (PdZn/ZnO/Al₂O₃). Both catalysts were studied by CO adsorption using FTIR spectroscopy. For the supported PdZn alloy catalyst (PdZn/ZnO/Al₂O₃), exposure to a mixture of methanol and steam, simulating methanol steam reforming reaction conditions, does not change the catalyst surface composition. This implies that the active sites are PdZn alloy like structures. The exposure of the catalyst to an oxidizing environment (O₂ at 623 K) results in the break up of PdZn alloy, forming a readily reducible PdO with its metallic form being known as much less active and selective for methanol steam reforming. However, for the metallic Pd°/ZnO/Al₂O₃ catalyst, FTIR results indicate that metallic Pd° can transform to PdZn alloy under methanol steam reforming conditions. These results suggest that PdZn alloy, even after an accidental exposure to oxygen, can self repair to form the active PdZn alloy phase under methanol steam reforming conditions. Catalytic behavior of the PdZn/ZnO/Al₂O₃ catalyst also correlates well with the surface composition characterizations by FTIR/CO spectroscopy.     

Complete Oxidation of Methane at Low Temperature over Pt Catalysts Supported on High Surface Area SnO2

The catalytic activity of Pt catalysts supported on high surface area tin(IV) oxide in the complete oxidation of CH₄ traces under lean conditions at low temperature was studied in the absence and in the presence of water (10 vol.%) or H₂S (100 vol.ppm). Their catalytic properties were compared to those of Pd/Al₂O₃ and Pt/Al₂O₃. In the absence of H₂S in the feed, Pt/SnO₂appears as a very promising catalyst for CH₄ oxidation, being even significantly more active under wet conditions than the best reference catalyst, Pd/Al₂O₃. Catalysts steamed-aged at 873 K were also studied in order to simulate long term ageing in real lean-burn NGV exhaust conditions. To this respect, Pt/SnO₂ is slightly less resistant than Pd/Al₂O₃. In the presence of H₂S, Pt/SnO₂catalysts are rapidly and almost completely poisoned, comparably to Pd/Al₂O₃and the catalytic activity is hardly restored upon oxidising treatment below 773 K. A synergetic effect between Pt and specific surface SnO₂sites active in CH₄oxidation is proposed to explain the superior catalytic behaviour of Pt/SnO₂.     

辉光放电等离子体增强制备甲烷催化燃烧的高分散Pd/Al2O3催化剂

A novel Pd/Al₂O₃ catalyst prepared by glow discharge plasma technology is reported.The results of H₂-chemisorption indicate that palladium dispersion of the plasma-prepared Pd/Al₂O₃ reaches 29.7%,which is about 5 times higher than Pd/Al₂O₃ prepared by conventional preparation.Meanwhile,the particle diameter of the plasma-prepared catalyst is 3.8 nm, but the particle diameter of the conventional catalyst is 20.4 nm.Such plasma-prepared Pd/Al₂O₃ catalyst shows a higher activity for catalytic combustion of methane than the conventional catalyst.Methane conversion reaches 90% at 400 ℃, but it is only near 30% for the conventional catalyst at the same temperature.     

Mathematical modeling of the partial hydrogenation of vegetable oil in a monolithic stirrer reactor

Experimental and theoretical studies on the partial hydrogenation of vegetable oil in a monolithic stirrer reactor are reported. A complete mathematical model of the reactor was developed, including hydrogenation and isomerization kinetics, catalyst deactivation, external gas–liquid and liquid–solid as well as internal mass transfer. The experimental studies were carried out in a Pd/Al₂O₃/Al monolithic stirrer reactor, at a wide range of temperatures (353–373 K), pressures (414–552 kPa), and catalyst loadings (0.00084–0.00527 kg_Pd,exp m^?3). Based on this model, simulated data can be used to evaluate the catalyst (Pd/Al₂O₃/Al) and the hydrogenation process in consecutive catalytic tests under different operating conditions. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3524–3533, 2014     

Ethanol reforming and partial oxidation with Cu/Nb2O5 catalyst

Ethanol reforming and partial oxidation were studied on Cu/Nb₂O₅ and Ni/Al₂O₃ catalysts. Compared to the Ni/Al₂O₃ catalyst, the Cu/Nb₂O₅ catalyst presents conversion as high as Ni/Al₂O₃ catalyst, however, for the same level of formation of hydrogen it occurs at much lower temperature on the Cu/Nb₂O₅ catalyst, 200 °C lower than for the Ni/Al₂O₃ catalyst, with remarkable little formation of CO, which can be attributed to the strong interaction between copper and niobia. Temperature-programmed desorption (TPD-ethanol) and surface reactions (TPSR) of partial oxidation of ethanol showed formation of ethylene, acetaldehyde, ethane and mainly H₂ and CO₂ besides little methane. DRIFTS results are in accordance with TPD analysis and the formation of acetate species at room temperature suggests reactivity of the surface and its oxidative dehydrogenation capacity. The adsorption of ethanol gives rise to ethoxide species, which form acetate and acetaldehyde that can be oxidized to CO₂ via carbonate. A comparison with reported results for Cu/Al₂O₃ this catalyst is promising, yielding high level of H₂ with little CO production during reforming and partial oxidation reaction. The maximum H₂ formation for the partial oxidation of ethanol was 41% at ratio (O₂/Et) 0.8, increasing to 50% at ratio 1.5. The H₂/CO is around 10 for the partial oxidation and 7 for steam reforming, which is excellent, compared to the Ni/Al₂O₃ catalyst with a factor 4–8 lower.     

Highly dispersed heterogeneous palladium catalysts by the introduction of plant tannin into porous Al2O3 supports

A new strategy was provided by the introduction of plant tannins in porous Al₂O₃ to solve the problems of thermal migration of Pd during catalyst preparation, which ensured the preparation of heterogeneous Pd catalysts with well dispersion and superior activity. Compared with the conventional Pd–Al₂O₃ catalyst, the as-prepared heterogeneous Pd catalyst exhibited considerably improved Pd dispersion, which was highly active for the catalytic hydrogenation of olefins.     

Transesterification of Soybean Oil Over Me/Al2O3 (Me = Na, Ba, Ca, and K) Catalysts and Monolith K/Al2O3-Cordierite

Four different Me/Al₂O₃ (Me = Na, Ba, Ca, and K) powder catalysts prepared by incipient-wetness impregnation, and a K/Al₂O₃-cordierite monolithic catalyst produced by the dipcoating technique were used for biodiesel production. The samples were characterized and studied in the transesterification of soybean oil with methanol at 120 °C and 500 rpm, with a alcohol/oil molar ratio = 32, and a catalyst load = 1 wt% for the powder catalyst and 0.5 wt% for the monolith. The Ca/Al₂O₃, Na/Al₂O₃ and K/Al₂O₃ powder catalysts reported a FAME (fatty acid methyl esters) formation of 94.7, 97.1, and 98.9% respectively after 6 h of reaction. On the other hand, Ba/Al₂O₃ showed little activity (7.6%). The leaching of the alkali and alkaline earth metal species during reaction was important, what indicates that the activity could be explained in terms of a homogeneous–heterogeneous catalyst effect. When the monolithic sample and the powder catalyst were compared (under identical reaction conditions), the production of FAME for the latter was 89.5–59.1% for the monolithic catalyst. After two consecutive runs, the monolithic catalyst presented a partial deactivation of 8% in the FAME yield. The present work shows that the use of monolithic catalysts in the transesterification of vegetable oils is a viable alternative.     

Characterization of Pd catalysts supported on USY zeolites with different SiO2/Al2O3 ratios for the hydrogenation of naphthalene in the presence of benzothiophene

A series of ultra-stable Y-type (USY) zeolites with different SiO₂/Al₂O₃ ratios in the range of 10–80 were used as supports for preparing Pd/USY at 2 wt% Pd loading. The FT-IR of hydroxyl groups of USY zeolites, the n-butylamine chemisorption and the temperature-programmed desorption were used in combination to characterize the zeolite acidity. TPR, H₂-TPD and chemisorption using H₂ were used to characterize the Pd reduction and dispersion. The hydrogenation of naphthalene was conducted at 200 °C in the presence of benzothiophene at different sulfur/metal ratios. The hydrogenation activity, selectivity, and the sulfur tolerance strongly depended on the SiO₂/Al₂O₃ ratio (thus the acidity) of the zeolites. The activity decreased with increasing SiO₂/Al₂O₃ in this range. The IR and n-butylamine TPD showed that both the amount and strength of Brönsted acidity decreased with the increase of the SiO₂/Al₂O₃ ratio. The good relationship between the acidity modification and catalytic performance suggests that the sulfur tolerance of Pd/USY zeolite might be due to the desired metal-support interaction, which resulted in larger amount of electron-deficient Pd. However, as shown in TGA and TPO-IR studies, the higher hydrogenation performance on more acidic zeolite also caused higher amount of carbonaceous species on the catalyst.     

吡啶改性Pd/SiO2催化剂用于H2和O2直接合成H2O2

引言过氧化氢(H2O2)是一种理想的绿色氧化剂,广泛应用于化学品合成、纺织、造纸、环保、食品、医药、冶金和农业等领域[1]。目前,蒽醌法[2-5]是工业上生产H2O2的主要方法。20世纪40年代,德国I.G.Farbenindustrie首先采用蒽醌法(又称Riedl-Pfleiderer法)工业化生产过氧化氢。该方法首先将2-烷基蒽醌(通常是2-乙基蒽醌)溶解于合适的有机溶剂中,溶液中的2-烷基蒽醌经催化剂催化加氢,被还原成蒽氢醌或5,6,7,8-四氢蒽氢醌,再经空气氧化得到蒽醌或四氢蒽醌和