Supported nanocomposite catalysts for high-temperature partial oxidation of methane

In order to utilize the vast potential of nanoparticles for industrial catalysis, it is necessary to develop methods to stabilize these particles at realistic technical conditions and to formulate nanoparticle-based catalysts in a way that facilitates handling and reduces health and safety concerns. We have previously demonstrated that metal nanoparticles can be efficiently stabilized by embedding them into a high-temperature stable nanocomposite structure. Building onto these results, we report here on the next step towards a simple, hierarchically structured catalyst via supporting platinum barium-hexaaluminate (Pt-BHA) nanocomposites onto a range of different conventional and novel support structures (monoliths, foams, and felts). The catalysts were characterized via SEM, TEM, XRD, porosimetry, chemisorption, and reactive tests in catalytic partial oxidation of methane to synthesis gas (CPOM), and compared to conventionally prepared Pt-catalysts. In particular silica felt supported Pt-BHA showed excellent activity and selectivity combined with good stability and very low noble metal requirement at the demanding high-temperature conditions of short-contact time CPOM. Overall, we see great potential for these supported nanocomposite catalysts for use in demanding environments, such as high-temperature, high-throughput conditions in fuel processing and similar energy-related applications.     

Supported Rh catalysts for the indirect partial oxidation of isooctane

The production of hydrogen from isooctane over three rhodium-based catalysts has been examined. The reaction entailed total oxidation of a proportion of the fuel followed by reforming of isooctane to produce hydrogen. Rhodium (1% wt) was impregnated on three different supports: alumina, ceria-alumina, and ceria-zirconia. No differences in catalytic activity were observed, but reaction yield changed with the support. Ceria-zirconia was found to be the preferred support since methanation did not occur over the catalyst.     

Supported foam–copper catalysts for methanol selective oxidation

Structural, mechanical, gas-dynamic and catalytic properties of copper catalysts supported on foam ceramics have been studied. Due to the three-dimensional open-porous cellular structure the foam catalysts have high gas permeability, mechanical strength, and low density. Catalytic activity and selectivity of the foam catalysts in the process of oxidation of methanol to formaldehyde exceed the characteristics of the conventional crystalline and granulated catalysts of the same composition. Different electronic states (ions, charged clusters, nanoparticles and microcrystals) of copper on the catalyst surface have been studied by the method of UV–Vis spectroscopy.     

Supported Co-based perovskites as catalysts for total oxidation of methane

Supported LaCoO₃ perovskites with 2, 5, 10, 15, 20 and 30 wt.% loading were prepared by impregnation of a Ce_0.8Zr_0.2O₂ support (40 m² g⁻¹) with: (i) a solution of La and Co nitrates and (ii) a “citrate” solution, namely containing La and Co nitrates, and citric acid. All precursors were decomposed and calcined at 700 °C for 5 h. XRD investigations indicated the formation of a pure perovskite phase only if citrates were used. These materials were tested as catalysts for methane combustion in the temperature range 300–700 °C. All catalysts showed a lower T₅₀ (the temperature at which the conversion level of methane is 50%) than the Ce_0.8Zr_0.2O₂ support or non-supported LaCoO₃. The activity increased continuously with the perovskite loading. The samples prepared from citrates were slightly more active than from nitrates. This is due to a more homogeneous surface, as indicated by XPS measurements. The presence of a well-characterized perovskite phase (as opposed to highly dispersed elements) seems necessary for good activity. A higher reaction rate per perovskite weight is observed for low loadings when compared to bulk LaCoO₃, but the variation with perovskite loading presents a breakpoint, suggesting complex interactions in the catalysts or in the oxidation mechanism.

In spite of the experimental impossibility to evaluate the area developed by the supported perovskite, an approximative approach strongly suggests a synergy between the support and supported species.     

Novel supports for nickel-based catalysts for the partial oxidation of methane

Zirconia-supported nickel catalysts with different amounts of aluminum (Al/Zr = 0.2, 1 and 2) were studied in this work in order to find alternative supports for nickel-based catalysts for the partial oxidation of methane. This reaction is a promising route for producing hydrogen and syngas for different applications. Samples were prepared by precipitation and impregnation techniques, characterized by several techniques and evaluated in the partial oxidation of methane in the range of 450–750 °C and 1 atm. It was found that aluminum affects the textural and catalytic properties of zirconia-supported nickel catalysts. The tetragonal phase of zirconia was stabilized by aluminum and gamma-alumina was also found in the aluminum-richest samples. Aluminum increased the porosity and the specific surface area of the solids. The catalytic activity also increased with the amount of aluminum in solids probably due to the stronger interaction of nickel with the support, which slowly generates active sites during the reduction step. The methane conversion and hydrogen selectivity increased with temperature, indicating no deactivation. The hydrogen to carbon monoxide molar ratio decreased due to aluminum but was not significantly affected by temperature. The coke produced was not harmful to the catalysts and aluminum affected its amount, although no simple relationship was found between these parameters. The most promising catalyst was the sample with aluminum to zirconium molar ratio of 2, which showed high activity and hydrogen selectivity and was stable under the reaction condition.     

Polyethylene carboxylate-bound triruthenium clusters as alcohol oxidation catalysts

We have found that addition of polyethylene oligomers containing a terminal carboxylic acid group to solutions of [(CH₃CH₂CO₂)₆Ru₃O(H₂O)₃] ⁺CH₃CH₂CO₂⁻ allows us to recover quantitatively and reuse this ruthenium cluster as a catalyst for oxidation of primary and secondary alcohols with oxygen.     

Propane partial oxidation to acrolein over combined catalysts

A novel approach for the partial oxidation of propane to acrolein, based on the use of layers of combined catalysts in a single reactor, provides good yields of acrolein with selectivity above 62%. The results depend strongly on the layer configuration, and reveal new mechanistic features for the process. This revised version was published online in August 2006 with corrections to the Cover Date.     

过渡金属氧化物修饰的金纳米催化剂苯甲醇氧化性能

采用一步法合成介孔二氧化硅负载的金纳米催化剂,以氯化锡为前驱体,通过浸渍法向金纳米催化剂中引入助剂氧化锡,得到过渡金属氧化物修饰的金纳米催化剂。通过N2吸附-脱附、X射线衍射、透射电镜和固体紫外漫反射光谱等对催化剂结构进行表征。将所合成的催化剂用于苯甲醇选择性氧化反应,考察助剂组分对催化剂性能的影响,结果表明,氧化锡的引入改变了金纳米颗粒的表面电子结构,增加了催化剂活性与选择性;但随着氧化锡含量继续增加,催化剂活性降低,这主要是因为金纳米颗粒表面过渡金属氧化物覆盖度增加,减少了催化剂活性组分与苯甲醇的接触。当氧化锡质量分数0.2%时,催化剂效果最佳,在100℃和氧气压力0.2 MPa下反应3 h,苯甲醇转化率25.7%,苯甲醛选择性75.9%,苯甲酸选择性15.8%,苯甲酸苄酯选择性6.3%。     

Supported Rh catalysts for methane partial oxidation prepared by OM-CVD of Rh(acac)(CO)2

The organometallics chemical vapour deposition (OM-CVD) technique, using Rh(acac)(CO)₂ as a precursor, was employed for the preparation of heterogeneous Rh catalysts supported on low surface area refractory oxides (α-Al₂O₃, ZrO₂, MgO and La₂O₃). Prepared systems were tested in the methane catalytic partial oxidation (CH₄-CPO) reaction in a fixed bed reactor and compared to a reference catalyst prepared from impregnation of Rh₄(CO)₁₂.Catalysts supported on Al₂O₃, ZrO₂ and MgO show better or comparable performances with respect to the reference system.Complete decomposition of Rh precursor during formation of the metal phase under reductive conditions was investigated by TPRD and confirmed by infrared and mass spectrometry data.Supported Rh phase was characterized by CO and H₂ chemisorption, CO-DRIFT spectroscopy and HRTEM microscopy in fresh and aged selected samples. Rh(I) isolated sites and Rh(0) metal particles were found on fresh catalysts; after ageing an extensive reconstruction occurs mainly consisting in a sintering of Rh isolate sites to metal particles but without large increase in mean particles size.Catalytic performances and Rh species balance were found to be dependent on the support material.     

Methanol partial oxidation on carbon-supported Pt and Pd catalysts

Different Pt and Pd catalysts supported on an activated carbon were prepared by using different metal precursors. Prepared catalysts were pretreated at 400 °C under different atmospheres to decompose the precursor compound and reduce the metal. After pretreatments, the supported catalysts were characterized by H₂ chemisorption, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy to know their metal dispersion, particle size, distribution and oxidation state. Afterwards, the catalysts were tested in methanol partial oxidation with two different O₂/CH₃OH molar ratios. Results obtained in this reaction were compared with those obtained for methanol decomposition in inert atmosphere. For Pt catalysts, there was an increase in methanol conversion and hydrogen production and a decrease in carbon monoxide production under oxidizing conditions. Both methanol conversion and partial oxidation reactions appear to be sensitive to Pt particle structure in the particle size range studied. Results obtained under oxidizing conditions differed between Pd and Pt catalysts. Finally, catalytic activity in methanol partial oxidation was more affected by Pt than Pd particle size in the size range studied.     

New catalytic system for oxidation of isopropyl alcohol with thin film catalysts

This paper describes a new catalytic system developed to study catalysts deposited as thin films on a metallic support. This device uses the electromagnetic induction for heating the metallic support. Therefore, it enables homogeneous sample heating, up to 400 °C·min^− 1 with a good regulation and a very low thermal inertia allowing fast cooling and accurate hold on temperature plateau. Catalysts SnO₂, 0.3 and 1 wt.% Pt on SnO₂ were deposited on stainless steel by an electrophoretic technique and evaluated in the abatement of isopropyl alcohol in air, a common model for VOCs.     

负载贵金属催化剂在挥发性有机物氧化反应中的应用

挥发性有机物(VOCs)是大气污染的主要来源,危害人体健康。催化氧化法是消除挥发性有机物的有效手段,其核心是高效催化剂,新型、高活性、高稳定性催化剂的研发具有重要意义。简要综述近年来负载Au、Pd和Pt贵金属催化剂对VOCs氧化消除的催化性能,分析VOCs氧化在典型催化剂表面形成的活性物种及其对催化活性的影响,并展望VOCs催化氧化的未来发展趋势。     

Supported heteropolycompounds as ecofriendly catalysts for 2,6-dimethylphenol oxidation to 2,6-dimethyl-1,4-benzoquinone

Supported catalysts were prepared by in situ deposition of the cesium salt of H₄PMo₁₁VO₄₀. Commercial silica was impregnated to incipient wetness with an aqueous solution of CsNO₃. The dried and calcined solid was then impregnated an aqueous solution of H₄PMo₁₁VO₄₀. Solids with 40% and 7% (w/w) of Cs₃HPMo₁₁VO₄₀ were obtained. To compare on behavior catalytic, a catalyst was prepared by silica impregnation with an aqueous solution of H₄PMo₁₁VO₄₀ (40%, w/w), using the incipient wetness technique. Impregnated silica particles showed a homogeneous distribution by scanning electron microscope (SEM). The Keggin structure was preserved for the salt in those catalysts according to the FT-IR and DRS characterization. The acidity of the solids with 40% and 7% (w/w) of Cs₃HPMo₁₁VO₄ was greater than that of the silica but lower than that of bulk salt. The catalysts were used in the oxidation of 2,6-dimethylphenol with aqueous hydrogen peroxide, in acetonitrile at 20 °C. The reaction was followed by UV–vis spectroscopy. The phenol conversion was 35% at 4 h for H₄PMo₁₁VO₄₀/SiO₂, 20% at 2 h and 29% at 135 h for 7% Cs₃HPMo₁₁VO₄/SiO₂, and 83% at 98 h for 40% Cs₃HPMo₁₁VO₄/SiO₂. The behavior of the latter was also studied by HPLC technique. Similar results were achieved with both techniques. The Cs₃HPMo₁₁VO₄/SiO₂ catalysts were almost totally insoluble in the reaction mixture.     

Low-temperature mild partial oxidation of ethanol over supported platinum catalysts

Supported platinum catalysts containing 1.2% Pt loaded on Al₂O₃ (1.2% Pt/Al₂O₃) and 1.9% Pt loaded on ZrO₂ (1.9% Pt/ZrO₂) were prepared by incipient wetness impregnation and sol–gel method, respectively. The activity of these catalysts in the partial oxidation of ethanol (POE) was examined in a fixed-bed reactor in a temperature range between 373 and 473 K. The results indicated that significant ethanol conversion (C_EtOH > 50%) was found at the low reaction temperature with a feed ratio of O₂/EtOH ratio >0.75. Oxygen molecules introduced in reactant were completely consumed in POE reactions performed. H₂, H₂O, CO and CO₂ were the major products detected. The selectivity of hydrogen (S_H2) and CO (S_CO) varied significantly with reaction conditions. High selectivity of hydrogen (S_H2 > 95%) and low selectivity of CO (S_CO  0%) were found from a mild oxidation at T_R = 373 K over Pt/ZrO₂. However, these two selectivities were drastically deteriorated through oxidation at high T_R, high O₂/EtOH ratio or over Pt/Al₂O₃ catalyst.     

甲烷部分氧化及重整反应多相催化剂的研究进展

介绍国内外甲烷制合成气技术中多相催化剂的研究进展,包括催化剂在水蒸气重整、甲烷部分氧化和二氧化碳重整制合成气技术中的研究情况,重点评述了催化剂的活性组分、助剂和载体方面的研究进展及存在的问题。     

载体对Au-Pd催化剂甲醇部分氧化性能的影响

采用沉积沉淀法制备了一系列Au-Pd双金属催化剂,研究了不同载体对Au-Pd双金属催化剂甲醇部分氧化性能的影响,并运用XRD、TPD和TPR等手段对催化剂进行了表征。结果表明,Au-Pd/CeO₂催化剂中形成的Au_xPd_y合金和氧空穴较多,致使Au-Pd/CeO₂催化剂的活性较高;CeO₂-TiO₂和CeO₂-ZrO₂复合载体较大的比表面积和固溶体的形成有利于H₂选择性的提高;Au-Pd/CeO₂-ZrO₂和Au-Pd/CeO₂-TiO₂催化剂有较高H₂产率的主要原因是H₂选择性的提高。     

催化湿式氧化法处理糖蜜酒精废液的催化剂研制

以非贵金属Cu、Fe、Mn、Ce为主要活性成分和TiO2、γ-Al2O3为载体制备催化剂,在高温高压下进行催化湿式氧化处理糖蜜酒精废液的试验,考察了载体、焙烧温度、成分配比对催化剂催化活性与稳定性的影响。结果表明:催化剂Fe-Mn/γ-Al2O3(摩尔比3:1:1)的催化效果好,金属离子溶出量低,且连续使用效果也较好。     

Promotion of palladium-based catalysts on metal monolith for partial oxidation of methane to syngas

Four different modifications of alumina were prepared for use as the support for a Pd catalyst used for the partial oxidation of methane to syngas. The catalysts were washcoated on a metallic monolith in order to determine their activities at high gas flow rates. Compared with the Pd/Al₂O₃ catalyst, enhanced partial oxidation activities were observed with the Pd/CeO₂/Al₂O₃, Pd/CeO₂/BaO/Al₂O₃ and Pd/CeO₂/BaO/SrO/Al₂O₃ catalysts. The palladium particles were better dispersed in the presence of CeO₂ and SrO. Adding BaO, CeO₂ and BaO–CeO₂ to γ-Al₂O₃ prevented the transformation of the alumina phase during the 3-day aging process at 1000 °C, providing the support with some level of thermal stability. The addition of small amounts of SrO to the CeO₂/BaO/Al₂O₃ support enhanced the thermal stability of the Pd particles and minimized their sintering. The triply promoted Pd catalyst studied in this work was effective in carrying out partial oxidation at high temperatures, with BaO and CeO₂ promoting the thermal stability of the support, CeO₂ and SrO dispersing the Pd particles and SrO anchoring the Pd particles strongly to the support. The composition of the catalyst which gave both the highest partial oxidation activity and the best thermal stability was Pd(2)/CeO₂(23)/BaO(11)/SrO(0.8)/Al₂O₃.     

Structure and activity of Sn-Mo-O catalysts: partial oxidation of methanol

This work deals with the catalytic behavior of a series of Sn-Mo-O catalysts in the partial oxidation of methanol. The catalysts of different Sn:Mo ratios, were prepared by co-precipitation and they were investigated by means of dynamic experiments, test reactions (methanol–formaldehyde partial oxidation, isopropyl alcohol decomposition) and physico-chemical characterization (XRD, BET, TPD of NH₃, TPR, XPS and EPR).It was observed that interdispersion between MoO₃ and SnO₂ favors a superficial architecture in which the Sn-Mo interaction plays a major role modifying the reactivity of the lattice oxygens and the reducibility of Mo ions and, therefore, the catalytic behavior. The partial oxidation of methanol induces a reordering of the catalyst structural organization leading to a Mo surface enrichment. The absence of chemical shifts for Sn (XPS) suggests that the O–Mo bond is mainly responsible for the methanol reaction.