Propane combustion over supported Pd catalysts

We prepared Pd catalysts supported on various metal oxides, viz. γ-Al₂O₃, α-Al₂O₃, SiO₂–Al₂O₃, SiO₂, CeO₂ and TiO₂ by an incipient wetness method and applied them to propane combustion. Several techniques: N₂ physisorption, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), CO chemisorption, temperature-programmed reduction (TPR) and temperature-programmed oxidation (TPO) were employed to characterize the catalysts. Pd/SiO₂–Al₂O₃ showed the least catalytic activity at high temperatures among Pd catalysts supported on irreducible metal oxides, viz. SiO₂, Al₂O₃ and SiO₂–Al₂O₃. Pd/γ-Al₂O₃ was much superior for this reaction to Pd/α-Al₂O₃. The Pd catalyst supported on reducible metal oxides (CeO₂ and TiO₂) with a less specific surface area showed the higher catalytic activity compared with that supported on reducible metal oxides with a higher specific surface area, even though the former had a less Pd dispersion than the latter. In the case of Pd/SiO₂–Al₂O₃, the initially reduced Pd catalyst was superior to the fully oxidized one. The oxidation of metallic Pd occurred in the presence of O₂ with increasing reaction temperature, which resulted in the change in the catalytic activity.     

Propane aromatization over Pt?Sn/ZSM-5 catalysts

Addition of Sn modifies the catalytic performance of Pt/ZSM-5. Total conversions decrease with increasing Sn/Pt ratio. Selectivity to aromatics is higher on the Pt–Sn samples. A Pt–Sn interaction has been confirmed by H₂ chemisorption and TPR experiments.

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Sn Pt/ZSM5. Sn/Pt . Pt–Sn. Pt–Sn H₂ .

     

Ring opening of ehtylcyclopentane over supported Pt catalysts

Ring opening of ethylcyclopentane (ECP) was studied over 6.3% Pt/SiO₂ (EUROPT-1) and 10% Pt/Al₂O₃, as a function of the hydrogen pressure. Both catalysts gave almost nonselective ring opening. Pt/Al₂O₃ produced also olefins, more side dealkylation and less fragmentation products. It is likely, that adlineation sites are operative over both catalysts.

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6,3% Pt/SiO₂ (EUROPT-1) 10% Pt/Al₂O₃, . . Pt/Al₂O₃ . , .

     

n-Hexane dehydrocyclization over Pt?Ni supported on alumina catalysts

Pt–Ni/-Al₂O₃ catalysts have been prepared and studied in n-hexane dehydrocyclization. The selectivity for benzene and toluene, a chain lengthening product formation was improved by Ni and correlated with its content.

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Pt–Ni/-Al₂O₃ -. Ni . Ni , .

     

载体对负载型NiSn催化剂丙烷脱氢性能的影响

研究了载体对负载型Ni Sn催化剂丙烷脱氢性能的影响,主要对比考察了以Si O2、Mg O、Al2O3、Mg Al2O4为载体的Ni Sn催化剂的丙烷脱氢性能。采用X射线衍射技术(XRD)、氮气吸附-脱附技术、氨气程序升温脱附技术(NH3-TPD)以及氢气程序升温还原技术(H2-TPR)对催化剂样品进行表征。结果表明,Si O2因具有较大的比表面积、大孔径、酸性较弱等特点,以其为载体制备所得催化剂中Ni2.67Sn2组分含量高,催化剂性能较高。     

Propane formation by aqueous-phase reforming of glycerol over Pt/H-ZSM5 catalysts

Solid acid supports such as H-ZSM5, H-Mordenite, γ-Al₂O₃, USY and Beta catalysts were modified with Pt. These Pt/oxide catalysts were found to be active for propane formation through aqueous reforming of glycerol in the presence of hydrogen. The reforming reactions, possibly, proceeded through reaction cycles of dehydration on acid sites and hydrogenation on Pt sites over the catalysts.     

负载型钯催化剂上生物质气化气催化燃烧

采用浸渍法制备了Pd/Al2O3、Pd/Ce/Al2O3、Pd/Mn/Al2O3、Pd/La/Al2O3四种催化剂。并借助XRD、BET对催化剂相结构、比表面积、孔结构进行了表征,在固定床反应器上考察了四种催化剂对CO、H2和CH4的催化燃烧性能。结果表明,随着La、Ce、Mn离子的引入使得催化剂的比表面积和孔容积不断降低;添加助剂Ce可以提高催化剂活性和热稳定性,助剂La可以提高催化剂的抗烧结能力,而助剂Mn在低温时可以提高催化剂活性,但并不能抑制催化剂的高温钝化。CO和H2的起燃顺序随催化剂的不同而不同,但四种催化剂对CO和H2的催化燃烧活性接近,均可以在低温条件下迅速燃烧,同时其燃烧特征温度明显低于CH4。     

Hydrogenation of chloronitrobenzenes over Pd and Pt catalysts supported on cationic resins

Liquid phase hydrogenation of chloronitrobenzene isomers (x-CNB x = 2, 3, 4) to the corresponding chloroanilines (x-CAN) at mild reaction conditions (0.6 MPa, 25°C, diethyl ether-methanol as solvents) over palladium and platinum catalysts containing 1 mass % of metal on trimethylammonium functionalized poly{styrene-co-divinylbenzene} (Dowex-D) was studied. The average selectivities to x-CAN over Pd/D-Cl and Pd/D-OH catalysts were 72 % and 42 %, respectively, at the x-CNB conversion of about 80 %. The average selectivities of 81 % and 84 % were achieved using Pt/D-Cl and Pt/D-OH, respectively, at the x-CNB conversion of approximately 90 %, whereas the average starting reaction rates were 1.2 × 10^?3 mol g^?1 s^?1 and 2.6 × 10^?3 mol g^?1 s^?1 (hydrogen consumption rate per mass of platinum), respectively. Under similar reaction conditions, using palladium catalysts supported on a resin with anionic groups anchored to polymeric chains at the average reaction rate equal to 3.8 × 10^?3 mol g^?1 s^?1 (hydrogen consumption rate per mass of palladium), the selectivities from 85 % (2-CAN and 3-CAN) to 95 % (4-CAN) were achieved (Kratky et al., 2002).     

Thermal coarsening of supported palladium combustion catalysts

An essential property of combustion catalysts is long-term (>8000 h) stability at high temperatures in an environment (approximately 1 atm of both oxygen and water vapor) that aggressively promotes sintering of the supporting oxide and coarsening of the active component. Extrapolation of accelerated coarsening rate measurements, determined from shorter exposures at higher temperatures, can be made with more confidence if the physical processes of the coarsening and sintering processes were well understood. The current work examines in detail the coarsening of a high-weight-loaded palladium catalyst supported by silica-stabilized alumina at 900 degrees C in such an aggressive environment. The results of this investigation showed that the Pd particle size distribution was consistently log-normal for time periods from 100 to 4000 h, the mean particle growth rate was roughly inverse second-order in mean particle diameter, and the support not only sintered but also underwent phase transformation. The results implicate both coalescence and Ostwald ripening as important coarsening processes.     

整体式担载型Pt基催化剂上航空煤油的裂解:助剂SrO和BaO的影响

考察了整体式担载型Pt基催化剂上国产3号航空煤油(RP-3)的常压裂解反应,着重探讨了添加BaO和SrO助剂对裂解效果的影响,以及裂解时间对积炭量的影响.采用全自动吸附仪、程序升温还原、X射线光电子能谱以及X射线衍射和扫描电镜等方法对催化剂进行了表征.结果表明,在整体式担载型Pt基催化剂上RP-3裂解的总产气量比热裂解提高了39.7%;BaO或SrO助剂的添加又使其总产气量又分别提高了25.6%和37.0%;同时添加BaO和SrO的催化剂,其催化裂解总产气量则提高了96.5%.BaO和SrO助剂均可有效地抑制积炭的生成,而两者间的协同作用,进一步抑制了RP-3催化裂解过程中积炭的生成.     

Hydrogenation of xylenes over supported Pt catalysts. Influence of different variables on their catalytic activity

In this work we studied and compared the catalytic activity of various supported Pt systems on the gas-phase hydrogenation of o-, m- and p-xylene. We analyzed the influence of different catalyst preparation variables (solvent, precursor, salt, support and catalyst reduction temperature used) on the catalytic activity and selectivity towards the corresponding cis-and trans-dimethylcyclohexanes.

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- o-, m- -. (, , ) - -.

     

Decomposition of methomyl over supported iron catalysts

Catalytic wet peroxide oxidation of methomyl over Fe-ZSM-5 and AlFe-pillared montmorillonite was carried out at room temperature, in a glass batch reactor, under constant airflow and halogen lamp light. Both catalysts have shown significant activity in the degradation reaction of methomyl at a concentration of 1.0×10⁻⁴ mol.     

镍基催化剂上乙醇水蒸气重整反应的研究

考察了载体对Ni催化剂乙醇水蒸气重整制氢反应性能的影响。结果表明,Ni/CeO2催化剂具有较好的低温活性和氢气选择性。对Ni担载量和焙烧温度考察发现,400℃焙烧的15%NiCeO2催化剂具有较好的催化性能;继续升高焙烧温度引起NiO和CeO2粒子的显著增大,导致对氢气选择性的降低。较小的Ni和CeO2粒子有利于乙醇水汽重整反应的进行,而大的粒子倾向于乙醇的分解反应。 350℃时,在反应过程中分别添加CO、CO2和CH4的结果表明没有发生CO和CO2甲烷化反应,而发生了一定程度的CH4水汽重整反应。     

Stereoselective stilbene epoxidation over supported gold-based catalysts

The gold reference catalyst Au/TiO(2) exhibits high activity in the stereoselective epoxidation of trans-stilbene in methylcyclohexane in the presence of 5 mol% TBHP, by taking part in a chain reaction involving the activation of molecular oxygen by a radical produced from methylcyclohexane.     

Hydrodechlorination of chlorobenzene over supported metal catalysts

The use of supported Pd catalysts, with low and high metal content, for the hydrodechlorination of chlorobenzene is presented in this article. Application of microwave irradiation during preparation of catalysts resulted in the synthesis of large Pd particles at moderate temperatures. The nature of the support played a key role in the formation of cationic Pd species. The extent of interaction of the Pd species with the support, the nature of metal precursor, particularly the residual chlorine on the surface were found to significantly affect the activity of the catalysts. In the case of bimetallic catalysts also microwave heating resulted in creation of bigger particles of Pd compared to those observed in conventionally heated catalysts. Besides, it minimized alloy formation as a result of which the activity of the catalysts in hydrodechlorination was found to be higher compared to that observed on conventionally prepared catalysts. Contrary to the general observation that low dispersed Pd catalysts are preferable for high stability, by means of the deposition-precipitation method adopted for catalyst preparation it was demonstrated that even highly dispersed (low Pd containing) catalysts can exhibit comparable activity and stability. An analysis of the nature of Pd species and its role in the stability of the catalysts is presented.IICT communication No. 051224     

Reduction of benzylideneaniline over supported Pd catalysts

In this work we have carried out a study on the liquid phase hydrogenation of benzylideneaniline, using dihydrogen over various supported Pd catalysts. Benzyl-ideneaniline reduction can be classified as insensitive to the catalyst structure. On the other hand, no compensating effect has been observed in performing the reaction over different supported Pd catalysts.

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Pd , . . Pd , .

     

实用型整体式钴基甲烷催化燃烧催化剂的研制

目前较为成熟的甲烷燃烧催化剂多为贵金属(Pt、Rh和Pd)催化剂,其中Pd催化剂最好。但贵金属易烧结,耐热性差,价格昂贵,应用受限。近年来,非贵金属燃烧颗粒状催化剂的研究报导较多,而有关整体式非贵金属燃烧催化剂的报导较少。后者压力降低,可减少床层过热,克服     

Phosphorus modification of supported Pt catalysts for carbon monoxide hydrogenation

Modifying effect of phosphorus on the catalytic activity of supported Pt and Pt–Fe catalysts for CO hydrogenation has been studied. Phosphorus-containing compounds decrease significantly the methane yield with increasing yield of C₂–C₇ hydrocarbons.

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CO Pt- Pt–Fe-. , C₂–C₇.

     

Wormholelike mesoporous carbon supported Pt Ru catalysts toward methanol electrooxidation

Wormholelike mesoporous carbons(WMCs) with three different pore diameters(D_p),namely WMC-F7(D_p=8.5nm),WMC-F30(D_p=4.4nm),and WMC-FO(D_p = 3.1nm) are prepared via a modified sol-gel process.Then PtRu nanoparticles with the particle size(d_(Pt)) of ~3.2 nm supported on WMCs are synthesized with a modified pulse microwave-assisted polyol method.It is found that the pore diameter of WMCs plays an important role in the electrochemical activity of PtRu toward alcohol electrooxidation reaction.PtRu/WMC-F7 with Dp 2d_(Pt) exhibits the largest electrochemical surface area(ESA) and the highest activity toward methanol electrooxidation.With the decrease in D_p,PtRu/WMC-F30 and PtRu/WMC-FO have much lower ESA and electrochemical activity,especially for the isopropanol electrooxidation with a larger molecular size.When D_p is more than twice d_(Pt),the mass transfer of reactants and electrolyte are easier,and thus more PtRu nanoparticles can be utilized and the catalysts activity can be enhanced.     

Hydrogenation of ethyl acetate over supported rhenium catalysts

Re/Sibunite is a more active and selective catalyst for hydrogenation of ethyl acetate to ethanol under elevated temperatures and hydrogen pressures than Re/θ-Al₂O₃ and Re/γ-Al₂O₃. The activity of the catalyst is increased on replacing NH₄ReO₄ with HReO₄ and treatment of the support with a 13% solution of HNO₃. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1006–1008, May, 1999.