Interaction of H2,n-butane and cis-2-butene with Pt and Pt In in NaY: a microcalorimetric study

Pt NaY and Pt In NaY adsorption properties have been compared by using probes like H₂, C₄H₁₀, 2-C₄H₈ and microcalorimetry. It appears that the addition of In to Pt does not change the initial heat of H₂ chemisorption but decreases the initial heat of butane and butene chemisorption.     

Adaptation of the microscopic properties of redox catalysts to the type of gas-solid reactor

Catalysts of selective oxidation usually work in a simultaneous redox mode in reactant/air cofed reactors. The solid must provide selective lattice oxygen according to a kinetic mechanism depending on operating conditions that differ from one reactor to another. Better catalytic performance can be obtained in a recirculating solids reactor because it allows separate optimization of the reduction and oxidation steps. Among the microscopic properties of the catalyst, the crystal morphology is to be taken into account because it influences its reactivity on stream. These considerations lead to a new approach of the catalyst-reaction-reactor trio.     

Platinum promoted zirconia-sulfate catalysts: one-pot preparation,physical properties and catalytic activity

A new innovative methodology for the single-stage preparation of ZrO₂-SO₄ and Pt/ZrO₂-SO₄ catalysts is reported, based on the sol-gel technique. Catalysts are characterized by analysis, XRPD, BET and IR methods and are tested in the isomerization of butane.     

膜催化氧化正丁烷制顺酐

以多孔玻璃管为基体，制备４种用于正丁烷氧化制顺酐的膜反应器。在一定的操作条件下，考察了固定床反应器与这４种膜反应器在正丁烷氧化制顺酐中的反应性能并加以比较，发现ＹＳＺ膜反应器可获得高于固定床反应器的选择性和收率。     

碳四烷烃催化裂解制低碳烯烃的研究进展

论述了碳四烷烃催化裂解制低碳烯烃的催化剂体系、影响因素及催化裂解方式。该催化剂体系包括硅铝酸盐及锆硫酸盐,氧化铝与碱金属或碱土金属的混合物,负载型催化剂等3种类型。其中分子筛(晶体硅铝酸盐)及其改性催化剂是研究开发的主要方向。除操作条件外,稀释剂、引发和抑制剂和裂解反应方式对催化裂解反应均有影响。催化裂解反应机理与催化剂的种类和反应条件相关。对于酸性分子筛催化剂有2种比较公认的机理:正碳离子机理,自由基与正碳离子机理两种形式。研究表明碳四烷烃,特别是正丁烷催化裂解制低碳烯烃具有良好的低碳烯烃收率,收率可达50%以上。     

The effects of Cl-induced alloying in Pt–Sn/Al2O3 catalysts on butane/H2 reactions

The effects of oxidation/reduction regeneration treatments, with and without 1,2-dichloropropane present as a chlorinating agent, on the structure of Pt(3%)–Sn(4.5%)/Al₂O₃ catalysts have been correlated with selectivities for butane/H₂ reactions. Particles of Pt⁰ fin Cl-free catalysts were partly covered by Sn⁰, but retained exposed ensembles of Pt atoms which were active for isomerisation, hydrogenolysis and dehydrogenation reactions, the latter becoming dominant at high reaction temperatures. Coking reduced Pt ensemble size and, hence, also favoured high selectivities for dehydrogenation as hydrogenolysis and isomerisation sites became poisoned. In contrast, the addition of 1,2-dichloropropane in an oxychlorination step before reduction promoted 1:1 Pt⁰–Sn⁰ alloy formation after reduction, the proportion of the total Pt in alloy being enhanced by increasing 1,2-dichloropropane concentration and oxychlorination temperature. The alloy surfaces were inactive for isomerisation and hydrogenolysis reactions, giving dehydrogenation as the sole catalytic reaction.     

Bulk and Surface Properties of a VPO Catalyst Used in an Electrochemical Membrane Reactor: Conductivity-, XRD-, TPO- and XPS-study

In the first part of this work, the electrical conductivity of vanadium phosphorous oxide (VPO) catalyst was investigated by means of the 2-probe EIS method. The VPO showed an extremely low conductivity at low oxygen partial pressure, which is the prevailing condition in the anodic compartment in an electrochemical membrane reactor (EMR). In the second part of this study, fresh as well as VPO catalyst already used in an EMR were characterised with XRD, XPS and temperature programmed oxidation (TPO). The XRD measurements revealed an unchanged bulk phase structure after operation in the EMR. Significant differences in the average oxidation states of vanadium in the catalyst layer in the EMR were determined via XPS, where the catalyst surface facing the electrolyte membrane was more oxidised than the surface facing the anodic gas compartment. The lowered uptake and release of oxygen was observed in TPO experiments for the catalyst used in the EMR.     

Dehydrocyclization of 1-hexene to benzene on Cu3Pt(111)

The disproportionation ofn-butane (and of isobutane) was catalyzed by sulfated zirconium oxide containing 1.5 wt% Fe, 0.5 wt% Mn, and 4.0 wt% sulfate at 2.0 atm and temperatures in the range of 30–60C. The reaction accompanies isomerization, which under some conditions is as much as one or two orders of magnitude faster than disproportionation. The conversion to each of the products increased with time on stream in a flow reactor, and then declined. The time on stream for maximum conversion was the same for each product. The results suggest that the disproportionation and isomerization reactions proceed through a common C₈ intermediate. Rates of the disproportionation reaction were determined at the time on stream corresponding to the maximum conversion at each temperature; for example, the rate of conversion ofn-butane into isopentane at 60C with ann-butane partial pressure of 0.58 atm was about 1×10^–7 mol/(g of catalyst s).     

Preparation of superacid of iron-supported zirconia for reaction of butane to isobutane

A highly active superacid of 2 wt% Fe-supported ZrO₂ for the skeletal isomerization of butane to isobutane was obtained by sfexposing Fe₂O₃/ZrO₂ to 1 N H₂SO₄ followed by calcining in air at 700°C for more than 24 h; the Fe₂O₃/ZrO₂ was prepared by impregnating zirconia gel with a solution of Fe(NO₃)₃ followed by drying at 300°C (2 wt% Fe). A much lower activity was observed with the opposite procedure, where the first impregnation was sulfation of the gel, followed by a second impregnation with the iron compound. It was proved from analysis of the sulfur content in the catalysts that residual sulfur species were not related with generation of the superacidic sites. XPS showed the catalyst to be Fe₂O₃ supported on ZrO₂.Superacids by metal oxides, VIII. For previous publications VI and VII in this series see refs. [10,11].     

Oxidation of Butane to Maleic Anhydride using Vanadium Phosphate Catalysts: Comparison of Operation in Aerobic and Anaerobic Conditions using a Gas-gas Periodic Flow Reactor

The use of a periodic flow reactor is described for the oxidation of butane to maleic anhydride to compare the catalytic performance of vanadium phosphate catalysts operating under aerobic and anaerobic conditions. It is found that for the catalyst prepared via a standard VPO method, operation in the absence of oxygen leads to a very small enhancement in selectivity when butane concentrations in the range 0.9–2.9% are used. Operation in the absence of oxygen leads to very small differences in conversion such that the overall yield is enhanced and this effect is maximised for reactor feeds containing 1.5% butane. However, the enhancement is negligible when the catalyst is operated at high conversion required for commercial operation, indicating that reactors operating with continuous flow with aerobic conditions are preferred. Similar experiments are conducted for a catalyst prepared by the VPD method and, in contrast, this catalyst gives lower butane conversion and maleic anhydride selectivity when operated in the absence of oxygen.