Influence of structural properties of catalysts at various stages of selective oxidation: from catalyst preparation to catalytic reactors

Solid oxides selective in mild oxidation exhibit a definite crystal morphology. Each crystal face displays a surface crystal field which rules the transformation of the reactant to a given product. The catalytic metastability of the surface which has to be maintained in the operating conditions prevailing in reactors depends on the reactivity of the bulk, because of oxygen diffusion process. Application to VPO, the catalyst for oxidation of n-butane to maleic anhydride, gives the opportunity to examine these properties in the series preparation–activation–catalysis–ageing, in relation to the type of catalytic reactor. This revised version was published online in August 2006 with corrections to the Cover Date.     

Membrane pilot reactor applied to selective oxidation reactions

The partial oxidation of butane to maleic anhydride was studied in a conventional fixed bed as well as a novel reactor configuration consisting of a porous metallic membrane immersed in a gas–solid fluid bed. The diameter of both reactors was at a commercial scale greater than 30 mm. A range of gas flow rates, temperatures and butane concentrations were tested. Maleic anhydride yield was generally higher in the membrane reactor due to higher butane conversion. Maleic productivity in the fixed bed equalled that observed in the membrane reactor when the gas–solid fluid bed was maintained at a higher temperature of as much as 30 °C. The butane feed rate to the membrane reactor was limited by hot spots. These hot spots were unanticipated and underscore the importance of increasing heat transfer in order to commercialize this technology.     

A Study on VPO Specimen Supported on Aluminum-Containing MCM-41 for Partial Oxidation of n-Butane to MA

Dispersed vanadium–phosphorus oxide species supported on Al-MCM-41 with different vanadium loadings have been synthesized for the first time for partial oxidation of butane to MA. It was found that the VPO species was dispersed over the Al-MCM-41 support material, both in the internal channel and on the external surface. With increasing vanadium loading, n-butane conversion increased but MA selectivity decreased considerably under the same reaction conditions. At lower conversions (<30%), rather high MA selectivity (ca. 70%) can be achieved on the low loading sample. Compared with the amorphous structure of large pore SiO₂ support, the unique structure of the MCM-41 and the incorporated Al³⁺ in the framework do have an impact on the reaction behavior of the supported VPO specimen. The chemical nature of the supported VPO species and the interaction between the applied VPO species and the support was found to vary notably with the content of vanadium in the sample and likewise affected the related physico-chemical characteristics and their reaction behaviors.     

同轴双锥两级气固快速分离器冷态实验研究

下行循环流化床反应器要求气固分离器具有分离效率高、气相停留时间短、压力损失小、设备磨损小等特点。利用气固二相在惯性上的差别,提出了一种新型同轴双锥两级气固快速分离器,并以FCC(F lu id Catalytic Crack ing)为循环物料对该型分离器的分离特性进行了研究。结果表明,同轴双锥两级气固分离器的分离效率在98%以上,气固分离器的压力损失在100 Pa以下,设备磨损小,能够满足下行循环流化床反应器的要求。     

超短接触旋流反应器混合腔内气固混合特性的数值模拟

采用欧拉双流体模型对超短接触旋流反应器内的气固两相流场进行了数值模拟,主要研究了混合腔内固相的体积分数分布情况。计算结果表明：混合腔内的气流在切向进气的作用下得到了一定的混合加速效果,切向的高速射流有效地缩短了气固停留时间,保证短接触反应效果。通过对两种不同混合腔结构反应器的对比计算发现,在相同入口速度条件下结构2（切向进气管位于混合腔顶部）较结构1（切向进气管位于混合腔下部）气固停留时间短,由于切向气流的迅速作用,增加了混合腔内的湍动强度,使催化剂颗粒迅速有效扩散、增强气固接触效果而更有利于催化裂化反应的进行,更易实现短接触操作要求。计算结果与实验测量结果的比较表明模型能有效地描述超短接触旋流反应器内气固两相流动形态。     

The beneficial effect of cobalt on VPO catalysts

The addition of Co to VPO formulations improves the yield of n-butane to maleic anhydride. In this work, different modes of impregnation and two different organic cobalt salts were used. The equilibrated catalysts were characterized using XRD, ³¹P SEM NMR, FT-IR and acetonitrile adsorption to evaluate Lewis acidity.

The best catalyst was obtained using Co acetyl acetonate for impregnation of the VOHPO₄·0.5H₂O precursor. This catalyst after equilibration had an optimum concentration of very strong Lewis acid sites, very low concentration of isolated V(V) centers, and no V(V) phases.     

Characterization of bimetallic rhodium-germanium catalysts prepared by surface redox reaction

The preparation of bimetallic rhodium-germanium/silica and rhodium-germanium/alumina catalysts was investigated by controlled surface reaction. Their catalytic performances were measured for two gas phase reactions (toluene hydrogenation at 323 K and cyclohexane dehydrogenation at 543 K) and for a liquid phase reaction (citral hydrogenation at 343 K).

Elemental analysis of bimetallic catalysts showed that germanium can be deposited by redox reaction between hydrogen activated on a parent monometallic rhodium catalyst and germanium tetrachloride dissolved in water (catalytic reduction method). EDX microanalysis of rhodium-germanium/silica catalysts indicated that rhodium and germanium were deposited in close contact on the silica support. However, on alumina-supported catalysts, germanium deposition occurred also separately on the support. For the different test reactions, the catalytic properties of rhodium were strongly altered by the addition of germanium. On alumina-supported catalysts, interesting catalytic effects were observed in citral hydrogenation when not only close contact exists between both metals but when, in addition, the second metal was deposited on the support in the close vicinity of rhodium.     

Heterogeneity analysis of gas-solid flow hydrodynamics in a pilot-scale fluidized bed reactor

Mesoscale drag model is of crucial significance for the reliability and accuracy in coarse-grid EulerianEulerian two-fluid model(TFM) simulations of gas-solid flow hydrodynamics in fluidized bed reactors.Although numerous mesoscale drag models have been reported in the literature,a systematic comparison of their prediction capability from the perspective of heterogeneity analysis is still lacking.In this study,in order to investigate the effect of several typical drag models on the hydrodynamic ...     

Characterization and activity of copper and nickel catalysts for the oxidation of phenol aqueous solutions

Catalysts based on CuO/γ-alumina, CuAl₂O₄/γ-alumina, NiO/γ-alumina, NiAl₂O₄/γ-alumina and bulk CuAl₂O₄ have been structurally characterized by BET, porosimetry, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Their catalytic behaviors have also been tested for the oxidation of 5 g/l phenol aqueous solutions using a triphasic tubular reactor working in a trickle-bed regime and air with an oxygen partial pressure of 0.9 MPa at a temperature of 413 K. The copper and nickel catalysts supported on γ-alumina have surface areas of the same order as the support γ-alumina of ca. 190 m²/g and high active phase dispersions which were also confirmed by SEM, whereas the bulk copper aluminate spinel has a surface area of ca. 30 m²/g. XRD detects the phases present and shows a continuous loss of CuO by elution and the formation of a copper oxalate phase on the surface of the copper catalysts which also elutes with time. The NiO was also eluted but less than the copper catalysts. Only the copper and nickel spinel catalysts were stable throughout the reaction. Phenol conversion vs. time shows a continuous overall decrease in activity for the CuO/γ-alumina and NiO/γ-alumina catalysts. In turn, the copper and nickel spinel catalysts reach steady activity plateaus of 40 and 10%, respectively, of phenol conversion. The bulk copper aluminate spinel shows an activity plateau of 20% of the conversion which is lower than that from the copper aluminate/γ-alumina catalyst due to its lower surface area. Nickel catalysts always have lower activities than the copper catalysts for the phenol oxidation reaction. The copper catalysts drive a mechanism of partial phenol oxidation to carboxylic acids and quinone-related products with very high specific rates, and the nickel catalysts mainly drive a mechanism of CO₂ formation with lower conversion but with a potential higher catalyst life. The triphasic tubular reactor using trickle-bed regime largely avoids the mechanism of polymer formation as a catalyst deactivation process.     

新型气固环流反应器内颗粒流动的CFD模拟

采用基于结构的EMMS曳力模型,对一种新型气固环流反应器中的颗粒流动特性进行数值模拟。模拟的固含率与颗粒速率预测值与实验数据具有一致性,验证了模型的适用性。模拟结果表明：导流筒表观气速增加,导流筒中的床层固含率减小,向上的颗粒速率增加;反应器中存在多个颗粒逆流和错流混合区,促进了颗粒沿径向的混合;槽孔处,导流筒中的固含率以及颗粒速率分布更加均匀,而环隙中存在颗粒浓集区;进料区在0≤L≤0.058 m,0< r/R< 0.3的范围内固含率增加并且颗粒存在明显的径向流动。     

Acid-base properties and the directions of oxidative transformation of methane over nickel-based catalysts

The reactions of dry (CO₂) reforming and partial oxidation of methane have been investigated in a membrane reactor. The membrane is composed of a dense thin silica (SiO₂) film supported on porous Vycor tubes and was synthesized by chemical vapor deposition. The hydrogen permeance of the membrane was 0.2–0.3 cm³/(cm² min atm) at 600°C combined with a H₂/N₂ selectivity of 200–300. Significant increases in methane conversion were attained in both reactions at 500–750°C, albeit at very low space velocities. The membrane permeance declined by 50% after exposure to feeds containing H₂O, but otherwise exhibited excellent stability under reaction conditions.     

Pd-based catalysts for catalytic wet oxidation of combined Kraft pulp mill effluents in a trickle bed reactor

Catalytic wet oxidation of combined pulp mill effluents was studied in a trickle bed reactor. Two types of supported Pd-based catalysts, eggshell and uniform catalysts, and a supported Pd–Pt uniform catalyst were employed. Supported Pd catalysts showed high activity for total organic carbon (TOC) and color removal at temperatures of 353–448 K and 1.84 MPa. Compared to uniform catalysts, the eggshell catalysts with a 0.2 wt.% Pd loading show promise for treatment of combined pulp mill effluents. High activity for TOC and color removal can be attributed to the high density of active Pd sites in the shell area and to the decrease of diffusion path for reactants and intermediates. No apparent deactivation of eggshell catalysts was observed after 40 h on stream. Potential application of the supported Pd catalysts for treatment of combined pulp mill effluents is discussed.     

New redox deposition-precipitation method for preparation of supported manganese oxide catalysts

A new preparation method has been developed to produce homogeneous coatings of manganese compounds on alumina-coated monoliths by redox deposition-precipitation using acetone as solvent. The deposition is produced by reduction of manganese permanganate with ethanol. The Lewis acid sites on the alumina catalyze this reaction. Thus, the precipitation is produced preferentially on the surface of the monolith and not in the bulk of the solution. Monoliths prepared by this method are very active for the complete oxidation of oxygenated volatile organic compounds (VOCs). These monoliths consist of a mixture of complex phases including aluminum, sulfated alumina, potassium sulfate and manganese oxide.     

MoV-based catalysts in ethane oxidation to acetic acid: Influence of additives on redox chemistry

The formation of acetic acid and/or ethylene by oxidation of ethane is strongly dependent on X additives or Y promotor added to MoVO-based catalysts. MoV_0.4X_0.12YO_z (X = Nb; Y = Pd;  = 10⁻⁴) catalysts were prepared by the slurry method and their structural properties were studied by in situ (redox conditions) XRD, Raman and XPS techniques. The reactivity during reduction and reoxidation was analysed by thermal analysis (TGA/DSC). The oxidation of ethane was carried out in a conventional fixed bed microreactor with on line analysis by gas chromatography. Results show that Nb exerts mainly a structural effect as it is responsible for the stabilisation of molybdenum (VI) by formation of solid solutions with V, and that Pd modifies the rate of reduction of the solid catalysts. The increase of selectivity to acetic acid observed by Pd promotion is likely due to the transformation of ethylene to acetic acid occurring on neighboring Pd–V active sites.     

Characterization and testing of sol-gel catalysts prepared as thin layers in a plate reactor

Catalytic plate reactors offer many advantages over conventional reactors, including a major reduction in size and much better temperature control. This study examines the characteristics of thin catalyst coats prepared by the sol-gel method and calcined at different conditions. Employing the catalyst as a thin layer (< 100 μm) on the surface of plate reactors reduces mass and heat transfer limitations compared with pellet catalysts and can improve the effectiveness factor. A sol-gel of Ni/Al₂O₃ catalyst, with good rheological properties and good adherence onto stainless steel substrate, was prepared and characterized. The effects of calcination temperature, nickel content and calcination environment on the catalyst properties were investigated. The results revealed that the highest catalyst surface area was obtained at 400 °C for all calcined coatings. The presence of nitrogen gas during drying and calcining seemed to increase the catalyst surface areas and improve its adherence properties. Rheological evaluation of the prepared coats proved to be an effective tool in characterizing the thin coatings. The Ni/Al₂O₃ catalyst exhibited high activity and achieved more than 80% conversion for steam reforming of methane. The reactions were not diffusion limited based on the values of activation energy.     

Aromatization of n-butane over new LD-HBS catalysts. Effect of the gallium oxide support

It is shown that even pure quartz, other silicas or aluminas can enhance the aromatization activity of a ZSM-5 zeolite. Incorporation of gallium oxide onto these supports increases further the production of aromatics. The use of supported gallium oxide co-catalyst obtained by co-evaporation of a colloidal silica and a Ga salt has led to extremely high aromatization performance for the hybrid catalyst.     

Oxidative dehydrogenation of n-butane on V/MgO catalysts. Influence of the type of contactor

A comparative study of the catalytic performance of a selective V-Mg-O catalyst in the oxidative dehydrogenation of n-butane is presented using three different types of reactor: (i) an adiabatic fixed-bed reactor; (ii) a fluidized-bed reactor; and (iii) an in situ redox fluidized-bed reactor. The results obtained indicate that the in situ redox fluidized-bed reactor outperforms the conventional fixed- and fluidized-bed reactors, especially at high n-butane conversions. Thus, a selectivity to C₄ olefins of 54% at n-butane conversions of 60% was achieved at 550°C using an in situ redox fluidized-bed reactor while selectivities to C₄-olefins lower than 43% were obtained on the other reactor types under the same reaction conditions (isoconversion and reaction temperature). This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of catalyst loading on gasliquid mass transfer in a slurry reactor: A statistical experimental approach

A statistical experimental design was employed to study the effects of pressure, temperature, catalyst loading, and mixing speed on the solubilities (C*) and volumetric gas/liquid mass transfer coefficients (k_L^a) for H₂, N₂, CO, CH₄ and C₂H₄ in a liquid mixture of hexanes containing iron oxide catalyst in a 4-litre agitated autoclave. Statistical correlations for k_L^a values for the gases used were developed. Mixing speed and solid concentration showed the strongest effects on k_L^a. At low catalyst concentrations, a maximum in k_L^a was observed and at concentrations > 37 mass%, k_L^a decreased by more than one order of magnitude.     

Catalytic partial oxidation of methane to synthesis gas in a ceramic membrane reactor

Methane has been selectively converted to synthesis gas using a two-zone fixed bed of a Ni/Al₂O₃ catalyst inside a modified ceramic membrane. The first zone of the reactor was surrounded by an impervious wall, and therefore behaved as a conventional fixed bed reactor. In the second zone, some of the reaction products could preferentially diffuse out of the reactor, which yielded higher than equilibrium methane conversions. The influence of the different operating conditions has been studied, and the performance of the membrane reactor has been compared to that of a fixed bed reactor. The membrane reactor has also been used at pressures above atmospheric (2 bar), with good conversions and selectivities.     

Redox solid catalysts for the selective oxidation of cyclohexane in air

The selective oxidation of cyclohexane to cyclohexanol, cyclohexanone and adipic acid using molecular oxygen as the oxidant and at moderate temperatures (403 K) has been investigated over four different cobalt‐containing aluminophosphate (AlPO) molecular sieves. There is a correlation between catalytic activity and the fraction of (framework) Co(II) ions that is first oxidised to Co(III) in air. CoAlPO‐36 (pore aperture 6.5 x 7.5 Å) exhibits significant activity for the oxidation of cyclohexane in contrast to CoAlPO‐18, which, although it has the highest fraction of oxidisable cobalt, does not show any activity chiefly because of its smaller pores.