The use of membranes in studies of reaction kinetics: arsenite catalysis of co2 hydration

The second-order catalytic rate constant for the industrially important CO₂ hydration catalyst, arsenite, has been determined using a novel membrane technique. The kinetic method involves the measurement of the steady-state flux of tagged CO₂ through an iramobilized liquid layer held within a thin, porous membrane; the liquid contains the catalyst and a basic buffer, sodium bicarbonate. The tracer flux is described by a set of linear equations, the solution of which yields the flux in terms of two dimensionless groups containing the kinetic and transport properties of the membrane phase. Experimental results agree with literature values on arsenite catalysis. The method is simple, accurate, and requires a minimum quantity of catalyst; it may have considerable applicability in studies of solution kinetics.     

Oligomerization of endo-dicyclopentadiene using a mesoporous catalyst in a fixed-bed reactor

The oligomerization of endo-dicyclopentadiene (endo-DCPD) over a mesoporous catalyst in a continuous-flow reactor at elevated pressure was studied to produce tricyclopentadiene (TCPD) and tetracyclopentadiene (TeCPD). The mesoporous material prepared from zeolite beta (MMZ_Hβ) was utilized as a catalyst. In addition, this study focused on the catalytic performance of the regenerated catalyst in comparison with the fresh catalyst. The TCPD and TeCPD were continuously produced through DCPD oligomerization over the MMZ_Hβ catalyst in a fixed bed reactor. At early time-on-stream, the conversion of endo-DCPD, the yield of TCPD and TeCPD, and the isomerization selectivity of TCPD in the fixed bed reactor were comparable to those in the batch-type reactor. The yield of oligomer containing TCPD and TeCPD decreased drastically from 28.5 % at 3 h time-on-stream to 21.5 % at 12 h time-on-stream, indicating that the catalyst was significantly deactivated. The in situ calcination in air flow at 500 °C was found to be effective for the regeneration of the used MMZ_Hβ catalyst.     

Computational fluid dynamics study of the dry reforming of methane over Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst in a membrane reactor. Coke deposition

This work investigates the dry reforming of CH₄ as an important process for the conversion of greenhouse gases to synthesis gas. The mixture of methane and CO₂ is readily available in the greenhouse gas which makes realization of dry reforming of methane process more convenient. The paper is an attempt to numerically analyse by computational fluid dynamics (CFD) the coking and gasification mechanisms in the lab-scale membrane module with a fixed-bed supported nickel catalyst (Ni/Al₂O₃). The concentrations and molar fluxes obtained by the simulation are compared with the experimental profiles to validate the CFD model. It was found that working in a catalytic fixed-bed membrane reactor, in the case of the dry reforming of methane and under specific conditions, was not critical, from the point of view of catalyst deactivation.     

Membrane-Supported Layered Coordination Polymer as an Advanced Sustainable Catalyst for Desulfurization

The application of a catalytic membrane in the oxidative desulfurization of a multicomponent model diesel formed by most refractory sulfur compounds present in fuel is reported here for the first time. The catalytic membrane was prepared by the impregnation of the active lamellar [Gd(H₄nmp)(H₂O)₂]Cl·2H₂O (UAV-59) coordination polymer (CP) into a polymethyl methacrylate (PMMA, acrylic glass) supporting membrane. The use of the catalytic membrane in the liquid–liquid system instead of a powder catalyst arises as an enormous advantage associated with the facility of catalyst handling while avoiding catalyst mass loss. The optimization of various parameters allowed to achieve a near complete desulfurization after 3 h under sustainable conditions, i.e., using an aqueous H₂O₂ as oxidant and an ionic liquid as extraction solvent ([BMIM]PF₆, 1:0.5 ratio diesel:[BMIM]PF₆). The performance of the catalytic membrane and of the powdered UAV-59 catalyst was comparable, with the advantage that the former could be recycled successfully for a higher number of desulfurization cycles without the need of washing and drying procedures between reaction cycles, turning the catalytic membrane process more cost-efficient and suitable for future industrial application.     

Cr掺杂的丙烷选择氧化制丙烯酸高效催化剂

在丙烷选择氧化制丙烯酸催化剂MoVTeNbOx的活性相M1基础上掺杂一定量的Cr,当Cr/Nb摩尔比为0.002时,催化剂具有很高的丙烯酸选择性(78.3%)和收率(50.7%);并采用X射线衍射、X射线光电子能谱、程序升温还原、O2程序升温脱附、NH3程序升温脱附和异丙醇氧化等手段对催化剂的构效关系进行了探讨.结果表明,适量Cr的添加可调节催化剂表面Mo6+,V5+和Te4+等物种含量,提高催化剂的氧化能力,使丙烷转化率增加.同时,适量Cr的添加使得催化剂表面酸强度下降,酸性位点数量减少,从而抑制丙烯酸的深度氧化,提高了丙烯酸选择性.     

Elimination of Carbon Monoxide in the Gas Streams by Dielectric Barrier Discharge Systems with Mn Catalyst

Elimination of CO in air stream using the plasma catalytic reactors was investigated. Two plasma catalytic systems were evaluated in this study, one consisting of a catalyst-bed packed in plasma zone of a dielectric barrier discharge (DBD) reactor directly (CID reactor), and the other (CAD reactor) consisting of a catalyst-bed after a DBD reactor. The examined operating parameters in this study included applied voltage, discharge power, the lengths of plasma zone and catalyst-bed, and inlet CO concentration. It was found that the glass packed DBD reactor without catalyst cannot eliminate CO in air stream effectively. When MnO_x catalyst applied to DBD reactors, the removal of 1000 ppm CO can achieve to 97% by both type reactors. Under constant energy input condition, the CO removal of a CID reactor increased with the decrease of the initial CO concentration and the increase of the length of catalyst beds. In addition, the operating energy consumption of CID system was lower than that of CAD system.     

CuCl2和HY分子筛的表面反应及Cu/Y分子筛的制备及其催化甲醇氧化羰基化

以CuCl₂为前驱物与HY分子筛进行固相离子交换制备了Cu/Y催化剂,采用热重方法研究了CuCl₂与HY分子筛的表面固相离子交换反应,结合活性测试表明催化剂中高度分散的CuCl和离子交换形式的Cu⁺物种是甲醇氧化羰基化合成碳酸二甲酯的催化活性中心。X射线光电子能谱表征和元素分析结果表明,活性金属Cu主要以CuCl形式存在于分子筛外表面,而在分子筛笼内则以交换的Cu⁺和少量吸附的CuCl形式存在。与以CuCl为交换铜源所制催化剂相比,以CuCl₂为铜源制备的催化剂Cu含量低,催化活性更高。     

TiO2 supported cobalt-manganese nano catalysts for light olefins production from syngas

Cobalt-manganese nano catalysts were prepared by sol-gel method. This research investigated the effects of different cobalt-manganese (Co/Mn = 1/1) loading, pH and calcination conditions on the catalytic performance of Co-Mn/TiO₂ catalysts for Fischer-Tropsch synthesis (FTS) in a fixed bed reactor. It was found that the catalyst containing 30wt%(Co-Mn)/TiO₂ was an optimal catalyst for the conversion of synthesis gas to light olefins especially propylene. The activity and selectivity of optimal catalyst were studied under different operational conditions. The results showed that the best operational conditions were H₂/CO= 1/1 molar feed ratio at 250 °C and GHSV= 1300 h^?1 under atmospheric pressure. Characterization of catalysts was carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption measurements.     

A membrane electrode assembly for the electrochemical synthesis of hydrocarbons from CO2(g) and H2O(g)

We report the electrochemical reduction of CO₂ into hydrocarbons using a new electrochemical membrane reactor holding a yet unreported membrane electrode assembly comprising a copper mesh cathode and a Ti felt coated with mixed metal oxide (MMO) catalyst anode separated by a proton conductive membrane. CO_2(g) was supplied to the cathodic reduction compartment, whilst humidified N₂ was supplied to the anodic oxidation compartment. The MMO anode produces protons transported across the proton exchange membrane and electrons transported via the external circuit to the copper cathode to reduce CO_2(g). Production rates of methane, propane, propene, iso-butane and n-butane were determined as a function of cell potential at temperatures between 30 and 70 °C and relative humidity between ca. 25% and 75%. Maximum methane concentration and the current efficiency for production of hydrocarbons were 3.29 ppm and 0.12%, respectively. Whilst the observed product spectrum is desirable, such low current efficiencies require systematic optimization of the catalytic membrane system, in particular an improved cathode with an optimum contact between proton conducting membrane, electrode and catalyst is desired.     

Performance of a mixed-conducting ceramic membrane reactor with high oxygen permeability for methane conversion

A mixed-conducting perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) ceramic membrane reactor with high oxygen permeability was applied for the activation of methane. The membrane reactor has intrinsic catalytic activities for methane conversion to ethane and ethylene. C₂ selectivity up to 40–70% was achieved, albeit that conversion rate were low, typically 0.5–3.5% at 800–900°C with a 50% helium diluted methane inlet stream at a flow rate of 34 ml/min. Large amount of unreacted molecular oxygen was detected in the eluted gas and the oxygen permeation flux improved only slightly compared with that under non-reactive air/He experiments. The partial oxidation of methane to syngas in a BSCFO membrane reactor was also performed by packing LiLaNiO/γ-Al₂O₃ with 10% Ni loading as the catalyst. At the initial stage, oxygen permeation flux, methane conversion and CO selectivity were closely related with the state of the catalyst. Less than 21 h was needed for the oxygen permeation flux to reach its steady state. 98.5% CH₄ conversion, 93.0% CO selectivity and 10.45 ml/cm² min oxygen permeation flux were achieved under steady state at 850°C. Methane conversion and oxygen permeation flux increased with increasing temperature. No fracture of the membrane reactor was observed during syngas production. However, H₂-TPR investigation demonstrated that the BSCFO was unstable under reducing atmosphere, yet the material was found to have excellent phase reversibility. A membrane reactor made from BSCFO was successfully operated for the POM reaction at 875°C for more than 500 h without failure, with a stable oxygen permeation flux of about 11.5 ml/cm² min.     

Oxidation reactions catalysed by molybdenum(VI) complexes grafted on UiO‐66 metal–organic framework as an elegant nanoreactor

A heterogeneous catalyst was synthesized by immobilizing Mo(CO)₃ in a UiO‐66 metal–organic framework. The benzene ring of the organic linker in UiO‐66 was modified via liquid‐phase deposition of molybdenum hexacarbonyl, Mo(CO)₆, as starting precursor to form the (arene)Mo(CO)₃ species inside the framework. The structure of this catalyst was characterized using X‐ray diffraction, and chemical integrity was confirmed using Fourier transform infrared and diffuse reflectance UV–visible spectroscopic methods. The metal content was analysed with inductively coupled plasma. Field emission scanning electron microscopy was used to measure particle size and N₂ adsorption measurements to characterize the specific surface area. This catalytic system was efficiently applied for epoxidation of alkenes and oxidation of sulfides. The Mo‐containing metal–organic framework was reused several times without any appreciable loss of its efficiency.     

Design and synthesis of a magnetic hierarchical porous organic polymer: A new platform in heterogeneous phase‐transfer catalysis

Recyclable phase transfer catalysts containing magnetic nanoparticles (MNPs) have been known as a major trend towards sustainable catalysts. In this study, a novel class of magnetic porous polymer on the basis of calix[4]resorcinarene was synthesized starting from silica‐coated Fe₃O₄ core‐shell nanoparticles. This compound was found as an efficient phase transfer catalyst to the conversion of benzyl halides into benzyl azides and cyanides in good yields. The catalyst could be used at least for five consecutive cycles without appreciable loss in the catalytic activity.     

Kinetics of oxidative dehydrogenation of isobutyraldehyde over Cs2HPMo12O40 catalyst

The kinetics of oxidative gas-phase dehydrogenation of isobutyraldehyde over Cs₂HPMo₁₂O₄₀ catalyst has been studied in a flow-through integral reactor at 523 K at atmospheric pressure. The catalytic reaction has been found to be accompanied by oxidation of isobutyraldehyde outside the catalyst bed. The rate of formation of methacrolein is satisfactorily described by the rate equation derived on presumption of change in the mean activation energy. The rate of the reaction in the homogeneous phase was described by empirical pseudo-first order equation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Development of Diethanolamine Selective Production Process Using Shape-Selective Zeolite Catalyst

Ethanolamines are conventionally produced on an industrial scale exclusively by the reaction of ethylene oxide (EO) with an aqueous solution of ammonia. The reaction is a typical consecutive reaction with three steps [NH₃ → NH₂(CH₂OH) → NH(CH₂OH)₂ → N(CH₂OH)₃]; therefore, it is difficult to produce diethanolamine with high selectivity. We developed a catalytic process for selective diethanolamine production from EO and anhydrous ammonia using a ZSM-5 zeolite catalyst modified with rare earth elements. This highly active catalyst was able to recognize the difference at molecular level between diethanolamine and triethanolamine. We also succeeded in producing a binderless molded zeolite catalyst having a shape suitable for a fixed-bed reactor. This catalyst does not give problematic impurities due to undesirable reactions over binders. The catalyst deterioration was overcome by developing a regeneration process using high temperature and high-density ammonia gas as a rinse medium.     

Thermal degradation of polyethylene into fuel oil over silica–alumina by a continuous flow reactor

A continuous flow reactor was operated at 420 °C and feed rate of 0–1.5 kg h⁻¹ for catalytic degradation of polyethylene (PE) over SA-1 silica–alumina in order to investigate the effect of catalyst on the reaction rate and the quantity and quality of degradation products. SA-1 was either mixed with the PE inside reactor or placed in a catalyst cage, the efficiency being slightly higher in the first case. The catalyst did not have a significant effect on the reaction rates but the volatile products clearly had lower molecular weights. More gases were produced on SA-1 compared to thermal degradation, containing higher amounts of C₄ and less amounts of C₂ compounds.     

Preparation and characterization of spherical PP/PB alloys with MgCl2-supported Ziegler-Natta catalyst

Polypropylene（PP）/polybutene-1（PB） alloys within reactor were prepared by MgCl₂-supported Ziegler-Natta catalyst with sequential two-stage polymerization technology.First,propylene homo-polymerizations were carried out to form isotactic polypropylene（iPP） particles containing active catalyst.Then,butene-1 was subsequently polymerized to form polybutene-1 phase inside the iPP particles.Finally,iPP/PB alloys with spherical shape and adjustable PB content were synthesized.The catalytic activity and catalytic stereospecificity of the Z-N catalyst in the two-stage polymerization process are discussed.The composition and physical properties of the PP alloys were characterized by FT-IR,¹³C-NMR,SEM,DSC and XRD.It was found that the in-reactor PP alloys are mainly composed of PP and PB with a little amount of poly（butene-co -propylene） random copolymers and poly（butene-block-propylene） block copolymers.SEM measurements verified that the PB phases with size in the range of 300-400 nm dispersed in the PP matrix uniformly.The incorporation of PB upon the PP matrix affects the properties of final products greatly.     

Methanol synthesis from carbon dioxide and hydrogen using a ceramic memebrane reactor

Methanol was synthesized from CO₂ and H₂ using a silica/alumina composite membrane reactor, which improved methanol conversion to 150% of the value in conventional reactor, by in situ removal of water formed in catalytic reaction. This revised version was published online in June 2006 with corrections to the Cover Date.     

Characterization of the Effects of Vanadium Traps in Cracking Catalysts by Imaging Secondary Ion Mass Spectrometry and Microactivity Test

The vanadium trapping effect of Mg and La containing additives in cracking catalyst contaminated with 2300 ppm Ni and 4700 ppm V has been analyzed by microactivity test (MAT) and imaging secondary ion mass spectrometry (SIMS). The results of SIMS imaging are consistent with cracking activity data and show that the La/spinel is a superior vanadium trap for the fluid catalytic cracking of hydrocarbons (FCC) operation. La/spinel serves as a dual function additive for both vanadium trap and SO_x removal. The optimum amount of La/spinel added to the cracking catalyst is about 15% by weight. This results in an increased catalytic activity, an increase in gasoline yield, and a decrease in coke and gas factors. The MgAl₂O₄ phase of Mg/Al₂O₃ additive is found capable of trapping vanadium while its MgO of Mg/Al₂O₃ phase can migrate to zeolite particles (the active component of the FCC catalyst) that, in turn, causes a decline in the activity of that catalyst.     

Hydrogen‐Permeable Tubular Membrane Reactor: Promoting Conversion and Product Selectivity for Non‐Oxidative Activation of Methane over an Fe©SiO2 Catalyst

Non‐oxidative methane conversion over Fe©SiO₂ catalyst was studied for the first time in a hydrogen (H₂) permeable tubular membrane reactor. The membrane reactor is composed of a mixed ionic–electronic SrCe_0.7Zr_0.2Eu_0.1O_3?δ thin film (≈20 μm) supported on the outer surface of a one‐end capped porous SrCe_0.8Zr_0.2O_3?δ tube. Significant improvement in CH₄ conversion was achieved upon H₂ removal from the membrane reactor compared to that in a fixed‐bed reactor. The Fe©SiO₂ catalyst in the H₂ permeable membrane reactor demonstrated a stable ≈30 % C₂₊ single‐pass yield, with up to 30 % CH₄ conversion and 99 % selectivity to C₂ (ethylene and acetylene) and aromatic (benzene and naphthalene) products, at the tested conditions. The selectivity towards C₂ or aromatics was manipulated purposely by adding H₂ into or removing H₂ from the membrane reactor feed and permeate gas streams.     

Selective wet air oxidation of diluted aqueous ammonia solutions over co-precipitated transition metal-aluminium catalysts

Catalytic wet air oxidation of ammonia over a co-precipitated transition metal-aluminium catalyst was investigated. Copper-aluminium (Cu-Al-O) catalyst exhibited the highest activity and N₂ selectivity among those prepared from Co, Fe, Mn, and Ni. 50% of 1500 ppm of ammonia could be removed from wastewater of pH 12 at 503 K under 2.0 MPa of air by using 4.0 g of catalyst without formation of toxic nitrogen containing compounds. Cu and Al ions were not found in solution after the reaction. It has been found that the catalytic performance of Cu-Al-O catalyst was strongly dependent on the preparation methods. The co-precipitated Cu-Al-O catalysts showed high N₂ selectivity. The presence of CuO is concluded to promote the reaction and CuAl₂O₄ in bulk phase is needed to stabilize the catalyst.