Hydrogenation of aromatics under mild conditions on transition metal complexes in zeolites. A cooperative effect of molecular sieves

The hydrogenation of aromatics, i.e. benzene, toluene, -methylstyrene, anisole, and ethyl benzoate, can be carried out under a very low (1/12000) catalyst to substrate ratio, and mild reaction conditions (80°C, 6 atm of H₂O), on Rh and Ni organometallic complexes anchored on USY zeolites. A strong cooperative effect between the faujasite surface and the transition metal surface complex is thought to be responsible for the simultaneous enhancement of concentrations of arene and H₂ in the neighborhood of the catalytic centers, and for the observed electronic effects.     

Membrane microreactors for catalytic reactions

Membrane microreactors (MMRs) combine the advantages of membrane separation and microreactors such as high area/volume ratio, enhanced mass and/or heat transfer, improved catalytic efficiency without equilibrium limitation, good operational safety and design flexibility. This article presents a short review of recent developments in MMRs and in particular highlights their applications in catalytic processing. The structure and fabrication of MMRs, the incorporation of catalysts with membranes, the flow characteristics as well as their applications in a variety of catalytic processes are presented. The prospects and challenges of MMRs in catalytic processing are also presented and discussed. © 2013 Society of Chemical Industry     

不对称催化加氢技术的研究及其发展趋势

总结了不对称催化加氢技术中手性催化剂的制备、催化机理以及催化工艺的研究，对未来不对称催化加氢技术的发展趋势提出了一些看法。多样化催化剂库的建立、非均相催化技术及其工程应用研究将是推动加氢技术快速发展的研究重点。     

Influence of intracrystalline diffusion in shape selective catalytic test reactions

Molecular dynamics simulations are used to measure the self diffusion constant D of linear decane and n-methylnonanes (n = 2, 3, 4, and 5) at a catalytically relevant temperature in seven 10 member ring zeolites. Two general behaviors are observed in D as the branch position is moved towards the center of the alkane chain. For three of the zeolites (MEL, MFI, and MTT), D decreases monotonically as expected based on a consideration of the bulkiness of the different isomers. For the other four, alkane diffusion is considered anamolous as D is not a monotonic function of branch position. For n-methylnonanes in three zeolites D shows a minimum at either n = 2 (FER), 3 (EUO), or 4 (TON). In AEL, D has a local maximum for n = 3. Alkane diffusion is anamolous in these zeolites because they have structural features that provide a unique hindrance to molecular motion along the main diffusion channel. The ability of the zeolite to hinder motion depends on the molecular structure of the isoparaffin, resulting in the anamolous behavior observed. The 10 member ring zeolites selected for this study represent the entire group for which known structures exist and values of the modified constraint index have been published. The diffusion data presented indicates that product shape selectivity may play some part in determining the modified constraint index. This revised version was published online in July 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.     

过渡金属/分子筛催化剂上选择性催化还原氮氧化物的研究进展

综述了近十年来过渡金属/分子筛催化剂上氨和碳氢化合物选择性催化还原NOx方面的研究进展。在NH3-SCR体系,着重介绍了铜基和铁基分子筛催化剂的研究状况,探讨了分子筛催化剂在该体系中的失活原因;在HC-SCR体系,总结了不同过渡金属、分子筛类型、还原剂、H2O和SO2等对催化剂活性的影响,探讨了目前比较公认的碳氢化合物选择性催化还原NOx的反应机理。最后展望了分子筛催化剂在选择性催化还原NOx领域今后的研究方向。     

Partial oxidation of light paraffins on supported superacid catalytic membranes

Superacid-supported catalytic membranes were found to be active and very selective in the partial oxidation of light paraffins (C₁–C₂) with H₂O₂ under mild conditions (T_R: 80–110°C; P_R: 1.4 bar) in a three-phase catalytic membrane reactor (3PCMR). Among different catalytic membranes investigated, Nafion-based ones showed the best performance in terms of both activity and selectivity. Addition of Fe²⁺ ions in the liquid phase enhances the reaction rate, however, a volcano-shaped trend between reaction rate and concentration of Fe²⁺ was observed. Reaction temperature drastically affects both reaction rate and product distribution. A reaction pathway based on the electrophilic hydroxylation of the C–H bond on superacid sites and subsequent reaction of the activated paraffin with OH radicals has been proposed.     

Ion oxide conductor as a catalytic membrane for selective oxidation of hydrocarbons

A catalytic membrane reactor using ion‐oxide conductors as catalysts is experienced in selective oxidative dimerization of propene to C₆‐dimers. Structural and textural properties, catalytic and non‐catalytic reactivities of M‐doped Bi₂O₃ (M = La, Ce, Eu, Er, V, Nb) are studied. TGA experiments show that dopants increase the rates of reduction and reoxidation of Bi₂O₃, but that the reoxidation of the catalysts is rate limiting. During catalysis, the best yields in 1,5‐hexadiene and benzene are obtained with cerium‐doped Bi₂O₃. This revised version was published online in July 2006 with corrections to the Cover Date.     

希夫碱类金属配合物催化剂催化氧化烯烃研究进展

分析了希夫碱金属配合物的结构特点及其催化氧化烯烃的研究现状,阐述了用于均相催化氧化的希夫碱、固载型希夫碱金属配合物催化剂的分类及其在氧化烯烃领域的应用研究。通过分析希夫碱类小分子金属配合物催化氧化烯烃的缺陷,得出非均相的负载型希夫碱类金属配合物催化剂是目前主要发展方向的结论。     

Interlayer-confined two-dimensional manganese oxide-carbon nanotube catalytic ozonation membrane for efficient water purification

Catalytic ozonation technology has attracted copious attention in water purification owing to its favorable oxidative degradation of pollutants and mitigation of membrane fouling capacity. However, its extensive industrial application has been restricted by the low ozone utilization and limited mass transfer of the short-lived radical species. Interlayer space-confined catalysis has been theoretically proven to be a viable strategy for achieving high catalytic efficiency. Here, a two-dimensional MnO₂-incorporated ceramic membrane with tunable interspacing, which was obtained via the intercalation of a carbon nanotube, was designed as a catalytic ozonation membrane reactor for degrading methylene blue. Benefiting from the abundant catalytic active sites on the surface of two-dimensional MnO₂ as well as the ultralow mass transfer resistance of fluids due to the nanolayer confinement, an excellent mineralization effect, i.e., 1.2 mg O_3(aq) mg^–1 TOC removal (a total organic carbon removal rate of 71.5%), was achieved within a hydraulic retention time of 0.045 s of pollutant degradation. Further, the effects of hydraulic retention time and interlayer spacing on methylene blue removal were investigated. Moreover, the mechanism of the catalytic ozonation employing catalytic ozonation membrane was proposed based on the contribution of the Mn(III/IV) redox pair to electron transfer to generate the reactive oxygen species. This innovative two-dimensional confinement catalytic ozonation membrane could act as a nanoreactor and separator to efficiently oxidize organic pollutants and enhance the control of membrane fouling during water purification.     

含氮化合物废气选择性催化氧化技术研究进展

通过对当前含氮化合物废气治理技术的对比分析,总结选择性催化氧化的相关技术优势。根据对含氮化合物的种类及来源分析,介绍氨气、腈类、胺类及其他含氮化合物的催化净化技术。重点总结催化剂的种类、研发进展和在实际使用中可能遇到的问题,同时展望含氮化合物废气选择性催化氧化技术的研发方向。     

Isobutane dehydrogenation reaction in a packed bed catalytic membrane reactor

A packed-bed catalytic ceramic membrane reactor (PBCMR) was used for the isobutane dehydrogenation reaction. The experimental results have shown that through the use of the membrane reactor one can attain better conversions and yields than in a conventional reactor operating under the same outlet pressure and temperature, and feed composition conditions.     

Synthesis of polymer-supported metal-ion complexes and evaluation of their catalytic activities

Polymer-supported transition-metal-ion complexes of the N,N′-bis(o-hydroxy acetophenone) propylenediamine (HPPn) Schiff base were prepared by the complexation of iron(III), cobalt(II), and nickel(II) ions on a polymer-anchored N,N′-bis(5-amino-o-hydroxy acetophenone) propylenediamine Schiff base. The complexation of iron(III), cobalt(II), and nickel(II) ions on the polymer-anchored HPPn Schiff base was 83.44, 82.92, and 89.58 wt%, respectively, whereas the unsupported HPPn Schiff base showed 82.29, 81.18, and 87.29 wt % complexation of these metal ions. The iron(III) ion complexes of the HPPn Schiff base showed octahedral geometry, whereas the cobalt(II) and nickel(II) ion complexes were square planar in shape, as suggested by spectral and magnetic measurements. The thermal stability of the HPPn Schiff base increased with the complexation of metal ions, as evidenced by thermogravimetric analysis. The HPPn Schiff base showed a weight loss of 51.0 wt % at 500°C, but its iron(III), cobalt(II), and nickel(II) ion complexes showed weight losses of 27.0, 35.0, and 44.7 wt % at the same temperature. The catalytic activity of the unsupported and supported metal-ion complexes was analyzed by the study of the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The supported HPPn Schiff base complexes of iron(III) ions showed a 73.0 wt % maximum conversion of phenol and 90.6 wt % epoxidation of cyclohexene, but unsupported complexes of iron(III) ions showed 63.8 wt % conversion of phenol and 83.2 wt % epoxidation of cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 wt % and 98.1 wt % with the supported HPPn Schiff base complexes of iron(III) ions, but it was low with the supported Schiff base complexes of cobalt(II) and nickel(II) ions. The selectivity for CTL and ECH varied with the molar ratio of the metal ions but remained unaffected by the molar ratio of hydrogen peroxide to the substrate. The energy of activation for the epoxidation of cyclohexene and oxidation of phenol with the polymer-supported Schiff base complexes of iron(III) ions was 10.0 and 12.7 kJ/mol, respectively, but it was found to be higher with the supported HPPn Schiff base complexes of cobalt(II) and nickel(II) ions and with the unsupported HPPn Schiff base complexes of iron(III), cobalt(II), and nickel(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Taylor-vortex membrane reactor for continuous gas-liquid reactions

A unique Taylor-vortex membrane reactor (TVMR) design for continuous gas-liquid reactions is presented in this work. The reactor consists of a cylindrical rotor inside a stationary concentric cylindrical vessel, and a flexible system of equispaced baffle rings surrounding the rotor. This restricts the annular cross section to a small gap between the baffles and the rotor, and divides the annulus into 18 mixing zones. The baffles support a 6 m long PFA tubular membrane that is woven around the rotor. At 4 mL/min inlet flow rate, the TVMR showed a plug-flow behavior and outperformed the unbaffled reactor, having 5–12 times lower axial dispersion. The continuous aerobic oxidation of benzyl alcohol was performed for 7 h using the Pd(OAc)₂/pyridine catalyst in toluene at 100 °C and 1.1 MPa oxygen pressure. A stable conversion of 30% was achieved with 85% benzaldehyde selectivity, and no pervaporation of organics into the gas phase.     

Modelling the kinetics of fast catalytic cracking reactions

Instantaneous kinetic constants and gasoline selectivities have been determined for catalytic cracking of n-hexadecane. The pulse technique was used in order to model the sequential build-up of coke which occurs on cracking catalyst within a riser transport-line reactor. The total amount of hydrocarbon injected per unit weight of catalyst was between 0 and 10. The mathematical model used to analyze the data was based on the unsteady state mass balance of the microcatalytic reactor with the assumption of plug flow. Results suggest a fast deactivation process during the run with fresh catalyst, while regenerated catalyst showed a slower deactivation. The catalyst regenerated three times evidenced a low apparent activation energy when temperature was increased from 500°C to 550°C.     

Theoretical investigation of a water‐gas‐shift catalytic membrane for diesel reformate purification

The novel application of a catalytic water‐gas‐shift membrane reactor for selective removal of CO from H₂‐rich reformate mixtures for achieving gas purification solely via manipulation of reaction and diffusion phenomena, assuming Knudsen diffusion regime and the absence of hydrogen permselective materials, is described. An isothermal, two‐dimensional model is developed to describe a tube‐and‐shell membrane reactor supplied with a typical reformate mixture (9% CO, 3% CO₂, 28% H₂, and 15% H₂O) to the retentate volume and steam supplied to the permeate volume such that the overall H₂O:CO ratio within the system is 9:1. Simulations indicate that apparent CO:H₂ selectivities of 90:1 to >200:1 at H₂ recoveries of 20% to upwards of 40% may be achieved through appropriate design of the catalytic membrane and selection of operating conditions. Under these conditions, simulations predict an apparent hydrogen permeability of 2.3 × 10^?10 mol m^?1 Pa, which compares favorably against that of competing hydrogen‐permselective membranes. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4334–4345, 2013     

MOR型分子筛膜反应器中丁二酸酯化反应研究

采用强酸性阳离子交换树脂作为催化剂,在耐酸性MOR型分子筛膜反应器中合成了丁二酸酯.采用X-射线衍射(XRD)和扫描电子显微镜(SEM)表征了MOR型分子筛膜反应前和重复使用10次后的膜层微观结构.考察了分子筛膜反应器中酸醇摩尔比、反应温度、催化剂用量以及膜面积与反应体积比(S/V)对丁二酸转化率的影响.结果表明,由于MOR型分子筛膜脱除反应副产物水,打破了丁二酸酯化反应的化学平衡,在接近理论的酸醇摩尔比条件下实现了丁二酸几乎完全转化.进一步考察了分子筛膜在反应体系中可重复使用性.     

Oxygen selective ceramic hollow fiber membranes for partial oxidation of methane

A BaCo_xFe_yZr_zO_3?δ (BCFZ) perovskite hollow fiber membrane was used to construct reactors for the partial oxidation of methane (POM) to syngas. The performance of the BCFZ fibers in the POM was studied (i) without any catalyst, (ii) with catalyst‐coated fibers, and (iii) with catalyst packed around the fibers. In addition to the performance in the POM, the stability of the BCFZ hollow fiber membranes was investigated for the different catalyst arrangements. Best stability of the BCFZ hollow fiber membrane reactor in the POM could be obtained if the reforming catalyst is placed behind the oxygen permeation zone. It was found that a direct contact of the catalyst and the fiber must be avoided which could be achieved by coating the fiber with a gold film. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Selectivity of partial hydrogenation reactions performed in a pore-through-flow catalytic membrane reactor

The selectivity of partial hydrogenation reactions of unsaturated substrates was studied in a membrane reactor operating at 323 K and 40 bar hydrogen pressure. The reactor system was constructed as a loop of a saturation vessel and a membrane module in which the reaction mixture was resaturated with hydrogen up to 100 times. In a porous membrane made from cross-linked polyacrylic acid palladium nanoparticles were incorporated as catalysts. A well-defined residence time within the membrane was achieved due to a defined pore structure of the membrane and a convective mass flow of the reaction mixture through the membrane. The selectivity for the partially hydrogenated products was investigated as a function of the pore size of the PAA membrane and was compared to commercially available catalysts. Compared to experiments with supported catalysts (Pd/C and Pd/Al₂O₃) in a slurry and a fixed bed reactor the selectivity for the desired products could be increased by 3% (1-octyne) up to 40% (geraniol).