丙烷氧化脱氢制丙烯介孔催化材料

介绍了丙烷氧化脱氢制丙烯介孔催化材料的研究进展,包括介孔分子筛和介孔金属氧化物催化剂,综述载体、活性组分和制备方法等对丙烷氧化脱氢催化性能的影响,着重评述提高介孔分子筛催化剂催化活性的方法。     

丙烷氧化脱氢制丙烯研究进展

开发新型丙烯制备工艺对于满足人们日益增长的丙烯需求具有重要意义。由于商业化无氧脱氢技术存在热力学平衡限制、反应温度高、催化剂易积炭等不足,近年来,人们将研究重心转向了丙烷氧化脱氢技术。本文简述了丙烷氧化脱氢制丙烯的发展现状,综述了近年来文献报道的丙烷氧化脱氢催化剂体系（V基、Cr基、Co基、Ni基、Mo基、Pt基、Ce基和非金属基催化剂）、机理研究和不同氧化剂选择,并对各自的优势和不足进行了简单分析。分析发现,虽然目前丙烷氧化脱氢催化剂的种类非常广泛,但产物丙烯的收率仍有待提高,机理研究也需要更加系统和深入。最后指出,系统研究丙烷氧化脱氢机理,并在此基础上开发先进催化剂,进一步提高丙烯的选择性和收率是未来丙烷氧化脱氢研究的重要方向。     

丙烷氧化脱氢制丙烯的钒基介孔催化材料研究进展

介绍了近年来丙烷氧化脱氢催化技术的最新研究进展,针对其中应用最广泛的钒基介孔催化剂,对其反应机理、载体性能和制备方法进行了综述,并比较了不同催化体系的丙烷氧化脱氢性能,提出了改善钒基介孔催化剂催化活性与选择性的途径。通过比较已经报道的同类研究结果,着重阐述了载体的孔结构对于氧化脱氢过程的影响,比表面积和孔径的优化对于提高催化剂的活性组分分散度以及活性位的数量效果明显。今后研究应着重提高催化剂孔道结构在高温下的稳定性以及使用寿命。     

Selective conversion of propane to propene by the catalytic oxidative dehydrogenation over cobalt and magnesium molybdates

Catalytic performances of various metal molybdates were tested in the oxidative dehydrogenation of propane to propene with molecular oxygen under an atmospheric pressure. Most of the molybdates tested promoted the selective oxidative conversion of propane to propene and among them cobalt and magnesium molybdates were found highest in the activity and selectivity. It was also found that their catalytic activities were highly sensitive to the catalyst composition, and it turned out that Co_0.95MoO _x and Mg_0.95MoO _x catalysts which have slightly excess molybdenum showed the highest activity in the oxidative dehydrogenation of propane. Under the optimized reaction conditions, higher reaction temperatures and lower partial pressures of oxygen, these catalysts gave 60% selectivity to propene at 20% conversion of propane. Since the molybdates having the surface enriched with molybdenum oxide tended to show high activity for the propane oxidation, surface molybdenum oxide clusters supported on metal molybdate matrix seem to be the active sites for the selective oxidative dehydrogenation of propane.     

Characterisation of vanadium-oxide-based catalysts for the oxidative dehydrogenation of propane to propene

Topics in Catalysis - The study is based on the previous development of α-Al2O3-supported multi-metal-oxide materials for oxidative dehydrogenation of propane by applying a combinatorial...     

On the NiMoO4 oxidative dehydrogenation of propane to propene: some physical correlations with the catalytic activity

The - and -phases of NiMoO₄ have been investigated with different techniques (X-ray diffraction, electrical conductivity, IR spectroscopy) in order to tentatively rationalise the different catalytic activities observed in the oxidative dehydrogenation of propane to propene. XRD analyses have shown that at 595 ° C, the -phase is already present but a temperature of 700 ° C is required to obtain a full conversion into a pure -phase. Electrical conductivity showed the presence of anionic vacancies. It is proposed that propene is formed by the reaction of propane with surface O^2- anions. The -phase is almost twice more selective in propene formation than the -phase for comparable conversion at identical temperatures. This could derive from different oxygen environments on the active catalytic site.     

Fundamental and combinatorial approaches in the search for and optimisation of catalytic materials for the oxidative dehydrogenation of propane to propene

An evolutionary approach was applied to create five generations of -Al₂O₃-supported multi-metal-oxides to be used as catalytic materials for the oxidative dehydrogenation of propane at 773 K. Each generation consisted of 56 differently composed materials, i.e., a total amount of 280 materials. These catalytic materials were tested in parallel. For the best materials propene yields from 7% (1st generation) to 9% (5th generation) were achieved. Some of these superior catalysts were characterised by XRD, XPS and EPR. A correlation between catalytic performance and the Mg/V ratio on the surface was found. Based on the structural knowledge obtained, from which the requirement of isolated or at least weakly interacting vanadium sites was derived, VO_x (2.8 wt.%)/MCM-48 and VO_x (2.8 wt.%)/MCM-41 catalysts with a high dispersion of vanadia were used as reference giving a maximal propene yield of 17 and 15%, respectively.     

VO_x/焦磷酸镧催化剂的丙烷氧化脱氢制丙烯催化性能

以嵌段共聚物P188为模板剂制备VO_x/焦磷酸镧催化剂。采用比表面分析仪、透射电镜、X射线光电子能谱和H_2-TPR对催化剂结构进行表征,并评价其丙烷氧化脱氢制丙烯的催化性能。结果表明,焦磷酸镧有一定的催化活性,但催化性能不高。当负载钒氧物种后,VO_x/焦磷酸镧催化剂催化活性有所增加,反应温度600℃时,丙烯产率达16.6%。原因主要是钒氧物种和可移动氧在丙烷氧化脱氢过程中起到重要作用。     

碳基硼基催化体系丙烷氧化脱氢催化剂的研究进展

以碳基硼基为代表的非金属催化剂氧化能力不如金属氧化物,这使得非金属催化体系如碳基和硼基催化剂对于丙烷氧化脱氢反应具有独特的优势。本文综述了应用廉价环保型改性碳基和硼基的非金属丙烷脱氢催化剂将丙烷转化为丙烯的技术前沿,阐述了有序介孔炭材料,纳米碳材料（纳米纤维、石墨烯、碳纳米金刚石等）和六方氮化硼材料各自的丙烷氧化脱氢机理以及通过杂原子改性后提高其催化活性的情况。并对其未来的发展方向以及丙烷氧化脱氢新材料领域的发展做了展望。     

An evidence of active surface MoOx over MgMoO4 for the catalytic oxidative dehydrogenation of propane

In order to clarify whether MgMo_xO_y catalysts with slight excess of molybdenum relative to the stoichiometric MgMoO₄ compound showed increased activities for propene formation in the propane oxidative dehydrogenation, we investigated the catalytic properties of MoO₃ supported on MgMoO₄ and of MgMo_xO_y catalysts treated with acid or base. Supporting MoO₃ on magnesium-rich MgMo_0.99O_y catalysts which are poorly active, or treating them with acetic acid to remove excess magnesium, resulted in drastic activity increases. On the other hand, the ammonia treatment of molybdenum-rich MgMo_1.05O_y catalysts which are highly active turned out to give a remarkable decrease in activity, because surface MoO_x dissolved in ammonia water. A clear correlation was observed between the catalytic activities for propane oxidation and the dehydration of 2-propanol to propene over the supported catalyst and the treated catalysts. Since the bulk structures were unchanged by supporting or by the treatments, the existence of MoO_x clusters formed on the surface of MgMoO₄ are responsible for the activities in the oxidative dehydrogenation of propane. This revised version was published online in July 2006 with corrections to the Cover Date.     

Oxidative dehydrogenation of propane to propene, 1: Kinetic study on V/MgO

The reaction kinetics of the oxidative dehydrogenation of propane to propene over a V/MgO catalyst were studied. Both propane and propene oxidation kinetics were measured independently to quantify the rates of the parallel and consecutive reactions to propene and carbon oxides. Specific experiments to evaluate reaction products effects showed that water inhibited reaction rates but co‐feeding CO₂ or propene had no measurable effect on selectivity or conversion. Kinetic data generated under integral reactor conditions and over an inert membrane reactor have also been used to estimate the kinetic parameters. Selectivity decreased as the oxygen partial pressure increased; however, propene yield was relatively insensitive to oxygen concentration. A dual site Mars‐van Krevelen model characterizes the reaction kinetics well. The role of lattice oxygen was established by alternating pulses of propane and oxygen. This redox model is able to predict the experimental tendencies observed in the three types of reactor studied.     

柱撑型钒基催化剂的制备及其丙烷氧化脱氢催化性能

以人工合成的3种不同层板组成的层状双羟基金属氢氧化物MgAl-CO₃-LDHs、CoAl-CO₃-LDHs和NiCr-CO₃-LDHs为载体,以偏钒酸钠NaVO₃为柱撑剂和钒前体,采用离子交换法制备了钒柱撑的催化剂样品（MgAlVO、CoAlVO和NiCrVO）,通过XRD、FTIR、XPS和Raman等手段表征了样品的物相、钒物种的存在形态以及钒的价态,以丙烷氧化脱氢制丙烯为模型反应,表征了所制备的催化剂样品的催化性能,着重探讨了LDHs载体的层板组成以及钒的含量对催化剂样品中的钒氧物种存在形态及其丙烷氧化脱氢催化性能的影响。结果表明：以20%理论含量的钒柱撑MgAl-CO₃-LDHs所制备的催化剂样品20%MgAlVO对丙烷氧化脱氢反应的催化性能较好,当反应温度为560℃时,丙烯收率可以达到11.3%,Raman光谱显示该催化剂样品中的钒以Mg₃V₂O₈和α-Mg₂V₂O₇两种形式共存,且晶格氧O^2-和吸附氧O^-所占的比例较为均衡,有利于获得较好的丙烷氧化脱氢催化性能,而在同样条件下制备的催化剂样品20%CoAlVO和20%NiCrVO中的钒物种只观察到分别以Co₃V₂O₈和Ni₃V₂O₈存在的正钒酸盐,前者对丙烯的收率不到8%,后者甚至完全得不到丙烯。     

丙烷脱氢催化反应机理及动力学研究进展

从化学反应原理、热力学性质和催化剂等角度出发,概述了丙烷无氧脱氢和有氧脱氢的反应体系;详述了无氧脱氢催化剂体系中的Pt系、Cr系和ZSM-5分子筛催化剂、氧化脱氢催化剂体系中的钒基催化剂V-Mg-O,V2O5/ZrO2上的脱氢反应机理和动力学研究。     

Synthesis of V-MCM-41 by template-ion exchange method and its catalytic properties in propane oxidative dehydrogenation

Vanadium has been introduced to MCM-41 without collapse of the mesoporous structure by exchanging VO²+ ions in the aqueous solution with the template cations in the uncalcined MCM-41. This template-ion exchange (TIE) method provides tetrahedrally coordinated vanadyl species dispersed in the channel of MCM-41. Such synthesized V-MCM-41 shows higher catalytic activity in the oxidative dehydrogenation of propane than that prepared by direct hydrothermal method.     

VO_x/焦磷酸铈催化剂丙烷氧化脱氢制丙烯催化性能研究

以嵌段共聚物P188为模板,以焦磷酸铈钠为载体,制备钒氧化物为活性组分的VO_x/焦磷酸铈催化剂。采用XRD、N_2吸附-脱附、TEM、XPS和H_2-TPR等进行表征,并把材料应用于丙烷氧化脱氢反应中,600℃条件下,丙烷转化率达41.57%,丙烯选择性78.06%,产率高达32.45%。优良的催化效能主要归因于焦磷酸铈钠、钒氧化物和钠物种的协同效应。     

Microwave-assisted catalytic oxidative dehydrogenation of ethylbenzene on iron oxide loaded carbon nanotubes

The catalytic performance of multi-walled carbon nanotubes (MWCNTs) modified by iron oxide has been investigated for oxidative dehydrogenation of ethylbenzene in an integral fixed-bed reactor conventionally-heated and under microwave-assisted conditions. The morphology and microstructural characteristics of the obtained composites before and after the catalytic reaction were characterized by transmission electron microscopy and X-ray diffraction. The content 3wt.% of iron oxide supported on MWCNTs was found optimal in respect of the ethylbenzene conversion and styrene selectivity. All prepared composites were found more selective in a microwave field in the temperature range 380-450 °C. The transformation of Fe₂O₃ into Fe nanocrystals encapsulated by polyhedral graphite shells was observed only under microwave-assisted reaction conditions.     

Influence of operating conditions,Si/Al ratio and doping of zinc on Pt-Sn/ZSM-5 catalyst for propane dehydrogenation to propene

The direct catalytic dehydrogenation of propane to propene is an important route to enhance propene production. In the present experimentation the focus was to investigate the influence of incipient operating conditions, Si/Al ratio of zeolite support and effect of zinc doping on Pt-Sn/ZSM-5 catalyst performance. The catalysts were extensively investigated by reaction tests in a continuous plug-flow quartz micro-reactor. The experimental data shows that the manipulation of operating parameters significantly improves the reaction performance, while huge dynamicity is observed in product distribution. Reaction temperature, 600 °C is found to be most suitable, while increasing the weight hourly space velocity (WHSV), propene selectivity improves at the expense of lower conversion. The OPE was drawn to observe overall reaction network. It was found that the acidity of zeolitic support plays a more important role in achieving desired product selectivity than additional metallic content. Accordingly, the Si/Al ratio of the ZSM-5 zeolite the pro- pene selectivity was enhanced, leading to remarkable improvement in the total olefins selectivity which was remarkably improved owing to a suppression of secondary reactions. At Si/Al ratio 300, the selectivity of propene and total olefins becomes stable at 73% and 90% respectively. The doping of Zn on Pt-Sn/ZSM-5 improves only propene selectivity, but is severely affected by quick deactivation.     

Nanoparticles of vanadia–zirconia catalysts synthesized by polyol-mediated route: Enhanced selectivity for the oxidative dehydrogenation of propane to propene

A polyol-mediated route was employed to obtain nanoparticles of vanadia–zirconia (10 nm) and Ti⁴⁺-modified zirconia catalyst for the selective oxidative dehydrogenation reaction of propane to propene. The catalytic activity and selectivity of samples thus prepared were compared with the values for the sample synthesized by the conventional impregnation method. More dispersed amorphous vanadia species on zirconia support could be obtained by polyol method compared to those obtained by conventional impregnation route, as discerned from transmission electron microscopy (TEM) and Raman studies. Raman spectra of samples prepared by polyol method indicated the presence of monovanadate and polyvanadate species on the zirconia support surface, whereas the impregnated sample showed the existence of aggregated vanadia besides mono and polyvanadate species though the vanadia loading was the same on all samples. XPS studies revealed that vanadia existed as both V⁵⁺ and V⁴⁺ in the samples prepared by the polyol method, whereas only V⁵⁺ state was seen in the impregnated sample. The catalysts prepared by polyol method exhibited enhanced selectivity for propene formation compared to the sample prepared by impregnation method. The enhanced selectivity is attributed to the presence of dispersed vanadia species with lower valence state of vanadium. The present results demonstrate that the polyol-mediated synthesis is an efficient method for the preparation of supported vanadia catalysts containing such active species.     

Direct synthesis and superior catalytic performance of V-containing SBA-15 mesoporous materials for oxidative dehydrogenation of propane

V-containing SBA-15 mesoporous materials have been directly synthesized in an acidic and peroxidic medium. Compared to V/SBA-15 and V/SiO₂ samples prepared by impregnation method, the materials thus synthesized show larger surface areas, higher dispersion and reducibility of VO _x species, and superior catalytic performance for oxidative dehydrogenation of propane.