Synthesis of Vanadium Phosphate Catalysts by Hydrothermal Method for Selective Oxidation of n-butane to Maleic Anhydride

Two vanadium phosphate catalysts (VPH1 and VPH2) prepared via hydrothermal method are described and discussed. Both catalysts exhibited only highly crystalline pyrophosphate phase. SEM showed that the morphologies of these catalysts are in plate-like shape and not in the normal rosette-type clusters. Temperature-programmed reduction in H₂ resulted two reduction peaks at high temperature in the range of 600–1100 K. The second reduction peak appeared at 1074 K occurred as a sharp peak indicated that the oxygen species originated from V⁴⁺ phase are having difficulty to be removed and their nature are less reactive compared to other methods of preparation. Modified VPH2 gave better catalytic performance for n-butane oxidation to maleic anhydride contributed by a higher BET surface area, high mobility and reactivity of the lattice oxygen associated to the V⁴⁺ which involved in the hydrocarbon’s activation. A slight increased of the V⁵⁺ phase also enhanced the activity of the VPH2 catalyst.     

丁烷氧化制顺丁烯二酸酐催化剂活性相的研究

通过活性测试及催化剂表征研究了用于丁烷氧化制顺酐VPO催化剂的反应控制步骤-脱氢反应的机理,分析了(VO)2P2O7(020)面的催化脱氢过程,同时对β—VOPO4相在催化脱氢过程中的作用进行了研究。丁烷氧化制顺酐VPO催化剂中,最重要的活性相是(VO)2P2O7,而(020)面是(VO)2R2O7的活性面。与此同时,β—VOPO4相也是重要的活性相,只有在β—VOPO4相与(VO)2R2O7协同作用下,方可对丁烷分子进行较适当地活化,使脱氢作为控制步骤能够顺利进行。     

正丁烷氧化制顺酐催化剂的制备及其催化性能

采用有机相法制备了具有优异催化性能的正丁烷氧化制顺酐钒磷氧(VPO)催化剂。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、扫描电镜(SEM)、氮气吸附脱附、X射线光电子能谱(XPS)、热重分析(TG)等方法对催化剂的制备过程进行了研究,分析了催化剂在整个制备过程中物相、价态、形貌和比表面积的变化。在固定床反应器上对正丁烷氧化制顺酐的反应条件进行研究,考察了反应温度、正丁烷浓度和反应空速等条件对催化剂性能的影响。结果表明,催化剂前驱体的主要物相为VOHPO4·0.5H2O。经活化后的催化剂活性相包括(VO)2P2O7(V4+)、VOPO4(V5+)和钒磷云母相(V4+和V5+混合相)。催化剂呈规则的片层结构,具有较高的比表面积,可以达到24.08 m2/g。催化剂在制备过程中需要经过干燥、焙烧和气氛活化,对催化剂的形成具有至关重要的作用。最佳的反应条件:反应温度为395℃,正丁烷摩尔分数为1.4%~1.5%,反应空速为2 000 h-1,此时正丁烷转化率为85%~87%,顺酐收率可达到59%~60%。     

烃类晶格氧选择氧化制顺酐的强制周期操作反应技术

综述了烃类选择氧化制顺酐的生产工艺、反应技术。重点介绍了人为非定态催化反应技术的特点及在烃类晶格氧选择氧化反应中的应用 ,并对烃类选择氧化制顺酐反应提出了今后研究的方向。     

V-Mo-O苯氧化制顺酐工业催化剂研究

V-Mo-O催化剂在工业上被应用子苯氧化制取顺丁烯二顺酐（简称顺酐）,其载体孔结构、催化剂组成、制备方法及活化方式等均影响催化及反应性能。     

正丁烷氧化制顺酐流化床催化剂的喷雾成型

对正丁烷氧化制顺酐流化床催化剂的颗粒成型进行了研究,在不同类型的粘合剂和喷雾成型的条件下,实验获得了不同颗粒尺寸和粒度分布的流化床催化剂。利用正交实验设计方法探讨了喷雾操作条件对催化反应活性的影响及其变化规律,同时确定了最佳喷零操作条件。研究发现,催化剂颗粒尺寸在20～200μm,平均粒径在70～80μm左右的催化剂对正丁烷流化床催化反应的效果最好。     

活化条件对碳四烃氧化制顺酐VPO催化剂的影响

以V2O5和磷酸为原料,异丁醇为还原剂,合成催化剂前体VOHPO4·0.5H2O,分别在正丁烷/空气、混合碳四/空气气氛中活化得催化剂VPDB和VPDC.采用X射线衍射(XRD)、氢气-程序升温还原实验(H2-TPR)和等离子发射光谱(ICP)等对催化剂进行表征,并考察其分别在正丁烷和混合碳四氧化制顺酐反应中的催化性能.结果表明,催化剂VPDB与VPDC的主要括性相均是(VO)2P2O7相,后者晶格氧的活性较高,比表面积相对较小,两者的钒平均价态分别为4.28和4.12.在相同反应条件下分别进行正丁烷和混合碳四催化氧化反应,VPDC的催化活性均高于VPDB,前者的顺酐选择性低于后者.在相同反应温度下,混合碳四的转化率远大于正丁烷,但混合碳四氧化产物顺酐的选择性较差,故混合碳四催化氧化的适宜反应温度低于正丁烷催化氧化.     

负载型Keggin杂多酸催化糠醛液相氧化制备顺酐

用不同比例的四水合钼酸铵、偏钒酸铵、钨酸、草酸和磷酸等合成了4种Keggin杂多酸,并以SiO_2为载体,采用浸渍法制备了负载型的Keggin杂多酸催化剂。采用红外光谱(FT-IR)、X射线衍射(XRD)、扫描电镜(SEM)和程序升温脱附(NH_3-TPD)等手段对催化剂进行表征。以合成的负载型杂多酸为催化剂,H_2O_2为氧化剂,二氯乙烷为溶剂,研究了催化剂催化糠醛液相氧化制备顺酐的性能,考察了催化剂种类和用量,溶剂、氧化剂用量,反应温度和反应时间对糠醛转化率和顺酐收率的影响。结果表明,以MoWP/SiO_2为催化剂,催化反应性能较好,较佳的工艺条件为反应温度60℃,反应时间3 h,催化剂与糠醛的质量比为0.09,二氯乙烷和糠醛物质的量之比为3,H_2O_2和糠醛物质的量之比为2.5,在此条件下糠醛的转化率为82.33%,顺酐的收率和选择性分别可达78.51%和95.36%。催化剂在使用5次后,顺酐的收率为64.18%,重复使用性能较好。     

A Model for the Phosphorus Dynamics of VPO Catalysts during the Selective Oxidation of n‐Butane to Maleic Anhydride in a Tubular Reactor

A model for the phosphorus dynamics in vanadium‐phosphorus oxide (VPO) catalysts for the oxidation of n‐butane to maleic anhydride was developed. According to the model, reversible sorption processes determine the phosphorus content of the catalyst. Simulations reveal that several phenomena can be successfully described. If no phosphorus is added to the reactant feed, the catalytic activity increases until runaway occurs. With addition of a proper amount of phosphorus, the loss can be compensated while excessive phosphorus addition results in complete catalyst deactivation. Adjusting the model parameters to experimental data may result in a model that can be used to optimize the performance of maleic anhydride reactors.     

正丁烷氧化制顺酐流化床催化剂的性能

考察了前驱体制备过程中磷酸含量对催化剂性能的影响。由较高含量制得的催化剂,其(VO)2P2O7相含量较多,正丁烷转化率较高。随着酸浓度的减小,δ-VOPO4相的含量逐渐增多,正丁烷转化率随之升高;而顺酐选择性开始时升高,达到最大值后逐渐降低。在酸质量分数为95 0%时制备的催化剂最佳,在丁烷体积分数为4 0%、空速为500h-1的反应条件下,顺酐收率可达45 49%。     

Tribomechanical pretreatment of vanadium phosphates: structural and catalytic effects

The influence of the tribomechanical pretreatment of the precursor vanadyl hydrogenphosphate hemihydrate, VOHPO₄·0.5H₂O, prepared in aqueous medium and of the catalyst vanadyl pyrophosphate, (VO)₂P₂O₇, on the structural and catalytic properties of (VO)₂P₂O₇ in the oxidation of n-butane to maleic anhydride was investigated. Due to the pretreatment the activity and selectivity of the catalyst were markedly increased. The increase in catalytic performance is explained as an effect of the particle size in connection with lattice imperfections. This revised version was published online in July 2006 with corrections to the Cover Date.     

Oxidation of Benzene to Maleic Anhydride in a Fluidized Bed Reactor

In this project, the selective oxidation of benzene to maleic anhydride (MAN) was studied. Gas phase catalytic oxidation of benzene was carried out in a laboratory scale fluidized bed reactor on six different types of catalysts, which have different compositions. Effects of temperature, flow rates of benzene and air and catalyst type on the reaction selectivity were investigated at atmospheric pressure. The experiments were performed over a temperature range of 325 to 400 °C, a space‐time (W/F_A0) range from 11.28 × 10⁵ to 31.9 × 10⁵ g s mol^–1, and benzene/air mole ratio changes between 0.0109 and 0.0477. It was seen that conversion of benzene to MAN increased with increasing temperature for the catalysts supported by silica gel, aluminum oxide and titanium oxide. From the results it was found that conversion increased with increasing flow rate of air. When the comparison of the catalysts were made, it could be said that catalysts supported by silica gel showed higher MAN conversions. So it can be concluded that catalysts supported by silica gel were more suitable catalysts for benzene oxidation to MAN in a fluidized bed reactor.     

Computer Simulation of the Performance of a Downer‐Regenerator CFB for the Partial Oxidation of n‐Butane to Maleic Anhydride

A reactor model for a downer‐regenerator circulating fluidized‐bed (CFB) during the partial oxidation of n‐butane to maleic anhydride is presented. Upflow reactors (risers) suffer from severe solids back mixing and gas‐solids‐separation, in comparison down flow reactors exhibit a more uniform gas‐solids flow and reduced backmixing, resulting in narrower residence time distributions. Due to the sensitivity of the VPO catalyst to over‐reduction, downer reactors present an interesting alternative to riser reactors. The reactor models for the downer and the regenerator fluidized‐bed are coupled with reduction and oxidation kinetics for the catalyst, respectively. The influence of the solids residence time distributions for the combined system of both reactors on the oxidation state of the catalyst is explored by a novel newly developed oxygen loading distribution. Simulation results suggest the limited solids‐flux in downers restrict the maximum butane concentrations, while the scale‐up is predicted to be uncritical.     

Preparation of Vanadium Phosphate Catalysts from VOPO4 · 2H2O: Effect of Microwave Irradiation on Morphology and Catalytic Property

The present work addresses the influence of microwave irradiation on undoped and doped vanadium phosphate catalysts. These catalysts were prepared via VOPO₄ · 2H₂O. The catalyst’s precursors‚ VOHPO₄ · 0.5H₂O were subjected to microwave irradiation and comparison was made with the conventional heating. The interaction of these complex materials with microwave and the addition of several doponts (Nb, Bi, Co, Mo) provide interesting improvements in catalyst preparation found to be a faster, develop higher surface area, higher activity and selectivity for the oxidation of n-butane to maleic anhydride. All the catalysts were characterized by using a combination of powder XRD, H₂-TPR, BET surface area and SEM.     

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.     

Half‐Sandwich Scorpionate Vanadium,Iron and Copper Complexes: Synthesis and Application in the Catalytic Peroxidative Oxidation of Cyclohexane under Mild Conditions

The new half‐sandwich scorpionate complexes [hydridotris(1‐pyrazolyl)methane]vanadium trichloride, ([VCl₃{HC(pz)₃}] 1 (pz=pyrazolyl), [tris(1‐pyrazolyl)methanesulfonate]vanadium trichloride, [VCl₃{SO₃C(pz)₃}] 2 , [hydrido(1‐pyrazolyl)methane]iron dichloride, [FeCl₂{HC(pz)₃}] 3 , lithium [tris(1‐pyrazolyl)methanesulfonate]dichloroferrate, Li[FeCl₂{SO₃C(pz)₃}] 4 , and [tris(1‐pyrazolyl)methanesulfonate]copper chloride, [CuCl{SO₃C(pz)₃}] 5 were synthesized, characterized and shown to act, as well as the related (tripyrazolylmethane)copper dichloride, [CuCl₂{HC(pz)₃}] 6 , as selective catalysts (or catalyst precursors) for the peroxidative oxidation (with hydrogen peroxide) of cyclohexane to cyclohexanol and cyclohexanone, under mild conditions (at room temperature and using an aqueous solution of H₂O₂). The iron complexes are the most active ones (reaching TON values up to ca. 690), the effects of a variety of factors are reported and the reaction is shown to proceed via both C‐ and O‐centred radical mechanisms, conceivably involving a metal‐based oxidant.     

Creation of a Monomeric Ruthenium Species on the Surface of Micro‐Size Copper Hydrogen Phosphate: An Active Heterogeneous Catalyst for Selective Aerobic Oxidation of Alcohols

A new micro‐size copper hydrogen phosphate (CHP) synthesized by the emulsion method combined with a monomeric ruthenium species was found to be a very effective catalyst for the selective oxidation of alcohols. Several kinds of alcohols were transformed into the corresponding aldehydes or ketones over the RuCHP catalyst by oxygen under very mild conditions. The results showed that the CHP material was perfect as a catalyst support due to its high ion‐exchange ability and adsorption capacity.     

周期性输入组分和扫气在改善钯膜反应器甲烷部分氧化制氢中的作用(英文)

The partial oxidation of methane under periodic operation over Ni/γ-Al2O3 catalyst was investigated in a Pd-membrane reactor.The effects of key parameters such as the inlet composition and the sweeping gas on methane conversion and the hydrogen recovery are numerically established with two periodic input functions.In order to analyze the effect of the inputs modulation,the reaction was performed under low steam to methane ratio at a moderate temperature and pressure.It was obtained that to achieve process intensification is to operate the process in a periodic way.The main results show that the periodic input functions can improve the performance of the process compared to the optimal steady state operation.Moreover,there is an optimum amplitude of manipulated inputs leads to a maximum of hydrogen recovery.It is noteworthy that the comparison between the predicted performance via the sinusoidal and the square ways show that the better average performance was obtained with the square way.     

Amplification of Periodic Temperature Disturbances in a Packed‐Bed Reactor: CO Oxidation over a CuO/Al2O3 Catalyst

Amplification of periodic variations of input temperature in a product‐inhibited reaction — CO oxidation over CuO‐γ‐Al₂O₃ — was investigated experimentally in an insulated packed‐bed reactor. At steady state the temperature profile was elongated compared with that of a reactant‐inhibited CO oxidation over Pt/Al₂O₃, studied elsewhere. Under periodic operation, amplitudes of the resulting travelling temperature waves, monitored downstream from the reaction front, were amplified to a greater extent than those in the reactant‐inhibited CO oxidation over Pt/Al₂O₃. The magnitude of the amplification depended on the perturbation frequency and showed resonance behaviour. The magnitude decreased monotonically with increasing perturbation amplitude.