The Selective Oxidation of Methanol to Formaldehyde on Iron Molybdate Catalysts and on Component Oxides

The reaction of methanol with an industrial iron molybdate catalyst, and with Fe₂O₃ and with MoO₃, has been investigated with a pulsed flow reactor and temperature-programmed desorption (TPD). The molybdena-based samples show only formaldehyde in TPD as the carbon-containing product, arising from the decomposition of a surface methoxy species. In contrast, haematite yields no formaldehyde, only CO₂ and H₂, which evolve coincidently at 290 °C, and indicates the presence of a formate intermediate on the surface. In turn, the reactor work shows high selectivity to formaldehyde for the molybdate materials and zero for haematite. The iron molybdate sample is more active than the molybdena, conversion beginning at 150 °C for the former and 270 °C for the latter. These data are discussed in terms of a global mechanism for the reaction and a tentative reaction enthalpy profile is proposed. The main differences between the iron and molybdenum samples arise from the stronger binding of oxygen in the former and the higher concentration of cation sites.     

Methanol Selective Oxidation to Formaldehyde over Iron-Molybdate Catalysts

This review deals with the important industrial reaction of formaldehyde manufacture by methanol oxidation over iron molybdate catalysts. Detailed reference is made to the used catalyst, preparation techniques (coprecipitation, sol-gel like, mechanical mixing, etc.) including unsupported and supported catalysts, promoters and characterization methods. The controversial active phase assignment (stoichiometric versus Mo rich iron molybdate) is discussed. The proposed reaction mechanisms and kinetic laws for the main and side reactions are examined. The catalyst deactivation processes are reviewed and the role of Mo excess on these processes is underlined. Finally conclusions and perspectives are presented.     

Selective Oxidation of Methanol to Formaldehyde Using Modified Iron-Molybdate Catalysts

Methanol selective oxidation to formaldehyde over a modified Fe-Mo catalyst with two different stoichiometric (Mo/Fe atomic ratio = 1.5 and 3.0) was studied experimentally in a fixed bed reactor over a wide range of reaction conditions. The physicochemical characterization of the prepared catalysts provides evidence that Fe₂(MoO₄)₃ is in fact the active phase of the catalyst. The experimental results of conversion of methanol and selectivity towards formaldehyde for various residence times were studied. The results showed that as the residence time increases the yield of formaldehyde decreases. Selectivity of formaldehyde decreases with increase in residence time. This result is attributable to subsequent oxidation of formaldehyde to carbon monoxide due to longer residence time.     

Surface Segregation in Iron Molybdate Catalysts

The high selectivity of iron molybdate catalysts for the production of formaldehyde from methanol is somewhat surprising in view of the very different behaviour of the individual oxides of Fe and Mo for this reaction. The former, on its own, is a complete combustor of methanol, whereas the latter is highly selective. Here we use STEM (scanning transmission electron microscopy) at high resolution to image the surface of small particles of the catalyst and to show that this high selectivity is due to the dominance of the surface region by molybdenum oxide.     

甲醇氧化羰基化合成碳酸二甲酯催化剂研究进展

碳酸二甲酯(DMC)是一种用途广泛的绿色化工原料。甲醇氧化羰基化法合成DMC具有产品选择性高、反应温度低、原子经济等优点,是合成DMC最重要的方法之一。综述了甲醇氧化羰基化合成DMC催化剂的研究进展,包括含卤素铜系催化剂和无卤素铜系催化剂,重点讨论了无卤素铜系催化剂的反应机理及活性炭、石墨烯和分子筛等载体对催化性能的影响。分析发现,载体中的介孔结构、缺陷位和表面基团能够加强Cu与载体间的相互作用,抑制Cu物种的团聚、流失以及活性Cu物种氧化,从而提高催化性能。     

Methanol Oxidation over Iron-Molybdate Catalysts: Optimization of the Process

This research aims to shed more light on the possibilities to optimize the process of selective oxidation of methanol over oxide catalysts using an adiabatic layer by determining border values of basic parameters of the process in the adiabatic layer that ensure a maximum rate of methanol oxidation at high selectivity. Laboratory experiments were performed to clarify the influence of the most important parameters of the process (temperature, space velocity and methanol concentration) on the efficiency of the adiabatic layer. An industrial experiment was carried out to verify the results obtained.     

金属催化剂选择性催化氧化甘油及其衍生物的研究

阐述了甘油氧化的路径,利用Pd、Pt和Au等金属催化剂,选择性催化氧化甘油及其衍生物制备甘油酸、1,3-二羟基丙酮、羟基丙酮酸、丙醇二酸和丙酮二酸等一系列重要化学品的研究,此方法选择性高,反应温和,对环境友好,前景广阔。     

丙烯选择性氧化制丙烯醛的催化剂研究

选择和制备了多种过渡金属单氧化物和复合氧化物催化剂。采用微反-色谱联用装置研究了它们对丙烯氧化制丙烯醛的催化性能。分别考察了反应温度、气体空速、原料配比的影响;其中所研制的金属原子比为2：3：1的Fe－V－Ti复合氧化物催化剂,在空速为10000h~(-1),反应温度为320℃,C3H6/O2=1:1的条件下,丙烯转化率为78%,丙烯醛选择性为95%,收率为74%,时空产率为5000g·L~(-1)·h~(-1)。     

The Selective Oxidation of 1,2-Propanediol by Supported Gold-Based Nanoparticulate Catalysts

The oxidation of 1,2-propanediol to form lactic acid and hydroxyacetone has been investigated using supported metal nanoparticles. A series of supported gold, palladium, platinum and combinations of these metals have been investigated. In the presence of base the major product formed is lactate, often in excellent yields as, under these conditions the terminal hydroxyl group is oxidised. In the absence of base, more vigorous conditions are required to elicit high conversions; surprisingly, a major product from such reactions is a mono-oxidation product hydroxyacetone, along with lactate.     

用于甲烷选择性氧化反应制甲醇的膜催化技术

研究了将甲烷选择性地一次氧化制取甲醇的膜催化技术。采用ZrO2－Y2O3陶瓷膜，在较温和的反应条件下（常压，460℃左右），可以将甲烷选择性地一次氧化成为甲醇。     

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Since the discovery of Metal Organic Frameworks (MOFs) in the early 1990s, the amount of new structures has grown exponentially. A MOF typically consists of inorganic nodes that are connected by organic linkers to form crystalline, highly porous structures. MOFs have attracted a lot of attention lately, as the versatile design of such materials holds promises of interesting applications in various fields. In this review, we will focus on the use of MOFs as heterogeneous oxidation catalysts. MOFs are very promising candidates to replace homogeneous catalysts by sustainable and stable heterogeneous catalysts.

The catalytic active function can be either the active metal sites of the MOF itself or can be introduced as an extra functionality in the linker, a dopant or a “ship-in-a-bottle” complex. As the pore size, pore shape, and functionality of MOFs can be designed in numerous ways, shape selectivity, and even chiral selectivity can be created. In this article, we will present an overview on the state of the art of the use of MOFs as a heterogeneous catalyst in liquid phase oxidation reactions.     

Selective Oxidation of Methanol to Dimethoxymethane over Mesoporous Al‐P‐V‐O Catalysts

The synthesis and application of bifunctional mesoporous Al‐P‐V—O catalysts with both acidic and redox sites for selective oxidation of methanol to dimethoxymethane (DMM) is described. The catalysts were characterized by N₂ adsorption/desorption, X‐ray diffraction, temperature‐programmed desorption, X‐ray photoelectron spectroscopy, and infrared spectroscopy. It is shown that porosity; redox property and surface acidity of the catalysts were greatly influenced by the Al/V/P ratio. The synergistic effect of phosphorus and vanadium was investigated. Al‐P‐V—O catalysts exhibited good catalytic activity because of the controlled reducibility and the acidic sites. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2587–2593, 2013     

甲醇直接氧化制备二甲氧基甲烷催化剂研究进展

作为一种新型的高性能柴油添加剂,二甲氧基甲烷的研究与生产受到越来越多的关注。论述了气相法甲醇部分氧化直接制备二甲氧基甲烷的机理,通过对甲醇部分氧化直接制备二甲氧基甲烷反应所用的Re、Ru、Mo、V等不同系列的催化剂的研究进展的综述,比较了各催化体系的特点;介绍了液相法甲醇直接氧化制二甲氧基甲烷的研究进展。最后对甲醇直接氧化制备二甲氧基甲烷提出了建议。     

The Oxidative Dehydrogenation of Ethylbenzene. Cobalt Molybdate Catalysts

The role of the catalyst and feed composition in the conversion and product distribution in the oxidative dehydrogenation of ethylbenzene, using a series of cobalt molybdate catalysts, was investigated.     

Deposition of PtxRu1−x Catalysts for Methanol Oxidation in Micro Direct Methanol Fuel Cells

Platinum-ruthenium electrodes (Pt_xRu_1-x) have been prepared by electrochemical and electroless deposition and investigated as catalysts for the oxidation of methanol in acidic solutions. Pt_xRu_1-x deposits were electrochemically deposited from acidic chloride electrolytes at potentials between −0.46 and 0.34 V (vs. NHE). The composition of the electrodeposit was estimated by energy dispersive X-ray spectroscopy and is a strong function of the electrode potential. An empirical model for the deposition process is presented and kinetic parameters are estimated and discussed. Also, the methanol oxidation activity of the Pt_xRu_1-x catalysts was characterized by cyclic voltammetry in 1.0 M CH₃OH, 1.0 M H₂SO₄ solutions. Electroless Pt_xRu_1-x samples were prepared in a modified Leaman bath with hydrazine dihydrochloride as the reducing agent. The kinetic results for the electrochemical deposition of Pt_xRu_1-x were directly applied and the deposition potential was estimated as approximately 0.40 V.