Epoxidation of olefines with PDMS membranes containing zeolite occluded manganese diimine complexes

A new composite catalyst for selective epoxidation of olefins with tert-butyl hydroperoxide (tBHP) is reported. The catalyst contains manganese diimine complexes (cis-Mn bis-2,2′-Bipyridyl), occluded within a NaY zeolite, in turn incorporated in a polydimethylsiloxane membrane (cis-[Mn(bpy)₂]²⁺-NaY-PDMS). The three-step synthesis consists of a Mn²⁺exchange of NaY, ligand sorption to form cis-[Mn(bpy)₂]²⁺-NaY and incorporation of the latter in a PDMS membrane. The major differences between [Mn(bpy)₂]²⁺-NaY as such and occluded in PDMS are observed in the sorption and catalytic characteristics. With the membrane system, the use of a solvent becomes obsolete. Whereas optimal cyclohexene oxidation with [Mn(bpy)₂]²⁺-NaY occurs with hydrogen peroxide in acetone, tBuOOH proves to be a better oxidant for [Mn(bpy)₂]²⁺-NaY-PDMS. The reactions in batch and fed-batch reactors are discussed. A simple regeneration procedure, monitored by FT-IR spectroscopy is proposed.     

A Study of the Specific Heats of the Compounds in the Sm_2O_3-BaO-CuO System

By means of X-ray diffraction and adiabatic scanning calorimeter,the specific heatsof five compounds in the Sm_2O_3-BaO--CuO system,such as Sm_2BaO_4,Sm_2CuO_4,BaCuO_4,Sm_2BaCuO_5,SmBa_2Cu_3O_(7-x),from -150℃ to 800℃ have been measured.It is found that the specific heats ofthese compounds increase smoothly with the increase of temperature.     

A method to estimate entropies and heat capacities applied to alkali oxides

We present a method that is useful in the estimate and assessment of heat capacity data. The approach is based on an analysis of the logarithmic average of the phonon frequencies. In this quantity, that may be easily derived from experimental data on the vibrational entropy, the influence of atomic masses can be exactly accounted for even in polyatomic solids. Our method is applied to Li₂O, Na₂O, K₂O, Rb₂O, and Cs₂O. In particular, literature data for K₂O are critically examined.     

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。     

Technique for Producing Mullite and Other Mixed-Oxide Systems

Mixed-oxide systems are of interest in a variety of technical ceramic applications. The key in many systems is to achieve a high degree of homogeneity, approaching the molecular level. A technique for producing mixed oxides via direct oxidation of mixtures of organometallic compounds is discussed as a potential route. Preliminary work performed on producing mullite is discussed.     

添加高效粘结剂的氧化锰矿粉冷固成团

以氧化锰矿粉为原料，添加ＺＢ粘结剂进行冷固成团，所得冷固团块不仅具有足够的机械强度，而且具有良好的耐湿性，适用于长距离运输和露天堆存，是一种可与块矿性能相媲美的优质炉料，为充分利用矿山及冶炼厂的锰矿粉找到了一条良好的途径．     

Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxides: Influence of vanadium loading on conversion and product selectivities

Gas-phase selective oxidation of toluene has been carried out on vanadium oxide systems (5–20 wt.% of V₂O₅, equivalent to 0.4–1.7 theoretical monolayers) supported on TiO₂–sepiolite (with titania loading around the theoretical monolayer, 12 wt.%) and on sepiolite. A study has been made on both the influence of vanadia loading and of the support on the catalytic behaviour of the supported vanadium systems. The reducibility by H₂ TPR was also studied as well as the acid and basic/redox sites from the results of conversion of the 2-propanol test reaction of the solids. Benzaldehyde, benzoic acid and several coupling products were the main ones detected, attaining over 50% selectivity towards the benzaldehyde and benzoic acid products at a total conversion around 10%. The activity and selectivity to the selective products exhibited by vanadium systems supported on mixed support were superior to those exhibited by the systems supported on sepiolite and increased notably in both series with the increase in vanadium loading. The best catalytic behaviour exhibited by the vanadium systems supported on mixed support, which also exhibited the highest density of sites capable of being reduced (as well as their reducibility) and of those responsible for propanone formation, could be attributed not only to the different balance of the vanadia species existing in the two supports (monomeric + oligomeric/polymeric), but also to such other factors as the nature of the support and, concretely, its chemical composition.     

Mn-containing catalytic materials for the total combustion of toluene: The role of Mn localisation in the structure of LDH precursor

Mg/Mn/Al mixed oxide systems of similar atomic ratios close to 2/0.5/1 were obtained by calcination of Mg,Al layered double hydroxide (LDH) type precursors containing Mn either in the cationic form within the brucite layer or as permanganate anions in the interlayer. The materials were characterised with PXRD, thermal analysis, XPS, ESR, TPR and BET. In mixed oxides derived from interlayer-doped precursor PXRD identified MgO–MnO solid solution and poorly crystalline Al-rich spinel phase, while those obtained from layer-doped LDH contained a better crystalline Mn-rich spinel. Surface of both materials was covered with poorly crystalline and/or amorphous Mn⁴⁺-containing phases. Higher reducibility of this surface coat in calcined layer-doped catalyst, as compared to interlayer-doped one, was attributed to the differences in the nature of underlying crystalline phases, and was considered the chief reason for the higher catalytic activity of this catalyst in the total oxidation of toluene.     

测辐射热计的微桥研制和Vox膜成膜研究

介绍了测辐射热汁的工作原理、器件结构的几何形状和研制状况,叙述了测辐射热计材料的特性及制备技术.