Formation of C4 species in the deactivation of a Pd/SiO2 catalyst during the selective hydrogenation of acetylene

The deactivation characteristics of Pd/SiO₂ in the selective hydrogenation of acetylene were correlated with changes in the amount of the C4 species produced. The amounts of butenes produced changed in parallel with the catalyst activity, indicating that the rate limiting step for butene production was the same as that for acetylene hydrogenation. On the other hand, the amount of 1,3-butadiene produced changed, showing a maximum with catalyst deactivation because 1,3-butadiene is an intermediate in the sequential reaction process which involves both the production and consumption of 1,3-butadiene. This was verified by a simultaneous TG/reaction experiment showing that 1,3-butadiene was a precursor of green oil. The catalyst showed a self-regenerative behavior in its activity and the amounts of C4 species produced during the early stage of deactivation because two opposite factors, which contributed to either the lowering or the promotion of activity, were involved in the process. A specific type of polymer species, produced during the initial period of deactivation, is proposed to be responsible for the promotion of catalyst activity.     

New approach to environmentally benign epoxidation: the solid-phase-system using urea–H2O2 and recyclable dodecatungstate on apatite

On the basis of new concept using a solid disperse phase we have developed an efficient catalytic solid-phase-system for epoxidations of alkenes using urea–hydrogen peroxide (urea–H₂O₂) complex and cetylpyridinium dodecatungstate ((CetylPy)₁₀[H₂W₁₂O₄₂]) catalyst on fluorapatite (FAp). The recovered solid catalyst phase was reused to keep the catalytic activity after several times. In the conceptual idea it is a key point that in situ solid-phase-activation of the catalyst with urea–H₂O₂ proceeds to form microcrystals of the active species dispersed on the solid phase. The dispersion of the catalyst on FAp in the case of tungstic acid (H₂WO₄) was suggested by EPMA analysis. We proposed the peroxo type of species keeping the parent polyoxometalate framework as novel active species from FT-IR spectroscopic studies. FAp phase plays important roles of dispersing the active species on its surface to have high catalytic activity and of stabilizing the active species to lead to high reusability.     

层状催化剂颗粒的优化设计——双组分等温平行反应体系

针对双组分等温平行反应体系,分析讨论了以提高催化剂活性和选择性为目标时催化剂活性组分的最优分布形式(为δ-函数分布),并给出了确定这种反应体系的催化剂的最佳活性层位置的计算方法。结果表明:以提高选择性为目标的最佳活性层位置比以提高活性为目标的要更靠近催化剂核心,实用的最优位置应介于二者之间。最后,本文还研究了反应动力学级数、本性选择性以及内扩散模数(Thiele 模数)等因素对最佳活性层位置的影响。     

Trifluoromethanesulphonic acid catalysed transalkylation between tetrabromobisphenol-a and toluene for the production of 2,6-dibromophenol

The preparation of 2,6-dibromophenol is described. This compound, useful as raw material for brominated poly(phenyleneoxide) and pyrogallol or derived pharmaceuticals/pesticides, was prepared in 80% (isolated) yield by a transalkylation reaction between tetrabromobisphenol-A and toluene. The catalyst, trifluoromethanesulphonic acid, can be simply recovered and recycled. Perfluorinated resin sulphonic acid (NAFION-H®, DuPont) did not effectively catalyse this transalkylation.     

Preparation and characterization of oxygen deficient perovskites,BaBiO3−x

Oxygen nonstoichiometry in the distorted perovskite BaBiO₃ has been studied by thermogravimetric analysis using controlled oxygen pressures. Three distinct regions of nonstoichiometry are observed with composition ranges which narrow as the temperature is lowered. Samples isolated from each region were shown by powder X-ray diffraction to retain the perovskite subcell but show different types of framework distortion. Low temperature reoxidation of the oxygen deficient phases is also described.     

担载型含稀土三组份体系在二氧化碳甲烷化反应中的催化性能

用浸渍法制备了一系列氧化锆担载的含稀土Ⅷ族金属催化剂，对其在二氧化碳甲烷化过程中的催化活性作了研究，并用漫反射紫外可见光谱，ＦＴＩＲ等手段对催化剂作了表征。结果表明，含稀土新型催化剂具有催化活性高，目标产物选择性好等优点；稀土主要以氧化物形式存在于催化剂表面，参与对氢及表面含碳物种的吸附及活化；含稀土三组份催化剂的活性与所添加稀土三价离子的４ｆ电子数有关。     

异丁烯两段催化氧化制甲基丙烯酸催化剂研究 Ⅰ．异丁烯气相氧化制甲基丙烯醛多元复合氧化物催化剂的研究

本文报导用于异丁烯（叔丁醇）选择氧化制ＭＡＬ（甲基丙烯醛）的多元复合氧化物催化剂的研究结果。同共沉淀法制备的催化剂的活性主要决定于其化学组成，同时受到制备条件的影响。最佳催化剂的主要物相组成为ＰｂＯ３，Ｂｉ２ＭｏＯ３．３、ＮｉＭｏＯ４、Ｓｂ２Ｏ３及ａ－Ｆｅ２Ｏ３小颗粒。在３５５℃，１０００～２５００ｈ－１空速范围，叔丁醇：水：空气＝１：３．３：７（摩尔比）的条件下可获得异丁烯转化率达９６％，ＭＡＬ选择性达８９％的结果。     

SO_4~（2－）／ZrO_2固体超强酸的失活与再生

初步探索了ＳＯ_４~２－／ＺｒＯ２固体超强酸的失活机理．并着重研究了催化剂的两种再生方法：灼烧法和溶剂洗涤法。催化剂主要是因结焦而失活，高温灼烧能基本恢复催化剂原有活性．且再生效果与灼烧温度有关。溶剂洗涤法有一定的再生能力，但不显著．     

Propylene epoxidation in a microreactor with electric heating

Gas phase propylene epoxidation on gold catalysts has attracted wide attention from industry and academia due to its high selectivity. However, it suffers from low propylene conversion and rapid catalyst deactivation. Experiments showed that propylene conversion could be increased by raising H₂, O₂, or C₃H₆ concentration in the feed, but the feed compositions were within the explosion limit. It was also shown that the activity of the used catalyst could be fully recovered, but the regeneration temperature was 280 °C, much higher than that for reaction. Therefore a microchannel reactor was devised to suppress explosion and was constructed with Fecralloy, to raise the temperature rapidly for catalyst regeneration by electric heating. In two minutes the temperature of the reactor could be raised from 50 to 300 °C. Catalysts were coated on the alloy belt by dip coating, and the performance of the reactor was evaluated under different operating conditions. Results showed that in the microreactor the overall reaction rate was controlled mainly by the intrinsic reaction rate, and also influenced by film diffusion to a certain extent. The deactivated catalyst was regenerated in the microchannel reactor and the activity was fully recovered.     

Liquid-phase stereoselective thymol hydrogenation over supported nickel catalysts

The stereoselective hydrogenation of thymol was studied in liquid phase over several nickel catalysts, modified by coimpregnation of inorganic compounds containing chlorine. The total activity of all catalysts studied was decreased and was on the same order of magnitude, indicating that chlorine even after reduction remains on the surface and is responsible for the poisoning effects. Such blocking of accessible sites results in similar reaction rates for the catalysts studied. Selectivity and stereoselectivity to menthols and menthones changed significantly. The modifiers could influence the rate of keto-enol transformations, which is thought to be the key selectivity and stereoselectivity governing step.