Determination of effectiveness factor of a partial internal wetting catalyst from adsorption measurement

The effect of partial internal wetting of catalyst pellets on apparent reaction kinetics at elevated temperatures and pressures is investigated experimentally and by modeling for benzene hydrogenation. A new method that combines adsorption and chemical reaction is introduced to study the kinetics influenced by capillary condensation of reagents at steady-state conditions. It is shown that the extent of liquid filling in the pellet interior has a critical effect on the global kinetics, and the current state of the catalyst depends on the history. Under certain conditions two steady states of the effectiveness factor exist. Moreover, either a decrease in temperature or increase in total pressure can increase the effectiveness factor. The model exhibits good agreement with experimental results.     

Aldol condensation of campholenic aldehyde and MEK over activated hydrotalcites

In this paper, activated Mg-Al hydrotalcites were used as catalysts in the aldol condensation of campholenic aldehyde and methyl ethyl ketone (MEK). These materials represent an attractive alternative to less environmentally friendly liquid bases in a number of base-catalyzed reactions involved in the pharmaceutical and fragrance industries. The presence of basic hydroxyl groups in the interlayer space leads to very active materials. However, the relation between the activity of reconstructed hydrotalcites and the rehydration procedure is still not well understood. Different rehydration protocols in combination with extensive characterization studies were performed, including XRD, SEM, IR spectroscopy and TPD of CH₃CN and CH₃NO₂. The materials were tested as catalysts in the aldol condensation of campholenic aldehyde and MEK, and relationships between the catalytic performance of the activated hydrotalcites and the rehydration procedure were derived. Several factors may influence the activity and selectivity of this reaction, such as the reaction temperature, the molar ratio of the reactants and the degree of rehydration of the hydrotalcite-like catalysts. The selectivity towards the formation of the desired branched isomer increases when performing the reaction at low temperatures.     

一类含查尔酮结构的光敏性二胺的合成研究

以醛、酮为原料经羟醛缩合反应合成了具有一类含查尔酮结构的光敏性二胺:1-(3-氨基苯基)-3-(4-氨基苯基)-2-丙烯-1-酮与对-二(间氨基肉桂酰)苯.通过优化实验得到最佳的合成工艺为:醛、酮在温度为0℃下,以乙醇为溶剂,氢氧化钠为催化剂,进行羟醛缩合反应3h.收率可达到86%,经液相色谱分析其纯度分别为99.92%,99.91%,紫外可见最大吸收波长分别为349nm、361nm.所得方法操作简便,收率较高,原料易得.并用元素分析、核磁共振、红外光谱等手段对产物的结构进行了表征.     

Organic–silicate hybrid catalysts based on various defined structures for Knoevenagel condensation

Two types of organic–inorganic hybrid base catalysts are prepared. Organic-functionalized molecular sieves (OFMSs), particularly “amine-immobilized porous silicates”, are designed based on common idea to immobilize catalytic active sites on silicate surface. Silicate–organic composite materials (SOCMs), such as “ordered porous silicate–quaternary ammonium composite materials”, are the precursors of ordered porous silicates obtained during the synthesis. Both the OFMS and the SOCM are used as the catalysts for Knoevenagel condensation. Among the OFMSs, there is clear tendency that the use of molecular sieve with larger pore volume and/or surface area gives the product in higher yield. Aminopropylsilyl (AP)-functionalized mesoporous silicates such as AP-MCM-41 gives the product in high yield under mild conditions. No loss of activity is observed after repeated use for three times. The SOCMs are also active for the same reaction. The precursors of the mesoporous silicates are more active than those of microporous silicates. This material can be repeatedly used without significant loss of activity. High activity is not due to the leached species. The active sites of the SOCM catalysts are considered to be SiO⁻ moieties located on the pore-mouth. Activity of the SOCM increases when the reaction is carried out without solvent, whereas decrease in activity of the OFMS is observed in the solvent-free system.     

聚乳酸的直接合成研究(Ⅱ)

研究了以乳酸单体为原料的直接熔融缩聚的工艺条件,包括工艺路线、原料含水率、催化剂种类、温度及余压对合成的影响。结果表明:采用适当的工艺能通过熔融缩聚法制备出高分子质量的聚乳酸,且具有良好的生物降解性能。     

3-取代苯基-5-羟基-5-三氟甲基异噁唑啉的合成

3 取代苯基 5 羟基 5 三氟甲基异口恶唑啉是合成具有异口恶唑结构的原卟啉原氧化酶抑制剂类除草剂的重要中间体。通过以下途径制得4个具有不同取代基的异口恶唑啉中间体:首先,在回流状态,n(甲醇钠)∶n(取代苯乙酮)=2∶1的甲醇钠存在下,取代苯乙酮与三氟乙酸乙酯缩合得到取代苯基 4,4,4 三氟 1,3 丁二酮;后者可在室温下,于二氯甲烷溶剂中,用氯化硫酰氯化,在侧链上引入氯原子;最后,以乙酸作溶剂,回流下,具有不同取代基的苯基 1,3 丁二酮与盐酸羟胺闭环得到产物。反应总收率大于95%。产品结构经质谱、核磁共振氢谱、碳谱确认正确。     

磁性漆酚缩甲醛微球的制备与表征

在共沉淀法合成磁流体的基础上,用悬浮缩聚法制备了磁性漆酚缩甲醛微球,并用X射线粉末衍射、透射电镜和热重分析等对微球进行结构表征。实验结果表明,Fe3O4磁流体的粒径为纳米量级,纳米Fe3O4粒子能够提高复合物的热性能。该微球粒径约1mm,是核壳结构,具有良好的耐溶剂性和耐热性。     

公式分层的谓词模态逻辑

由于必然模态词□的引入,谓词模态逻辑的公式在一个可能世界中的真假值可能依赖于其可达的可能世界.在谓词模态逻辑中存在个体跨可能世界相等问题.针对这一问题,Lewis提出了对应物理论,并且在对应物理论中用对应物关系来表示个体跨可能世界相等.但是,当一个对象具有一个以上的对应物时,谓词模态逻辑中的跨可能世界相等关系无法与对应物关系建立一一对应.通过限制谓词模态逻辑中全称量词∀的范围,给出了一种公式分层的谓词模态逻辑.它是谓词模态逻辑的一个子逻辑,并且其语言与谓词模态逻辑的语言是相同的.但其公式是分层定义的,使得∀可以出现在□的范围内,并且□不能出现在∀的范围内.由于任意形如∀x□φ（x）的表达式都不是该逻辑的公式,以量词开头的公式在一个可能世界w中的真假值只依赖于w,该逻辑避免了个体跨可能世界相等问题.给出了该逻辑的语言、语法和语义,并证明了该逻辑是可靠的和完备的.     

树脂固体酸催化剂用于合成尿囊素研究

对三阳离子交换树脂在乙醛酸与尿素缩合反应中的催化活性进行了研究。实验得到其最佳反应条件为：尿素与乙醛酸摩尔比4：1，反应温度70℃，反应时问8h。在此条件下，尿囊素产率达到69．6％。实验结果还表明，阳离子交换树脂催化剂优于HZSM-5分子筛催化性能。     

基于WINCE系统软件开发的内存研究

WINCE系统内存配置较小,嵌入式软件如果出现内存泄露问题,将会导致系统的可用内存不足,甚至出现系统崩溃。为此针对WINCE操作系统内存的管理和应用,通过引入一个在实时更新动态图的过程中出现内存泄露的案例,阐述了关于内存管理和内存应用的重要知识点,包括内存模型和内存分配方式,分析了在该案例中出现内存泄露的原因,提出了与案例中出现的内存泄露相似问题的解决方法,并针对一般情况下如何防止内存泄露作了简单介绍,最后详细阐述了案例中为了优化内存所做的工作,对编程者有很好的指导作用。