Hydroxyls nests in defective silicalites and strained structures derived upon dehydroxylation: vibrational properties and theoretical modelling

Defective silicalite, an efficient and selective catalyst in the gas phase Beckmann rearrangement reaction, has been characterised by infrared spectroscopy and by molecular modelling techniques. We report a detailed IR study on the effect of outgassing treatments at increasing temperature on silanols bands and on framework modes. The effect of a temperature decrease up to 100 K (during the IR measurement) on the H-bonding interactions has also been investigated. The interaction of silanols with mesitylene, a probe molecule which cannot penetrate the channels, has been studied in order to distinguish between internal and external OH groups. Molecular mechanics and ab initio methods have also been used to model the structure and the vibrational features of a properly designed nest in order to support the assignments of the IR spectrum.     

我国木质素油田化学品的发展现状

本文综述了我国木质素类（碱木质素或木质素磺酸盐）油田化学品的最新进展，其中包括钻井液处理剂、油井水泥添加剂、堵水剂、调剖剂、稠油降粘剂和表面活性剂驱油的牺牲剂。目前我国木质素类堵水剂、调剖剂和稠油降粘剂的研究和应用方面已达到或超过世界先进水平，改性木质素磺酸盐的研究也接近国际先进水平，但钻井处理剂和水泥添加剂仅为美国的1／9，许多木质素化学品仍为空白。因此，这些油田化学品仍然是吸引人去研究的课题，期望不久的将来会有较大的进展。     

Current problems in the modelling of chemical reactors

Modelling of chemical reactors is reviewed with an emphasis on process development and scale-up. A distinction is made between modelling of chemical kinetics, of rate processes in volume elements and of whole reactors. Examples are mainly taken from papers presented at the Sixth International Symposium on Chemical Reaction Engineering. Special attention is given to the modelling of single phase reactors, fixed beds, trickle beds, fluid beds, and gas bubble reactors.     

陶瓷热压铸成型的超临界CO2流体脱蜡

利用超临界CO2流体萃取技术从陶瓷热压铸成型坯体中萃取有机粘合剂。对陶瓷热压铸成型中所使用的有机载体组分进行研究，对陶瓷热压铸成型超临界CO2流体脱蜡工艺条件进行了探索。研究了陶瓷坯体厚度、萃取压力，温度及时间对萃取率和陶瓷坯体脱蜡质量的影响。结果表明：由60％(质量分数，下同)非极性分子石蜡(熔点57℃)和40％极性分子蜂蜡(熔点58℃)组成的混合蜡作为热压铸浆料的有机载体，在压力为30MPa，温度为45℃的超临界CO2流体中脱脂可获得无缺陷的陶瓷热压铸成型生坯，脱蜡时间从34h减少到3h。由超临界CO2流体脱蜡后烧成的陶瓷试件具有小的变形及高的致密度。     

Biomass pyrolysis in a circulating fluid bed reactor for the production of fuels and chemicals

An approach for biomass flash pyrolysis in a circulating fluid bed (CFB) reactor with continuous solids regeneration is described in this study. The unit is capable of performing conventional and catalytic biomass pyrolysis with the proper solid selection. The production of improved quality liquid products in a direct step through catalytic pyrolysis is investigated in this work. Both conventional and catalytic biomass pyrolysis can be effectively performed in this CFB unit. Flash pyrolysis conditions were achieved and liquid product yields of ∼70 wt% (on biomass feed) were obtained. The effect of specific operating variables including the type of inorganic solid material and the solid/biomass ratio was established on the final liquid product quality and yield. Solid materials considered included silica sand, a commercial fluid catalytic cracking catalyst and a ZSM-5 additive. Catalytic biomass pyrolysis generally leads to the production of additional water, coke and gases compared to conventional pyrolysis. However, the obtained liquid product quality and composition is improved.     

东河储层损害机理分析

钻井液和酸化体系与储层流体不配伍是造成油层损害的主要原因。东河砂岩含有不同类型敏感性矿物,利用常规钻井液和酸化技术难以达到保护储层的目的。本文在分析东河储层敏感性损害机理前提下,提出保护油层的2项措施。     

Transitions of saturated monoacid triglycerides: Modeling conformational change at glycerol during α→β′→β transformation

The glycerol region geometry of modeled saturated monoacid triglycerides was altered by bond rotations and minor angle distortions to convert theoretical α-forms into bent β′- and β-forms. Direct α to β conversion involves lateral disruption of fatty chain packing to generate side-chain character typical of the β-form. Such disruption, which could contribute to fat bloom, allows additional molecular movement and shifts in molecular mechanics energy (MME) that may approximate thermal changes observed by differential scanning calorimetry during α to β transformations. Energy calculations at 100 points throughout each transformation identified plausible conversion routes. A two-stage conversion, α to either of two stereospecific β′-forms bent at glycerol followed by subsequent conversion to β, showed less chain movement and more favorable MME than direct α to β conversion. The preferred path, based on energy profiles of each conversion, involves a β′-D form and rotation of carbonyl to α-carbon bonds in chain #2 and a side chain (chain #3).     

水电站进水塔动水压力研究和探讨

基于理想流体,将进水塔简化成水中悬臂梁体系,推导了其受迫振动时的动力响应方程,给出了进水塔内外表面动水压力的解析表达式。与有限元法、水工抗震规范公式计算结果进行了对比,分析验证了该方法在进水塔结构上的适用性及准确性。结果表明:动水压力表达式与结构振型密切相关。该方法的动水压力曲线趋势与有限元方法相似,均在水面以下某深度处迅速变大及达到最大值后曲线值减小弯回,两者最终在塔体底部收于相近的值;最大值大于有限元法,其最大值处曲线折回明显,幅度较大。弹性模量和进水塔高度对动水压力的曲线形态和数值有重要影响。同时,输入激励荷载的频率对动水压力影响巨大,尤其频率与进水塔某阶频率相近时会导致动水压力的异常增大。该方法对分析进水塔动水压力具有参考价值。     

The influence of fluid elasticity on wall effects for creeping sphere motion in cylindrical tubes

Experimental results are presented of wall effect for the slow motion of spheres in elastic, constant-viscosity liquids. The results are correlated in terms of diameter ratio for d/D < 0.3, and Weissenberg number We < 5. Weissenberg number is defined as We = 2θV_m/d, with θ the Maxwellian relaxation time (θ = N₁/2τγ). The wall effect is found to be adequately described by Newtonian expressions for small Weissenberg number, We < 0.01. For larger values of the Weissenberg number, We > 0.2, virtually no wall effect is discernible; the small effect observed is correlated by the wall factor expression The wall effect observed is ascribed to the influence of fluid elasticity alone, since all the fluids used were elastic to a greater or lesser extent, but showed no shear thinning.      

超临界流体技术应用研究

超临界流体技术具有许多传统技术所没有的快速，高效，低能耗，污染少等优点，在材料制备，医药工业，生物工程，食物，环境，化工等许多方面展现了广阔的应用前景。综述了其在萃取，材料制备和作为反应介质等方面的应用。