用MOCVD法制备铁系云母珠光颜料

以Fe(CO) 5为物源 ,在常压喷动流化反应器中 ,以金属有机化学气相沉积 (MOCVD)法对云母粉进行包覆 ,制备铁系 -云母珠光颜料。实验结果表明 :在沉积温度 2 5 0℃ ,氧气流量 3mL·s-1,沉积时间 5min时能得到棕色色泽的珠光颜料 ;随着沉积温度的提高和反应时间的延长 ,可获得红棕、金红、橙红、深红等不同色泽的珠光颜料。用色差仪测定颜料的明度值L 、红度值a 、黄度值b ;X衍射仪表征颜料的表面成分 ;酸滴定计算氧化物的涂覆率。探讨了温度、时间、氧量对珠光颜料表面成分和珠光光泽的影响     

氧泵型催化膜反应器中甲烷氧化偶联反应(Ⅰ)——氧泵型催化膜的制备及其反应性能

本文采用1％Sr/La_2O_3-Ag-YSZ氧泵型催化膜反应器进行了甲烷氧化偶联反应研究。比较了不同制备方法的催化膜的反应性能,结果发现浸涂法(Ag-YSZ管随旋转轴转动涂制)制备的膜性能最佳。研究了操作条件对甲烷氧化偶联反应的影响。研究证明,传递氧与气相氧同时进料是一种较好的反应方式。结果表明,利用该反应器不仅可以简化分离过程,而且还可得到更高的C_2烃选择性。     

DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN A HOLLOW FIBER MEMBRANE REACTOR†

A hollow fiber membrane reactor, which resembles a tube-and-shell heat exchanger, was developed for homogeneous catalytic reactions with gas reactants and products. The gas stream flows through the tube side while the reaction takes place in the catalyst solution which fills the shell side. The separation load of product from the catalyst solution can be reduced by using a hollow fiber membrane reactor instead of a conventional bubble column reactor. The reactor operates in a plug-flow pattern with a large mass transfer area per unit volume of catalyst solution

This concept was investigated experimentally using the direct oxidation of ethylene to acetaldehyde reaction in an aqueous solution of palladium (H) chloride-cupric chloride with a silicone rubber membrane reactor and a polypropylene membrane reactor. It was experimentally demonstrated that membrane reactors could achieve higher production rates per unit volume of catalyst than the conventional sparged reactor. The experimental data were in good agreement with the predictions by the mathematical model. The conditions under which the membrane reactor will be more advantageous than the conventional sparged reactors can be readily ascertained with the analytical solution of the simplified membrane reactor model.     

EFFECT OF SUSPENDED FIBRES ON MACRO-MIXING AND MICRO-MIXING IN A STIRRED TANK REACTOR

The effects of suspended fibre on macroscale and microscale mixing in a small stirred tank reactor were studied under batch conditions using the competitive, consecutive azo coupling between 1-naphthol and diazotized sulfanilic acid. The mixing quality was determined from the distribution between the mono and bis substituted reaction products. Nylon (2 and 3 millimeters in length) and fully bleached softwood kraft pulp (FBK) fibre suspensions were examined at volumetric concentrations up to the limit that complete suspension motion could be maintained in the vessel at impellet rotational speeds of 7 and 10s^-1. The adsorption of the product dyes on the fibre was found to be proportional or very nearly proportional to their concentrations in the aqueous phase and did not interfere with the assessment of mixing in the suspension.

Suspended fibres were found to slightly increase the 'critical feed time' of the diazotized sulfanilic acid, corresponding to an increase in the macromixing or bulk blend lime of the vessel. Continued increase in the fibre concentration led to the formation of a well mixed cavern centered on the impeller and the creation of stagnant regions adjacent to the vessel walls. The departure from the Newtonian fibre-free case is due to changes in the flow through and distribution of the energy dissipative regions in the vessel. The most effective location for chemical addition to ensure good microscale mixing remains in the impeller vicinity.     

Study of the copper leaching in the wet oxidation of phenol with CuO-based catalysts: Causes and effects

Catalytic wet oxidation of phenol as a model pollutant has been performed in a three phase fixed-bed reactor (FBR) by using a commercial catalyst based on copper oxide in order to analyze the variables affecting significantly the copper leaching. It has been found that temperature has an almost negligible influence in the range studied (70–160 °C). On the contrary, an important effect of the pH value was noticed. The copper leaching reduces when the pH of the solution fed to the reactor increases, being almost negligible at pH ≥ 5. Moreover, the composition of the reaction media also influences the leaching. Higher copper concentrations than those expected by the effect of the acid aqueous media have been measured in the reactor effluent when phenol, catechol, hydroquinone, p-benzoquinone and maleic acid are present in the reaction media. On the contrary, oxalic acid has a negative influence on the leaching, since it captures the copper in solution to form copper oxalate which precipitates on the catalyst surface. For a previously acidified medium, the acetic and formic acids do not have any other effect on the copper leaching. It has been also demonstrated that as copper in solution decreases, so does phenol conversion, because the homogeneous catalysis contributes significantly to the oxidation reactions even in fixed-bed reactors.     

真空间歇精馏分离橙花醇和香叶醇的研究

橙花醇和香叶醇是重要的基础香料,沸点差仅为2℃,具有热敏性。以往研究中应用减压间歇精馏分离橙花醇和香叶醇的混合物,一次精馏得到90%以上的产品收率低(仅为46%),且塔釜温度较高,操作周期长,不宜于工业生产。本文针对沸点差较小的热敏性物系,采用减压高效间歇精馏方法对橙花醇和香叶醇的混合物进行了分离研究。通过考察全回流时间、回流比、加热负荷和压力等操作因素对分离效果的影响,确定了适宜的操作条件,塔顶压力为600Pa～700Pa,塔压降为4800Pa～4900Pa,釜温在150℃～152℃之间,全回流6h,采用20 1,10 1,5 1的变回流比操作。实验结果显示,单塔精馏即可得到含量大于90%的橙花醇和香叶醇,收率在65%以上,提高20%无热分解现象,过程稳定,为工业生产奠定了基础。     

微孔无机膜反应器研究

主要介绍了无机膜在化学反应中的应用－－膜反应器研究，对膜反应器的特点、类型、应用、影响因素以及与其它反应器的比较进行了评述，并对其应用前景进行了展望。     

Continuous production of structured phospholipids in a packed bed reactor with lipase from <Emphasis Type="Italic">Thermomyces lanuginosa</Emphasis>

The possibilities of producing structured phospholipids between soybean phospholipids and caprylic acid by lipase-catalyzed acidolysis were examined in continuous packedbed enzyme reactors. Acidolysis reactions were performed in both a solvent system and a solvent-free system with the commercially immobilized lipase from Thermomyces lanuginosa (Lipozyme TL IM) as catalyst. In the packed bed reactors, different parameters for the lipase-catalyzed acidolysis were elucidated, such as solvent ratio (solvent system), temperature, substrate ratio, residence time, water content, and operation stability. The water content was observed to be very crucial for the acidolysis reaction in packed bed reactors. If no water was added to the substrate during reactions under the solvent-free system, very low incorporation corporation of caprylic acid was observed. In both solvent and solvent-free systems, acyl incorporation was favored by a high substrate ratio between acyl donor and phospholipids, a longer residence time, and a higher reaction temperature. Under certain conditions, the incorporation of around 30% caprylic acid can be obtained in continuous operation with hexane as the solvent. Presented at the 95th American Oil Chemists' Society Annual Meeting and Expo in Cincinnati, Ohio, May 10, 2004.     

2-[N-甲基-N-(2-吡啶基)氨基] 乙醇制备条件的优化

2-[N-甲基-N-(2-吡啶基)氨基]乙醇是合成罗格列酮(Rosighitazone)的一种中间体，罗格列酮是新型噻唑烷二酮类胰岛素增敏剂，通过两轮优化设计，实验室小试得到了较好的反应条件．为工业化生产提供了基础数据。     

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.