Packed-microtubes model for flowthrough chromatography of protein

A mathematical model for flowthrough (perfusion) chromatography, namely packed-microtubes (PMT) model, has been proposed for a column packed with biporous (BiP) anion exchanger in which the mesopores and flowthrough pores are created with liquid and solid porogens, respectively. The model is established based on the assumption that the BiP particle is made up of packed microtubes. Bovine serum albumin (BSA) is used as a model protein and three kinds of anion exchangers (i.e., mesoporous, macroporous and BiP resins) are used as adsorbents to determine the model parameters and to evaluate the model. Adsorption equilibrium and finite bath experiments are performed to determine the adsorption isotherms and kinetics parameters. Both the bound amounts of the protein on the surface of the mesopores and macropores are experimentally determined and taken into account in the mathematical model. With all the model parameters determined by independent experiments or calculated from available correlations, model simulations are performed and compared with the experimentally determined breakthrough profiles of the BiP column. It is found that the model predictions agree reasonably well with the experimental data obtained under various conditions and the PMT model fit experimental data better than the modified double linear driving force (LLDF) model proposed by Leitão and Rodriogues (1999. Biochemical Engineering Journal 3, 131) in which the adsorbent particle is considered to be made up of packed microparticles. The results indicate that the PMT model is more reasonable for this kind of BiP adsorbent.     

Chemistry of hydrogen sulphide under coal liquefaction conditions: 1. Modelling hydrogen transfer catalysis

The work reported here represents initial attempts to develop a complete kinetic and mechanistic understanding of the reaction chemistry of H₂S under coal liquefaction conditions, using both model systems and coal. Hydrogen sulphide was found to promote/catalyse the transfer of hydrogen from tetralin to 2-hydroxyquinoline (2-HOQ). The presence of H₂S can increase the rate of hydrogen transfer from tetralin to 2-HOQ by a factor of 10 compared with the same reaction run in the absence of H₂S. The energy of activation for hydrogen transfer was found to decrease by ≈5 kcal mol⁻¹ in the presence of H₂S. The presence of H₂S was also found to promote loss of oxygen from 2-HOQ to form small amounts of quinoline. No evidence of CC or CN bond cleavage in 2-HOQ was noted under any of the reaction conditions studied. These results suggest that the presence of H₂S reduces the temperatures necessary to promote effective hydrogen transfer from tetralin by 50–75 °C. Moreover, they imply that similar effects occur in H₂S-promoted coal liquefaction.     

气化炉复合炉衬的传热计算

新型 (多喷嘴对置 )水煤浆气化炉拟采用水冷管和耐火浇铸料组成的复合炉衬结构 .炉内的高温高压对复合炉衬的高温侵蚀十分严重 ,是影响其寿命的重要因素 ,因此合理设计气化炉复合炉衬的结构对充分发挥其材质的作用具有十分重要的意义 .建立了气化炉复合炉衬的传热计算的数学模型 ,同时编制了模型求解的计算程序 ,并用某工艺条件对复合炉衬的温度分布进行了计算 .结果表明 ,该方法可有效计算出复合炉衬的温度分布情况 ,为复合炉衬的设计、运行和维护提供理论依据     

Molecular association complex of urea with polyethylene: 3. Structural studies of the complex

The crystal structure of urea-polyethylene complex in the hexagonal form, obtained by one of our preparation methods, is analysed by X-ray power diffractometry. In this analysis, the fixed molecular parameters of urea are used, and three models with respect to rotational disorder of the guest polyethylene molecule are assumed. It is shown that the host lattice structure constructed by urea molecules is essentially the same as that of urea-n-paraffin complex. Effects of the disorder structure of the guest on X-ray scattering of the complex are presented. However, there is a difficulty in identifying the disorder structure by X-ray analysis. With the aid of a potential energy calculation between the hexagonal urea tunnel and the guest molecule, a rotational disorder model is preferred.     

相转移催化法合成多聚乙二醇二环氧甘油醚

以多聚乙二醇和环氧氯丙烷为原料合成了多聚乙二醇二环氧甘油醚。NaOH为催化剂,季铵盐为相转移催化剂。结论为:作为催化剂NaOH固体效果优于NaOH溶液;四正丁基硫酸氢铵(TBAS)催化醚化反应效果最佳,GC监测表明,二醚的选择性达98％以上;n(多聚乙二醇):n(环氧氯丙烷):n(NaOH):n(TBAS)= 1:10:7:0．08;反应温度55-60℃;反应时间1．5 h;产率83％。     

Mathematical models of the thermal decomposition of coal: 3. Density,porosity and contraction behaviour

Mathematical models are proposed to predict the true density of coal, semi-coke and coke and the porosity of a coke oven charge during carbonization. These models are combined in a further model which predicts the hitherto unexplained ‘twin-peaked’ contraction curve observed for semi-coke. It is found that the first contraction peak results from the relatively high rate of mass loss occurring towards the end of the primary devolatilization stage. The second peak occurs because of the increase in true density arising from the elimination of hydrogen from the semi-coke.     

2,6-萘二甲酸二甲酯与一些二甲基萘所形成的激基复合物

2,6-萘二甲酸二甲酯与一些二甲基萘可以形成激基复合物。本文通过稳态和动态荧光光谱研究了这类激基复合物的形成与分子结构的关系。结果表明,尽管这些二甲基萘的电离能基本相同,但因取代基位置不同使分子中电荷分布不同,从而影响了激基复合物的形成能力。     

THE ROLE OF INTERFACIAL PHENOMENA IN A LIQUID-LIQUID REACTION SYSTEM: EXTRACTION OF PROPANOIC ACID BY TRIOCTYLAMINE

The kinetics of extraction of propanoic acid from water to isobulanol by reaction with trioctylamine have been investigated. Mass transfer was modelled by extending the approach used in absorption with chemical reaction, as it is usually done for liquid-liquid reactions. The presence of the amine, however, gave rise to phenomena that cause this method to fail, producing inconsistent results. In order to explain these data, the presence of relevant interfacial phenomena must be supposed.     

COMPUTER SIMULATION OF HYDRODEMETALLATION IN FIXED-BED REACTORS

An isothermal model for hydrodemetallation (HDM) of crude oils in catalytic fixed-bed reactors is proposed. This model involves a consecutive reaction mechanism, which is capable of accounting for particle deposit profiles with interior maxima. Consistent with the fact that HDM catalysts are conglomerates formed by precipitation, the porous catalyst itself is modeled as randomly overlapping spheres of equal size. The metal is deposited as growing metal sulfide crystallites on the inner surface of the catalyst. These crystallites originate from a certain number of randomly scattered nuclei and increase in size as the deposition proceeds. The random sphere model for the catalyst and the deposit provides the changes in the catalyst pore structure—local porosity and surface area.

The mass transport within the domain of the particle is due to restricted liquid diffusion, since the diameter of the metal bearing compound (porphyrin) and the intermediate are comparable to the pore size. The diffusion restrictions taken into account are the enhanced drag imposed on a molecule by adjacent pore walls and steric partitioning.

Since the deposition process is much slower than diffusion and reaction, the pseudo-steady-state assumption can be justified. The equations of conservation for mass are solved by orthogonal collocation on finite elements. Based on this solution technique a computer simulation program of HDM is designed that allows two modes of operation: constant temperature and constant conversion. The simulation program “SIMULA” is highly flexible with regard to reaction kinetics, catalyst structure, reactor design, and operating conditions. In comparison to a base case with uniform activity, the effect of intraparticle (radial) and bed (axial) activity profiles on the conversion rate is discussed. For the case investigated, a radial distribution of activity higher at the center of the particle than at the edge can increase catalyst life by 25%, but axial distribution was less successful.     

模拟三相流化床中颗粒尺寸对单气泡传质系数的影响

本文在模拟三相流化床中,测量了单气泡的传质系数,实验结果表明颗粒直径对气-液传质系数影响显著。颗粒直径较大时,传质系数有明显提高。