DCV-GCMD方法模拟近临界条件下乙烯、苯与乙苯在圆柱形孔道中苯烃化反应条件下的吸附和传递性质

Abstract A cylindrical pore model was used to represent approximately the pore of β-zeolite catalyst that had been used in the alkylation of benzene with ethylene and spherical Lennard-Jones molecules represented the components of the reaction system-ethylene, benzene and ethylbenzene. The dual control volume-grand canonical molecular dynamics (DCV-GCMD) method was used to simulate the adsorption and transport properties of three components under reaction in the cylindrical pore at 250℃and 270℃in the pressure range from 1 MPa to 8 MPa. The state map of the reactant mixture in the bulk phase could be divided into several different regions around its critical points. The simulated adsorption and transport properties in the pore were compared between the different near-critical regions. The thorough analysis suggested that the high pressure liquid region is the most suitable region for the alkylation reaction of benzene under the near-critical condition.     

载体对镍催化剂催化间二硝基苯加氢制间苯二胺反应性能的影响

The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.     

涡流桨搅拌槽内流动非稳定性的大涡模拟

The aim of this work is to investigate the flow instabilities in a baffled, stirred tank generated by a single Rushton turbine by means of large eddy simulation （LES）. The sliding mesh method was used for the coupling between the rotating and the stationary frame of references. The calculations were carried out on the ＂Shengcao-21C＂ supercomputer using a computational fluid dynamics （CFD） code CFX5. The flow fields predicted by the LES simulation and the simulation using standard κ-ε model were compared to the results from particle image velocimetry （PIV） measurements. It is shown that the CFD simulations using the LES approach and the standard κ-ε model agree well with the PIV measurements. Fluctuations of the radial and axial velocity are predicted at different frequencies by the LES simulation. Velocity fluctuations of high frequencies are seen in the impeller region, while low frequencies velocity fluctuations are observed in the bulk flow. A low frequency velocity fluctuation with a nondimensional frequency of 0.027Hz is predicted by the LES simulation, which agrees with experimental investigations in the literature. Flow circulation patterns predicted by the LES simulation are asymmetric, stochastic and complex, spanning a large portion of the tanks and varying with time, while circulation patterns calculated by the simulation using the standard κ-ε model are symmetric. The results of the present work give better understanding to the flow instabilities in the mechanically agitated tank. However, further analysis of the LES calculated velocity series by means of fast Fourier transform （FFT） and/or spectra analysis are recommended in future work in order to gain more knowledge of the complicated flow phenomena.     

基于人工神经网络的滴流床脉冲流频率的预测

An extensive database (946 measurements) for the frequency of pulsing flow in trickle beds was established by collecting the experimental results published over past 30 years. A new correlation based on artificial neural network (ANN) to predict the pulsation frequency was developed. Seven dimensionless numbers (groups) employed in the proposed correlation were liquid and gas Reynolds, liquid Weber, liquid Eǒtvǒs, gas Froude, and gas Stokes numbers and a bed correction factor. The comparisons of performance reported in the of literature and present correlations show that ANN correlation is a significant improvement in predicting pulsation frequency with an average absolute relative error (AARE) of 10% and a standard deviation less than 18%.     

运用层次分析法对化学产品的环境经济性能集成评价

With the increasing public consciousness on environmental issues, chemical products and process designs require simultaneous satisfaction and compromise of environmental and economical requirements. To fulfill the two conflicting while complementary objectives, a systematic approach for life cycle design of a chemical product is proposed in this article. Multiattribute decision-making is adopted in a trade-off consideration of both technical economical evaluation and environmental impacts assessment using the analytic hierarchy process （AHP） approach. On the basis of an evaluation of the relative importance of the criteria multicriteria decision making is performed. In this study, an AHP model is used to derive single a criteria score by analyzing the environmental impact and life cycle cost of a product, respectively. And a fluctuant weight analysis is put forth to calculate the integrated index of the product to enable products to be ranked or selected intuitionally and conveniently. The proposed AHP model has been applied to a case study, a comparative study on chamber cleaning with NF3 and C2F6. The resuits show that the protposed AHP model is Capable of providing a rational and relevant evaluation.     

用改进ECT技术测定油气两相流中空泡分数的测量研究

To measure the void fraction online in oil-gas pipeline, an improved electrical capacitance tomography (ECT) system has been designed. The capacitance sensor with new structure has twelve internal electrodes and overcomes the influence of the pipe wall. The data collection system is improved by using high performance IC (integrated circuit). Static tests of bubble flow, stratified flow and annular flow regime are carried out. Measurements are taken on bubble flow, stratified flow and slug flow. Results show that the new ECT system performs well on void fraction measurement of bubble flow and stratified flow, but the error of measurement for slug flow is more than 10%.     

牛奶中分离的乳酸菌CGMCC1306中谷氨酸脱羧酶的分离纯化及酶学性质研究

A Lactobacillus brevis CGMCC 1306 isolated from fresh milk without pasteurization was found to have higher glutamate decarboxylase （GAD） activity. An effective isolation and purification procedure of GAD from a cell-free extract of Lactobacillus brevis was developed, and the procedure included four steps： 30%-90% saturation （NH4）2SO4 fractional precipitation, Q sepharose FF anion-exchange chromatography, sephacryl S-200 gel filtration, and resource Q anion-exchange chromatography. Using this protocol, the purified GAD was demonstrated to possess electrophoretic homogeneity via SDS-PAGE. The purification fold and activity recovery of GAD were 43.78 and 16.95%, respectively. The molecular weight of the purified GAD was estimated to be approximately 62 kDa via SDS-PAGE. The optimum pH and temperature of the purified GAD were 4.4 and 37℃, respectively. The purified GAD had a half-life of 50rain at 45℃ and the Km value of the enzyme from Lineweaver-Burk plot was found to be 8.22.5＇-pyridoxal phosphate （PLP） had little effect on the regulation of its activity.     

SRK状态方程用于聚合物体系的汽液和气液平衡

A simple extension of cubic equations of state （EOS） to polymer systems has been proposed. The Soave-Redlich-Kwong （SRK） EOS was taken as a prototype to be used to describe the PVT behavior of polymer melts in a wide temperature and pressure range. Combined with a modified Huron-Vidal gE-mixing rule it was applied for modeling vapor-liquid equilibria of polymer-solvent solutions and the solubility of supercritical gases in polymer melts. Satisfactory results are obtained.     

293.15K到333.15K温度下一些氨基酸及其相应基团水溶液中的偏摩尔体积研究

Abstract Densities of aqueous solutions of eight amino acids, glycine, L-alanine, L-valine, L-isoleucine, L-serine, L-threonine, L-arginine and L-phenylalanine, are measured as a function of amino acid concentration from 293.15 K to 333.15 K. These data are used to calculate the apparent molar volume Vφ^0 and infinite dilution apparent molar volume Vφ^0 (partial molar volume). Data of five amino acids are used to correlate partial molar volume Vφ^0 using group contribution method to estimate the contributions of the zwitterionic end groups (NH ,COO-) and CH2 group, OH group, CNHNHNH2 group and C6H5(phenyl) group of amino acids. The results show that Vφ^0 values for all kinds of groups of amino acids studied increase with increase of temperature except those for CH2^φ group, which are almost constant within the studied temperature range. Data of other amino acids, L-valine, L-isoleucine and L-threonine, are chosen for comparison with the predicted partial molar volume Vφ^0 using the group additivity parameters obtained. The results confirm that this group additivity method has excellent predictive utility.     

输入训练神经网络的维数约简算法及其在化工过程建模中的应用

Many applications of principal component analysis （PCA） can be found in dimensionality reduction. But linear PCA method is not well suitable for nonlinear chemical processes. A new PCA method based on improved input training neural network （IT-NN） is proposed for the nonlinear system modelling in this paper. Momentum factor and adaptive learning rate are introduced into learning algorithm to improve the training speed of IT-NN. Contrasting to the auto-associative neural network （ANN）, IT-NN has less hidden layers and higher training speed. The effectiveness is illustrated through a comparison of IT-NN with linear PCA and ANN with experiments. Moreover, the IT-NN is combined with RBF neural network （RBF-NN） to model the yields of ethylene and propylene in the naphtha pyrolysis system. From the illustrative example and practical application, IT-NN combined with RBF-NN is an effective method of nonlinear chemical process modelling.     

壁面粗糙度对气粒两相流动中颗粒行为影响的实验研究

The effect of wall roughness on particle behavior in two-phase flows in a horizontal backward-facing step is studied using a phase-Doppler particle anemometer. The results show that the wall roughness widens the particle velocity probability density distribution, enhances the redistribution of particle velocity into different directions,reduces the particle longitudinal mean velocity and increases the longitudinal and transverse fluctuation velocities and Reynolds shear stress. The effect of roughness on particle motion in the recirculation zone is weaker than that in the fully developed flow region. The effect of roughness for small particles is restricted only in the near-wall region, while that for large particle diffuses to the whole flow field.     

中孔酸性蒙脱石基复合材料催化邻苯二酚-叔丁醇烷基化反应研究

The liquid phase alkylation of catechol with tert-butyl alcohol to produce 4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite and novel acidic porous montmorillonite heterostructures (PMHs). Upon all catalysts tested, 4-TBC is the main product and 3-tert-butyl catechol (3-TBC) and 3,5-di-tert-butyl catechol are the side products. The synthetic PMHs showed higher conversion of catechol and better selectivity to 4-TBC compared to other solid acid catalysts tested. Over the PMHs derived from H-exchanged montmorillonite through template extraction processes, the suitable reaction temperature is ca 410 K, the ratio of catechol to tert-butyl alcohol is 1:2. Increasing the amount of catalyst (lower weight hourly space velocity) can improve the conversion of catechol and influence the selectivity slightly. The reasonable reaction time is ca 8 h.The type and strength of acidity of H-montmorillonite and PMH were determined by pyridine adsorption FT-IR and ammonia temperature-programmed desorption techniques. The medium and strong acid sites are conducive to producing 4-TBC and the weak acid sites to facilitating the 3-TBC formation. The differences between the PMHs from calcination and those fi‘om extraction are attributed to proton migration and acidity change in the gallery surface.     

T-形分叉槽道纤维悬浮湍流场的数值模拟

The concentration and orientation of fiber in a turbulent T-shaped branching channel flow are investigated numerically. The Reynolds averaged Navier-Stokes equations together with the Reynolds stress turbulent model are solved for the mean flow field and the turbulent kinetic energy. The fluctuating velocities of the fluid are assumed as a random variable with Gaussian distribution whose variance is related to the turbulent kinetic energy. The slender-body theory is used to simulate the fiber motion based on the known mean and fluctuating velocities of the fluid. The results show that at low Reynolds number, fiber concentration is high in the flow separation regions, and fiber orientation throughout the channel is widely distributed with a slight preference of aligning along the horizontal axis. With increasing of Re, the high concentration region disappears, and fiber orientation becomes ho- mogeneous without any preferred direction. At high Reynolds number, fiber concentration increases gradually along the flow direction. The differences in the distribution of concentration and orientation between different fiber aspect ratio are evident only at low Re. Both Re and fiber aspect ratio have small effect on the variance of orientation angle.     

炭粒床高效工业除尘装置的设计与开发

The new dust removal technical route using the carbon-granular bed filter, packed of carbon particles with appropriate grade derive from an online-process vibration sieve, to replace the traditional baggy filter had been developed successfully for capturing the micro-carbon dusts produced from pulverization of petroleum coke,and the green close loop of carbon materials is thus completed in the combined pulverizing and classifying system and pulverized carbon dust removal process. The high dust removal efficiency greater than 99%, low outlet dust concentration less than 100 mg-m-S, low pressure drop through dust filtration chamber less than 980 Pa, simple and easy design, and flexible and stable operation were achieved also with the carbon-granular bed filter in both bench and industrial scale operations.     

用重整化群理论研究硬核Asakura-Oosawa流体的相平衡

An analytical equation of state (EOS) for hard core Asakura-Oosawa (AO) fluid is established by combining the AO potential, the first-order perturbation theory and the radial distribution function (RDF) for the hard sphere fluid.The phase equilibria are studied by using the renormalization-group (RG) theory. The obtained results agree well with the simulation data. Investigation shows that the attractive range parameter plays an important role in the phase equilibria for AO fluid.     

分批精馏过渡段放持液操作方式

The new mode of operation for slop cut withdrawal in batch distillation, i.e., draining Column liquid holdup at the end of slop cut period, was proposed. And the stopping criterion for the operation was investigated, Experiments were carded out with isopropanol-n-propanol binary system and isopropanol-n-propanol-n-butanol ternary system in a distillation column with a liquid collector installed between the reboiler and the column section, Experimental results in a Ф 45mm batch column show that the proposed policy can overcome the flywheel effect caused by column liquid holdup and thus cut down operation time and energy consumption 31%-61%.     

废轮胎热解炭黑的表面修饰及其在平版印刷油墨中的应用

Pyrolysis has the potential of transforming waste into valuable products. Pyrolytic carbon black （PCB） is one of the most important products resulting from the pyrolysis of used tires. One of the most significant applications of modified pyrolytic carbon black is its use as pigment for offset printing ink to obtain high added values. Inverse gas chromatography （IGC） results show that a large quantity of inorganic matters and carbonaceous deposit are removed by treating the pyrolytic carbon black with nitric acid solution. Plenty of active sites originally occupied by inorganic ash and coke are recovered. The surface energy of pyrolytic carbon black （TWPC） modified by titanate-coupling agent-especially the specific interaction γs^SP determined by the specific probe molecule, toluene-shows the strong interaction between the TWPC and the synthetic resins. The offset printing ink performance confirms the IGC prediction. And TWPC has the great potential of applications in printing ink industry as pigment.     

高温高压下湿空气循环中增湿塔的计算研究

Humidification is an important step in humid air turbine system. The calculation on humidification is carried out at 423.15—573.15K, 5—15MPa. The results suggest that to produce high-enthalpy moist air, high water temperature and large water flow are needed. The water temperature is the most sensitive parameter to the humidification tower. And it is better for the humidification tower to work at temperature higher than 523 K when the system pressure is higher than 5 MPa. The comparison between the model used in this paper and ideal model shows that the ideal model can be used in simulation to simply the calculation when the temperature is lower than 473 K and pressure is lower than 5 MPa.     

用对应态基团贡献法估算有机物偏心因子

A new estimation method was proposed by combining the corresponding state principle with the group contribution method through introducing the concept of assumed-critical properties. Combining it with the Reidel equation, a new acentric factor correlation equation （CSGC-Reidel） was developed. Contribution values of 70 groups were obtained by correlating acentric factor data of 228 organic compounds of 14 type substances including saturated hydrocarbons, unsaturated hydrocarbons, cyclanes, aromatics, oxygen compounds, nitrogen compounds, halohydrocarbons, etc. The average error of acentric factor is 3.52% between the literature data and the predicated with the new estimation method.     

应用降膜结晶法将十二烷二酸从同系物中分离及精制

Separation and purification of dodecanedioic acid (DDDA) from its homologous compounds were studied experimentally by falling film crystallization (FFC). The influences of various operation parameters, including crystallizing time, flow rate of melt and temperature of glycerine bath, on purity of DDDA and crystallizing rate were investigated. Over 99% (by mole) DDDA was obtained for a feed composition of 96% (by mole). The main factors affecting the separation efficiency are flow rate of melt and temperature of glycerine bath. The crystallizing layer of DDDA was further purified by sweating and blasting. A set of optimized operation data are provided for better understanding the mechanism of heat and mass transfer in FFC, and for further industrial application of DDDA purification process.