硅烷处理N2O氧化苯生产苯酚催化剂抑制结碳失活研究

The main cause to the deactivation of ZSM-5 catalyst, used for oxidation of benzene to phenol (BTOP) by nitrous oxide, is that the carbon deposition on the catalyst surface blocks the mouth of pores of the catalyst.In the experiments, ZSM-5 catalyst was modified by chemical surface deposition of silicon, and then the effect of modification condition on the catalyst activation was studied. The catalyst samples were characterized by XRF,EPS, XRD, TEM, N2 adsorption at low temperature, pyridine adsorption-infrared technique and etc. All the above results show that the uniform SiO2 membrane can be formed on ZSM-5 crystal surface. The SiO2 membrane covers the acid centers on ZSM-5 surface to inhibit surface coking, to avoid or decrease the possibility of ZSM-5 pore blockage so that the catalyst activity and stability can be improved efficiently. The optimum siliconiting conditions determined by the experiments are as follows: 4% load of silanizing agent, volume (ml)/mass (g) ratio of hexane/ZSM-5=15/1, and 16 h of modification time. Compared with the samples without siliconiting treatment,the samples treated under the above optimum condition can increase the productivity of phenol by 14% for 3 h reaction time and by 41% for 6 h reaction time respectively.     

基于魏格纳分布的鼓泡流化床中结焦早期诊断

An experimental verification is reported on the early predicting index of agglomeration in bubbling fluidized bed. Coarse quartz sand, which has the same density but larger diameter than the bed material, was used to simulate the initial agglomerated particle. Wigner distribution was used to analyze the pressure fuctuation of the tested bed, and the average amplitude of local domain frequency （LDF） and local peak weighted average frequency （LPWA） under different operating conditions were measured and compared. The results showed that the LDF is sensitive to the agglomeration phenomena and had quick response to the incipient agglomeration in fluidized beds. It can be concluded from the results that these two parameters could be taken as the characteristic indexes to the agglomeration in fuidized beds.     

一种用于计算机辅助产物设计中基于BP-NN优化问题的求解方法

Because of the powerful mapping ability, back propagation neural network (BP-NN) has been employed in computer-aided product design (CAPD) to establish the property prediction model. The backward problem in CAPD is to search for the appropriate structure or composition of the product with desired property, which is an optimization problem. In this paper, a global optimization method of using the a BB algorithm to solve the backward problem is presented. In particular, a convex lower bounding function is constructed for the objective function formulated with BP-NN model, and the calculation of the key parameter a is implemented by recurring to the interval Hessian matrix of the objective function. Two case studies involving the design of dopamine β-hydroxylase (DβH) inhibitors and linear low density polyethylene (LLDPE) nano composites are investigated using the proposed method.     

杂合基因算法在酵母中间代谢途径代谢通量分析中的应用

A scheme of investigating the intracellular metabolic fluxes in central metabolism of Saccharomyces cerevisiae based on isotope model and tracer experiment was developed. The metabolic model applied in this study includes the Embden-Meyerhof-Parnas pathway, the pentose phosphate pathway, the tricarboxylic acid cycle, CO2 anaplerotic reactions, ethanol and acetate formation, and pathways involved in amino acid synthesis. The approach of hybridized genetic algorithm combined with the sequential simplex technique was used to optimize a quadratic error function without the requirement of the information on the partial derivatives. The impact of some key parameters on the algorithm was studied. This approach was proved to be rapid and numerically stable in the analysis of the central metabolism of S.cerevisiae.     

质子传导陶瓷电解质燃料电池特性分析

An electrolyte model for the solid oxide fuel cell (SOFC) with proton conducting perovskite electrolyte is developed in this study, in which four types of charge carriers including proton, oxygen vacancy (oxide ion), free electron and electron hole are taken into consideration. The electrochemical process within the SOFC with hydrogen as the fuel is theoretically analyzed. With the present model, the effects of some parameters, such as the thickness of electrolyte, operating temperature and gas composition, on the ionic transport (or gas permeation) through the electrolyte and the electrical performance, i.e., the electromotive force (EMF) and internal resistance of the cell, are investigated in detail. The theoretical results are tested partly by comparing with the experimental data obtained from SrCe0.05M0.05O3-α(M=Yb, Y) cells.     

胞外高分子物质对基质在复合生物膜内传质速率影响的测定

A model, for evaluating the effect of porosity and volume fraction of extracellular polymeric substances (EPS) within multispecies biofilms on the effective diffusivity, is developed and experimentally validated, based on the extraction of EPS from intact biofilms. The amount of EPS in biofilms significantly affects the effective diffusivity. For biofilms with porosity of 77%—95% in the top layers and 54%—58% in the bottom layers, the value of De/Dw decreases from 0.52—0.83 in the top layers to 0.23—0.31 in the bottom layers. Generally, the effective diffusivity in the heterotrophic/autotrophic biofilms is slightly lower than that in the heterotrophic biofilms, due to the lower porosity in the heterotrophic/autotrophic biofilms.     

基于双槽式孔板组合和神经网络技术的凝析天然气流量计开发

A slotted orifice has many superiorities over a standard orifice. For single-phase flow measurement, its flow coefficient is insensitive to the upstream velocity profile. For two phase flow measurement, various characteristics of its differential pressure （DP） are stable and closely correlated with the mass flow rate of gas and liquid. The complex relationships between the signal features and the two-phase flow rate are established through the use of a back propagation （BP） neural network. Experiments were carried out in the horizontal tubes with 50ram inner diameter, ooerated with water flow rate in the range of 0.2m^3·h^-1 to 4m3·h^-1, gas flow rate in the range of 100m^3·h^-1 to 1000m^3·h^-1, and pressure at 400kPa and 850kPa respectively, where the temperature is ambient temperature. This article includes the principle of wet gas meter development, the experimental matrix, the signal processing techniques and the achieved results. On the basis of the results it is suggested that the slotted orifice couple with a trained neural network may provide a simple but efficient solution to the wet gas meter development.     

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.     

酚醛树脂改性煤焦油沥青中制得的中间相球体的结构特征

Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morphology of mesophase spheres and the structure of the MCMB carbonized at 1000℃ for lh using scanning electron microscope （SEM） and XRD, it was found that phenolic resin accelerated the formation and coalescence of mesophase spheres. Some of the obtained MCMB were hi- or tri-spheres with the distorted microtextural carbon layers. Hexamethylenetetramine in the pitch modified by phenolic resin accelerated the condensation of phenolic resin and consequently expedited the combination of mesophase spheres, which was proved by the formation of some tetra-spheres. Owing to the cross-linkage of the additives, MCMB with complex structure were obtained.     

约束优化控制的约束调整与目标协调及在重油分离器过程中的作用

In this paper, the feasibility and objectives coordination of real-time optimization (RTO) are systemically investigated under soft constraints. The reason for requiring soft constraints adjustment and objective relaxation simultaneously is that the result is not satisfactory when the feasible region is apart from the desired working point or the optimization problem is infeasible. The mixed logic method is introduced to describe the priority of the constraints and objectives, thereby the soft constraints adjustment and objectives coordination are solved together in RTO. A case study on the Shell heavy oil fractionators benchmark problem illustrating the method is finally presented.     

用考虑颗粒尾涡效应的双时间尺度耗散模型模拟流体的湍流变动

Presently developed two-phase turbulence models under-predict the gas turbulent fluctuation, because their turbulence modification models cannot fully reflect the effect of particles. In this paper, a two-time-scale dissipation model of turbulence modification, developed for the two-phase velocity correlation and for the dissipation rate of gas turbulent kinetic energy, is proposed and used to simulate sudden-expansion and swirling gas-particle flows. The proposed two-time scale model gives better results than the single-time scale model. Besides, a gas turbulence augmentation model accounting for the f＇mite-size particle wake effect in the gas Reynolds stress equation is proposed. The proposed turbulence modification models are used to simulate two-phase pipe flows. It can properly predict both turbulence reduction and turbulence enhancement for a certain size of particles observed in experiments.     

设计过程工业多杂质用水网络的计算方法

This paper introduces a non-iterative algorithmic procedure to design water utilization networks with multiple contaminants in process plants. According to the water pinch analysis rules, the processes in water utilization systems were first divided into three groups, then water-supply priority algorithm was proposed. The results of case studies showed that the water networks designed by this method gave water consumption lower than that estimated by other approaches. In addition, the procedure was subiect to no limitation on the problem scale.     

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.     

混合制冷工质核态沸腾的传热研究

Heat transfer coefficients in nucleate pool boiling were measured on a horizontal copper surface for refrigerants, HFC-134a, HFC-32, and HFC-125, their binary and ternary mixtures under saturated conditions at 0.9MPa. Compared to pure components, both binary and ternary mixtures showed lower heat transfer coefficients.This deterioration was more pronounced as heat flux was increased. Experimental data were compared with some empirical and semi-empirical correlations available in literature. For binary mixture, the accuracy of the correlations varied considerably with mixtures and the heat flux. Experimental data for HFC-32/134a/125 were also compared with available correlated equation obtained by Thome. For ternary mixture, the boiling range of binary mixture composed by the pure fluids with the lowest and the medium boiling points, and their concentration difference had important effects on boiling heat transfer coefficients.     

颗粒尾涡增强湍流的大涡模拟以及气固两相流中湍流变动的数值模拟

The turbulence enhancement by particle wake effect is studied by large eddy simulation （LES） of turbulent gas flows passing a single particle. The predicted time-averaged and root-mean-square fluctuation velocities behind the particle are in agreement with the Reynolds-averaged Navier-Stokes modeling results and experimental results. A semi-empirical turbulence enhancement model is proposed by the present-authors based on the LES resuits. This model is incorporated into the second-order moment two-phase turbulence model for simulating vertical gas-particle pipe flows and horizontal gas-particle channel flows. The simulation results show that compared with the model not accounting for the particle wake effect, the present model gives simulation results for the gas turbulence modulation in much better agreement with the experimental results.     

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.     

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%.     

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.     

反应与催化精馏耦合提纯乳酸新工艺的研究

The purification of lactic acid based on the esterification of raw lactic acid from fermentation broth and then the catalytic distillation hydrolysis of methyl lactate simultaneously to achieve pure lactic acid is reported. The esterification kinetics of lactic acid with methanol catalyzed by strong-acid cation-exchange resins (Amberlyst-15,D001, D002, NKC, 002) was studied under the condition that simulates the real catalytic environment. Experimental results were correlated by a Langmuir-Hinselwood model and the nonideality of the solution was taken into account by using activities calculated by the universal quasichemical functional group activity coefficient (UNIFAC) method.A good agreement between the model and the experimental data was achieved. Continuous purification experiments were conducted to find the optimum column configuration and operation condition for the system. The effects of various parameters, e.g. the length of different section of the column, feed rate and ratio of reactants, packing material and catalyst type, were studied. This novel system shows good separation results in lab scale, and is potential for industrial application.     

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.