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.     

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.     

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.     

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.     

用NRTL方程推算高压汽液平衡并同时描述过量焓

The non-random two liquids （NRTL） equation together with the Pitzer/Curl Virial equation of state are used to investigate the simultaneous representation of excess enthalpies （h^E） and vapour-liquid equilibria （VLE） and the VLE prediction from h^E data. The calculation strategy for properly determining NRTL parameters and the effect of their temperature dependence on the simultaneous correlation of h^E and VLE data and the VLE extrapolation are analysed in detail.     

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.     

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.     

燃烧法制备二氧化钛催化剂的条件对其可见光催化性能的影响

Titania catalysts were synthesized by a solution combustion method （SCM）. Photodegradation of 4-chlorophenol （4-CP） using the synthesized catalysts was studied under both visible light （λ≥420nm） and sunlight irradiation. The effect of preparation conditions on photocatalytic activities of the synthesized catalysts was investigated. The optimal photocatalytic activity of the catalyst （denoted as A1 ） was obtained under the following synthesis conditions： ignition temperature of 350~C, fuel ratio （ φ） of 1 and calcination time of lh. The degradation and mineralization ratio of 4-CP were 78.2% and 53.7% respectively under visible light irradiation for 3h using catalyst A1. And the catalyst A1 also showed high photocatalytic activity under sunlight irradiation.     

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.     

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%.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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%.     

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.     

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.