用于甲烷偶联的SrCe0.95Yb0.05O3-α中空纤维膜反应器建模

Proton-hole mixed conductor, SrCe0.95Yb0.05O3-α(SCYb), has the potential to be used as a membrane for dehydrogenation reactions such as methane coupling due to its high C2-selectivity and its simplicity for fabricating reactor systems. In addition, the mixed conducting membrane in the hollow fibre geometry is capable of providing high surface area per unit volume. In this study, mechanism of methane coupling reaction on the SCYb membrane was proposed and the kinetic parameters were obtained by regression of experimental data. A mathematical model describing the methane coupling in the SCYb hollow fibre membrane reactor was also developed.With this mathematical model, various operating conditions such as the operation mode, operation pressure and feed concentrations affecting performance of the reactor were investigated. The simulation results show that the cocurrent flow in the reactor exhibits higher conversion of methane and higher yield of ethylene compared to the countercurrent flow. In order to achieve the highest C2 yield, especially of ethylene, pure methane should be used as feed and the operating pressure be 300 kPa. Air can be used as the source of oxygen for the reaction and it soptimum feed velocity is twice of the methane feed velocity. The air pressure in the lumen side should be kept the same as or slightly lower than the vressure of shell side.     

用于VOC回收的PVDMS-Al2O3中空纤维复合膜

Sorption isotherm of chloroform in polyvinyl dimethylsiloxane （PVDMS） polymer film was measured via the gravimetric method, and this film was confirmed experimentally to be good membrane material to recover chloroform from gas stream with high sorption capacity. A new PVDMS-Al2O3 composite hollow fibre membrane was further prepared by coating a PVDMS film on the outer surface of Al2O3 hollow fibre porpous substrate prepared by a dry/wet phase inversion method. Microstructure of the composite membranes was examined by scanning electron microscopy （SEM）, indicating the PVDMS coating layer was uniform, free of defects, and around 15μm thick. Performance of the PVDMS-Al2O3 composite hollow fibre membranes for chloroform recovery was investigated. By comparing the experimental data that derived from a mathematical model, the permeabilities of chloroform and nitrogen in the PVDMS polymer membrane were obtained. The effects of temperature and feed flow rate on the chloroform recovery and permeate concentration were investigated both experimentally and theoretically.     

PVDMS-Al_2O_3 Composite Hollow Fibre Membranes for Chloroform Recovery from Gas Streams

Sorption isotherm of chloroform in polyvinyl dimethylsiloxane(PVDMS)polymer film was measured via the gravimetric method,and this film was confirmed experimentally to be good membrane material to recover chloroform from gas stream with high sorption capacity.A new PVDMS-Al_2O_3 composite hollow fibre membrane was further prepared by coating a PVDMS film on the outer surface of Al_2O_3 hollow fibre porpous substrate prepared by a dry/wet phase inversion method.Microstructure of the composite membranes was examined by scanning electron microscopy(SEM),indicating the PVDMS coating layer was uniform,free of defects,and around 15μm thick.Performance of the PVDMS-Al_2O_3 composite hollow fibre membranes for chloroform recovery was investigated.By comparing the experimental data that derived from a mathematical model,the permeabilities of chloroform and nitrogen in the PVDMS polymer membrane were obtained.The effects of temperature and feed flow rate on the chloroform recovery and permeate concentration were investigated both experimentally and theoretically.     

用于污水处理的柔性纤维膜反应器氧传递及动力学研究

A flexible fibre biofilm reactor was developed for treatment of organic wastewaters. The hydrodynamic characteristics and mass transfer coefficients of oxygen were studied and compared with those of the conventional activated sludge processes. Tracer experiments were performed to obtain the residence time distributions of the reactors. The results indicated that both reactors could be treated as mixed flow reactors. The effects of flow rates of water and air on the overall mass transfer coefficient of oxygen were investigated, and the correlations between the mass transfer coefficient and the ratio of flow rates were obtained. Compared to the conventional activated sludge reactor, the mass transfer coefficients in the flexible fibre reactor were similar to but slightly lower, and less sensitive to the variation in the ratio of flow rates. It indicated that the fibre packing in the reactor hindered the oxygen transfer to some extent.     

流向变换强制周期操作合成甲醇反应器的模型化

An accurate one-dimensional,heterogeneous model taking account of axial dispersion and heat transfer to the reactor wall,and heat conduction through the reactor wall for methanol synthesis in a bench scale reactor under periodic reversal of flow direction is presented.Adjustable parameters in this model are the effectiveness factors for each of the three reactions occurring in the synthesis and a factor for the bed to wall heat transfer coefficient correlation.Experimental data were used to evaluate these parameters and reasonable values of these parameters were obtained.The model was found to closely predict the reactor performance under a wide range of parameters were obtained.The model was found to closely predict the reactor preformance under a wide range of operating conditions,such as carbon oxide concentrations,volumetric flow rate,and cyclic period.     

Modeling of a Reverse Flow Reactor for Methanol Synthesis Modeling of a Reverse Flow Reactor for Methanol Synthesis

An accurate one-dimensional, heterogeneous model taking account of axial dispersion and heat transfer to the reactor wall, and heat conduction through the reactor wall for methanol synthesis in a bench scale reactor under periodic reversal of flow direction is presented. Adjustable parameters in this model are the effectiveness factors for each of the three reactions occurring in the synthesis and a factor for the bed to wall heat transfer coefficient correlation. Experimental data were used to evaluate these parameters and reasonable values of these parameters were obtained. The model was found to closely predict the reactor performance under a wide range of operating conditions, such as carbon oxide concentrations, volumetric flow rate, and cyclic period.     

基于精细自由基反应机理的丙烷裂解炉炉管CFD模拟(英文)

In the radiant section of cracking furnace, the thermal cracking process is highly coupled with turbulent flow, heat transfer and mass transfer. In this paper, a three-dimensional simulation of propane pyrolysis reactor tube is performed based on a detailed kinetic radical cracking scheme, combined with a comprehensive rigorous computational fluid dynamics（CFD） model. The eddy-dissipation-concept（EDC） model is introduced to deal with turbulence-chemistry interaction of cracking gas, especially for the multi-step radical kinetics. Considering the high aspect ratio and severe gradient phenomenon, numerical strategies such as grid resolution and refinement, stepping method and relaxation technique at different levels are employed to accelerate convergence. Large scale of radial nonuniformity in the vicinity of the tube wall is investigated. Spatial distributions of each radical reaction rate are first studied, and made it possible to identify the dominant elementary reactions. Additionally, a series of operating conditions including the feedstock feed rate, wall temperature profile and heat flux profile towards the reactor tubes are investigated. The obtained results can be used as scientific guide for further technical retrofit and operation optimization aiming at high conversion and selectivity of pyrolysis process.     

pH控制在管状流动反应器中的应用(英文)

Tubular flow reactors are mainly used in chemical industry and waste water discharged units. Control of output variables is very difficult because of the existence of high dead-time in these types of reactors. In the present work, sodium hydroxide and acetic acid solutions were sent to the tubular flow reactor. The aim was to control pH at 7 in the nonlinear region. The pH control of a tubular flow reactor with high time delay and a highly nonlinear behavior in pH neutralization reaction was investigated experimentally in the face of the various load and set point changes. Firstly, efficiency of conventional Proportional-Integral-Derivative (PID) algorithm in the experiments was tested. Then self-tuning PID (STPID) control system was applied by using the ARMAX model. The model parameters were calculated from input–output data by using PRBS signal as disturbance and Bierman algorithm. Lastly, the experimental fuzzy control of pH based on fuzzy model was achieved to compare the success of fuzzy approach with the performance of other control cases studied.     

Diffusion Characteristics in Microcapsules

An equation of diffusion for microcapsules(hollow sphere)was developed,employing the mathematicalmodel for the diffusion characteristics of solid sphere.In the proposed equation,a combination diffusion coeffi-cient was introduced as a substitute for the diffusion coefficient in the solid sphere mathematical model and ex-pressed as a function of the diffusion coefficient inside solution of hollow sphere,as well as in the polymer mem-brane.With this modified model,the diffusion coefficients of glucose in NaCS(sodium cellulose sulfate)-PDADMAC(Poly-diallyl-dimethyl-ammonium chloride)membrane and in Ca-alginate gel membrane were deter-mined.The diffusion coefficient in NaCS-PDADMAC membrane was found to be 2.12×10~(-11)m~2·s~(-1)and thatin Ca-alginate membrane 2.62×10~(-10)m~2·s~(-1).     

A safe and efficient process for the preparation of difluoromethane in continuous flow

Difluoromethane is typically produced vialiquid-phase fluorination as performed in a batch reactor. However,this process suffers from some problems, e.g., severe corrosion of the reactor, high safety risk, and the regeneration of the catalyst. In this paper, a flow process as performed in the tubular reactor was designed. The optimum conditions for continuous synthesis of difluoromethane were obtained as follows: the reaction temperature was 100℃, the molar ratio of dichloromethane to hydrogen fluoride was 1.6:1 and the reaction time was 300 s. The operation of the cyclic process was stable for 24 h with the conversion per pass of hydrogen fluoride up to 16.2%.The unreacted raw materials were easily reused. The deactivation of the common catalyst, antimony pentachloride, was investigated by catalyst concentration curve and XPS analysis. The approach proposed in this work is proven to be safe, efficient and low amount of catalyst.     

合成气制二甲醚三相淤浆床反应器的数学模型研究

A mathematical model for a bubble column slurry reactor is presented for dimethyl ether synthesis from syngas. Methanol synthesis from carbon monoxide and carbon dioxide by hydrogenation and the methanol dehydration are considered as independent reactions, in which methanol, dimethyl ether and carbon dioxide are the key components. In this model, the gas phase is considered to be in plug flow and the liquid phase to be in partly back mixing with axial distribution of solid catalyst. The simulation results show that the axial dispersion of solid catalysts, the operational height of the slurry phase in the bubble column slurry reactor, and the reaction results are influenced by the reaction temperature and pressure, which are the basic data for the scale-up of reactor.     

EFFECT OF FLOW PATTERNS ON EPOXIDATION OF PROPYLENE WITH ETHYLBENZENE HYDROPEROXIDE

The process of producing propylene oxide by epoxidation of propylene with ethylbenzene hydroper-oxide is one of the most promising methods in recent years.In order to select an optimum reaction equip-ment technologically,the mathematical models of epoxidation reactor for plug flow,single-stage andmultistage perfect mixing have been founded in this paper by means of the kinetic model on epoxidationand the effects of various flow patterns on the reaction are also discussed.The analyses show that themultistage reactor is a more ideal one for industrial equipment,and its optimum operating conditions aresuggested.     

Modeling and experimental studies of methyl methacrylate polymerization in a tubular reactor☆

In this study, rheological examination of the mixture of a tubular reactor in which methyl methacrylate was po-lymerized has been studied. The n (flow behavior index) value of Power Law Model of mixture contained in the reactor has been determined within the span of 0.3492 to 0.9889 by curve fitting. Employing these numerical data for velocity profile, the reactor has been modeled. Moreover, the functions of the reactor have been com-pared in the three modes of plug, mixed and laminar flow. The results obtained in this research indicate that the polymethyl methacrylate mixture contained in the reactor is pseudo-plastic. Moreover, as the conversion grows, the velocity profile starts as a parabolic profile and approaches the plug mode;although it never reaches the plug. The other conclusions borne in this study indicate that when the reactor's radius is decreased, the conversion rate grows. However, as decreasing the radius would also reduce the productions rate, this procedure is not economical. Finally, in this modeling, the amount of conversion is equal to 56.47%at the end and according to its laboratory proportion which is 55.88%, it has reached the conclusion that the modeling duly undertaken is applicable and valid.     

An integrated model for predicting the flame propagation in crimped ribbon flame arresters

Crimped ribbon flame arresters are important safety devices in the chemical industry,especially for the dangerous situations.Although proper design of arresters by the numerical simulation method is promising,its reliability and accuracy are dependent upon the mathematical model.In this work,an integrated mathematical model for the microchannel in the crimped ribbon flame arresters was set up;the fluid flow behavior and the sensitivities of four chemical kinetics mechanisms of propane-air on the accuracy were analysed.It is shown that turbulence is predominant in the microchannel of the crimped ribbon flame arresters under the deflagration and detonation conditions,and a new quenching criterion for the numerical simulation is proposed.The kinetics mechanism of Mansouri et al.among the four ones is the most accurate due to the best agreement of the predicted outlet temperature at the experimental flameproof velocity with the autoignition temperature of propane-air.The species mass fraction profiles and the temperature distribution,which are too difficult to measure due to the tiny dimension of the microchannel in experiments,are captured.The fundamental insights into chemical reactions and heat loss are well portrayed.It can be concluded that the integrated mathematical model established in this work can be used as a reliable tool for modeling,selecting and designing such type of crimped ribbon flame arresters with the propane-air medium in the future.     

周期性输入组分和扫气在改善钯膜反应器甲烷部分氧化制氢中的作用(英文)

The partial oxidation of methane under periodic operation over Ni/γ-Al2O3 catalyst was investigated in a Pd-membrane reactor.The effects of key parameters such as the inlet composition and the sweeping gas on methane conversion and the hydrogen recovery are numerically established with two periodic input functions.In order to analyze the effect of the inputs modulation,the reaction was performed under low steam to methane ratio at a moderate temperature and pressure.It was obtained that to achieve process intensification is to operate the process in a periodic way.The main results show that the periodic input functions can improve the performance of the process compared to the optimal steady state operation.Moreover,there is an optimum amplitude of manipulated inputs leads to a maximum of hydrogen recovery.It is noteworthy that the comparison between the predicted performance via the sinusoidal and the square ways show that the better average performance was obtained with the square way.     

反渗透处理煤层气产出水中试示范及其控制模型研究(英文)

This study presents the first demonstration project in China for treatment of coal-bed methane(CBM) co-produced water and recycling.The work aims to provide a research and innovation base for solving the pollution problem of CBM extraction water.The reverse osmosis(RO) unit is applied to the treatment of CBM co-produced water.The results indicate that system operation is stable,the removal efficiency of the total dissolved solids(TDS) is as high as 97.98%,and Fe,Mn,and F-are almost completely removed.There is no suspended solids(SS) detected in the treated water.Furthermore,a model for the RO membrane separation process is developed to describe the quantitative relationship between key physical quantities-membrane length,flow velocity,salt concentration,driving pressure and water recovery rate,and the water recovery restriction equation based on mass balance is developed.This model provides a theoretical support for the RO system design and optimization.The TDS in the CBM co-produced water are removed to meet the "drinking water standards" and "groundwater quality standards" of China and can be used as drinking water,irrigation water,and livestock watering.In addition,the cost for treatment of CBM co-produced water is assessed,and the RO technology is an efficient and cost-effective treatment method to remove pollutants.     

Modeling-based optimization of a fixed-bed industrial reactor for oxidative dehydrogenation of propane

An industrial scale propylene production via oxidative dehydrogenation of propane(ODHP)in multi-tubular reactors was modeled.Multi-tubular fixed-bed reactor used for ODHP process,employing 10000 of small diameter tubes immersed in a shell through a proper coolant flows.Herein,a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence ole fin over V_2O_5/γ-Al_2O_3catalyst was presented.Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions,gas process and coolant temperatures,as well as other parameters affecting the reactor performance such as pressure.Furthermore,the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%.The optimized length of the reactor needed to reach 100%conversion of the oxygen was theoretically determined.For the single-bed reactor the optimized length of 11.96 m including 0.5m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72m for the first and 7.32 m for the second reactor were calculated.Ultimately,the use of a distributed oxygen feed with limited number of injection points indicated a signi ficant improvement on the reactor performance in terms of propane conversion and propylene selectivity.Besides,this concept could overcome the reactor runaway temperature problem and enabled operations at the wider range of conditions to obtain enhanced propylene production in an industrial scale reactor.     

生物质热裂解实验和模型研究(英文)

The analysis on the feedstock pyrolysis characteristic and the impacts of process parameters on pyrolysis outcomes can assist in the designing,operating and optimizing pyrolysis processes.This work aims to utilize both experimental and modelling approaches to perform the analysis on three biomass feedstocks—wood sawdust,bamboo shred and Jatropha Curcas seed cake residue,and to provide insights for the design and operation of pyrolysis processes.For the experimental part,the study investigated the effect of heating rate,final pyrolysis temperature and sample size on pyrolysis using common thermal analysis techniques.For the modelling part,a transient mathematical model that integrates the feedstock characteristic from the experimental study was used to simulate the pyrolysis progress of selected biomass feedstock particles for reactor scenarios.The model composes of several sub-models that describe pyrolysis kinetic and heat flow,particle heat transfer,particle shrinking and reactor operation.With better understanding of the effects of process conditions and feedstock characteristics on pyrolysis through both experimental and modelling studies,this work discusses on the considerations of and interrelation between feedstock size,pyrolysis energy usage,processing time and product quality for the design and operation of pyrolysis processes.     

聚碳酸酯连续熔融酯交换过程的反应闪蒸模拟

A model of the continuous melt transesterification process of bisphenol-A and diphenyl carbonate in a continuous stirred tank reactor to produce polycarbonate is presented. The model is developed by using the molecular species model of polycarbonate melt polycondensation and the modeling method of reactive flash. Liquid phase is treated as perfect mixed flow and the vapor phase is assumed following the ideal gas law. With this model, the continuous melt transesterification process of bisphenol-A and diphenyl carbonate is examined with respect to different orocess parameters.     

绝热固定床反应器甲醇脱水合成二甲醚的实验和模型研究

One-dimensional heterogeneous plug flow model was employed to model an adiabatic fixed-bed reactor for the catalytic dehydration of methanol to dimethyl ether. Longitudinal temperature and conversion profiles predicted by this model were compared to those experimentally measured in a bench scale reactor. The reactor was packed with 1.5 mm γ-Al2O3 pellets as dehydration catalyst and operated in a temperature range of 543-603 K at an atmospheric pressure. Also, the effects of weight hourly space velocity (WHSV) and temperature on methanol conversion were investigated. According to the results, the maximum conversion is obtained at 603.15 K with WHSV of 72.87 h－1.