Homogeneous metathesis for the production of propene from butene

The cross-metathesis of 1-butene and 2-butene is described for the production of propene and 2-pentene using Phobcat, a homogeneous Grubbs first generation-type catalyst bearing 9-cyclohexyl-9-phosphabicyclo-[3.3.1]-nonane as ligand. In a closed system at 20 bar and 50 °C, the reaction mixture composition at different 1-butene:2-butene feed ratios is in fair agreement with the calculated composition at equilibrium based on thermodynamic data. Compared to heterogeneous metathesis over a WO₃/SiO₂ catalyst, the homogeneous reaction exhibits better reaction control and selectivity to the desired products.     

A porous carbon membrane reactor for the homogeneous catalytic hydration of propene

A porous carbon membrane contactor was studied to determine whether such a reactor could be used for homogeneous catalytic reactions. The hydration of propene, catalysed by an aqueous solution of phosphoric acid, was selected as a suitable model reaction. Experiments at high pressure and temperature were conducted in a laboratory-scale gas phase continuous reactor equipped with a flat carbon membrane contactor. It was shown that reasonably stable operation of the reactor could be achieved at high operating pressures by tailoring the porous structure of the carbon membrane and coupling the reactor with an on-line feedback pressure controller. The reactor operated in a mass transfer limited regime due to mass transfer resistance in the liquid filled membrane pores. Periodic oscillation of transmembrane pressure was shown to reduce mass transfer resistance and considerably improve the overall reactor performance.A dynamic model of the reactor was developed and the results of simulations compared favourably with experiments and the performance of a commercially operated conventional reactor employing a supported liquid phase (SLP) catalyst.     

Periodically operated trickle-bed reactor for EAQs hydrogenation: Experiments and modeling

The influence of periodic operation on a consecutive reaction, the hydrogenation of 2-ethylanthraquinones (EAQs) over Pd/Al₂O₃, on a laboratory-scale trickle-bed reactor (TBR) was studied. The effects of operating parameters including cycle period, split, pressure, temperature, and time-average flow rate on the performance were experimentally examined in comparison with the steady-state operation. The results showed that under the interested operating conditions the conversion and the selectivity improved by 3-21% and 1-12%, respectively. A dynamic model consisting of a set of partial differential equations (PDEs) was developed to simulate the periodic operation of TBR for EAQs hydrogenation. The PDEs were converted into a set of ordinary differential equations (ODEs) using the method of lines (MOL) and then numerically solved by the semi-implicit Runge-Kutta method. The developed model was verified by simulating the effect of cycle period and split on the conversion and the selectivity enhancement and compared with the experimental results. It was found that the model was reliable and satisfactory when the cycle period was less than 200 s.     

复合式膜生物反应器强化脱氮除磷的实验研究

在传统好氧膜生物反应器(MBR)的基础上,结合厌氧/缺氧/好氧(A2/O)工艺开发了复合式A2/O膜生物反应器,并对其处理小区生活污水中的氮、磷等污染物的特性进行了研究。实验表明:在各自合适的条件下复合式A2/O膜生物反应器可保证化学需氧量(COD)的平均去除率达到90.17%,NH4+-N的去除率可达到92.32%,总氮(TN)平均去除率可达到72%,而总磷(TP)的平均去除率达到71.23%。     

A model for Kolbe electrolysis in a parallel plate reactor

A parallel-plate reactor model is developed for the Kolbe electrolysis of acetate to ethane and carbon dioxide with hydrogen evolution as the counterelectrode reaction. The parallel-plate reactor is considered to consist of three zones: a turbulent bulk region in which streamwise convection is the dominant mass-transport mechanism (plug-flow model) and a thin diffusion layer at each electrode where diffusion and migration mass transport are dominant (Nernst diffusion-layer model). The acetic acid solution is supported with sodium hydroxide, and the reactor is under steady cell-potential control. Gaseous products are tracked by a hypothetical gas layer which increases in thickness in the streamwise direction. The gas phase is assumed to be an ideal, three-component mixture of hydrogen, carbon dioxide and ethane; the liquid phase consists of acetate, proton, acetic acid, and sodium and hydroxyl ions. The model predicts streamwise profiles of concentration, current density, gas-void fraction, and gas and liquid velocities in addition to reactant conversion, and cell-polarization characteristics. The average current density exhibits a maximum at a base-to-acid ratio of 0.96 due to the weak-acid/strong-base chemistry and a broad maximum at an interelectrode spacing of 0.37 cm resulting from minimized ohmic losses.     

A mathematical model for a biological fluidized bed reactor

A physical model is given in the present report for representing a three-phase biological fluidized bed reaction system which consists of microorganism-coated particles, waste water and air. The system is assumed to be well fluidized. The physical model can be represented by two differential equations describing, respectively, the substrate axial dispersion and diffusion/reaction. Numerical values of the physical parameters are selected from the literature or estimated from semi-empirical equations. The governing system equations are solved by an iterative finite-difference scheme. The theoretical predictions are compared with several experimental measurements and the agreement between them found to be very good, validating the physical model reported here.     

The simulated moving-bed reactor for production of bisphenol A

Bisphenol A was produced from acetone and phenol over an ion-exchange resin catalyst at 50–90°C. Phenol was used as solvent. The reaction proceeded under the excess phenol condition. The reaction rate was proportional to the acetone concentration in the initial period of the reaction. After the acetone conversion exceeded approximately 50%, the reaction rate became lower than expected by the first-order reaction rate. This was ascribed to water adsorption onto the resin. Batch adsorption and breakthrough experiments showed that water was adsorbed approximately seven times stronger than acetone and that bisphenol A was not adsorbed. Using the reaction rate equation for bisphenol A production, the adsorption isotherms and overall mass transfer coefficients of the components, the numerical simulation of the 3-zone-type simulated moving-bed reactor was carried out. High resin flow rate was required in order to remove water out of the reaction zone, and a high liquid flow rate was also required to desorb water from the resin in the recovery zone. As far as the flow rates were set appropriately, water was successfully removed to prevent the catalyst deactivation and the long-term stable production of BPA was allowed.     

A reactor network model for predicting NOx emissions in gas turbines

The numerical prediction of NOx emissions from gas turbines is addressed in this paper. Generated from Computational Fluid Dynamics (CFD), a Reactor Network (RN) is defined to model the NOx formation with a detailed chemistry. An optimized procedure is proposed to split the reactive flow field into homogeneous zones considered as Perfectly Stirred Reactors (PSR). Once connected together, they result in a Chemical Reactor Network (CRN) that yields a detailed composition regarding species and temperature in the combustion chamber. Sensitivity studies are then performed to estimate the influence of air humidity and gas turbine load on NOx predictions. The NOx emissions predicted are in good agreement with the measured data in terms of levels and trends for the case studied (a gas turbine flame tube fed with natural gas and functioning at a pressure of 15 bar). Finally, the RN methodology has shown to be efficient estimating accurately NOx emissions with a short response time (few minutes) and small CPU requirements.     

A comparative study of a fluidised bed reactor and a gas lift loop reactor for the ibe process: Part III. Reactor performances and scale Up

Continuous fermentations using Clostridium spp. DSM 2152 immobilised in calcium alginate beads to produce butanol and isopropanol from glucose were carried out in a fluidised bed reactor with liquid recycle (FBR, 10.9 dm³ working volume, 41 % solids) and in a gas lift loop reactor (GLR, 11.4 dm³ working volume, 32% solids). In the FBR in-situ produced non-coalescing gas bubbles had a negligible influence on the fluidisation pattern and the steady state results of the fermentation were in accordance with those predicted by a reactor model. The FBR was operated reliably for 5 weeks without decrease of activity. The GLR behaved as a three phase reactor because of the recycled fermentation gas. The steady state fermentation results were as predicted by the GLR model. Scale up to a 50 m³ FBR and a 65 m³ GLR led to development of a plug flow with recycle model for the FBR and a stirred tank model for the GLR. On the basis of overall reactor performance and ease of integration with a simultaneous product recovery the FBR is preferred to the GLR for application in a large scale butanol/isopropanol process using immobilised Clostridia spp.     

A dual functional staged hydrogen purifier for an integrated fuel processor–fuel cell power system

This paper describes the operation of a dual functional, membrane/catalytic CO_x methanator, hydrogen purifier that is well-suited for an integrated fuel processor/fuel cell power system. In combination with a pressure swing reformer (PSR) and a PEMFC, the system provides high overall efficiency and portability for distributed power or onboard vehicle use. Gas testing results illustrate the ability of the purifier to produce fuel cell purity hydrogen at peak power flux. The durability of this purifier is shown by its ability to meet target hydrogen purity even with a membrane that permeates >3000 ppm CO. Gas purge streams from both fuel cell electrodes are combined with the membrane retentate and combusted in the PSR combustion cycle to provide heat for the reforming reaction leading to high thermal efficiency. Most significantly, it is shown that staging of this purifier, enables recovery of some fraction of the purified hydrogen at pressures substantially approaching that of the feed hydrogen partial pressure. This creates an onboard source of high pressure hydrogen to be optionally fed to a storage device for use during vehicle startup, or to the fuel cell, either directly or via the storage device, under high power load conditions. The beneficial impact of this two-stage, dual functional purifier on membrane cost, dependability and fuel processor/fuel cell integration, will be discussed.     

A photocatalytic membrane reactor for gas-phase reactions using porous titanium oxide membranes

Photocatalytic membrane reactors using porous titanium oxide membranes having pore sizes of several nanometers were utilized for a gas-phase reaction of methanol. Air mixed with methanol (MeOH) vapor, the concentration of which was controlled in the range of 500–6000 ppm, was fed to the photocatalytic membrane reactor in the range of 50–500 cm³/min using several types of flow patterns. Photocatalysis with membrane permeation resulted in a large decomposition rate, compared to photocatalysis without membrane permeation. The characteristics of the reaction such as decomposition ratio of MeOH, the conversion of the decomposed MeOH to CO₂ and H₂O were found to be a function of the residence time in the reactor. The photocatalytic reaction was analyzed based on pseudo-first-order kinetics to ascertain its simplicity, and the fitted curves were found to be in a relatively good agreement with the experimental data. Apparent rate constants with and without membrane permeation were 2.5 and 1.5×10⁻⁶ m s⁻¹, respectively, indicating that the performance of the photocatalytic reaction system with membrane permeation was enhanced.     

A mathematical model for the dehydrogenation of methylcyclohexane in a packed bed reactor

A model for the dehydrogenation of methylcyclohexane in a tubular reactor over an industrial catalyst Pt-Sn/Al₂O₃ has been established. This model takes into account the axial dispersion at the inlet of the catalytic bed reactor as well as the heat transfer at the wall of the reactor. The heat transfer at the wall is satisfactorily represented by using a heat transfer coefficient correlation for which the parameters are obtained by fitting to the experimental data. The model provides a good representation of the radial and axial temperature profiles in the packed bed and can be also used to calculate the conversion.     

A compact ellipsoidal cavity type microwave plasma reactor for diamond film deposition

Electric field distribution in ellipsoidal microwave cavities with different sizes was modeled by the finite difference time-domain method (FDTD). The influence of varying size on the performance of the ellipsoidal cavities was studied. Through the simulations, eight series of resonant patterns were found. Based on this simulation result, a compact ellipsoidal cavity type microwave plasma chemical vapor deposition reactor has been proposed and its performance was predicted. It is shown that such a compact ellipsoidal cavity type reactor retains the same ability to concentrate microwave energy into its focus, facilitating both production of high density plasmas and deposition of diamond films.     

A dense Pd/Ag membrane reactor for methanol steam reforming: Experimental study

This paper focuses on an experimental study of the methanol steam reforming (MSR) reaction. A dense Pd/Ag membrane reactor (MR) has been used, and its behaviour has been compared to the performance of a traditional reactor (TR) packed with the same catalyst type and amount. The parameters investigated are reaction time, temperature, feed ratio and sweep gas flow rate. The few papers dealing with MR applications for the MSR reaction mainly analyse the effect of temperature and pressure on the reaction system. The investigation of new parameters permitted to better understand how the fluid-dynamics of the MR influences the hydrogen separation effect on methanol conversion and product selectivity. The comparison between MR and TR in terms of methanol conversion shows that the MR gives a higher performance than the TR at each operating condition investigated. Concerning hydrogen production, the experiments have shown that the overall selectivity towards hydrogen is identical for both MR and TR. However, the MR produces a free-CO hydrogen stream, which could be useful for direct application in proton exchange membrane fuel cells. A comparison, in terms of methanol conversion versus temperature, with literature data is also included.     

A new and original microwave continuous reactor under high pressure for future chemistry

A new and original high pressure reactor has been designed and developed for continuous flow chemistry under microwaves at industrial scale. The reactor originality is that the microwave applicator is the reactor itself. It allows then the use of metallic and thick walls for the reactor adapted to a use at high pressures and high temperatures. Wave propagation coupled to heat transfer was simulated using COMSOL Multiphysics® and the design was optimized to minimize wave reflections and maximize energy transfers in the reacting medium. This leads to extremely good energy yields. Experiments confirm that the microwave energy is fully absorbed by the reacting medium. The reactor allows continuous chemical reactions at a kg/h scale, under microwave heating, up to 7 MPa and 200°C. The double dehydration of hexylene glycol has been performed under various operating conditions demonstrating then the operability of this new reactor. © 2016 American Institute of Chemical Engineers AIChE J, 63: 192–199, 2017     

氯乙烯聚合釜传热和操作参数设计计算

对于氯乙烯悬浮聚合釜传热设计和聚合过程操作参数选择问题，在建立氯乙烯引发剂浓度方程、传热模型、结构模型基础上，开发出一套计算机辅助设计程序，利用本程序可以有效便捷地计算出所需的聚合釜结构参数和工艺条件，为工程设计提供依据。     

A hybrid membrane-emulsion reactor for the enzymatic hydrolysis of lipids

A hybrid reactor, consisting of a stirred vessel, a hydrophilic membrane loop and a hydrophobic membrane loop, is presented for the continuous enzymatic hydrolysis of soybean oil in an emulsion. The permeates of the hydrophilic and the hydrophobic membrane consist of a single water phase and a single lipid phase, respectively. No lipase activity could be detected in the permeates of both membranes, which implies that all enzyme is retained in the system. An important advantage of this system is that it combines the high surface area in an emulsion with the containment of lipase in a membrane reactor. It is further shown that the stability of the system can be improved considerably by the addition of CaCl₂ to the water phase. Under comparable conditions the enzyme stability in the hybrid reactor is lower than the stability in a stirred vessel. The composition of the emulsion appears to influence the flux of the membranes. The flux of the hydrophobic membrane increases with an increasing oil fraction of the emulsion while the flux of the hydrophilic membrane has an optimum for two different oil fractions—0 and 0.55 (v/v).     

A scale-up strategy for low-temperature methanol synthesis in a circulating slurry bubble reactor

Slurry bubble column reactors are being increasingly utilized in the large-scale conversion of coal or natural gas to liquid hydrocarbons and alcohols. A new suite of tools for developing low-temperature methanol synthesis in circulating slurry bubble reactors is explored in this study. The scale-up strategy consisting of hydrodynamics in cold flow units, catalyst performance evaluation in an autoclave, and process investigation in a pilot-scaled circulating slurry bubble reactor is presented. This methodology should be helpful for designing and scaling-up the low-temperature methanol synthesis and other related processes in slurry bubble column reactors, which will enhance and speed them towards commercial application.     

A two-phase compartments model for the selective oxidation of n-butane in a circulating fluidized bed reactor

A phenomenological model for the partial oxidation of n-butane to maleic anhydride (MAN) in a gas–solid riser reactor is proposed. The model captures the main transport–kinetic interactions at both the particle and reactor scale. Two different kinetic models from the literature that either include or neglect the role of solid-state diffusion of oxygen in the catalyst bulk are compared in terms of their impact on overall reactor performance. The use of computational fluid dynamics (CFD) as a means of defining a macroscopic cell-type model for describing the flow patterns in an industrial-scale gas–solids riser is also described. Predictions for the conversion of n-butane and yield of MAN are presented as a function of selected operating variables, and the impact of the variable model parameters on the predictions is briefly assessed. It is shown that the predictions are particularly sensitive to the kinetic model. The relative importance of the interactions between the chemical kinetics and the hydrodynamics is also highlighted.     

A novel ceramic membrane reactor system for the continuous enzymatic synthesis of oligosaccharides

The continuous enzymatic production of galactosyl-oligosaccharides (GOS) from lactose as a substrate using a new type of ceramic membrane reactor system was investigated. GOS are non-digestible oligosaccharides and have recently attracted interest as prebiotics. However, the composition of oligosaccharides fraction and the variability in β-glycosidic linkages depend on the enzyme source. In the study presented below, native, physically immobilized, β-galactosidase from Kluyveromyceslactis (EC 3.2.1.23) was used as enzyme to catalyse transgalactosylation reaction to produce GOS, competed against the hydrolysis of lactose into its two component monosaccharides, glucose and galactose. To optimize GOS yielded, process conditions were varied: the average residence time of the enzyme was varied in the range of 13 to 24 min, the trans-membrane pressure (TMP) was in the range of 1 to 2 bar and the initial concentration of substrate was varied from 10 to 30% (w/w). Regarding the conditions investigated here, the maximum oligosaccharide concentration exceeded 38% (w/w) when the average residence time was 24 min, the TMP was 2 bar and an initial lactose concentration of 30% (w/w) was adjusted.