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.     

复分解电渗析清洁生产谷氨酸钠新工艺

谷氨酸钠（sodium glutamate,NaGA）是味精（monosodium glutamate,MSG）的主要成分,其传统生产方法为"等电点结晶-酸碱中和"法,传统工艺存在工艺流程长、酸碱消耗大、环境污染严重等问题,而且其谷氨酸钠产品液浓度尚未达到结晶工艺所需的浓度。为此本文提出复分解电渗析离子重组工艺来清洁生产谷氨酸钠,并对该工艺进行了实验验证及过程优化。复分解电渗析可实现原料液的一步转化,直接获得高浓度谷氨酸钠产品液,在优化条件下,最终产品液浓度为1.79mol/L （约30.2%）,转化率为91.2%,能耗为2.98kW·h/kgNaGA,其副产（NH₄）₂SO₄可作为生产铵肥的原料,不存在二次污染。此工艺具有工艺流程短、酸碱零消耗、无二次污染的优点,而且所得谷氨酸钠产品液浓度达到了结晶工艺所需的浓度要求,这对电驱动膜过程在味精产业的应用具有重要意义。并通过对树脂填充床电渗析与普通电渗析、均相离子交换膜与异相离子交换膜的比较实验,验证了选用异相膜树脂填充床电渗析生产谷氨酸钠的合理性。     

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.     

A porous structured reactor for hydrogenation reactions

A novel combination of catalyst carrier and reactor design was developed for intensified production of vitamin intermediates. The so called Design Porous Structured Reactor (DPSR) is a laser sintered porous 3D-structure that can be tailored to the desired reaction properties such as fluid conditions or heat removal and can also act simultaneously as catalyst support.The selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) under solvent-free conditions was chosen as the reaction to evaluate the potential of DPSRs in comparison to conventional batch reactors. DPSR experiments were performed at varying temperatures and liquid flow rates.DPSRs exceeded batch performance in terms of selectivity, yield and turnover frequency in the analyzed process parameter range. However, DPSRs showed some mass transfer effects. Selectivities and yields increased with higher liquid flow rate due to reduced system pressures and sharper residence time distributions.Overall mass transfer coefficients for DPSRs were determined based on an isothermal non-ideal plug flow model applying heterogeneous Langmuir–Hinshelwood kinetics to account for the chemical conversion. The model showed sufficient accuracy to describe the occurring mass transfer processes.DPSRs were found to be viable alternative for batch reactors, demonstrating the potential for process intensification with an inherent potential for further improvement.     

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.     

Electro-membrane reactor: A powerful tool for green chemical engineering

Electro-membrane reactors use electro-membranes for preferentially diffusive/electrophoretic migration or electroosmotic separation of in-situ reactive products, thereby maximizing the reaction rate and transport efficiencies of the products. These reactors are widely employed in the chemical engineering sectors such as green chemical synthesis, biorefining, electrocatalytic reduction/oxidation, and water treatment. In this review article, we provide an overview of the recent advances in three categories of electro-membrane reactors in chemical engineering sectors from three categories: (1) Electro-membrane reactors based on stacked ion-exchange membranes for resources recovery; (2) Electro-membrane reactors via Faraday reactions on functional anodes/cathodes for substance transformation; and (3) Closed-loop chemical reactions and substance separation via coupling of Faraday reactions and stacked membranes. The increasing demand for low-carbon economy has accelerated the advancement of environmentally friendly chemical engineering and sustainable processes and necessitates the use of electro-membrane processes. The macro perspective provides a timely reference for researchers and engineers.     

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 continuous tubular reactor for core–shell latex particles

High solids content poly(butyl acrylate)/poly(methyl methacrylate) core–shell latex particles were produced using miniemulsion polymerisation in a continuous linear tubular reactor. The resulting products were and shown to be comparable to a batch process. Final solids contents of 41 and 48 wt.% were shown to be possible in a simple tubular reactor. Differential scanning calorimeter analysis indicated that core–shell particles were formed under these conditions. © 2011 Canadian Society for Chemical Engineering     

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 study on periodic boundary condition in direct numerical simulation for gas–solid flow

Direct numerical simulation(DNS) of gas–solid flow at high resolution has been carried out by coupling the lattice Boltzmann method(LBM) for gas flow and the discrete element method(DEM) for solid particles. However,the body force periodic boundary condition(FPBC) commonly used to cut down the huge computational cost of such simulation has faced accuracy concerns. In this study, a novel two-region periodic boundary condition(TPBC) is presented to remedy this problem, with the flow driven in the region with body force and freely evolving in the other region. With simulation cases for simple circulating fluidized bed risers, the validity and advantages of TPBC are demonstrated with more reasonable heterogeneity of the particle distribution as compared to the corresponding case with FPBC.     

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.