Non-isothermal two-membrane reactors for reversible gas phase reactions

The performance of a non-isothermal two-membrane reactor for reversible chemical reactions in gas phase has been analyzed by numerical simulation. The analyzed reactions were of the form: aA = bB + cC. Two membranes, that are permeable to all the components of the reaction mixture, are supposed to be the most permeable to one of the two reaction products, satisfying the condition of reverse products permselectivities. The reactant is taken to be the slowest permeating component. A negative temperature influence on the permeabilities of components has been assumed. Co-current plug flow pattern has been accepted. It has been shown that it is possible to enhance reactant conversion above that of a conventional reactor for both endothermic and exothermic reversible reactions, including adiabatic and non-adiabatic case. By using a two-membrane reactor, considerable lowering of feed temperatures is enabled for an endothermic reaction. For endothermic reactions, there is the optimum feed temperature, whereas for exothermic reactions, the higher the temperature, the lower is the attained conversion. In reactor design, the optimal external heat exchange for both endothermic and exothermic reactions can be determinated.     

Applicability of a double-membrane reactor for thermal decomposition of water: a computer analysis

A theoretical study of applicability of double-membrane reactor for direct thermal decomposition of water is presented. The analysis is based on an isothermal, steady state, plug flow reactor model. One of the two membranes was supposed to be hydrogen permeable, and the other one, oxygen permeable. The simulations were performed for T=2000 K, it being the upper limit of temperatures of practical interest. With a high vacuum in separation zones, the double-membrane configuration theoretically enables complete conversion providing high values of Damkohler number and total rate ratio. When a sweep gas is introduced into separation zones, significant water conversions can also be provided by a countercurrent single membrane reactor, but considerably lower than those obtained in a double-membrane reactor. The double-membrane reactor seems to be a promising solution for the water splitting reaction, deserving experimental investigations.     

A LUMPING KINETICS FOR MODIFIED FT REFORMING PROCESS Ⅱ.EXPERIMENTAL AND KINETICS PARAMETERS ESTIMATION

IntroductionInthefirstpatofacsinvestigation,athree-lumpmodelisproposedforthereaCtionsystemofMFTrefonning.However,theveryimportantworkforthekineticsanalysisistOd~inetheparametersinthekineticsequations.Becausethereisnopriormethodfordotennnungthesep~ers,expe…     

Determination of rate constants by a double-line flow injection method incorporating a well-stirred tank reactor

Equations have been derived for the concentration-time profiles of reactants and products in a first order reaction obtained on passage of a reactant plug through a single well-stirred tank reactor. When taken together with the equations for physical dispersion of such a reactor under plug flow conditions, an expression for the reaction rate constant was derived which allowed its experimental determination in a relatively simple fashion. The method was tested for reactions between cerium and oxalic acid and between dichromate and ascorbic acid, for which values of the rate constants of around 2 x 10(2) sec(-1) and 5.5 x 10(3) sec(-1) were obtained. Good agreement with other experimentally determined values was obtained. The scope and the limitations of the proposed method are critically discussed with the aid of some model calculations. The range of values for which the method might be suitable is approximately 10(-3)-10(-1) sec(-1). An equation analogous to a peak-width equation was derived as a further development of this approach. Good agreement with the previously determined values were obtained for both systems. The extension of the method to reactions other than first order is discussed.     

Gasification of Powdered Solid Fuel in the Filtration Combustion Mode

A new procedure for gasification of powdered solid fuel in a flow of a gaseous oxidant in the course of filtration of the mixture through an inert packing was suggested and tested. This procedure allows the productive capacity of a single reactor to be increased owing to acceleration of the reactions, i.e., to an increase in the reaction surface area with a decrease in the fuel particle size. As shown in cold (without ignition) experiments, the powdered fuel was partially accumulated in the inert porous packing, which led to the pressure buildup in the reactor. In gasification experiments with ignition, the powdered fuel was not accumulated in the reactor if the temperature in the fuel feeding zone was no less than 500°С. In this case, the linear velocity of the gas increased owing to thermal expansion, and this velocity was sufficient for the coal particles fed to the reactor to be entrained by the flow.     

Uses of the transit time distribution in kinetic flow systems

We investigate the distribution of transit or residence times of a trace reactant in laminar flow. We present measurements of this distribution for hydrogen atoms in a typical flow system, and show that the results are consistent with known theory and previous measurements of the diffusion coefficient. The use of the measured distribution as a diagnostic of flow behavior is discussed. It is also shown that the measured or calculated transit time distribution can provide a convenient means of correcting results of kinetic measurements for the departure from plug flow. In the case of firstorder, and also second-order decay of a single reactant, this correction is a useful approximation to the more rigorous solution of the partial differential equation for diffusion and reaction in laminar flow. Effects of the deviation from plug flow on a complex rection system are illustrated qualitatively for the H + NO₂ titration system.     

A Semi‐Microscopic Modeling for Polymer Flow Reactors

Summary: A nonisothermal plug‐flow reactor for ethylene polymerization is reexamined so as to illustrate the principle and effect of a refined, semi‐microscopic modeling. The novel feature of the current simulation is the application of a Monte Carlo scheme to exactly solve the free‐radical polymerization involved, whereas a reptation‐based molecular theory is introduced in a self‐consistent manner to simulate more accurately the reactant fluid viscosity during polymerization. The simulation is shown to capture some in‐depth consequences of reaction‐transport coupling that cannot be revealed by a traditional, macroscopic type of modeling. The principle of a future extension for dealing with more complex flow reactors is briefly discussed.

Comparison of the predicted temperature profile between Monte Carlo‐based simulation and the ones using moment equations together with two different weight distributions is shown with experimental data for LDPE.     

Use of a membrane reactor to improve selectivity to intermediate products in consecutive catalytic reactions

Through modeling it has been shown that a concentric-tube catalytic membrane reactor can be used to increase the selectivity for the intermediate products of a consecutive reaction scheme. The reactants are fed to the tube-side of the reactor where the catalyst is also located. The wall of the tube is permeable, allowing the intermediate products to pass through to the annular space instead of undergoing further reaction. The annular space is swept by an inert gas flow and contains no catalyst. Both permselective and non-permselective membranes have been considered in both co-current and counter-current flow regimes. In contrast to most catalytic membrane reactor applications where reactions are reversible and thermodynamically limited, in the present study the reactions considered are irreversible and are under kinetic control.     

Direct partial oxidation of methane to methanol： Reaction zones and role of catalyst location

Direct partial oxidation of methane to methanol was investigated in a specially designed reactor. Methanol yield of about 7%-8% was obtained in gas phase partial oxidation. It was proposed that the reactor could be divided into three reaction zones, namely pre-reaction zone, fierce reaction zone, and post-reaction zone, when the temperature was high enough to initiate a reaction. The oxidation of methane proceeded and was completed mostly in the fierce reaction zone. When the reactant mixture entered the post-reaction zone, only a small amount of produced methanol would bring about secondary reactions, because molecular oxygen had been exhausted in the fierce reaction zone. A catalyst, if necessary, should be placed either in the pre-reaction zone, to initiate a partial oxidation reaction at a lower temperature, or in the fierce reaction zone to control the homogeneous free radical reaction.     

Investigating the effects of conductivity on zone overlap with EMMA: computer simulation and experiment

In this paper, we demonstrate, using both experiment and simulation, how sample zone conductivity can affect plug-plug mixing in small molecule applications of electrophoretically mediated microanalysis (EMMA). The effectiveness of in-line mixing, which is driven by potential, can vary widely with experimental conditions. Using two small molecule systems, the effects of local conductivity differences between analyte plugs, reagent plugs and the BGE on EMMA analyses are examined. Simul 5.0, a dynamic simulation program for CE systems, is used to understand the ionic boundaries and profiles that give rise to the experimentally obtained data for EMMA analyses for (i) creatinine determination via the Jaffe reaction, a reaction involving a neutral and an anion, and (ii) the redox reaction between gallate and 2,6-dichloroindophenol, two anions. Low sample conductivity, which is widely used in CE analyses, can be detrimental for in-line reactions involving a neutral reactant, as rapid migration of the ionic component across a low conductivity neutral zone results in poor reagent plug overlap and low reaction efficiency. Conversely, with two similarly charged reagents, a low conductivity sample plug is advantageous, as it allows field-amplified stacking of the reagents into a tight reaction zone. In addition, the complexity of simultaneously overlapping three reagent zones is considered, and experimental results validate the predictions made by the simulation. The simulations, however, do not appear to predict all of the observed experimental behavior. Overall, by combining experiment with simulation, an enhanced appreciation for the local field effects in EMMA is realized, and general guidelines for an advantageous sample matrix can be established for categories of EMMA analyses.     

T形微反应器共沉淀法制备Mg-Al层状双金属氢氧化物及其粒径可控性

采用T形微反应器通过共沉淀法制备了Mg-Al层状双金属氢氧化物(LDHs)纳米颗粒, 考察了流速、混合盐溶液浓度和温度等对产物粒径及其分布的影响. 实验结果表明, 所制备的LDHs样品的形貌和晶体结构与传统共沉淀法结果一致, 但本方法制备的样品粒径小、分布窄. 随着流速增大, 温度升高, 所合成的LDHs样品平均粒径减小, 分布变窄; 而随着混合盐溶液浓度的增大, 所得LDHs样品粒径增大, 分布变宽.     

Modeling of carbonaceous feedstock pyrolysis in a countercurrent tubular reactor

A mathematical model of carbonaceous feedstock pyrolysis in a countercurrent tubular reactor was proposed. It was shown that the pyrolysis in a tubular reactor in which porous carbonaceous feedstock is heated in a countercurrent flow of a heated gas can be highly efficient.     

The PVT and thermal properties of HF

The PVT and thermal properties of pure HF have been revised. The available data,which cover two distinct regions, one at low and one at high pressure, have been organized in a consistent set of data; volume properties and enthalpy have been plotted in the temperature range between 0°C and 300°C, for pressures up to 300 atm.Some experimental work has also been done to test the volume properties of HF in the presence of an inert gas at moderate temperatures and pressures. At these conditions the association factor, which for pure HF is a function of temperature and molar volume, appears to be strongly affected by the presence of inerts.     

A STUDY ON MEMBRANE PROCESS WITH |?-ALUMINA MEMBRANE REACTOR FOR ETHYLBENZENE DEHYDROGENATION TO STYRENE

The membrane reaction of ethylbenzene(EB) dehydrogenation to styrene(ST) has been studied by using K2O/Fe2O3 industrial catalyst and alumina ceramic membrane developed by our institute. In comparison with the packed bed reactor (that is, plug flow reactor, abbr. PFR) in industrial practice, the yield of styrene was increased by 5%~10% in the membrane reactor. Furthermore, mathematical modeling of membrane reaction has been studied to display the principle of optimal match between the catalytic activity and the membrane permeability.     

Synthesis of perfluoroalkanes in high-temperature fluorination of graphite with fluorine in a reactor with a free-falling graphite bed

Reaction between fluorine and graphite in a reactor with a free-falling bed of graphite was studied in relation to the temperature in the reaction zone, ratio of the feeding rates of fluorine and graphite, and dilution of fluorine with an inert gas.     

Rayleigh-Taylor instabilities in reaction-diffusion systems inside Hele-Shaw cell modified by the action of temperature

The influence of temperature in the buoyancy driven Rayleigh-Taylor instability of reaction-diffusion fronts is investigated experimentally in Hele-Shaw cells. The acid autocatalysis of chlorite-tetrathionate reaction coupled to molecular diffusion yields exothermic planar reaction-diffusion fronts separating two miscible reactant and product solutions. The resulting chemical front moves downwards invading the fresh reactants, leaving the products of the reaction behind it. The density of the product solution is higher than the reactant solution; hence, the traveling front is buoyantly unstable and develops density fingers in time (Rayleigh-Taylor instability) when the products are above the reactants. The kinetic constant of a chemical reaction varies due to thermal effects. This may stabilize the exothermic descending front when temperature is increased, so that the mixing zone decreases, modifying the fingering patterns, until it almost disappears. The authors study the influence of the temperature variation on the instability pattern figure observed in the chlorite-tetrathionate reaction for long times, corresponding to the nonlinear regime.     

Getting Ring‐Closing Metathesis off the Bench: Reaction‐Reactor Matching Transforms Metathesis Efficiency in the Assembly of Large Rings

Reported is the first study of the influence of reactor configuration on the efficiency of a challenging ring‐closing metathesis (RCM) reaction. With the intention of increasing the generality of RCM scaleup and reducing its dependence on substrate modification, macrocyclization of an unmodified, low effective‐molarity diene was explored using different reactor types, in conjunction with a commercial, homogeneous Grubbs catalyst. Optimized performance is compared for a conventional batch reactor (BR), a continuous plug‐flow reactor (PFR), and a continuous stirred‐tank reactor (CSTR). In the PFR, maximum conversion is achieved most rapidly, but product yields and selectivity are adversely affected by co‐entrapment of ethylene with the catalyst, substrate, and product in the traveling “plug”. Use of the CSTR, in which ethylene is efficiently swept out, affords an order‐of‐magnitude increase in total turnover numbers, and reduces the required catalyst loadings by 25× relative to the BR (to 0.2 mol %), while improving RCM yields and selectivity to quantitative levels. Continuous‐flow methodologies that support liberation of the ethylene co‐product thus show great promise for industrial uptake of RCM.     

Oscillatory control of sample dispersion in a continuous flow system

A new strategy for the instrumental control of sample dispersion in continuous flow systems is presented. The method is based on shaking a loosely held straight reactor while the sample travels through the flow injection manifold. This external disturbance yields a sample transport more similar to the plug flow type because of the changes promoted on the flow pattern. Up to a three-fold increase in peak height, a comparable reduction in peak width and a more Gaussian peak profile are observed when the signals obtained with the shaken reactor are compared with those obtained with the same reactor but static. Improvements in the analytical performance as a function of different operational variables are shown for systems with or without a chemical reaction. Analytical implications and possible uses are discussed since this strategy allows the control of dispersion by simply selecting the frequency and amplitude of oscillation.     

Rapid Optimization of Reaction Conditions Based on Comprehensive Reaction Analysis Using a Continuous Flow Microwave Reactor

Generally, the flow method has the advantage of a precise control over the reaction parameters and a facile modification of the reaction conditions, while a continuous flow microwave reactor allows for the quick optimization of reaction conditions owing to the rapid uniform heating. In this study, we developed a “9+4+1 method” to optimize reaction conditions based on comprehensive reaction analysis using a flow microwave reactor. The proposed method is expected to contribute to the synthesis of various fine and bulk chemicals by reducing cost and wastage, and by conserving time.