Oxidation of ethyl alcohol in trickle bed reactors: Analysis of the conversion rate

The interpretation of results of a chemical reaction carried out in a trickle bed reactor is not immediate when the key reactants are volatile; in fact some authors state that the overall conversion rate increases at very low liquid flow rates, i.e. when the catalyst is unevenly wetted. In these conditions, the reactants may penetrate inside the catalyst pellets directly through the “dry” zones; therefore the mass transfer resistance is diminished and the conversion rate can be increased. To investigate this phenomenon tests on the catalytic oxidation of ethyl alcohol dissolved in water were performed at different operating conditions in a trickle bed reactor. An interpretation of the results was tried by using two different models based on partially wetted particles. This approach considers both the cases in which “dry” zones are active or not for mass transfer and mass transfer rates are affected or not by the chemical reaction.     

Mass transfer‐limited wet oxidation of phenol

Catalytic wet oxidation carried out in a continual three‐phase trickle‐bed reactor contributes to the sustainability of chemical technology. It was found that the hydrodynamics and the mass‐transfer of reactants could have a significant impact on the performance of the trickle‐bed reactor. An aqueous phenol oxidation was tested at different temperatures and liquid feed rates and the activities of both the CuO‐supported catalyst and the extruded active carbon were compared. To avoid the impact of liquid maldistribution, a bed of catalyst particles diluted with fine glass spheres was also used. Rate‐limited conditions of both liquid‐ and gas‐phase presented reactants were determined. Under the conditions of gas component transfer limitation, a better wetting of the diluted catalyst bed can lead to a worsening in the reactor performance due to the lower overall reaction rates. © 2001 Society of Chemical Industry     

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.     

液相反应物起限制性作用的滴流床反应器模型评价

在实验滴流床反应器内用含２３％Ｃｕ，１７％Ｃｒ的氧化铝催化剂进行过氧化氢的等温分解，以测试不同操作条件下液相色反应物围化率空时的依赖关系。实验证实对氧化氢分解是一个液相反应物起限制性作用的１级反应，模型预测与实验数据的比较表明：除催化剂效率因子以外，必须考虑外部质量传递和催化剂不完全润湿的影响，Ｄｕｄｋｏｖｉｃ提出考虑催化剂总效率因子的近似模型完全能够模拟上述２种影响。     

Cyclic mass transport phenomena in a novel reactor for gas–liquid–solid contacting

This study introduces a novel reactor concept, referred to as the Siphon Reactor, for intensified phase contacting of gas–liquid reactants on heterogeneous catalysts. The reactor comprises a fixed catalyst bed in a siphoned reservoir, which is periodically filled and emptied. This serves to alternate liquid–solid and then gas–liquid mass transfer processes. As the duration of each phase can be manipulated, mass transfer can be deliberately harmonized with the reaction. Residence time experiments demonstrate that, in contrast to periodically operated trickle‐bed reactors, the static liquid hold‐up is exchanged frequently and uniformly due to the complete homogeneous liquid wetting. A mathematical model describing the siphon hydrodynamics was developed and experimentally validated. The model was extended to account for a heterogeneously catalyzed gas–liquid reaction and capture the influence of siphon operation on conversion and selectivity of a consecutive reaction. © 2016 American Institute of Chemical Engineers AIChE J, 63: 208–215, 2017     

浆态床甲醇合成反应过程数学模拟

在固定床等温积分反应器中回归了LP201催化剂上的甲醇合成反应动力学参数,在液固拟均相、全混流、气相流动形式分别为全混流、平推流的基础上建立了浆态床搅拌反应器中甲醇合成反应的数学模型. 模拟结果显示,根据所得动力学参数,计算结果与实验结果吻合良好;气相甲醇合成过程中气相流动形式明显影响反应效率;在液相甲醇合成过程中,气相的流动形式对反应影响不大;气液传质阻力对反应有较显著的影响,必须与反应过程同时加以考虑.     

Kinetic studies in a batch reactor using ion exchange resin catalysts for oxygenates production: Role of mass transfer mechanisms

Oxygenated compounds are usually produced by a reversible liquid phase reaction using ion exchange resins with a bidisperse pore structure as catalyst. Mass transport is mainly controlled by diffusion through the macropores and the mass transfer resistance in the gel microspheres is negligible. Therefore, in this paper a mathematical model of the batch reactor considering diffusion of the species in the external film and then macropore diffusion inside the particle and reaction in the gel microspheres was developed. The numerical solution is implemented through the numerical package PDECOL and detailed explanations of the procedure used are presented. The model was applied to the diethylacetal synthesis using ethanol and acetaldehyde as reactants and Amberlyst 18 as catalyst. The experimental data are fitted with a two-parameter model based on a Langmuir-Hinshelwood rate expression in order to get the true reaction kinetics. The influence of the mass transfer mechanisms is evaluated in terms of the effectiveness factor history during the transient state of the batch reactor. The values of the effectiveness factor calculated at equilibrium with the batch reactor model are compared with those calculated from a steady state infinite bath model.     

Hydrodynamik und Stofftransport in einem Perlschnurreaktor für Gas/Flüssig/Fest‐Reaktionen

In this work, a pellet string reactor was characterized with respect to hydrodynamics and mass transfer. The catalyst packing consists of a cylindrical channel with a diameter of 1.41 mm, which was filled with spherical catalyst particles, having an outer diameter of 0.8 mm. Under reaction conditions (liquid phase hydrogenation of α‐methylstyrene) overall (gas‐liquid‐solid) volumetric mass transfer coefficients for hydrogen between 0.8 and 5.5 s^–1 were computed. Due to high mass transfer rates and simple reactor geometry, pellet string reactors can be applied in industry as highly efficient reaction units.     

Evaluation of published kinetic models for tert-amyl ethyl ether synthesis

The published kinetic models for liquid phase synthesis of tert-amyl ethyl ether (TAEE) by addition of ethanol to isoamylenes on acidic ion exchange resins were evaluated by comparison with own experimental data. Fixed bed and batch reactor experiments were carried out in liquid phase on Amberlyst-35 ion exchange resin as catalyst. Among the published kinetic models, our experimental data fits the best with the model published by [J.A. Linnekoski, A.O. Krause, L.K. Rihko, Kinetics of the heterogeneously catalyzed formation of tert-amyl ethyl ether, Ind. Eng. Chem. Res. 36 (1997) 310–316.]. In the simulation study for the fixed bed reactor experiments, the influences of axial mixing, liquid–solid mass transfer and internal diffusion steps on the overall process kinetics were theoretically evaluated. The results evidenced that on the working temperature domain, significant kinetic limitations by internal diffusion can appear for catalyst pellets size over 1 mm. The external mass transfer step has a weak influence on the process kinetics and can be important only at lower limit of the flow rates domain. Our computations evidenced also a negligible influence of the axial mixing on the reactants conversion in the experimental fixed bed reactor, on the working domain investigated.     

Liquid-solid mass transfer in a trickle-bed reactor measured by means of a catalytic reaction

Global rates of reaction (the hydrogenation of cyclohexene to cyclohexane on Pd/Al₂O₃) were measured in a trickle-bed reactor at various gas and liquid flow rates. The liquid superficial velocity was higher than 1.2 × 10⁻² m/s so as to achieve complete wetting of the catalyst particles. Liquid-solid mass transfer coefficients were calculated from the rate data. In the low interaction regime, the coefficients depend on both the gas and liquid rates, in contrast with most of the previous studies. At the transition to the high interaction regime, a significant change in the values of the coefficients was observed. The experimental liquid-solid mass transfer coefficients are in good agreement with values predicted by correlations published in the literature.     

Ethanol oxidation in a trickle-bed reactor using a hydrophobic catalyst: Effect of dilution with hydrophilic particles

Ethanol oxidation at moderate temperature and atmospheric pressure is carried out in a trickle-bed reactor using a hydrophobic catalyst and pure oxygen as the oxidizing agent. The influence of diluting the hydrophobic catalyst with different proportions of the hydrophilic inert support is particularly studied by performing comparative experiments at different operating conditions. Reactor performance is not significantly modified when the hydrophobic catalyst is diluted with the hydrophilic support in a 50% mass proportion. For a larger dilution, 75% (w/w), significant differences in ethanol conversions are found for certain conditions, presumably due to the influence of the liquid holdup, gas–liquid interfacial areas and wetting efficiency characterizing a bed with a major proportion of hydrophilic particles.     

The gas–liquid contacting effect on the operation of small scale upflow hydrotreaters

The effect of reactor geometry and bed dilution on the extent of gas oil hydrodesulfurization was tested by conducting hydrodesulfurization experiments in two laboratory reactors of different scale with non-diluted and diluted beds in ascending flow. The superficial gas and liquid velocities and the catalyst bed height were kept constant while the main difference between the two reactor scales was the reactor diameter. The diluted bed of the mini-reactor showed the best performance and its results were identical in upflow and downflow mode. The differences between the performance of the mini- and the bench-scale reactor operating in upflow mode have been investigated. Reactor performance simulation was attempted by a mathematical model that takes into account axial dispersion of the liquid phase and gas–liquid mass transfer. Bench-scale reactor operation was characterized by lower mass transfer rates than the corresponding mini-scale one. Combining model predictions and mock up operation it is concluded that the stronger mass transfer resistances calculated for the bench-scale reactor are associated with poorer gas distribution through the catalyst bed. Reduction of the bed diameter results in better gas–liquid contact by forcing the gas bubbles to distribute more effectively into the liquid phase.     

外环流气升式反应器中催化丙烯环氧化反应

本论文研究了外环流气升式反应器中TS-1催化丙烯环氧化反应,以单位催化剂空时收率为目标,进行了反应工艺条件的优化,考察了结构参数,上升管与下降管横截面积之比Ar Ad对反应的影响。     

MASS TRANSFER WITH CHEMICAL REACTION IN PARTIALLY WETTED FLAT PLATE CATALYST PELLETS: RIVULET FLOW ANALYSIS

Mass transfer with chemical reaction is analyzed in a system formed by a flat plate solid catalyst, partially wetted by a flowing rivulet of a liquid in contact with a stagnant pure gas. The paper solves the fluid dynamic problem of the liquid phase first, and afterwards incorporates the mass transfer and the chemical reaction. The system is assumed to be isothermal and at steady state, with a first order kinetics whose limiting reactant is in the gas phase. This work studies the influence of the gas-liquid surface tension, the liquid reactant flow rate, the liquid viscosity and the angle of inclination of the solid, upon the wetting factor. The model proposed also predicts the effect of these parameters and the Thiele modulus on the overall effectiveness factor and the molar flux of the limiting gaseous reactant at the catalytic solid-liquid interface in a direct way. This approach makes the wetting factor a non-manipulated variable.     

Parallel hydrogenation for the quantification of wetting efficiency and liquid–solid mass transfer in a trickle‐bed reactor

A novel method for the measurement of wetting efficiency in a trickle‐bed reactor under reaction conditions is introduced. The method exploits reaction rate differences of two first‐order liquid‐limited reactions occurring in parallel, to infer wetting efficiencies without any other knowledge of the reaction kinetics or external mass transfer characteristics. Using the hydrogenation of linear‐ and isooctenes, wetting efficiency is measured in a 50‐mm internal diameter, high‐pressure trickle‐bed reactor. Liquid–solid mass transfer coefficients are also estimated from the experimental conversion data. Measurements were performed for upflow operation and two literature‐defined boundaries of hydrodynamic multiplicity in trickle flow. Hydrodynamic multiplicity in trickle flow gave rise to as much as 10% variation in wetting efficiency, and 10–20% variation in the specific liquid–solid mass transfer coefficient. Conversions for upflow operation were significantly higher in trickle‐flow operation, because of complete wetting and better liquid–solid mass transfer characteristics. © 2010 American Institute of Chemical Engineers AIChE J, 2011.     

Influence parameters in the ozonation of phenol wastewater treatment using bubble column reactor under continuous circulation

The ozonation of phenol wastewater treatment system has been investigated with effective mass transfer between gas and liquid phase in a bubble column reactor. The designed bubble column reactor was investigated for increasing the rate of mass transfer of ozone, the rate of oxidation of phenol in the solution, the solubility and decomposition rate of ozone in the distilled water were also studied at different flow rates. The decomposition rate constants were calculated based on pseudo first order kinetics. The oxidation of phenol was investigated in order to provide the overall reaction rate constant for the reaction between ozone and phenol at 25 °C. The influence of the operating parameters like initial phenol concentration, ozone flow rate and pH for the destruction of phenol by ozonation were studied. The pseudo first order rate constant was depending on the initial concentration of phenol solution. A comparison of TOC removal percentage between bubble column reactor and bubble diffuser using ozonation were reported.     

Gas–solid adhesion and solid–solid agglomeration of carbon supported catalysts in three phase slurry reactors

In the study of three phase slurry reactors the slurry phase is conventionally treated as a quasi homogeneous liquid phase with altered sorption and reaction capacity due to the presence of catalyst particles. This approach may be utterly wrong in any case where phase segregation of the solid takes place. This phenomenon is relatively little studied and it will be demonstrated that it may have a considerable impact on the operation of three phase reactors. Two examples of segregation, i.e. gas–solid adhesion and solid–solid agglomeration, are to be discussed. Taking the example of carbon and alumina supported palladium catalysts employed in the hydrogenation of methyl acrylate towards methyl propionate, the segregation of the catalyst phase by adhesion to gas bubbles is studied. This adhesion may take place up to complete coverage of the gas bubbles but it may also be entirely absent. A quantitative model is developed based on the film theory, the particle to bubble collision probability and the impact of the size of adhering particles on the effective film thickness. This model is used to describe adhesion under non-stagnant conditions and the impact it has on the overall G–L mass transfer rates. The conversion rate of a mass transfer limited model reaction, i.e. the hydrogenation of methyl acrylate to methyl propionate, is studied in a stirred tank reactor for two different catalysts (Pd/C and Pd/Al₂O₃) in order to verify the model. It is quantitatively demonstrated that G–L mass transfer rates may be increased considerably as a result of adhesion. The second, closely related, phenomenon studied is the segregation of the solid and liquid phase by agglomeration of the catalyst particles. This behaviour is of particular importance as it leads to a substantial increase in the effective particle size resulting in a decreased conversion rate.     

Conversion rates in a laboratory trickle-bed reactor during the oxidation of ethanol

We examined the conversion rate during the oxidation of ethanol in a trickle-bed reactor in a wide range of hydrodynamic conditions, temperatures and concentrations. The results have confirmed the findings of other authors that mass transfer of the gaseous reactant to the catalyst surface also takes place through zones of liquid which are not effective during a physical process. However, they have also shown an influence of the temperature and concentration of the volatile liquid reactant never reported before. This effect has been qualitatively explained by assuming that the supply of the ethanol to liquid zones with a poor renewal occurs mainly by an evaporation—condensation process. Accordingly, the data were well correlated by the ratio between the partial pressures of ethanol and oxygen in the gas phase.     

Performance of a large scale packed recirculating reactor for homogeneous catalytic oxidation of car-3-ene

Autooxidation of car-3-ene was carried out in a large scale packed recirculating reactor, where the catalyst cobalt acetylacetonate and the liquid were recirculated and sprayed on top of an inert packing. Gas is introduced from the bottom. The mass transfer parameters and mixing characteristics of the reactor were determined. The effect of catalyst quantity, operating pressure on car-3-ene conversion, and selectivity for various products were studied. The reaction system was mathematically modelled, and the simulation compared with the observed behaviour. The rate constants of the elementary reaction steps had been determined separately in a laboratory reactor.     

耦合传质的羰基化固定床反应器传热模拟分析

固定床反应器中进行强放热反应时, 反应器的热点温度对操作参数变化敏感,容易引起飞温,导致转化率下降,影响催化剂寿命。为强化羰基化固定床反应器内热质传递与化学反应的协同性,建立考虑颗粒内扩散影响的羰基化固定床反应器拟均相一维传热模型,考察操作参数对床层热点温度、反应转化率、床层温升的影响。不仅体现传热传质和反应的协同作用,而且影响关系明晰、求解方便。为保证反应转化率,本实验条件下确定催化剂颗粒直径小于等于1.5 mm。反应器入口温度/冷却剂油温既要满足床层热稳定性需求,又要使反应转化率和床层温升都在合理范围内。模拟结果表明在床层入口温度升高的同时,可通过降低冷却剂油温获得良好的反应转化率和较小的床层温升。在此基础上,考察入口环氧乙烷浓度对反应转化率和床层温升的影响。本研究可为固定床反应器满足转化率要求、床层合理温升而选择催化剂颗粒直径、床层入口温度、冷却剂油温和床层入口浓度等操作参数提供计算依据。