Trickle bed reactor diluted with fine particles and coiled tubular flow-type reactor for kinetic measurements without external effects

Gas and liquid velocities in laboratory scale trickle bed reactors are one or two orders of magnitude lower than those in commercial reactors. Then, the kinetic data may include the external effects. This shortcoming of laboratory scale trickle bed reactor can be resolved by diluting the catalyst bed with fine inert particles. The catalyst bed dilution increases dynamic liquid holdup, pressure drop, gas–liquid mass transfer coefficient. Hydrogenation of 2-phenylpropene on Pd/Al₂O₃ was performed with the trickle bed reactor diluted with fine inert particles and the coiled tubular flow-type reactor to compare the kinetics with that of the basket type batch reactor. The trickle bed reactor diluted with fine inert particles is suitable to obtain the reaction rate without external effects even if the liquid velocity is low. The coiled tubular flow-type reactor should be used at high gas velocities.     

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.     

Influence of Particle Size and Single‐Tube Diameter on Thermal Behavior of Fischer‐Tropsch Reactors. Part II. Eggshell Catalysts and Optimal Reactor Performance

The optimal combination of particle and tube size for simulation of a single tube of a wall‐cooled multitubular Fischer‐Tropsch (FT) reactor with cobalt as catalyst was determined. The maximum size of the tubes, realized without temperature runaway, enhances with increasing particle size until an optimal value is reached, thereby improving the production rate of liquid fuels per tube. Reasons for this are that heat transfer to the cooled tube wall for a given tube size is considerably enhanced by increasing the particle size and that the influence of pore diffusion on the effective rate of FT synthesis gets stronger with rising particle size, which reduces the temperature sensitivity of the reactor and decreases the danger of a temperature runaway. The simulations indicate that the use of FT eggshell catalysts is not an option for fixed‐bed reactors. The temperature sensitivity of the reactor is strongly enhanced, which decreases the maximum tube size and with that the productivity per tube. All these effects are valid in general for wall‐cooled fixed‐bed reactors. Respective criteria are presented.     

三维上流式反应器床层流动和返混特性

采用内径为280 mm的上流式反应器,以空气模拟气相、甘油和水混合溶液模拟渣油。用3种不同粒径的氧化铝球形工业催化剂颗粒为填充颗粒,考察了不同模拟物系的颗粒粒径、颗粒密度、液相黏度、不同床层的高径比和不同操作条件对上流式反应器内床层压降及其波动、床层轴向返混的影响规律。得到模拟工业运行物系和操作条件的上流式反应器床层总压降关联式,相对误差在12%以内。床层总压降均随床层高径比、颗粒密度和液相黏度增加而增大,但随颗粒粒径的增大而减小,床层压降波动随表观气速增加而增大。填充颗粒粒径越小、颗粒密度越小、高径比越大,床层内轴向返混越严重;床层内压降和轴向返混均随表观气速的增加而增大。     

A comparison of auto-thermal and conventional methanol synthesis reactor in the presence of catalyst deactivation

This study proposed a one-dimensional dynamic plug flow model to analyze and compare the performance of an auto-thermal and a conversional methanol synthesis reactor in the presence of catalyst deactivation. An auto-thermal two-stage industrial methanol reactor type is a system with two catalyst beds instead of one single catalyst bed. In the first catalyst bed, the synthesis gas is partly converted to methanol in a water-cooled reactor. In the second bed which is a gas-cooled reactor, the reaction heat is used to preheat the feed gas to the first bed. To analyze the effect of important control variables on the rector performance, steady state and dynamic simulations are utilized to investigate effect of operating parameters on the performance of reactors. The simulation results show that there is a favorable profile of temperature along the two-stage auto-thermal reactor type in comparison with conventional single stage reactor type. In this way the catalysts are exposed to less extreme temperatures and, catalyst deactivation via sintering is reduced. Overall, this study resulted in beneficial information about the performance of the reactor over catalyst life-time.     

上流式反应器气液相间传质特性的实验研究

上流式反应器设置在固定床渣油加氢反应器前有利于提高渣油原料适用性,延长装置运行时间。实验研究了上流式反应器气液相间传质,采用五齿柱形氧化铝催化剂模拟工业催化剂颗粒,水溶液模拟渣油,空气模拟氢气,采用无氧水物理吸收和亚硫酸钠化学吸收的方法,测定了在高气液比的条件下上流式反应器床层气液相间传质特性实验。考察了表观气速、表观液速、填料粒径、内构件、催化剂级配和床层高径比对液相体积传质系数和气液相界比表面积的影响规律。实验数据表明,液相体积传质系数随着气、液速的增大而增大;随填料颗粒增大而减小;在床层内安装合适的内构件或增大反应器高径比,能够促进气液相间传质。基于实验数据拟合了适合上流式反应器液相体积传质系数和气液相界比表面积的经验关联式,拟合误差最大分别为12%和24%;表明所建气液相间传质的经验关联式能更好地预测上流式反应器中的气液相间传质特性。     

三相鼓泡淤浆床环氧乙烷合成反应器数学模拟及工程分析

建立了加压三相鼓泡淤浆床环氧乙烷合成反应器的数学模型 ,计入了催化剂颗粒在床层中沉降形成沿床高浓度分布对反应的影响以及由于惰性液相载体部分返混对传递的影响 ,进一步利用经实验验证的上述数学模型模拟不同表观气速、床高、反应器直径 (扣除传热元件截面积 )、进口乙烯摩尔分数等参数对床层中催化剂浓度随床高的分布、出口环氧乙烷摩尔分数、环氧乙烷选择率以及单位质量催化剂环氧乙烷年产量的影响 .通过模拟分析预示了工业三相床环氧乙烷反应器的合理尺寸、表观气速、环氧乙烷选择率以及时空产率 ,为工业化提供必要的设计依据     

网格法求解三套管氨合成塔催化床径向浓度和温度分布

在柱坐标系中建立了描述三套管氨合成塔催化床径向浓度和温度分布的数学模型.采用网格法计算了管间催化床不规则截面的浓度分布和温度分布.计算方法快速、有效.     

High‐Pressure High‐Temperature Transparent Fixed‐Bed Reactor for Operando Gas‐Liquid Reaction Follow‐up

A 3‐MPa, 350 °C fixed‐bed reactor was designed to follow‐up gas‐liquid‐solid reactions on a millimetric size heterogeneous catalyst with Raman spectroscopy. The transparent reactor is a quartz cylinder enclosed in a Joule effect heated stainless‐steel tube. A methodology to determine how to focus the microscope for liquid and solid phase characterization is presented. The setup was validated by performing diesel hydrodesulfurization on a CoMo/alumina extrudate catalyst with a conversion very close to expected values along with the acquisition of Raman spectra of the solid catalyst showing an evolution of the catalyst phase during sulfidation.     

Green process technology for peroxycarboxylic acids: Estimation of kinetic and dispersion parameters aided by RTD measurements: Green synthesis of peroxycarboxylic acids

Synthesis of peroxypropionic and peroxyacetic acids from hydrogen peroxide and their carboxylic acids was carried out in a continuous fixed-bed reactor, demonstrating the concept of green process technology: biodegradable chemicals are made with the aid of heterogeneous catalysts. This reactor was constructed with several sampling locations along its length, allowing a better kinetic investigation. A profound study of the mean residence time distribution (RTD) was performed to analyze the behavior of the flow pattern at different liquid flow rates and catalyst loadings by using step and impulse methods with different tracer molecules. It was found that impulse experiments with HCl as a tracer is the most reliable method to study the RTD, because of this tracer does not interact with the catalyst. Based on the RTD study, it was demonstrated that the temperature (in the range 30–60 °C) and the catalyst distribution inside the reactor do not affect the flow pattern, but the ratio of the catalyst mass-to-liquid ratio affects the mean residence time and the liquid dispersion. Furthermore, it was shown that the presence of an axial dispersion is negligible when the average particle diameter is <1.38 mm, e.g., Péclet number exceeds 100. The kinetic study was carried out at different mean residence times (from 10 to 55 min), at different wet catalyst loadings (from 25 to 49 g) and reactor temperatures (from 30 to 60 °C). Mathematical models comprising kinetic and dispersion parameters were developed to compare the estimated parameters obtained from the continuous fixed-bed reactor with the ones obtained from a batch reactor.     

Radioisotope tracer study in trickle bed reactors

The residence time distribution (RTD) of liquid phase in trickle bed reactors has been measured for air‐water system using radioisotope tracer technique. Experiments were carried out in a glass column of internal diameter of 0.152 m packed with glass beads and actual catalyst particles of two different shapes. From the measured RTD curves, mean residence time of liquid was calculated and used to estimate liquid holdup. The axial dispersion model was used to simulate the experimental data and estimate mixing index, ie. Peclet number. The effect of liquid and gas flow rates on total liquid holdup and Peclet number has been investigated. Results of the study indicated that shape of the packing has significant effect on holdup and axial dispersion. Bodenstein number has been correlated to Reynolds number, Galileo number, shape and size of the packing.     

Gas‐Liquid Mass Transfer in a Bench‐Scale Trickle Bed Reactor used for Benzene Hydrogenation

The gas‐liquid mass transfer coefficients (MTCs) of a trickle bed reactor used for the study of benzene hydrogenation were investigated. The Ni/Al₂O₃ catalyst bed was diluted with a coarse‐grained inert carborundum (SiC) particle catalyst. Gas‐liquid mass transfer coefficients were estimated by using a heterogeneous model for reactor simulation, incorporating reaction kinetics, vapor‐liquid equilibrium, and catalyst particle internal mass transfer apart from gas‐liquid interface mass transfer. The effects of liquid axial dispersion and the catalyst wetting efficiency are shown to be negligible. Partial external mass transfer coefficients are correlated with gas superficial velocity, and comparison between them and those obtained from experiments conducted on a bed diluted with fine particles is also presented. On both sides of the gas‐liquid interface the hydrogen mass transfer coefficient is higher than the corresponding benzene one and both increase significantly with gas velocity. The gas‐side mass transfer limitations appear to be higher in the case of dilution with fine particles. On the liquid side, the mass transfer resistances are higher in the case of dilution with coarse inerts for gas velocities up to 3 · 10^–2 cm/sec, while for higher gas velocities this was inversed and higher mass transfer limitations were obtained for the beds diluted with fine inerts.     

Heterogeneous Modeling Approach for Gas‐Limited Reactions in an Inclined Rotating Fixed Bed Reactor

A heterogeneous modeling approach for an inclined rotating fixed bed reactor with concentric internal tube is introduced. The novel reactor is designed to intensify the mass transfer of gas‐limited heterogeneous catalyzed reactions by intermittent catalyst wetting, which is enabled exposing the packed bed to rotation and inclination. A simulation study for the hydrogenation of α‐methylstyrene is presented. In particular, the influence of period length and different wetting‐draining cycles on the space‐time yield of the reactor is analyzed.     

Lurgi型甲醇合成反应器的模型化(Ⅱ)工况模拟与适宜操作条件

利用在MK-101催化剂上合成甲醇的宏观动力学表达式和以前关于小直径固定床传热特性的研究结果,建立了Lurgi型甲醇合成塔拟均相一维和二维数学模型,据此对Lurgi型甲醇合成塔在一系列不同催化剂剂龄下的工况进行了模拟计算,获得了与生产实际相符的结果和适宜操作参数范围.     

用于活性组分分布在颗粒表层的催化剂评价的等温积分反应器

设计了颗粒催化剂实验室筛选及考评装置 ,给出了活性组分分布在催化剂外表层的环柱状气相乙烯氧乙酰化合成醋酸乙烯催化剂的考评实例 .通过无梯度反应器研究了该催化剂的宏观反应动力学 ,采用反应 -传热模型对气相乙烯氧乙酰化合成醋酸乙烯多重反应进行了模拟计算 .实验和模拟计算结果吻合 ,表明所采用的装量 30ml微型积分反应器 ,当催化剂与惰性载体的稀释比为 1∶2时 ,可实现床层内等温操作 ,用于筛选活性组分分布在环柱状载体外表层催化剂 ,有良好的可比性     

Intensification of Deep Hydrodesulfurization Through a Two-stage Combination of Monolith and Trickle Bed Reactors

Deep hydrodesulfurization (HDS) is an important process to produce high quality liquid fuels with ultra-low sul-fur. Process intensification for deep HDS could be implemented by developing new active c...     

Gas holdup and overall volumetric mass transfer coefficient in a modified reversed flow jet loop reactor

Experiments were conducted in a modified reversed flow jet loop reactor having the liquid outlet at the top of the reactor to determine the gas holdup and overall volumetric mass transfer coefficient in the air-water system. The influence of gas and liquid flow rates, and the draft tube to reactor diameter ratio were studied. It was observed that both gas holdup and volumetric mass transfer coefficient increased with increased gas and liquid flow rates and were found to be significantly higher in the modified reactor compared to the conventional one. The optimum draft tube to reactor diameter ratio was found to be in the range of 0.4 to 0.5. Empirical correlations are presented to predict gas holdup and overall volumetric mass transfer coefficient in terms of operational and geometrical variables.     

Modeling and simulation of a small-scale trickle bed reactor for sugar hydrogenation

Laboratory-scale trickle bed reactor was modeled and simulated, taking into account axial dispersion, gas–liquid, liquid–solid and internal mass transfer as well as catalyst deactivation under isothermal conditions. For catalyst particles dynamic and steady state models were developed, including both mass and heat balances. Catalyst deactivation was included in the model by using the final activity concept for the catalyst particles. A well-working numerical algorithm (method of lines) was applied for solving the reactor model with Matlab 7.1 and the results followed experimental trends very well. The steady-state reactor model was based on simultaneous solution of mass balances. The aim was to illustrate how these parabolic partial differential equations could be solved with a step-by-step calculation for a selected geometry. The final model verification was done against experimental data from the hydrogenation of arabinose to arabitol on a ruthenium catalyst.     

Catalytic wet oxidation of substituted phenols in the trickle bed reactor

Continual catalytic wet oxidation of phenol and its derivatives as a suitable chemical pretreatment before a biological treatment process was investigated. The evaluation of (i) the influence of amino-, carboxy- and sulfo- phenol substituents on the course of the oxidation of hydroxyl-aromatics, (ii) the catalytic ability of an active carbon, and (iii) the influence of reaction conditions, viz. temperature (120–160°C) and oxygen partial pressure (2–5 MPa) in the continuous trickle bed reactor, is presented. The active carbon type catalyst seems to be active enough for phenol oxidation, but it is not so effective for aromatic acids. The results of trickle bed operation were strongly influenced by hydrodynamics, viz. wetting efficiency. An insufficient catalyst wetting compensates for an effect of residence time in the bed and undesirable fluctuation of conversion appears at the low liquid velocities which are typical for waste water treatment processes. It is possible to achieve an optimal value of reactor productivity. © 1998 SCI     

An NMR Imaging Study of Steady-State and Periodic Operation Modes of a Trickle Bed Reactor

NMR imaging has been applied to study the steady-state and the periodic operations of a functioning trickle bed reactor. It has been revealed that under conditions of the continuous supply of a liquid reagent to the catalyst bed, the bed was mostly filled with the liquid phase and was characterized by the uniform and stationary distribution of a liquid phase, whereas under conditions of the periodic supply of a liquid reagent to the catalyst bed with the same liquid flow velocity the bed was mostly dry and was characterized by a non-stationary distribution of the liquid phase. The oscillations of the liquid phase content within the bed, corresponding to the modulated liquid flow, have been observed. It has been shown that performing the hydrogenation reaction in a trickle bed reactor under conditions of the periodic supply of a liquid reagent to the catalyst bed leads to the intensification of the hydrogenation process. It becomes apparent in the significant increase of the temperature of the catalyst bed as well as in the increase of the conversion degree in the regimes under forced time-varying liquid flow rates in comparison to the steady-state regime of the reactor operation.