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.     

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...     

Cumene Hydroperoxide Hydrogenation on a Pd/Al2O3 Catalyst in a Trickle Bed Reactor – Kinetics of Hydrogenation and Deactivation

Liquid‐phase hydrogenation using a Pd/Al₂O₃ catalyst provides a potential technique for the reduction of cumene hydroperoxide (CHP) to α‐cumyl alcohol (CA). In this paper, CHP hydrogenation was carried out in a cocurrent downflow trickle‐bed reactor over a wide range of reaction conditions to study the reaction and deactivation kinetics. The proposed intrinsic rate expression for CHP hydrogenation is based on an Eley‐Rideal mechanism that accounts for an irreversible surface reaction between the absorbed CHP with nonabsorbed hydrogen molecules. During CHP hydrogenation, an exponential decay in activity of the Pd/Al₂O₃ catalyst and the presence of residual activity were observed. A kinetic deactivation model with residual activity was developed. Based on reaction and deactivation kinetics, catalyst deactivation was attributed to oxidation of the catalyst surface by CHP. The presence of residual activity was due to the partial reduction of oxidized catalyst surface by hydrogen.     

管式固定床反应器柱状颗粒床层流体流动模拟与实验研究

针对管式固定床反应器内管束数量多、规模大等特点,选取单个管束作为特征结构。对装填不同直径柱状颗粒的管束,采用程序坐标定位的方法,建立柱状颗粒床层的物理模型。采用DEM与CFD联合数值仿真方法,探究反应管内径与柱状颗粒的等比表面积球当量直径之比(管径比Di/dp)对柱状颗粒床层流体流动的影响,并建立单管固定床反应器试验台,采用差压测试方法进行实验研究。结果表明,当Di/dp由5.37增至12.75时,床层空隙率和流体分布均匀性均得到改善,壁面效应的影响由床层中心减弱到管壁。基于数值模拟及实验结果对Di/dp=12.75的柱状颗粒床层进行床层压降Ergun公式常系数修正,CFD模拟计算的结果与拟合公式吻合较好。研究结果能为固定床反应器压降预测提供参考。     

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     

Hydrodynamics and flow regime transition study of trickle bed reactor at elevated temperature and pressure

The hydrodynamics in a trickle bed reactor (TBR) in non-ambient conditions are studied for air-water and air-acetone (pure organic liquid of low surface tension) systems. A flow map experiments for air-water and air-acetone systems are performed in a pilot plant reactor of 0.05 m i.d. and 1.25 m height. It has been demonstrated from the experimental results that the pressure drop tends to increase with increasing superficial gas and liquid velocity and reactor pressure, while it tends to decrease with increasing bed temperature. The results also show that the dynamic liquid holdup increases with increasing liquid velocity and decreases with increasing superficial gas velocity, reactor pressure and bed temperature. The dynamic liquid holdup and pressure drop values are obviously higher than those measured for air-water system at the same fluid fluxes, reactor pressure and bed temperature due to the surface tension effects. For higher reactor pressure and temperature, the trickle to pulse transition boundary shifts towered higher superficial velocities of both gas and liquid.     

Kinetic model development and simulation of simultaneous hydrodenitrogenation and hydrodemetallization of crude oil in trickle bed reactor

One of the more difficult tasks in the petroleum refining industries that have not been considered largely in the literature is hydrotreating (HDT) of crude oil. The accurate calculations of kinetic models of the relevant reaction scheme are required for obtaining helpful models for HDT reactions, which can be confidently used for reactor design, operating and control. In this work, an optimization technique is employed to evaluate the best kinetic models of a trickle bed reactor (TBR) process utilized for hydrodenitrogenation (HDN) and hydrodemetallization (HDM) that includes hydrodevanadization (HDV) and hydrodenickelation (HDNi) of crude oil based on pilot plant experiments. The minimization of the sum of the squared errors (SSE) between the experimental and estimated concentrations of nitrogen (N), vanadium (V) and nickel (Ni) compounds in the products is used as an objective function in the optimization problem to determine the kinetic parameters.A series of experimental work was conducted in a continuous flow isothermal trickle bed reactor, using crude oil as a feedstock and the commercial cobalt-molybdenum on alumina (Co-Mo/γ-Al₂O₃) as a catalyst.A three-phase heterogeneous model based on two-film theory is developed to describe the behaviour of crude oil hydroprocessing in a pilot-plant trickle bed reactor (TBR) system. The hydroprocessing reactions have been modelled by power law kinetics with respect to nitrogen, vanadium and nickel compounds, and with respect to hydrogen. In this work, the gPROMS (general PROcess Modelling System) package has been used for modelling, simulation and parameter estimation via optimization. The model simulations results were found to agree well with the experiments carried out in a wide range of the studied operating conditions. The model is employed to predict the concentration profiles of hydrogen, nitrogen, vanadium and nickel along the catalyst bed length in three phases.     

流化床粉煤气体热载体快速热解反应器的计算

在冷态模拟实验和煤热解动力学计算的基础上,对粉煤气体热载体快速热解提升管反应器的高度进行了计算。利用高速摄像粒子测速法结合互相关算法研究了不同气体流量和不同颗粒粒径时固体颗粒在热解提升管中的运动速度,通过求解神府煤热解动力学方程,得到了不同粒径神府煤颗粒热解挥发分析出的时间,从而确定了快速热解提升管反应器的高度。研究结果表明:当气体流量在850 m3/h,粉煤的粒径主要集中在0.7—3.0 mm时,提升管的高度应选择在10.0 m。     

Mathematical simulations of the performance of trickle bed and slurry reactors for methanol synthesis

Three- and two-phase reactor models were developed to simulate the performance of trickle bed and slurry reactors for methanol synthesis. The combination of orthogonal collocation and quasi-linearization was used to solve the trickle bed reactor model incorporating resistance to interparticle and intraparticle diffusion and resistance to mass transfer between gas and liquid phases. Model parameters were estimated independently from either published correlations or literature data. The model predicts significant resistance to intraparticle diffusion on the performance of trickle bed reactors. However, comparisons between pilot size trickle bed and slurry reactors illustrate the superior performance of trickle bed reactors over the slurry reactors for methanol synthesis even with diffusion limitations.     

Trickle bed hydrodynamics and flow regime transition at elevated temperature for a Newtonian and a non-Newtonian liquid

Despite the hydrodynamics of trickle beds experiencing high pressures has become largely documented in the recent literature, trickle bed hydrodynamic behavior at elevated temperatures, on the contrary, largely remains terra incognita. This study's aim was to demonstrate experimentally the temperature shift of trickle-to-pulse flow regime transition, pulse velocity, two-phase pressure drop, liquid holdup and liquid axial dispersion coefficient. These parameters were determined for Newtonian (air-water) and non-Newtonian (air-0.25% Carboxymethylcellulose (CMC)) liquids, and the various experimental results were compared to available literature models and correlations for confrontation and recommendations. The trickle-to-pulse flow transition boundary shifted towards higher gas and liquid superficial velocities with increasingly temperatures, aligning with the findings on pressure effects which likewise were confirmed to broaden the trickle flow domain. The Larachi-Charpentier-Favier diagram [Larachi et al., 1993, The Canadian Journal of Chemical Engineering 71, 319-321] provided good predictions of the transition locus at elevated temperature for Newtonian liquids. Conversely, everything else being kept identical, increasingly temperatures occasioned a decrease in both two-phase pressure drop and liquid holdup; whereas pulse velocity was observed to increase with temperature. The Iliuta and Larachi slit model for non-Newtonian fluids [Iliuta and Larachi, 2002, Chemical Engineering Science 46, 1233-1246] predicted with very good accuracy both the pressure drops and the liquid holdups regardless of pressure and temperature without requiring any adjustable parameter. The Burghardt et al. [2004, Industrial and Engineering Chemistry Research 43, 4511-4521] pulse velocity correlation can be recommended for preliminary engineering calculations of pulse velocity at elevated temperature, pressure, Newtonian and non-Newtonian liquids. The liquid axial dispersion coefficient (D_ax) extracted from the axial dispersion RTD model revealed that temperatures did not affect in a substantial manner this parameter. Both Newtonian and power-law non-Newtonian fluids behaved qualitatively similarly regarding the effect of temperature.     

Modeling of an industrial fixed bed reactor based on lumped kinetic models for hydrogenation of pyrolysis gasoline

In this work, a mathematical model of an industrial fixed bed reactor for the catalytic hydrogenation of pyrolysis gasoline produced from olefin production plant is developed based on a lumped kinetic model. A pseudo-homogeneous system for liquid and solid phases and three pseudo-components: diolefins, olefins, and parraffins, are taken into account in the development of the reactor model. Temperature profile and product distribution from real plant data on a gasoline hydrogenation reactor are used to estimate reaction kinetic parameters. The developed model is validated by comparing the results of simulation with those collected from the plant data. From simulation results, it is found that the prediction of significant state variables agrees well with the actual plant data for a wide range of operating conditions; the developed model adequately represents the fixed-bed reactor.     

C9-aldehyde hydrogenation over nickel/kieselguhr catalysts in trickle bed reactor

The objective of the present study was to select the optimal catalyst and operating conditions for the manufacture of C₉-alcohol, using C₉-aldehyde and hydrogen, in a trickle bed reactor. When CaO, Ce₂O₃ or MgO was added as a promoter to the Ni/kieselguhr catalyst, the BET and Ni surface areas were increased. In the reaction for the manufacture of C₉-alcohol, using C₉-aldehyde and hydrogen in a batch reactor, a Ni–MgO/kieselguhr catalyst showed the highest activity. In addition, the catalyst using Na₂CO₃ as a precipitant showed the highest activity. According to the result of an experiment to find the optimal reaction conditions for C₉-alcohol synthesis, using C₉-aldehyde and hydrogen in a trickle bed reactor loaded with Ni–MgO/kieselguhr catalyst, the highest yield of C₉-alcohol was 91.5 wt% at 130 °C, 400 psi and WHSV = 3. The C₉-aldehyde hydrogenation performance of the Ni–MgO/kieselguhr catalyst was similar to that of a Cu/ZnO/Al₂O₃ catalyst, but superior to that of Cu–Ni–Cr–Na/Al₂O₃ and Ni–Mo/Al₂O₃ catalysts. In a long-term catalysis test, the Ni–MgO/kieselguhr catalyst showed higher stability than the Cu/ZnO/Al₂O₃ catalyst.     

Semi-batch reactor for kinetic measurements of catalyzed olefin co-polymerizations in gas and slurry phase

A multi-purpose setup is presented for homo- and co-polymerizations of ethylene and 1-hexene in slurry and gas phase. Polymerization experiments have been executed semi-batch with a heterogeneous metallocene catalyst under industrial conditions. During the gas phase polymerization, the monomer concentrations have been measured and controlled online. The activities for both monomers have been measured with flow meter technique.The polymerization kinetics presented have been measured in a very accurate and reproducible way in isothermal (within ) and isobaric mode (within 0.15 bar). The concentrations of monomer and co-monomer have been kept constant within 5% of the set point. The activity for ethylene was 50% higher in the presence of 1-hexene compared to a homo-polymerization.     

Pd-based catalysts for catalytic wet oxidation of combined Kraft pulp mill effluents in a trickle bed reactor

Catalytic wet oxidation of combined pulp mill effluents was studied in a trickle bed reactor. Two types of supported Pd-based catalysts, eggshell and uniform catalysts, and a supported Pd–Pt uniform catalyst were employed. Supported Pd catalysts showed high activity for total organic carbon (TOC) and color removal at temperatures of 353–448 K and 1.84 MPa. Compared to uniform catalysts, the eggshell catalysts with a 0.2 wt.% Pd loading show promise for treatment of combined pulp mill effluents. High activity for TOC and color removal can be attributed to the high density of active Pd sites in the shell area and to the decrease of diffusion path for reactants and intermediates. No apparent deactivation of eggshell catalysts was observed after 40 h on stream. Potential application of the supported Pd catalysts for treatment of combined pulp mill effluents is discussed.     

Application of Magnetic Resonance Imaging (MRI) for investigation of fluid dynamics in trickle bed reactors and of droplet separation kinetics in packed beds

Magnetic Resonance Imaging technique was used to investigate the fluid dynamics of multiphase flow in two different applications: (a) stationary two-phase flow in trickle beds, and (b) time-dependent droplet separation in granular bed filters. The experiments were carried out with different gas/liquid systems at either atmospheric conditions or at elevated pressure and temperature. Two-dimensional and three-dimensional image data were then evaluated to quantify the porosity profiles and gas/liquid distribution in packed beds. The results compare well with data from integral measurements.     

提升管与气-固环流床层耦合反应器颗粒相循环比的模型及预测

引言Geldart A类颗粒气-固环流技术是一种利用气-液环流原理,并结合气-固聚式流化体系特点而开发的一种新型流态化技术[1],具有气固接触效率高、传质传热性能好等优点,被广泛用于石油炼制领域中的催化裂化汽提器、提升管出口粗旋快分的预汽提器、外取热器、石油焦燃烧器和降烯烃反应器等装备中[2]。     

Optimal design and operation of an industrial three phase reactor for the oxidation of phenol

Among several treatment methods catalytic wet air oxidation (CWAO) treatment is considered as a useful and powerful method for removing phenol from waste waters. In this work, mathematical model of a trickle bed reactor (TBR) undergoing CWAO of phenol is developed and the best kinetic parameters of the relevant reaction are estimated based on experimental data (from the literature) using parameter estimation technique. The validated model is then utilized for further simulation and optimization of the process. Finally, the TBR is scaled up to predict the behavior of CWAO of phenol in industrial reactors. The optimal operating conditions based on maximum conversion and minimum cost in addition to the optimal distribution of the catalyst bed is considered in scaling up and the optimal ratio of the reactor length to reactor diameter is calculated with taking into account the hydrodynamic factors (radial and axial concentration and temperature distribution).     

管式搅拌反应器中流动特性实验及模型研究

为进一步研究带机械搅拌装置的新型管式反应器内流动特性,采用刺激-响应技术,测定流体在不同操作条件下的停留时间分布(RTD)曲线并与无搅拌停留时间分布曲线作对比,计算了平均停留时间分布的统计特征值。用混合时间表征混合特性,用Peclet操作准数表征轴向扩散特性。结果表明,适当增大转速、流量或降低水位,都有利于反应器内流体的均匀混合。大体上随流量的减少和液位的升高停留时间有延长的趋势,转速变化对停留时间的影响不显著。在搅拌转速不超过400 r/min时,混合时间随着搅拌转速的增大而缩短。在实验范围内,反应器相当于3个串联全混槽反应器。     

Effect of phase maldistribution on performance of two-phase catalytic monolith reactor and its comparison with trickle bed reactor

Monolith reactors are widely considered as an alternative to the conventional trickle bed reactor. For the commercial deployment of monolith reactors, comparative performance studies are required. Reliable comparative and performance studies require a detailed understanding of the effect of phase distribution/maldistribution on the performance studies. In this work, performance and comparative studies were carried out in a relatively large column that was 4.8 cm in diameter. Experiments were performed in the same conditions that were used in studies for which phase distribution data were available. Since the properties of the catalyst used were different in both the reactors, the apparent kinetics were studied to facilitate the comparison. The hydrogenation of alpha-methyl styrene (AMS) was used as a test reaction. From the performance studies, it was found that the effect of maldistribution on the performance was stronger than the catalyst availability. From the comparative studies, it was found that the monolith reactor with maldistributed flow conditions provides higher productivity than the trickle bed reactor.