Modeling and simulation of simulated countercurrent moving bed chromatographic reactor for oxidative coupling of methane

Oxidative coupling of methane (OCM) is a reaction of industrial importance but per pass equilibrium conversion and product yield in a single reaction column is severely low. The simulated countercurrent moving bed chromatographic reactor (SCMCR) has been reported to significantly improve the methane conversion and C₂-product yield. This paper addresses the mathematical modeling of a five section SCMCR for OCM, which is particularly important for understanding the operation of this SCMCR system. In order to obtain the various process parameters, a realistic and rigorous kinetics was adopted in reactors for OCM and subsequently a kinetic model was developed which can best describe the associated kinetics of OCM in SCMCR. Adsorption isotherm parameters were then derived based on the experimental breakthrough curves acquired using single adsorption column. The proposed mathematical model demonstrated extremely good predictions of the experimental results. Finally, effects of operating parameters, such as switching time, methane/oxygen feed ratio, raffinate flow rate, eluent flow rate, etc., on the behavior of the SCMCR were studied systematically.     

A novel process for the ethyl lactate synthesis in a simulated moving bed reactor (SMBR)

A novel approach for the synthesis of ethyl lactate using a simulated moving bed reactor was evaluated by experiments as well as by simulations. A mathematical model considering external and internal mass-transfer resistances and variable velocity due to change of liquid composition was developed to describe the dynamic behaviour of the SMBR and it was validated by the experiments performed; it was observed that the experimental results were well predicted by the model. The effect of operating parameters, as the feed composition, SMBR configuration and switching time on the SMBR performance parameters at the optimal operating points and/or reactive/separation regions was studied. It was shown that the SMBR is a very attractive technology for the production of ethyl lactate, since under appropriate conditions the lactic acid conversion can be driven to completion and productivity as high as and purity of 95% can be obtained.     

Analysis and demonstration of a control concept for a heat integrated simulated moving bed reactor

Successful operation of a simulated moving bed reactor requires a strategy to control switching of the inlet and outlet positions between different fixed-bed segments. This is due to the narrow operation window in which an ignited state can be maintained and complete conversion is assured in exothermal irreversible reactions. This work compares three control concepts, which are either based on monitoring the reaction front or the leading thermal front. Another feature investigated is the length of the observation time considering a single switching period and a complete cycle. For the concept favored some efforts regarding parameterization are made. The wider range of temperature set-points applicable can be related to stability limits of an associated hypothetical true moving bed reactor. Responses to step inputs in feed concentration and total flow rate are investigated experimentally in order to evaluate the performance of the controller suggested. An ignited state of the reactor could be maintained successfully for 3.5 days.     

Numerical simulation and optimisation of unconventional three‐section simulated countercurrent moving bed chromatographic reactor for oxidative coupling of methane reaction

The simulated countercurrent moving‐bed chromatographic reactor (SCMCR) has been reported to significantly enhance methane conversion and C₂ product yield for oxidative coupling of methane (OCM) reaction, which is otherwise a low per pass conversion reaction. A mathematical model of an unconventional three‐section SCMCR for OCM was first developed and solved using numerically tuned kinetic and adsorption parameters. The model predictions showed good agreement with available experimental results of SCMCR for OCM. Effects of several process parameters on the performance of SCMCR were investigated. A multi‐objective optimisation problem was solved at the operating stage using state‐of‐the‐art AI‐based non‐dominated sorting genetic algorithm with jumping genes adaptations (NSGA‐II‐JG), which resulted in Pareto Optimal solutions. It was found that the performance of the SCMCR could be significantly improved under optimal operating conditions. © 2011 Canadian Society for Chemical Engineering     

Multi-objective optimization of simulated countercurrent moving bed chromatographic reactor for oxidative coupling of methane

A comprehensive optimization study on a simulated countercurrent moving bed chromatographic reactor (SCMCR) is reported in this article for oxidative coupling of methane (OCM) reaction. The selection of the operating parameters such as the switching time, make-up feed rate, methane to oxygen ratio in feed, length of columns and flow rates in different sections are not straightforward in an SCMCR. In most cases, conflicting requirements and constraints govern the optimal choice of the decision (operating or design) variables. An experimentally verified mathematical model was selected to optimize the performance of the SCMCR for OCM. A few multi-objective optimization problems were solved for both existing setup and at design stage. The optimization was performed using a state-of-the-art AI-based non-traditional optimization technique, non-dominated sorting genetic algorithm with jumping genes (NSGA-II-JG), which resulted in Pareto optimal solutions. It was found that the performance of the SCMCR could be improved significantly under optimal operating conditions.     

A study of a simulated moving bed adsorber based on the axial dispersion model

On the basis of the axial dispersion model, the concentration profiles for a simulated moving bed adsorber were theoretically predicted. Experimentally, an apparatus consisting of four sections was employed. Glucose and sorbitol were separated from the liquid dissolved with these components both co-currently and counter-currently. The experimental results seemed to support the predicted curves.     

厌氧移动床生物膜反应器侧伸式搅拌装置的试验研究

选取三种CBY型桨,对厌氧移动床生物膜反应器中采用的侧伸式搅拌装置进行了深入研究.试验考察了三种桨型的功率准数、时间准数,并通过考察其临界转速的方法探讨其最优桨型、最佳安装角度.CBY-3型桨在同样的填充量下临界功率较另两桨型低,混合时间短,优于CBY-2和CBY-1型桨.在水平偏角α为15～20 °,向下偏角β为1～5 °时得到搅拌的最低临界转速.为厌氧移动床生物膜反应器搅拌装置的设计提供了参考.     

模拟移动床改进进料模式提高生产效率的模型化研究(英文)

A new feeding mode for a simulated moving bed(SMB)is proposed.The outlet stream from zone Ⅱ is collected at regular intervals.The concentration of the solution is increased by dissolving raw materials and then fed to zone Ⅲ as the feed stream during the next collection interval. In this feeding mode,the concentration of the stream fed to zone Ⅲ is identical to that of original feed,while in a conventional SMB,the feed is diluted by mixing with the outlet stream of zone Ⅱ before feeding to zone Ⅲ.The new feeding mode increases the inlet concentra tion of zone Ⅲ.A modeling investigation shows that higher inlet concentration of zone Ⅲ increases the height of concentration band in SMB,improving the separation performance significantly.In comparison with the traditonal feeding mode,the new feeding mode increases the productivity by 23.52% and decreases the solvent consumption by 22.56%,so as to increase the raffinate and extract concentrations by 53.17% and 20.38%,respectively.The collection interval for the outlet stream from zone Ⅱ has no effect on the separation performance after reaching the steady state,so that the collection interval can be increased to make the operation more convenient.     

模拟移动床改进进料模式实验研究

常规的模拟移动床色谱II区流出液与原料液在线混合进入III区,会导致进料浓度的降低,从而影响模拟移动床的生产效率。而新的进料模式,将II、III区断开,定期收集II区流出液,在II区流出液中溶解一定量的原料,使其浓度与初始进料浓度相等,然后在下一个周期中作为原料进到III区。以α-生育酚的制备为研究对象,对模拟移动床新型进料模式和传统进料模式进行对比,结果表明,新型进料模式比传统进料模式生产效率提高了53.04%,溶剂消耗减少了35%。同时,在新型进料模式下α-生育酚在SMB系统内部的最高浓度提高了77.24%,而非α-生育酚在SMB系统内部的最高浓度提高了67.31%。在改进进料模式下,α-生育酚的生产能力得到了提高。     

Modelling and simulation of an oxychlorination reactor in a fluidized bed

Taking 1,2‐dichloroethane from the oxychlorination reaction is a commercially very important process due to the large application of the 1,2‐dichloroethane in the chemical industry of PVC production. This work presents the modeling and simulation of an oxychlorination reactor with a fluidized bed. The pseudo‐homogeneous model with one‐dimensional flow in steady state was applied based on the theory of fluidized bed in two phases. It allows the sensitivity analysis of the operational and project parameters of the reactor. The ordinary differential equations system that represents the mathematical model of the reactor was solved through the application of the numerical method of Newton–Raphson's. The results obtained have proved that the developed model represents the system suitably, in spite of the one‐dimensional model. The effect of different parameters was investigated through the sensitivity analysis, and the results show that the parameters that have the largest influence on the reactor performances are: fluidized bed height, bubble diameter, residence time, cupric chloride weight in the catalyst, and emulsion phase temperature.     

废食用油脂固定床酶法合成生物柴油研究

利用废食用油脂合成生物柴油,既能够实现废弃物的清洁利用,又能提供可再生的绿色能源。采用固定化假丝酵母脂肪酶为催化剂,在三级固定床反应器内,采用分级流加甲醇的方式,每级醇油摩尔比为1∶1,探讨了酶质量分数、溶剂质量分数、水质量分数、温度、反应液流速等与产物中甲酯质量分数的关系。实验结果表明,当油中酶、溶剂、水的质量分数分别为25%,15%,10%,反应液流速为1.2 mL/min,温度为45℃时,产物中甲酯质量分数达到最大值91.08%,其中油酸甲酯质量分数最高。产品经过精制后,理化性质符合美国和德国生物柴油标准,绝大多数指标优于我国0#柴油。     

二甲苯模拟移动床分离过程建模与仿真

模拟移动床（SMB）是混合二甲苯分离的重要技术。模拟移动床区域回流比是决定产品质量的关键参数。在真实移动床（TMB）建模方法基础上,结合实际工况数据,建立了模拟移动床吸附分离过程机理模型,并通过分析区域回流比对产品质量的影响,得到不同产品质量要求以及进料品质的情况下区域回流比的操作区间。仿真结果表明,TMB建模方法能较好地描述模拟移动床实际工况。基于机理模型对操作区间的分析结果可以为模拟移动床分离过程的工艺设计和操作提供指导意见。     

Simulation of true moving bed adsorptive reactor: Detailed particle model and linear driving force approximations

A new true moving bed (TMB) adsorptive reactor model with a detailed particle approach is presented introducing the formulation of the mass balance for the solid phase in counter-current moving systems. The system studied here is the enzymatic inversion of sucrose into fructose and glucose and subsequent separation of glucose/fructose; the reaction occurs both in the outer fluid phase and inside particles. Model equations include film mass transfer, intra-particle diffusion resistance, axial dispersion for the outer fluid phase, plug flow of the solid phase and linear adsorption equilibrium of glucose/fructose. This new model is compared with previous LDF-type approximations for reactive systems and applied to pure separative TMB process. The numerical solution of model equations is obtained for transient and steady state with commercial and public domain packages (gPROMS and COLNEW). The influence of the particle size and reaction rate constant is analyzed in the (γ₂×γ₃) reactive/separation region.     

Mathematical modeling,steady state simulation,parametric analysis and optimization of SO2 capture in a countercurrent moving bed (CaO and C) reactor

The use of absorbents based on calcium for the reduction of SO₂ emissions from power plants has been studied for the last 30 years. The present work is part of a research project aimed at the development of a moving bed limestone filter. It is placed after burning in order to capture the SO₂ from the flue gases of pulverized lignite combustors. A heterogeneous mathematical model was developed for the steady‐state simulation of a gas–solid countercurrent moving bed reactor. The mathematical model was solved using the method of finite elements and gave results for the temperature and conversion profile along the reactor. Also, parametric analysis (for T_g,in, T_s,in, u_s, q_o, , , d_o, z_o) was performed and useful conclusions concerning the behavior of a moving bed reactor in different conditions were drawn. Finally, optimization of conditions was performed to give an SO₂ conversion higher than 0.95. The results are of important technological interest as a dry process in applications of SO₂ capture. © 2018 Society of Chemical Industry     

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。     

流化床与沸腾床内部微生物群落演变与分析

用流化床反应器和沸腾床反应器处理焦化废水,对两种反应器运行效能及微生物群落变化进行对比研究。结果表明,提高污泥负荷后流化床COD去除率优于沸腾床反应器。提高进水污泥负荷对沸腾床内微生物的冲击更大,致使其种群丰富程度下降明显。研究结果证明,流化床在宏观去除率、维持菌种丰富度方面具有较大优势。     

Comparison between simulated moving bed and reverse flow chromatographic reactors for equilibrium limited reactions

A staged linear model, containing five parameters, is developed to compare equivalent simulated moving bed chromatographic reactors (SMBCR) and reverse flow chromatographic reactors (RFCR). A first order reversible reaction and linear adsorption equilibrium, with preferential adsorption of the reactant is assumed. The analysis uses simple, easily computable analytical solutions that rigorously represents the transients in the cyclic steady state for both the RFCR and the SMBR. A comparison between the two types of reactors is carried out to determine the maximum conversion attainable and the range of operation where these systems have advantages over conventional steady state reactors. It is found that the maximum conversion of both reactors is similar. The range of operation in terms of amount of catalyst and range of switching times favors the RFCR, while the conversion at low separation factors favors the SMBCR.     

Separation of amino acids by simulated moving bed under solvent constrained conditions for the integration of continuous chromatography and biotransformation

A large number of promising enzyme reactions, such as diastereospecific carbon-carbon bond formation by aldolases, suffers from an unfavorable position of the reaction equilibrium. Combining continuous chromatography and enzymatic reactions should allow for a new in situ or online product recovery process to achieve high reaction productivity and yield and make these biocatalysts economically more attractive. The integration imposes a series of constraints on the chromatographic separation, mainly on the applicable solvent, which is at the same time the reaction medium for the enzymatic reaction. We exploit this concept for a model process, the integrated biocatalytic production of L-allo-threonine from glycine and acetaldehyde. Of crucial importance for this process is the separation of the two physicochemically similar amino acids glycine and threonine, in particular in the presence of additional compounds such as the second starting material and enzyme cofactors. This separation was first investigated on a lab-scale simulated moving bed (SMB) unit under enzyme compatible conditions. After triangle theory-based identification of SMB operating points, the two amino acids could be efficiently separated, applying aqueous eluents with minor content of organic co-solvent at neutral pH on a weak cation exchanger resin. Remarkably, the separation performance with respect to the two amino acids was only slightly reduced by coupling the SMB to a continuously operated enzyme membrane reactor, whose efflux contained, in addition to the amino acids, acetaldehyde and the cofactor pyridoxal-5-phosphate. This represents an important step to the future design of even further integrated biocatalytic reaction-separation schemes.     

非均质移动颗粒床的渗流换热模型与数值模拟

针对非均质移动颗粒床的换热过程,建立了其渗流换热的数学模型,提出了COADI-GS算法,采用此算法对移动颗粒床的气固换热过程进行流热耦合数值模拟。通过对均质与非均质这两种不同移动颗粒床换热模型的仿真结果进行比较,发现两者的床内温度分布有较大差异,非均质移动颗粒床模型能更为准确地描述床层内的渗流换热过程。计算结果表明,供风压力的增加虽有利于熟料颗粒的冷却,但会降低回收风的温度;颗粒温度随床层移动速度的增加而升高,近似为线性关系。