Reactor Modeling of Gas‐Phase Polymerization of Ethylene

A model is developed for evaluating the performance of industrial‐scale gas‐phase polyethylene production reactors. This model is able to predict the properties of the produced polymer for both linear low‐density and high‐density polyethylene grades. A pseudo‐homogeneous state was assumed in the fluidized bed reactor based on negligible heat and mass transfer resistances between the bubble and emulsion phases. The nonideal flow pattern in the fluidized bed reactor was described by the tanks‐in‐series model based on the information obtained in the literature. The kinetic model used in this work allows to predict the properties of the produced polymer. The presented model was compared with the actual data in terms of melt index and density and it was shown that there is a good agreement between the actual and calculated properties of the polymer. New correlations were developed to predict the melt index and density of polyethylene based on the operating conditions of the reactor and composition of the reactants in feed.     

Two-phase modeling of a gas phase polyethylene fluidized bed reactor

A two-phase model is proposed for describing the behavior of a fluidized bed reactor used for polyethylene production. In the proposed model, the bed is divided into several sequential sections where flow of the gas is considered to be plug flow through the bubbles and perfectly mixed through the emulsion phase. Polymerization reactions occur not only in the emulsion phase but also in the bubble phase. Voidages of the emulsion and bubble phases are estimated from the dynamic two phase structure hydrodynamic model. The kinetic model employed in this study is based on the moment equations. The hydrodynamic and kinetic models are combined in order to develop a comprehensive model for gas-phase polyethylene reactor. The results of the model are compared with the experimental data in terms of molecular weight distribution and polydispersity of the produced polymer. A good agreement is observed between the model predictions and actual plant data. It has been shown that about 20% of the polymer is produced inside the bubble phase and as such cannot be neglected in modeling such reactors.     

气相法聚乙烯冷凝模式操作的模拟研究(Ⅰ) 反应器运行状态的分析

建立了气相法聚乙烯冷凝模式操作反应器的两相模型 .模型涉及气泡相和乳化相中的热量和质量守衡、乳相和泡相之间的热量传递和质量传递、乳相中的聚合反应以及乳相中粒子的停留时间分布等 .通过模型研究了常规操作和冷凝操作时操作变量和反应器运行状态变量之间的关系 .模型模拟结果与工业的常规操作和冷凝操作数据符合较好 .得到了冷凝操作时时空收率、低温区域、聚合物灰分等的变化规律以及催化剂特性对冷凝操作的影响规律 .提出了适合于冷凝操作的催化剂类型     

Effect of Polymer Growth Rate and Diffusion Resistance on the Behavior of Industrial Polyethylene Fluidized Bed Reactor

The two‐phase model developed for the UNIPOL polyethylene process is improved by introducing polymer diffusion resistance, this means modelling of polyethylene fluidized bed reactors has been examined on two levels, at small scale of individual polymer particle, and macroscale of the whole reactor. The model utilizes the multigrain model that accounts for the reaction rate at catalyst surface to explore the static and dynamic bifurcation behavior of the fluidized bed catalytic reactor. Detailed bifurcation diagrams are developed and analyzed for the effect of polymer growth factor and Thiele modulus (the significance of the porous medium transport resistance is characterized by Thiele modulus) on reactor dense phase monomer concentration and reactor temperature as well as polyethylene production rate and reactor single pass conversion for the safe temperature region. The observations reveal that significant diffusion resistance to monomer transport exists, and this can mask the intrinsic rate constants of the catalyst. The investigation of polymer growth factor indicates that, the nascent stage of polymerization is highly gas phase diffusion influenced. Intraparticle temperature gradients would appear to be negligible under most normal operating conditions.     

A bubbling fluidized bed solar reactor model of biomass char high temperature steam-only gasification

A two phase biomass char (biochar) steam gasification model based on the systems kinetics is developed in a bubbling fluidized bed with concentrated solar heat as source of energy. The model calculates the dynamic and steady state profiles, as well as the complex parameters of fluidized beds. This robust model is capable of predicting the temperature and concentration profiles of gases in the bubble, emulsion gas and solid phases. The Rosseland equation is used to calculate the radiative transfer within the bed. Due to the nature of the fluidized bed, the small bed thermal conductivity and bigger void between particles, there is a large temperature gradient throughout the bed, indicating that the system is highly non-isothermal. The set-up of a fluidized bed with solar irradiation in the upper side of the reactor is found to be a less efficient gasifying system in comparison with a packed bed, but could be optimized if the source of heat is changed to the bottom of the reactor. The trends and responses of the model are in good agreement with the experimental trends reported in the literature. Hydrogen is the principal product followed by carbon monoxide, the carbon dioxide production is small and the methane production is negligible.     

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.     

IMPORTANCE OF DISPERSED SOLIDS IN BUBBLES FOR EXOTHERMIC REACTIONS IN FLUIDIZED BEDS

Ignition of activated carbon particles were measured in a vertical tube reactor of 4 cm ID, where single particles fell consecutively through a gas mixture containing oxygen.

A two dimensional fluidized bed reactor 24 cm wide, 51 cm high and 2.5 cm in thickness was used for visual observation through a wide front window 24 cm × 35 cm covered with a silica glass plate 1 cm thick. Activated carbon particles were fluidized incipientiy by air, and a gas mixture containing oxygen was injected upwards into the bed through a nozzle positioned 5 cm above the distributor, forming single bubbles intermittently.

It was observed that carbon particles dispersed in rising bubbles were ignited abruptly at emulsion phase temperatures above 550°C. Experimental findings from the fluidized bed were compared with those from the tube reactor, suggesting that the igniting conditions for particles dispersed in bubbles are nearly the same as for single particles falling in the tube reactor.     

Monitoring the fluidized bed reactor for polyethylene polymerization based on fibre optic acoustic emission sensor

This paper presents applications of a new class of fibre optic acoustic emission (FOAE) sensor to monitor the operation of fluidized bed reactors used in polyethylene production. Specifically, the sensor was implemented to detect undesired, abnormal phenomena related to particle agglomeration, wall sheeting, fine overflow, and variations in the superficial gas velocity. The experiments were executed using a fluidized bed cold model setup for polyethylene powders with average particle sizes of 250, 1000, and 2000 μm. The results demonstrated that the presence of agglomerated particles in the fluidized bed reactor increases the kurtosis of the acoustic emission (AE) signal. Furthermore, the overflow of small particles can be detected by mounting the FOAE sensor below the gas distributor plate and monitoring an increase in the root mean square (RMS) of the AE signal. The AE signal RMS increased with the rising superficial gas velocity. Besides, forming a sheet layer on the reactor wall decreased the AE signal RMS. The proposed sensor's main benefits are its simple design, rapid response to abnormal conditions in the fluidized bed reactor, immunity against electromagnetic noise, high-temperature resistance, and safety in hazardous areas.     

Modeling a fluidized bed reactor by integrating various scales: Pore,particle, and reactor

This work proposes a novel population-balance based model for a bubbling fluidized bed reactor. This model considers two continuum phases: bubble and emulsion. The evolution of the bubble size distribution was modeled using a population balance, considering both axial and radial motion. This sub-model involves a new mathematical form for the aggregation frequency, which predicts the migration of bubbles from the reactor wall toward the reactor center. Additionally, reacting particles were considered as a Lagrangian phase, which exchanges mass with emulsion phases. For each particle, the variation of the pore size distribution was also considered. The model presented here accurately predicted the experimental data for biochar gasification in a lab-scale bubbling fluidized bed reactor. Finally, the aggregation frequency is shown to serve as a scaling parameter.     

拟泡-乳曳力模型在大型高温费托流化床反应器中的CFD模拟研究

以带冷却盘管的大型高温费托流化床反应器为研究对象,开展三维计算流体力学模拟研究。传统双流体模型基于局部平均的假设,认为单位控制体内气固两相均匀分布,网格尺寸必须足够小才能正确揭示局部非均匀结构的所有细节。采用双流体模型模拟大型工业化流化床装置时,将导致网格数量过于庞大,远超现有计算能力。为提高计算效率的同时不损失模拟精度,提出了基于局部非均匀假设、适用于粗网格的拟泡-乳三相非均匀曳力(PBTD)模型。该模型将流化床分为乳化相气体、乳化相颗粒以及气泡三相,分别建立守恒方程,体现气泡的非均匀特性对气固曳力的影响。乳化相内气固曳力以及气泡相与乳化相内颗粒的曳力分开考虑。采用PBTD模型耦合传质和反应模型,建立基于局部非均匀假设的高温费托合成反应器三维流动-传递-反应模型,包括各相守恒控制方程、气泡尺寸模型、相间物质和动量交换模型、高温费托合成反应动力学模型以及初始和边界条件,预测反应器内的流场和组分浓度分布。研究结果表明:在粗网格条件下,非均匀曳力模型可以预测床层内相含率的分布情况,预测的床层膨胀高度与经验公式计算值接近,偏差为1.2%。反应器出口气体组分的质量分数与试验测量值相近,偏差在1.5%~16.0%。模拟结果证实,基于非均匀假设的PBTD模型适用于模拟工业规模的鼓泡流化床反应器,对其设计开发和工业运行具有指导价值。     

IMPORTANCE OF DISPERSED SOLIDS IN BUBBLES FOR EXOTHERMIC REACTIONS IN FLUIDIZED BEDS

Ignition of activated carbon particles were measured in a vertical tube reactor of 4 cm ID, where single particles fell consecutively through a gas mixture containing oxygen.

A two dimensional fluidized bed reactor 24 cm wide, 51 cm high and 2.5 cm in thickness was used for visual observation through a wide front window 24 cm × 35 cm covered with a silica glass plate 1 cm thick. Activated carbon particles were fluidized incipientiy by air, and a gas mixture containing oxygen was injected upwards into the bed through a nozzle positioned 5 cm above the distributor, forming single bubbles intermittently.

It was observed that carbon particles dispersed in rising bubbles were ignited abruptly at emulsion phase temperatures above 550°C. Experimental findings from the fluidized bed were compared with those from the tube reactor, suggesting that the igniting conditions for particles dispersed in bubbles are nearly the same as for single particles falling in the tube reactor.     

A Novel Fluidized‐Bed Membrane Dual‐Type Reactor Concept for Methanol Synthesis

A novel fluidized‐bed membrane dual‐type methanol reactor (FBMDMR) concept is proposed in this paper. In this proposed reactor, the cold feed synthesis gas is fed to the tubes of the gas‐cooled reactor and flows in counter‐current mode with a reacting gas mixture in the shell side of the reactor, which is a novel membrane‐assisted fluidized bed. In this way, the synthesis gas is heated by heat of reaction which is produced in the reaction side. Hydrogen can penetrate from the feed synthesis gas side into the reaction side as a result of a hydrogen partial pressure difference between both sides. The outlet synthesis gas from this reactor is fed to tubes of the water‐cooled packed bed reactor and the chemical reaction is initiated by the catalyst. The partially converted gas leaving this reactor is directed into the shell of the gas‐cooled reactor and the reactions are completed in this fluidized‐bed side. This reactor configuration solves some drawbacks observed from the new conventional dual‐type methanol reactor, such as pressure drop, internal mass transfer limitations, radial gradient of concentration, and temperature in the gas‐cooled reactor. The two‐phase theory of fluidization is used to model and simulate the proposed reactor. An industrial dual‐type methanol reactor (IDMR) and a fluidized‐bed dual‐type methanol reactor (FBDMR) are used as a basis for comparison. This comparison shows enhancement in the yield of methanol production in the fluidized‐bed membrane dual‐type methanol reactor (FBMDMR).     

Observation of 3‐D Structure of Bubbles in a Fluidized Catalyst Bed

The interface area between the bubble and emulsion phases in a fluidized catalyst bed is one of the important parameters used to analyze and design the fluidized bed reactor. We used a fast‐scanning X‐ray CT system to observe the bubble shape and structure. We then obtained the transient 2‐dimensional cross sectional gas‐phase distribution in a fluidized catalyst bed. Using image‐processing techniques, pseudo 3‐dimensional images of the bubbles were reconstructed. The bubble structure was studied based on the 3‐dimensional images and the previously obtained results in a 2‐dimensional fluidized bed. It was found that the bubble shape was not spherical but complicated, and that the bubbles ascending in a fluidized catalyst bed consisted of some smaller bubbles.     

Dynamic modeling of gas phase propylene homopolymerization in fluidized bed reactors

A new model with comprehensive kinetics for propylene homopolymerization in fluidized bed reactors was developed to investigate the effect of mixing, operating conditions, kinetic and hydrodynamic parameters on the reactor performance as well as polymer properties. Presence of the particles in the bubbles and the excess gas in the emulsion phase was considered to improve the two-phase model, thus, considering the polymerization reaction to take place in both the bubble and emulsion phases. It was shown that in the practical range of superficial gas velocity and catalyst feed rate, the ratio of produced polymer in the bubble phase to the total production rate is roughly between 10% and 13%, which is a substantial amount and cannot be ignored. Simulation studies were carried out to compare the results of the improved two-phase, conventional well-mixed and constant bubble size models. The improved two-phase and well mixed models predicted a narrower and safer window at the same running conditions compared with the constant bubble size model. The improved two-phase model showed close dynamic behavior to the conventional models at the beginning of polymerization, but starts to diverge with the evolution of time.     

EFFECTS OF HYDROCARBON LIQUID FEED IN POLYETHYLENE POLYMERIZATION PROCESS ON PARTICLE SURFACE TEMPERATURE

In the fluidized bed gas phase polymerization of polyethylene (PE), the heat generated by the exothermic polymerization process is dissipated into the gas mixture flowing past the polymer particles. The polymer particle temperature is determined by the extent of convective heat transfer and other mechanisms of heat removal. In addition to the heat removal by convective heat transfer, liquid hydrocarbon (HC) is often injected into the reactor to further remove heat by evaporation but without partaking in the reaction. The effects of adding this liquid HC on the particle surface temperature have been investigated numerically by means of a one-dimensional polar model. Results indicate that the primary mechanism for removal of the heat of polymerization from the particles is by means of convective heat transfer to the bulk gas, which amounts to 99.5% removal of total heat of polymerization. The PE particle temperature rises only by 1–2°C above the surrounding bed gas mixture. The addition of liquid HC to the feed, however, has a pronounced effect on controlling the reactor gas temperature as most of this liquid is evaporated to the gaseous phase before it reaches the polymer particles. To state it clearly, heat of polymerization is transferred from the particles to the reactor bulk gas predominantly by convection, and part of this heat is subsequently absorbed by evaporation of the fresh liquid HC in the feed. Comparison with a detailed computational fluid dynamic (CFD) model of polymerization in a generic gas phase reactor has also been conducted. The results confirm that the particle temperature rise above the reactor gas temperature is consistent with the one-dimensional model. However, local gas temperature variations are present in the reactor due to the unsteady gas-solid hydrodynamics. Hence, there are some zones that are a few degrees hotter/colder than the bulk reactor temperature with corresponding increase/decrease in particle temperature in these zones.     

EFFECTS OF HYDROCARBON LIQUID FEED IN POLYETHYLENE POLYMERIZATION PROCESS ON PARTICLE SURFACE TEMPERATURE

In the fluidized bed gas phase polymerization of polyethylene (PE), the heat generated by the exothermic polymerization process is dissipated into the gas mixture flowing past the polymer particles. The polymer particle temperature is determined by the extent of convective heat transfer and other mechanisms of heat removal. In addition to the heat removal by convective heat transfer, liquid hydrocarbon (HC) is often injected into the reactor to further remove heat by evaporation but without partaking in the reaction. The effects of adding this liquid HC on the particle surface temperature have been investigated numerically by means of a one-dimensional polar model. Results indicate that the primary mechanism for removal of the heat of polymerization from the particles is by means of convective heat transfer to the bulk gas, which amounts to 99.5% removal of total heat of polymerization. The PE particle temperature rises only by 1-2°C above the surrounding bed gas mixture. The addition of liquid HC to the feed, however, has a pronounced effect on controlling the reactor gas temperature as most of this liquid is evaporated to the gaseous phase before it reaches the polymer particles. To state it clearly, heat of polymerization is transferred from the particles to the reactor bulk gas predominantly by convection, and part of this heat is subsequently absorbed by evaporation of the fresh liquid HC in the feed. Comparison with a detailed computational fluid dynamic (CFD) model of polymerization in a generic gas phase reactor has also been conducted. The results confirm that the particle temperature rise above the reactor gas temperature is consistent with the one-dimensional model. However, local gas temperature variations are present in the reactor due to the unsteady gas-solid hydrodynamics. Hence, there are some zones that are a few degrees hotter/colder than the bulk reactor temperature with corresponding increase/decrease in particle temperature in these zones.     

Chemical vapor deposition and homogeneous nucleation in fluidized bed reactors: silicon from silane

Two models are developed to treat the simultaneous chemical vapor deposition (CVD) on solid particles and gas-phase nucleation of solid fines in a fluidized bed reactor. The first assumes both gas and solids to be well mixed. The second distinguishes between the grid, bubble and emulsion region of the bed. The population balance is used to describe the size distribution of fines, and the growth of large particles is ascribed to CVD and capture of fines. The results of the two models are compared to the experimental data from the JPL six-inch fluidized bed reactor. Good agreement between predictions and experimental data is established for the production rate, gas conversion and quantity of fines formed. The suppression of fines is most efficient when a CSTR flow pattern is approached in the bed.     

控制气相PE流化床高度对装置运行周期的影响

分析了聚合过程中控制流化床床高对聚合物粒径,催化剂聚合产率和装置运行周期的影响.增加流化床床高,有利于聚合物粉料对反应器上部扩大段的冲刷,有效减少了粉料堵塞循环回路和反应器结块的发生几率,提高了聚合反应器运行周期.     

Dynamics and stability of ethylene polymerization in multizone circulating reactors

Multizone circulating bed reactors (MZCR) have the exclusive characteristics of producing polymers of different molecular weights in a single particle. Traditional fluidized bed reactors, on the other hand, can produce only one kind of molecular weight with relatively narrow distribution. A dynamic model for the MZCR is used to illustrate the basic dynamic behavior of the new reactor design used for polyethylene production. The model is used to study the copolymerization of ethylene with butene. Several parameter sensitivity analyses are performed to show the computer-simulated time responses for reactor temperature, number-average molecular weight, weight-average molecular weight, catalyst feed rate and the monomer/comonomer concentration along the reactor length. At certain operating conditions dynamic instability is observed and the results for the effect of cooling water temperature, catalyst feed rate, monomer and comonomer initial feed concentration on the reactor temperature and polymer molecular weight reveal that the system is very sensitive to disturbances in the heat exchanger coolant temperature. Also, at some operating conditions, the reactor temperature oscillates above the polymer melting temperature. Temperature runaway above polymer softening point is a serious problem which may cause polymer melting and hence reactor shutdown. The oscillatory behavior of the reactor temperature necessitates a suitable temperature control scheme to be installed.     

Experimental investigation on mechanisms of fine particles generation for the Borealis Borstar multistage olefin polymerization process

Simultaneous production of large amount of undesired fine particles is a big trouble in the Borstar multistage olefin polymerization process. Aiming at reducing the fine particles, the formation mechanism and formation location of the fine particles were thus studied. First, the influence of catalyst nature was considered. Second, the ash content, bulk density, morphology, and molecular weight distribution of polyethylene with different particle sizes from the small‐scale loop prepolymerization reactor, supercritical loop reactor, and gas phase fluidized bed reactor were studied, respectively. In combination with particle growth model, scanning electron microscope, gel permeation chromatography, and laser particle size analyzer, the particle morphology and growth kinetics were investigated. The results showed that fine particles were mostly generated in the supercritical loop reactor, and were significantly affected by the particle size distribution, residence time distribution, and particle fragmentation of the catalyst. Furthermore, scanning electron microscope images showed the catalysts with low activity tended to generate more fine particles. Based on these results, several strategies for reducing the amount of fine particles were proposed, which could be applied in the industrial process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46589.