Melt polymerization of bisphenol‐A and diphenyl carbonate in a semibatch reactor

The effect of thermodynamic phase equilibrium on the kinetics of semibatch melt polycondensation of bisphenol‐A and diphenyl carbonate was studied for the synthesis of polycarbonate. In the melt‐polymerization process, a partial loss of diphenyl carbonate occurs as the reaction by‐product phenol is removed from the reactor. To obtain a high molecular weight polymer under high temperature and low‐pressure conditions, a stoichiometric mol ratio of the two reactive end groups needs to be maintained during the polymerization. In this work, vapor–liquid equilibrium data for a binary mixture of phenol and diphenyl carbonate are reported and they are used in conjunction with the Wilson equation to calculate the exact amounts of diphenyl carbonate and phenol returned from a reflux column to the reactor. A good agreement between the reactor model simulations and the experimental polymerization data was obtained. It was also observed that diphenyl carbonate is quickly consumed during the early stage of polymerization and the fraction of evaporated diphenyl carbonate refluxed to the reactor is essentially constant during this period. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1253–1266, 2001     

Influence of Non‐Condensable Gases on the Dynamic Behaviour of an Auto‐Refrigerated CSTR Polymerization Reactor

A polymerization reactor connected to a semi‐flooded horizontal condenser is presented. A model of the process was developed, taking into account the influence of non‐condensable gases in the system. The results obtained show that the model developed was able to reproduce the major dynamic characteristics, even with the presence of non‐condensable gases. It is shown that the non‐condensable gases have great influence on the reactor state, which never reaches a steady‐state; these gases accumulate in the system, increasing the pressure and temperature, and reducing the area of contact and the mass of liquid, therefore needing to be purged regularly, otherwise the system will collapse.     

Experimental investigation of vinyl chloride polymerization at high conversion—reactor dynamics

A series of suspension polymerizations of vinyl chloride monomer (VCM) was carried out in a 5-L pilot plant reactor over the temperature range, 40–70°C. The reactor pressure and monomer conversion were monitored simultaneously every 7–8 min. The critical conversion X_f, at which the liquid monomer phase is consumed, was considered to occur when the reactor pressure fell to 98% of the vapor pressure of VCM for suspension at the polymerization temperature. The reactor model predictions of pressure are in excellent agreement with the experimental data over the entire conversion and temperature ranges studied. The mechanism of reactor pressure development for VCM suspension polymerization is discussed herein in some detail. For isothermal batch polymerization, the reactor pressure falls in two stages due to the effect of polymer particle morphology on pressure drop. The first stage is due to the volume increase of the vapor phase as a result of volume shrinkage due to conversion of monomer to polymer. The monomer phase is not yet consumed at this stage, but it is trapped in the interstices between primary particles creating a mass transfer resistance; therefore, the reactor pressure drops slowly. The second stage is due to both the volume increase of the vapor phase and to the monomer in the vapor phase diffusing into the polymer phase because of the subsaturation condition with respect to monomer in the polymer phase. The reactor pressure drops dramatically with an increase in monomer conversion at this stage. The present model can be used to predict reactor dynamics during suspension polymerization under varying temperature and pressure conditions.     

Modeling of ethylene polymerization with difunctional initiators in tubular reactors

The severe thermodynamic conditions of the high‐pressure ethylene polymerization process hinder ethylene from going to full conversion. One remedy to improve the monomer conversion is to make effective use of difunctional peroxides. Multifunctional peroxides can accelerate the polymerization rate, produce branching, and modify the rheological properties of molten polymers. This article proposes a kinetic model based on a postulated reaction mechanism for ethylene polymerization initiated by difunctional initiators in a high‐pressure tubular reactor. Three peroxides suitable for ethylene polymerization were compared for their effectiveness. Compared to dioctanoyl peroxide, the two difunctional peroxides considered performed much better for the higher temperature regions of the reactor and gave ethylene conversions nearly twice as high for only half of the initial amount of dioctanoyl. They also generated low‐density polyethylene polymer with a broader molecular weight distribution and longer chain branching. These two important polymer characteristics can influence the end‐product rheological properties. Injecting fresh ethylene at different points along the reactor improved the conversion and produced more branched polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

气相法聚乙烯工艺冷凝态操作模式的稳定性和动态行为

气相法聚乙烯工艺冷凝态操作模式由于显著提高了循环气移热能力和反应器时空产率,已成为流化床乙烯聚合工艺的主流操作模式。建立了气相法聚乙烯工艺冷凝态操作模式的数学模型,包括流化床反应器模型,多级换热器模型和反应温度、压力以及循环气组成的控制模型。基于此,采用流程模拟方法,计算了系统在反应器温度采用闭环控制时的稳态解;根据系统对小扰动的动态响应特点,定性判断了反应器温度采用开环控制和闭环控制时聚合反应系统的稳定性;考察了系统对1-己烯分压和催化剂进料速率的阶跃响应特性。结果表明,反应器温度采用闭环控制时,聚合反应系统在所考察操作条件下均是稳定的,而采用开环控制时,解曲线被分叉点分割为稳定区域和不稳定区域。反应器温度对1-己烯分压阶跃变化的动态响应表明聚合反应系统存在长、短周期两类振荡,表明冷凝态操作模式下乙烯聚合反应过程是一个多控制回路耦合的复杂过程。     

Barocalorimetric technique for monitoring pressurized copolymer reactors

The problem of on‐line estimation of the conversion and composition evolutions in a pressurized batch copolymer reactor with temperature and pressure measurements was addressed. The estimation model consisted of mass and energy balances with a pressure equation built from phase‐equilibrium considerations. The application of a nonlinear geometric estimation approach yielded the underlying solvability condition with physical meaning, a straightforward estimator construction, and a conventional‐like tuning procedure. The resulting barocalorimetric estimator was an on‐line dynamic measurement processor with a model‐based predictor and a measurement‐driven corrector, and whose implementation did not require the polymerization rates and heat‐transfer coefficient function dependencies. The technique was tested with a representative laboratory styrene–butadiene system. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 475–482, 2005     

管式反应器中苯乙烯连续本体热聚合过程模型化和数值模拟

建立了管式层流反应器中苯乙烯本体热聚合过程的模型。数值模拟了反应介质流速和温度沿反应器的轴向和径向的分布,考察了反应器的几何尺寸、壁温、反应介质入口温度和流量对反应器出口转化率和产物相对分子质量的影响。结果表明,反应器的几何尺寸和反应器壁温及进料质量流量对单体转化率影响较大,而入口温度影响不大。     

Influence of Pressure on the Hydrodynamics and Mass Transfer Parameters of an Agitated Bubble Reactor

The present study deals with the pressure effects on the hydrodynamic flow and mass transfer within an agitated bubble reactor operated at pressures between 10⁵ and 100 × 10⁵ Pa. In order to clarify the flow behavior within the reactor, liquid phase residence time distributions (RTD) for different operating pressures and gas velocities ranging between 0.005 m/s and 0.03 m/s are determined experimentally by the tracer method for which a KCl solution is used as a tracer. The result of the analysis of the liquid‐phase RTD curves justifies the tank‐in‐series model flow for the operating pressure range. Good agreement is obtained between theoretical and experimental results assuming the reactor is operating as perfectly mixed. Two parameters characterizing the mass transfer are identified and investigated in respect to pressure: the gas‐liquid interfacial area and volumetric liquid‐side mass transfer coefficient. The chemical absorption method is used. For a given gas mass flow rate, the interfacial area as well as the volumetric liquid mass transfer coefficient decrease with increasing operating pressure. However, for a given pressure, a and k_La increase with increasing gas mass flow rates. The mass transfer coefficient k_L is independent of pressure.     

Microwave Super‐Heated Boiling of Organic Liquids: Origin,Effect and Application

This paper reports the state of the art of the microwave super‐heated boiling phenomenon. When a liquid is heated by microwaves, the temperature increases rapidly to reach a steady temperature while refluxing. It happens that this steady state temperature can be up to 40 K higher than the boiling point of the liquid. With the same reactor, overheating is not observed under conventional heating. The bulk temperature of a microwaved solvent under boiling depends on many factors: physical properties of the solvent, reactor geometry, mass flow, heat flow, and electric field distribution. The influence of these factors is studied and discussed. The kinetics of homogeneous organic reactions shows an extension of Arrhenius behaviour into the super‐heated temperature region. Reaction rate enhancement of order 10–100 can thus be achieved, which is normally only possible under pressure. Finally, we present a model predicting reaction kinetics and yields under classical and microwave heating, based on predicted temperature profiles in agreement with experimental data.     

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.     

工业聚合反应装置：Ⅷ.聚烯烃装置

简介了低密度聚乙烯、高密度聚乙烯和聚丙烯生产工艺及其聚合反应器。     

用微扰理论建立水的分子热力学模型

提出1种水的分子热力学模型,从微扰理论出发,建立了自由能及其它热力学函数的关系式.水分子间作用包括硬球、色散、静电及诱导几个部分.通过同时关联0～300°C下饱和水蒸气压及液体密度数据获得分子参数,还预测了水的蒸发焓及饱和水蒸气的比容,比较了文献中处理水的几种理论方法.结果表明,本模型简单,且较接近实际.     

A COMPREHENSIVE MATHEMATICAL MODEL FOR A MULTIZONE TUBULAR HIGH PRESSURE LDPE REACTOR

In this study a comprehensive mathematical model of high pressure tubular ethylene polymerization reactors is presented. A fairly general reaction mechanism is employed to describe the complex kinetics of ethylene polymerization. To determine the variation of molecular properties along the reactor length the method of moments is applied to the infinite set of species balance equations to transform it into a low order system of differential equations in terms of the leading moments of the number chain length distribution. Detailed algebraic equations are given describing the variation of kinetic rate constants, thermodynamic and transport properties of the reaction mixture with temperature, pressure and composition. A new correlation is derived to describe the change of reaction viscosity with reactor operating conditions. The model permits a realistic calculation of temperature and pressure profiles, monomer and initiator concentrations, molecular properties of LDPE (i.e. M_n, M_m, LCB and SCB) as well as the variation of inside film heat transfer coefficient with respect to the reactor length. Simulation results are presented illustrating the effects of initiator concentration, inlet pressure, chain transfer concentration and wall fouling on the polymer quality and reactor operation. The present model predictions are in good agreement with experimental observations in industrial high pressure tubular LDPE reactors.     

Modelling of polymerization kinetics and molar mass development in the nitroxide-mediated polymerization (NMP) of styrene in supercritical carbon dioxide using the PC-SAFT equation of state

A mathematical model for polymerization kinetics and molar mass development in the nitroxide-mediated polymerization (NMP) of vinyl monomers in supercritical carbon dioxide (scCO₂) has been developed. The method of moments is used for molar mass development. The perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state is used to estimate the number of stable phases present at equilibrium in the reaction mixture, critical number average chain length at which polymer particles are formed, and monomer concentration in each phase. Pure and binary PC-SAFT interaction parameters are estimated from liquid–liquid equilibrium (LLE) and liquid–vapour equilibrium (LVE) experimental data at 60 to 129°C. The effect of pressure on monomer conversion and molar mass development in the polymerization of styrene (Sty) using benzoyl peroxide (BPO) and 2,2,6,6-Tetramethylpiperidinyl-1-oxyl (TEMPO) at 120°C and 300–500 bar is studied. It was observed that increasing pressure increases polymerization rate without significantly affecting molar mass development.     

Thermophysical properties of dimethyl ether at near- and supercritical pressures using generalized cubic EoS

The present work has devised the approach for efficiently estimating the thermophysical properties of dimethyl ether (DME) at high pressure conditions relevant to its potential application for compression ignition engines. From a practical standpoint, the thermodynamic properties such as density, heat capacity, enthalpy, entropy, and speed of sound are formulated based on a generalized cubic equation of state (EoS). Comparisons with reference data from a highly accurate empirical multi-parameter EoS demonstrate that the present thermodynamic model has reasonable accuracy for engineering purpose over a wide range of pressure and temperature. By combining it with a transport model which extends the kinetic gas theory with dense-fluid correction, the viscosity and thermal conductivity of DME are also reproduced well for the thermodynamic states from compressed liquid to supercritical fluid.     

Modeling of a Buss‐Kneader as a polymerization reactor for acrylates. Part I: Model validation

The Buss‐Kneader is generally known as a compounding device. Although a reasonable number of papers have been published on extruders as polymerization reactors, only little is known about the behavior of the Buss‐Kneader when used as a polymerization reactor. Its good mixing properties in the radial and axial directions make it a suitable reactor for exothermal polymerization reactions. This paper describes experiments with the co‐polymerization of n‐butyl acrylate and hydroxyethyl methacrylate in a Buss‐Kneader. For model calculations the Buss‐Kneader was treated as a plug flow reactor with axial dispersion. Experimental results on axial temperature profile, monomer conversion and molecular weight are compared with model calculations. Model parameters are based on independently measured data on the heat transfer coefficient, axial dispersion and polymerization kinetics.     

Thermodynamics of wax formation in the fischer-tropsch synthesis products

A new method is suggested for calculating the thermodynamic equilibrium in a multicomponent multiphase system without chemical reactions. This method is based on ideas of statistical physics and non-equilibrium thermodynamics and includes numerical minimization of the Gibbs energy of the complex system. Component concentrations and the physically realizable roots of the equation of state are calculated as the steady state solutions of the set of ordinary differential equations that is implied by the procedure of seeking the probability maximum for the realization of the equilibrium distribution. The approach developed here is used to calculate the equilibrium distribution of the concentrations of vaporous, liquid, and solid substances in the Fischer-Tropsch synthesis products. A thermodynamic model of the formation of solid paraffins from the synthesis products is presented. The calculation of the properties of pure substances and liquid and gaseous products is based on the Lee-Kesler equation of state. The wax formation thermodynamics is considered in the regular solid solution approximation (Hildebrand-Scott model) and in the solid solution approximation taking into account the nonideality of the system (NRTL model). The calculated mass fractions of vaporous, liquid, and solid synthesis products are presented as a function of temperature for different values of the chain propagation constant.     

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.     

Temperature distribution effects during polymerization of methacrylate‐based monoliths

Monolithic stationary phases are becoming increasingly important in the field of liquid chromatography. Methacrylate‐based monoliths are produced via free‐radical bulk polymerization. The preparation of large‐volume monoliths is a major problem because the intensive heat released during polymerization causes distortion of the porous monolithic structure. This work presents experimental measurements of temperature distributions during polymerization in moulds of different sizes and at various experimental conditions. A mathematical model for the prediction of temporal and spatial temperature distribution during the polymerization of methacrylate‐based monolithic columns is introduced. The polymerization is described by an unsteady‐state heat conduction equation with the generation of heat related to the general kinetics of polymerization. Predictions from the mathematical model are in good agreement with the experimental measurements at different experimental conditions. A method for construction of large‐volume monolithic columns is presented and an attempt is made to adopt the developed mathematical model in annular geometry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2326–2334, 2003