环流流化床反应器中乙烯气相聚合反应研究

研究开发了１种新型的用于乙烯气相聚合反应的环流流化床反应器。通过对工业Ａ催化剂和实验室自制的ＱＣＰ－０１催化剂的乙烯气相聚合反应评价及聚合物产品的颗粒形态等方面的研究,认为环流流化床反应器具有聚合反应平稳、催化剂的聚合活性高、产品粒径分布均匀等特点,是１种具有良好应用前景的新型反应器。     

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.     

Gas‐Phase Assisted Surface Polymerization Behavior of β‐Propiolactone on Inorganic and Organic Substrates and Consequent Composite Production

Summary: Gas‐phase assisted surface polymerization (GASP) of β‐propiolactone (βPL) was investigated using substrate‐supported anionic initiators to produce a strongly bonded poly(β‐propiolactone) (PPL)/CaO composite and a novel PPL crystalline deposit with a high melting point value on Al plates. The polymerization of βPL smoothly proceeded in the gas phase to give high‐molecular‐weight PPLs having high PDI values. An almost linear relationship between value and incremental increase in the deposit suggested the living nature of the GASP of βPL. The obtained polymer‐coated substrates, especially PPL/CaO composite, showed strong interaction at the organic/inorganic interface. Moreover, the thermal and structural analyses of deposits revealed that some specific conformations were formed on CaO powder and Al plate surfaces to give highly crystallized deposits. These results demonstrate that the GASP is an effective method for coating any substrate that has a complex shape and a surface morphology.

Accumulation process of poly(β‐propiolactone) on CaO as substrate‐supported initiator during GASP.     

Model‐Aided Design of a Three‐Phase Gas‐Lift Reactor for Oxidation Accompanied by Catalyst Reversible Deactivation

A mathematical model of a three‐phase gas‐lift reactor (GLR) is developed to aid the design of a target reactor for simultaneous substrate catalytic oxidation in riser and a deactivated reactivation catalyst in the downcomer section of the multifunctional reactor. In the GLR model, the hydrodynamics of a real GLR and the kinetics of glucose oxidation by air over a palladium catalyst are incorporated. The GLR model searches for the optimal geometry of the target reactor. With regard to the GLR optimal geometry, the reactor productivity is maximal for given input operational conditions. An algorithm of the GLR model is presented together with simulation results of the target GLR and with insight into the parametric sensitivity of the model. Effects of the reaction components concentrations and the gas‐phase superficial velocity on the location of the target reactor optimal geometry and on the reactor productivity are discussed.     

Steady‐State Model for Olefin Polymerization With a Two‐Site Vanadium Catalyst in a Continuous Stirred‐Tank Reactor

Summary: In this study, a process for continuous EP(D)M production is examined and a mechanistic kinetic model is developed to explain the behavior exhibited by this vanadium‐catalyzed solution polymerization process. The catalyst system without promoter and without hydrogen, produces polymer with bimodal molecular weight distributions (MWDs), while the addition of catalyst promoter causes an order of magnitude increase in catalyst productivity and eliminates the higher‐MW component in the MWD. The addition of hydrogen also precludes bimodal MWDs, regardless of the presence of promoter. In all cases, the polymerization rate has a zero‐order rather than a first‐order response to monomer concentration. The zero‐order response of polymerization rate to monomer concentration is described using a mechanism of monomer coordination to form a stable complex prior to insertion. The bimodal MWDs at high monomer feeds (corresponding to low monomer conversion), in the absence of catalyst promoter and hydrogen, are explained by a two‐site type catalyst model in which both monomer insertion and the formation of the second‐site type occur after the monomer forms a stable coordinated complex with the first catalyst site type. The model reconciles the molecular weight development with these seldom‐discussed features of vanadium catalysis.

Propylene acting as a coordinating ligand at a coordinatively unsaturated vanadium catalyst site (adapted from ref.^[7]).     

Multizone circulating reactor modeling for gas‐phase polymerization. I. Reactor modeling

A new gas‐phase technology for polyolefin production is being developed to be commercially available for large‐scale production between 2004 and 2005. This new technology uses a multilane circulating reactor, which consists of two interrelated zones where two distinct and different fluodynamic regimes are realized, between which the polymer particles are kept in continuous circulation. This article presents a mathematical model for the multilane circulating reactor presenting the typical behavior of the reactor operation and a parameter sensibility analysis. Simulations were conducted for polyethylene production. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1042–1052, 2004     

Non‐Linear Predictive Control of a Three‐Phase Catalytic Reactor

In this work, the predictive control of a three‐phase catalytic reactor is considered. A predictive control algorithm, which has a non‐linear internal model represented by functional link networks, is proposed. This network structure has been shown to have a good non‐linear approximation capability, with the advantage that the estimation of its weight is a linear optimization problem. The results show the potential of the proposed procedure when it is applied to the 2‐methyl‐cyclohexanol production process, which is a non‐linear, distributed parameter and time‐varying process, typical of many important industrial systems.     

气相法PE催化剂技术进展及研究设想

就国内外气相法ＰＥ催化剂的研究和技术进展进行综述，并对各种ＰＥ催化剂的制备和性能加以简要介绍，对齐鲁石油化工公司ＰＥ中试装置今后的研究工作提出的设想。     

烯烃气相聚合反应器技术专利新进展

综述了国内外在优化分布板和导流设备、调节反应器内静电量、在线监测流化床的温度和高度等状态参数方面的专利进展。指出需要增强分布板中心区域的气速，改善冷凝液的进料位置，提高在线监测的准确度。     

Multizone circulating reactor modeling for gas‐phase polymerization. II. Reactor operating with gas barrier in the downer section

A new gas‐phase technology for polyolefin production is being developed to be commercially available for large‐scale production between 2004 and 2005. This new technology uses a multizone circulating reactor, which consists of two interrelated zones where two distinct and different fluodynamic regimes are realized, between which the polymer particles are kept in continuous circulation. In the first part, we presented a mathematical model for the reactor, and this second part of the article we present simulations when a gas barrier is introduced in the top of the downer section and its implications in the polymer characteristics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1053–1059, 2004     

锦纶聚合釜温度模糊自适应PID控制系统研究与仿真

锦纶聚合釜温度具有非线性、大滞后等特点,使用传统PID控制器的控制效果不够理想。在建立聚合釜温度数学模型的基础上,采用模糊算法与PID控制相结合的模糊自适应PID控制算法,实现PID参数自整定,提高控制精度。基于MATLAB平台构建釜温控制系统模型,仿真结果表明所提模糊自适应PID控制算法效果优于传统PID控制。     

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.     

Gas‐phase‐assisted surface polymerization of methyl methacrylate with Fe(0)/TsCl initiator system

To obtain a high polymer coated Fe(0) surface, gas‐phase‐assisted surface polymerization (GASP) of methyl methacrylate (MMA) was investigated using a zero‐valent iron (Fe(0))/p‐toluene sulfonylchloride (TsCl) initiator system, resulting in successful high polymer production on the solid surface. GASP was found to be initiated by radical species that might have been generated via redox reactions with Fe(0), Fe(II), Fe(III), and TsCl. From ¹H‐NMR analysis, the p‐toluene sulfonyl group was found at one end of the polymer chain. The molecular weight of obtained PMMA drastically decreased with increase in the composition ratio of Fe(0) in the initiator system, and increased with increase in polymer yield. From the results, it was assumed that the physically controlled polymerization of MMA proceeded by immobilized active species at gas–solid interfaces. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1879–1886, 2007     

Study of Hydrodynamics,Mixing and Gas‐Liquid Mass Transfer in a Split‐Rectangular Airlift Reactor

Global hydrodynamic characteristics, liquid mixing and gas‐liquid mass transfer for a 63 L split‐rectangular airlift reactor were studied. Correlations for gas holdup and overall liquid circulation velocity were derived for the air‐water system as a function of the specific power input; these were compared to data and correlations for reactor volumes between 4.7 L and 4600 L. A partial recirculation of small bubbles in the riser was observed when U_gr > 0.03 m/s, which was attributed to the use of a single‐orifice nozzle as the gas phase distributor. The dimensionless mixing time and the overall axial dispersion coefficient were nearly constant for the range of gas flow rates studied. However, values of K_L/d_B were greater than those reported in previous studies and this is caused by the partial recirculation of the gas phase in the riser. While scale effects remain slight, the use of a gas distributor favouring this partial recirculation seems adequate for mass transfer in split‐rectangular airlift reactors.     

Gas‐Solid Flow in an Airlift Loop Reactor: A Cluster Structure‐Dependent Drag Model

The hydrodynamic characteristics and heterogeneous structures in an airlift loop reactor (ALR) are analyzed by a computational fluid dynamics (CFD) approach. Based on the two‐fluid model, a modified cluster structure‐dependent (CSD) drag model under consideration of the cluster effects is applied to the prediction of the non‐uniform flow structure in the ALR. In comparison with experimental data and the traditional drag model, the present model enables a better prediction. The distributions of the local granular temperature in different regions of the ALR are indicated. The granular temperature in the particle diffluence region was found to be higher than that in the draft tube and annular zones.     

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.     

Numerical Simulation of the Two‐Phase Fluid Field in a Gas‐Around‐Liquid Spray Nozzle

A new gas‐around‐liquid spray nozzle (GLSN) was designed, and the two‐phase flow fluid field in this nozzle was simulated numerically. Flow characteristics under different structural parameters were obtained by changing the L/D ratio of the premixing chamber, incident angle, and inlet pressures. Increasing the L/D ratio and incident angle improved flow characteristics such as atomization flow, outlet velocity, and turbulence intensity. The nozzle performed optimally at an L/D ratio of 0.5 and incident angle of 60°. The atomization flow decreased with higher gas pressure and increased with higher liquid pressure. The outlet velocity mainly depended on the inlet gas pressure, not on the inlet liquid pressure. These results provide an indication for optimum structures and parameters of the GLSN.     

Comparison of Olefin Polymerization Processes with Metallocene Catalysts

Summary: Solution and gas phase processes of the polymerization of ethene are compared using new types of pentalenyl bridged ansa‐metallocenes such as [Me₃Pen(Flu)]ZrCl₂. As of the bridge, the catalyst system is remarkable thermostable up to 105 °C and a deactivation of the metallocene on the silica support can be suppressed. Compared to the non‐supported catalyst in a solution process, the application of the heterogenized system in a gas phase process leads to a decrease in activities while molar masses of the polyethenes are similar. Due to a higher degree of short chain branches of 20–30 per 1 000 carbon atoms instead of 10–17, the melting temperatures are 10 °C lower than those for polymers obtained in the solution process.

Basic structure of the here used pentalenyl bridged ansa‐metallocenes.