Optimal operating strategies for emulsion terpolymerisation

Optimal control policies for emulsion terpolymerisation of styrene, methyl methacrylate (MMA) and methyl acrylate (MA) were determined in a semi-batch reactor using the multi-objective dynamic optimisation method. A comprehensive dynamic model was used for the design of optimal control. The control vector parameterisation (CVP) approach was implemented for constrained optimisation for emulsion terpolymerisation reactors. The feed rates of styrene, MMA, MA, surfactant and initiator, and the temperature of the reactor were used as manipulating variables to produce terpolymers of desired composition, molecular weight distribution (MWD) and particle size distribution (PSD). The particle size polydispersity index (PSPI), molecular weight polydispersity index (MWPI) and the overall terpolymer composition ratios were incorporated in the objective functions to optimise the PSD, MWD and terpolymer composition, respectively. The optimised operational policies were validated with experiments via one stirred tank polymerisation reactor.     

Online inferential product attribute estimation for optimal operation of emulsion terpolymerisation: Application to styrene/MMA/MA

An advanced model for process design and control of emulsion terpolymerisation was developed. A test case of emulsion terpolymerisation of styrene (Sty), methyl methacrylate (MMA) and methyl acrylate (MA) was investigated on state of the art facilities for predicting, optimising and control end-use product properties including global and individual conversions, terpolymer composition, the average particle diameter and concentration, glass transition temperature, molecular weight distribution, the number- and weight-average molecular weights and particle size distribution.The model equations include diffusion-controlled kinetics at high monomer conversions, where transition from a ‘zero-one’ to a ‘pseudo-bulk’ regime occurs. Transport equations are used to describe the system transients for batch and semi-batch processes. The particle evolution is described by population balance equations which comprised a set of integro-partial differential and nonlinear algebraic equations. Backward finite difference approximation method is used to discretise the population equation and converts them from partial differential equations to ordinary differential equations. The model predictions were experimentally validated in the laboratory and were found to be in excellent agreement, thus paving the way for further application of the model.     

On-line multi-variable predictive control of molar mass and particle size distributions in free-radical emulsion copolymerization

A multi-variable model predictive control (MPC) was formulated to solve control problems associated with a combination of regulation and targeting desired set-points. We investigated the simultaneous control of key polymer properties: the particle size (PSD) and molecular weight distribution (MWD) by manipulating the flow rates of the monomers (styrene, MMA), surfactant, initiator and the temperature of the reactor. A multi-input-multi-output (MIMO) formulation was constructed for the constrained optimal control problem to maximize the width of the PSD (with M_n at a constant set-point), and to maximize the average molar mass. The strategy developed within a gPROMS-API-DCS environment allowed real-time implementation of model-based control of the process. The optimal control problem was implemented via an interface to a dynamic optimization code. Major improvements in process operation and polymer property control resulted on the implementation of our multi-variable MPC algorithm. The manipulation of the four flow rates and the temperature increased the degree of freedom in the system and achieved tighter PSD and MWD control. The on-line performance of MPC for MWD and PSD control was found to be satisfactory.     

Open-loop control of particle size distribution in semi-batch emulsion copolymerization using a genetic algorithm

The open-loop generation of an optimal feed profile to attain a target particle size distribution (PSD) in the semi-batch emulsion co-polymerization of vinyl acetate and butyl acrylate is described. A nominal model of the process based on population balancing is utilized for this purpose. A Genetic Algorithm is employed as the optimization strategy. The optimal recipes generated in these studies are implemented on an experimental emulsion polymerization reactor. The end-point PSD obtained in these experiments closely matches the target in spite of the model uncertainties and process disturbances. Examination of the evolution of the PSD up to the end point provides useful information for feedback control strategies.     

Surface–particle–emulsion model of heat transfer between a fluidized bed and an immersed surface

A mathematical model, the surface–particle–emulsion heat transfer model (SPE model), is developed. Considering the variance of voidage in emulsion in the vicinity of an immersed surface, heat transfer near the surface is treated as that through dispersed particles touching the surface and through the emulsion when the distance from the surface is larger than one particle diameter. A stochastic model of particle packing density on a surface is developed to calculate the coverage ratio of particles on the surface. Based on the SPE model, a heat transfer model for a horizontally immersed tube in a fluidized bed is developed. The calculation results are in reasonable agreement with experimental data from the authors and the literature. The model shows better qualitative and quantitative prediction for local heat transfer coefficients around a horizontally immersed tube in a fluidized bed.     

乙醛生产过程中的软测量实现

针对乙醛生产过程 ,建立关键过程变量粗乙醛浓度的软测量模型 ,并在此基础上建立粗乙醛的实时收率预测模型。对软测量实现中涉及到的回归变量选择、样本预处理、回归一致性分析、实时校正机制等关键技术进行讨论。该系统的预测值与离线分析值平均相对偏差为 1.2 %。     

Neurocontrol of a multi-effect batch distillation pilot plant based on evolutionary reinforcement learning

The time cost of first-principles dynamic modelling and the complexity of nonlinear control strategies may limit successful implementation of advanced process control. The maximum return on fixed capital within the processing industries is thus compromised. This study introduces a neurocontrol methodology that uses partial system identification and symbiotic memetic neuro-evolution (SMNE) for the development of neurocontrollers. Partial system identification is achieved using singular spectrum analysis (SSA) to extract state variables from time series data. The SMNE algorithm uses a symbiotic evolutionary algorithm and particle swarm optimisation to learn optimal neurocontroller weights from the partially identified system within a reinforcement learning framework. A multi-effect batch distillation (MEBAD) pilot plant was constructed to demonstrate the real world application of the neurocontrol methodology, motivated by the nonsteady state operation and nonlinear process interaction between multiple distillation columns. Multi-loop proportional integral (PI) control was implemented as a reduced model, reflecting an approach involving no modelling or significant controller tuning. Rapid multiple input multiple out nonlinear controller development was achieved using SSA and the SMNE algorithm, demonstrating comparable time and cost to implementation in relation to the reduced model. The optimal neurocontroller reduced the batch time and therefore the energy consumption by 45% compared to conventional multi-loop SISO PI control.     

Actuator Fault Tolerant Control Based on a MIMO-MPC: Application in a Double-Pipe Heat Exchanger

In this work, an experimental fault tolerant control (FTC) implementation is presented. The FTC is based on a multi-input multi-output (MIMO) model predictive control (MPC). The aim of the FTC is to keep on operating a double-pipe counter-current heat exchanger even if the main actuator of the heat exchanger is stuck open. To develop the FTC, an adaptive observer was implemented in order to design a fault detection and isolation (FDI) system. In the FDI system, the cold and hot water flow rate estimations by the adaptive observer are compared to the control signals provided by the MPC. The results of the implementation of the FTC using a MIMO model predictive control were compared to the results obtained in a previous work which was developed using model-following control.     

Emulsion gel beads prepared by sedimentation polymerization using two-fluid atomization and their Pd(II) ion adsorption properties

An emulsion gel adsorbent which was a polymeric hydrogel containing randomly distributed oil microdroplets of an extractant was developed for improved metal adsorption in our previous study. This study focuses on the preparation of monodisperse, millimeter- or sub-millimeter-sized emulsion gel beads, for which a novel production method combining sedimentation polymerization and two-fluid atomization is proposed. The method involves the drop-wise addition of a pre-gel oil-in-water emulsion solution into a silicone oil through a nozzle, with nitrogen gas flow, and the subsequent free-radical polymerization of the pre-gel droplets during their descent. A novel type of emulsion gel bead composed of a poly(ethylene glycol) methyl ether acrylate hydrogel and di-n-hexylsulfide as an extractant was developed. The size of the emulsion gel beads was controlled by adjusting the gas flow rate. The emulsion gel beads successfully adsorbed Pd(II) ions that were used as a model metal.     

Transitional emulsion polymerisation: Zero-one to pseudo-bulk

The transitional behaviours of emulsion polymerisation for styrene and butyl acrylate (BA) monomers from zero-one to pseudo-bulk regime were mechanistically investigated. A dynamic mathematical model, which incorporates cross-over mechanism from zero-one to pseudo-bulk kinetics was developed for emulsion polymerisation and compared with experimental data for conversion, particle size and molar mass. Particles smaller than cross-over size follow zero-one kinetics and particles greater than cross-over size, they follow pseudo-bulk kinetics. In our mechanistic approach, particles nucleated from micelles, grow until the cross-over size is attained, based on zero-one kinetics, and subsequently continue to grow based on pseudo-bulk kinetics. Key findings from our work are that the developed transitional model predictions agree reasonably with experimental data on process and product attributes such as conversion, average molecular weight, molecular weight distribution (MWD), average particle size and particle size distribution (PSD). Optimal strategies for semibatch operation was developed using reaction temperature and monomer feed rate as process variables with specified initial conditions.     

Feedback controllability assessment and control of particle size distribution in emulsion polymerisation

In this article, the importance of particle size distribution (PSD) control as a means for the inferential control of the rheology of emulsion polymers is illustrated. A controllability assessment is presented to illustrate the attainability or otherwise of bimodal PSD using feedback control through a consideration of the process mechanisms—measurement limitations and process constraints that prevent the implementation of feedback corrections. The suitability of a batch-to-batch iterative feedback PSD control is demonstrated, which could act in addition to any in-batch feedback control, the latter being less feasible in certain cases, as argued in this article. A detailed population balance model is used for the batch-to-batch control, which simplifies model update and feedback correction.     

Automatic generation of procedures for the simulation of multistage separators using computer algebra

We successfully extended a computer algebra program (Thermath), orginally developed for the automatic computer implementation of physical property calculations, in order to perform the global phase stability test and to generate code for the steady state simulation of multistage separators. Analytical derivatives of the modeling equations and of the thermodynamic properties were rapidly obtained and automatically implemented in Fortran 77 using Thermath. Even though the final assembly of the code was doen manually, the largest portion of the program corresponds to automatically generated code. A program for the simulation of extraction columns was developed and showed excellent agreement with results available in the literature. The global phase stability program was tested in the identification of liquid-liquid phase transitions, showing results coherent with those from the extraction column program. Quadratic convergence rates in the Newton-Raphson method were obtained with both programs, as should be expected when the functions and their derivatives are correctly implemented.     

AUTOMATIC GENERATION OF PROCEDURES FOR THE SIMULATION OF MULTISTAGE SEPARATORS USING COMPUTER ALGEBRA

We successfully extended a computer algebra program (Thermath), orginally developed for the automatic computer implementation of physical property calculations, in order to perform the global phase stability test and to generate code for the steady state simulation of multistage separators. Analytical derivatives of the modeling equations and of the thermodynamic properties were rapidly obtained and automatically implemented in Fortran 77 using Thermath. Even though the final assembly of the code was doen manually, the largest portion of the program corresponds to automatically generated code. A program for the simulation of extraction columns was developed and showed excellent agreement with results available in the literature. The global phase stability program was tested in the identification of liquid-liquid phase transitions, showing results coherent with those from the extraction column program. Quadratic convergence rates in the Newton-Raphson method were obtained with both programs, as should be expected when the functions and their derivatives are correctly implemented.     

气相石蜡聚合在流化床催化反应器中的数学模型和先进控制

In this study, the developments in modeling gas-phase catalyzed olefin polymerization fluidized-bed reactors （FBR） using Ziegler-Natta catalyst is presented. The modified mathematical model to account for mass and heat transfer between the solid particles and the surrounding gas in the emulsion phase is developed in this work to include site activation reaction. This model developed in the present study is subsequently compared with well-known models, namely, the bubble-growth, well-mixed and the constant bubble size models for porous and non porous catalyst. The results we obtained from the model was very close to the constant bubble size model, well-mixed model and bubble growth model at the beginning of the reaction but its overall behavior changed and is closer to the well-mixed model compared with the bubble growth model and constant bubble size model after half an hour of operation. Neural-network based predictive controller are implemented to control the system and compared with the conventional PID controller, giving acceptable results.     

高频脉冲电场作用下乳状液液滴动力学模型

基于乳状液中液滴在电场中的受力情况的分析,建立了W/O乳状液中液滴振荡固有频率公式,从理论角度分析和解释了高频脉冲电场对W/O乳状液的破乳机理,从力学的角度分析了最佳频率存在的理论基础,并推导出了最佳频率的计算公式。该固有频率与液滴尺寸、界面张力、黏度、温度、密度等有关。为了验证最佳频率公式的可靠性,用正辛烷乳状液进行了室内实验。实验结果表明,理论最佳频率公式的预测结果与实验测得的最佳频率结果吻合,经修正后与白油实验结果也非常接近。     

防冻性聚乙酸乙烯酯乳液胶粘剂的合成

研制了一种改性的聚乙酸乙烯酯 (PVAc)乳液,通过添加适量的BA、MMA和AA单体进行核壳共聚,用保护胶体聚乙烯醇后缩醛化和乳化剂改性相结合的方法,成功地解决了通用聚乙酸乙烯酯乳液的防水性、防冻性及贮存稳定性较差的问题.     

Solution and emulsion polymerization with partially neutralized methacrylic acid

Polymerizations of partially neutralized methacrylic acid (MAA) were performed in both solution and emulsion systems. Polymerizations of MAA in solution were performed at an overall degree of neutralization ranging between 0 and 1. The rate of polymerization of the acid is found to decrease as the degree of neutralization increases due to increased electrostatic repulsion of the dissociated acid species (anions). The degree of neutralization of the unreacted monomer increases as the conversion increases. A kinetic model based on a copolymerization mechanism is used to describe the reaction behavior. Partially neutralized methacrylic acid was also polymerized with styrene in a seeded emulsion system. The reaction rates of both the acid and styrene decrease as the overall degree of neutralization increases. A previously developed emulsion copolymerization kinetic model is extended to account for reaction of the anions and used to investigate the overall “terpolymerization” of the acid, anions, and styrene.     

叔胺型丙烯酸酯共聚物乳液室温可见光交联研究

本研究以甲基丙烯酸甲酯、丙烯酸丁酯、N -羟甲基丙烯酰胺、甲基丙烯酸二甲氨基乙酯为共聚单体进行乳液聚合制备叔胺基丙烯酸酯共聚物乳液 ,然后在该共聚物乳液中加入光敏性乙烯基不饱和单体和可见光下分解的光敏引发剂 ,共混物涂膜于自然光下室温固化交联。考察了光敏引发剂用量、交联单体种类和用量、交联时间对乳胶膜交联程度的影响。结果表明 ,以异丙基硫杂蒽酮为光引发剂 ,分别以甲基丙烯酸缩水甘油酯、三丙二醇二丙烯酸酯及三羟甲基丙烷三丙烯酸酯为交联单体时 ,乳胶膜交联度在 0 5～ 1h内 >70 % ,2h内 >80 %。