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Measurement and control of polymerization reactors
John R. Richards∗ , John P. Congalidis
E. I. du Pont de Nemours and Company, Experimental Station, Wilmington, Delaware 19880, USA Received 9 February 2006; received in revised form 2 May 2006; accepted 16 May 2006 Available online 25 July 2006
Abstract The measurement and control of polymerization reactors is very challenging due to the complexity of the physical mechanisms and polymerization kinetics. In these reactors many important variables, which are related to end-use polymer properties, cannot be measured on-line or can only be measured at low sampling frequencies. Furthermore, end-use polymer properties are related to the entire molecular weight, copolymer composition, sequence length, and branching distributions. This paper surveys the instrumentation technologies, which are of particular interest in polymerization reactors with emphasis on, for example, measurement of viscosity, composition, molecular weight, and particle size. This paper presents a hierarchical approach to the control system design and reviews traditional regulatory techniques as well as advanced control strategies for batch, semibatch, and continuous reactors. These approaches are illustrated by focusing on the control of a commercial multiproduct continuous emulsion polymerization reactor. Finally, the paper captures some of the trends in the polymer industry, which may impact future development in measurement and reactor control. © 2006 Elsevier Ltd. All rights reserved.
Keywords: Process control; Polymerization reactors; Solution copolymerization; Emulsion copolymerization; Mathematical modeling; Reactor control
1. Introduction Consistent polymer properties are of paramount importance to end-user manufacturers who must produce the polymer in its ﬁnal form and shape for the intended application. These properties are the result of complex polymer architecture and composition formed in reaction and perhaps further inﬂuenced in isolation and extrusion processes. Producing consistent, uniform, and in-speciﬁcation polymer for the end-user are the tasks of the polymer process measurement and control systems. Polymer processes, whether batch or continuous, rarely run under exactly speciﬁed conditions; disturbances move the process away from desired trajectories. However, in order to operate such processes safely and in order to set the characteristics of the products optimally, a set of process manipulated variables must be kept constant or systematically modiﬁed over the duration of the reaction or in the course of the various reaction steps. Ray, Soares, and Hutchinson (2004) recently reviewed the main developments of polymer reaction engineering from the early days of polymer science to the current challenges of today.
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The purpose of this contribution is to discuss the various measurement and control techniques of importance to engineers and scientists designing and operating polymer reactors and associated equipment. We have attempted to summarize and update the information already provided in our previous work (Congalidis & Richards, 1998; Richards & Congalidis, 2005; Richards & Schnelle, 1988). The framework for our discussion is the hierarchical approach summarized in Fig. 1, which has proved very useful in the successful application of process control in a complex industrial environment as shown in an earlier review by Richards and Schnelle (1988). It has been our own experience and learning that the same hierarchical approach is particularly important in the control of polymer reactors. Process knowledge, which is usually captured in an experimentally validated mathematical model, is the cornerstone of a successful control strategy. This is particularly true for polymerization reactors, where the in-depth knowledge of process operation in terms of the effect of operating variables on polymer properties can be used to great advantage in the design of the control system and can result in a much more straightforward (and therefore easy to maintain) strategy than would have been possible otherwise. This point will be illustrated in Section 3 and particularly by using the examples referred to in Figs. 2 and 3.
0098-1354/$ – see front matter © 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.compchemeng.2006.05.021
We will concentrate our discussions on the Fig. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 Fig. temperature. 1. and analyzers are the prerequisites for the design of the basic control system to regulate pressure. and on-line scheduling and optimization strategies to compute set points for the regulatory controls. The use of polymerization reactor modeling in conjunction with control design was discussed by the authors in an earlier publication (Congalidis. 1989).e. In many instances advanced control applications have failed in an industrial environment not because the algorithms were necessarily faulty but because the basic regulatory control system performed poorly. In this contribution we have attempted to cover control topics that we believe should be of interest to a wide spectrum of engineers and scientists in the polymer industry.. In other instances the basic regulatory control may have been in place but some of the elements of advanced regulatory control (for example cascade control and ratio control) were not being implemented resulting in degradation of reactor performance in terms of consistent polymer properties.P. Solution copolymerization with recycle loop (Congalidis et al. 2005). The measuring instrument produces a signal. 2. multivariable model based control algorithms. Only when the elements of the regulatory control system are in place and are properly designed and maintained can the control engineer attempt. level. Richards. a process analyzer) was poorly maintained. 2. in most cases a measurement transmitter is operated between the sensor and the measurement device. either because of inadequate design (leading to operation in an openloop mode) or because one of the critical measurements (i. Electrical signals are much more commonly used today than pneumatic signals. & Ray. This requirement is fulﬁlled directly by some measuring methods. transmitters. Process knowledge together with the appropriate sensors. J. We have therefore elected to discuss all elements of the process control hierarchy as they apply to polymer reactor control fully realizing that the lower levels of control would be obvious to the academic community or to experienced industrial practitioners.R. . in increasing order of complexity. however.1448 J. The process control hierarchy (Richards & Congalidis. the implementation of more advanced regulatory control strategies. and ﬂow (PTLF). which must be transformed in such a way that it can be registered by an indicator or recorder and further processed. 1989). Richards. Measurement techniques The measurement technique to be chosen is principally determined by the measured quantity and by the accuracy by which the variable must be measured.
measurement techniques that are more speciﬁc to polymer processes. dilatometry and gravimetry The density of liquids is monitored by displacement and ﬂoat-type densitometers. Rodriguez et a al. Many of these instruments can be connected photometrically or mechanically to produce a usable electrical signal (Lipt´ k. 1999. solution or melt. 2003).. 2004). Richards. 2005.2. It is then reweighed and the percent solids determined. The effects of process and measurement noise can be minimized by signal conditioning or ﬁltering (Richards & Congalidis. radiation. with multiple techniques present even in a single installation. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 1449 Fig.1. and Kiparissides (1999). All of the techniques to follow represent polymer measurement state-of-the-art and are listed here due to either their novelty or their frequent utilization. 2003. & Mellichamp. a 2. The percentage of total solids in a polymer sample can be determined by the gravimetric method through moisture weight loss. Chatzi. hydrometers. Viscosity may be constant (Newtonian). 3.J.. vibration. Lipt´ k. More advanced instruments are oscillating Coriolis.R. Edgar. the viscosity can be related to the molecular weight of the polymer (Kammona et al. During a measurement stochastic errors can be introduced. and ultrasonic densitometers. They form the cornerstone for all control strategies both regulatory and advanced. These measurements are reviewed in Richards and Congalidis (2005) and Lipt´ k (2003). volume changes are monitored by following the change in height of the solution inside a graduated capillary tube. A summary table of on-line hardware sensor classiﬁcation techniques for polymerization reactors can be found in Kammona. 2003). temperature. Viscosity measurement Viscosities are of interest in polymer technology in order to follow the course of a polymerization reaction or to monitor continuously the quality of a product. For polymer systems.P. PTLF measurements Pressure. 2003). Seborg. ﬂow and weight are very important basic measurements for polymer processes. 1998). a Dilatometers measure the volume shrinkage during the course of liquid polymerization reactions and are mainly used for laboratory measurement of monomer conversion. or shear thinning (pseudoplastic) with shear rate. and hydrostatic densitometers. Conversion is monitored with a computer-linked photodetector that tracks the meniscus in the capillary and records the height changes (Rodriguez. In most cases viscosity is measured by capillary viscometers or rotating viscometers. The capillary viscometer may . 2. Then it is put into an oven at high temperature for a time to remove all volatiles. shear thickening (dilatant). level. As monomer is converted to polymer. Densitometry. Emulsion terpolymerization process with recycle loop (Congalidis & Richards. & Archer. Cohen. J. They are based on the principle that polymers are denser than their monomers. 2. Ober. The sample is loaded onto a pan and the weight determined.3.
It is evident that the Melt Index varies inversely proportionally to the polymer molecular weight. 2004. & Asua. Optical analytical devices are also built for measuring radiation in the ultraviolet (UV) and the visible spectral region. Ara´ jo. Rinaldi. particularly used in the rubber industry. Richards. the coaxial cylinder apparatus is the most commonly used in practice. The principle of the GC is that a carrier gas (helium) is passed over a tubular column of a ﬁne solid.. 2.P. It is now being used to provide a means of studying pure rotational and vibrational transitions in molecules. is a variant of the cone-and-plate viscometer.5. The viscosity of the measured ﬂuid is computed from the torque on the driving shaft (Lipt´ k. Many methods depend on the separation of a ﬂuid mixture. A differential refractometer is commonly a used as a concentration detector in the efﬂuent of a gel permeation chromatography (GPC) column for molecular weight determination. Schork. McCord. This technique can be used to measure chain molecular structure. IR and FTIR can be applied to polymer solutions or solid ﬁlms for composition analysis and are particularly useful for copolymer composition determination. the compound absorbs energy at discrete frequencies (Rodriguez et al. These frequency bands correspond to frequencies of vibrations of the bonds in the molecules. 2003). The refractive index (RI) of a mixture is a function of the composition of the mixture and their respective refractive indices (Kammona et al. 2005. Sayer. Near IR spectroscopy has been used to control a polymerization reactor to produce solution polymers with well-deﬁned molecular weight (Othman. a A mass spectrometer source produces ions and information about a sample may be obtained by analyzing the dispersion of ions when they interact with the sample using the mass-to-charge ratio. magnetic and electrical methods can also be used for composition measurement.R. the result of the analysis is only of current interest and too late for control decisions to be made. a 2003) as infrared spectrographic analysis (IR) permits in many cases to follow the appearance or the disappearance of one or more characteristic absorption frequency bands. In order to monitor compositions continuously. and copolymer sequence lengths. Reis. e. 1993. 1999).. Sometimes mass spectrometers are used after a separation step such as gas chromatography or liquid chromatography for fraction identiﬁcation. 2003). Raman scattering of light by molecules may be used to provide chemical composition and molecular structure and is currently being applied to polymers (Elizalde. . & Suau.g. pH measurements). An indirect method to obtain a measure of molecular size that is quick and inexpensive is the Melt Indexer (Rodriguez et al.g. 2004). and occasionally polarographic methods. Lipt´ k.1450 J. 1999.. in many cases. Lima.. 2003). 2003). The Melt Index is deﬁned as the number of grams of polymer extruded in 10 min through a capillary 2. J. Beside the a coaxial device the cone-and-plate viscometer is also used. Among these the process gas chromatography (GC) stands out (Kammona et al. However. Leffew et al. A sample is injected into the carrier gas stream and the gas efﬂuent from the column is run past a detector such as a ﬂame ionization detector.g. an inverted cone faces a solid plate and the apex of the cone just touches the plate. Egraz. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 also be employed in-line for monitoring of molecular weight in polymerizations as described in Vega. Measurement of composition The composition of raw materials. one needs automatically functioning analytical instruments that can continuously obtain the composition of a mixture. The measured liquid is in the free gap. Calibration is based on the fact that all conditions being equal. electrochemical potential methods (e. One must ﬁrst analyze the spectrum of the IR radiation and then measure the corresponding frequencies. Operational measuring instruments are usually differential refractometers or critical angle refractome- ters (Lipt´ k. 2003). The surface tension can give an indication of whether or not micelles are present. 1999.. Optical methods are common (Kammona et al. and samples of the various steps of a reaction is normally measured at the laboratory using the appropriate physical and chemical analytical methods. Stewart. 2003). particularly it may be of interest to measure the surface tension of the emulsion. Nuclear magnetic resonance (NMR) is based on the principle that when a hydrogen containing compound is in a strong magnetic ﬁeld and exposed to radio frequency signals. inducing the molecule to undergo a change (Rodriguez et al. It can also deduce isotactic–atactic ratios and other structure variations as shown for example in Wyzgoski. Mass spectrometry and NMR are currently not in routine on-line process use but can be used to calibrate other on-line methods. and Pinto (2001).. In this device. Raman spectroscopy is dependent on the collision of incident light quanta with the molecule. a given hydrocarbon will require the same length of time to pass through the column to the detector (elution time) (Lipt´ k. purity of boiler feeding water). 2004). which is important in particle nucleation above the critical micelle concentration (CMC) (Schork. the ﬂame ionization detector in gas chromatographs or the photo-ionization of gases with UV light as tracking measuring instrument of hydrocarbons in air). The measurement of the angular velocity of the cup and the angular deﬂection of the bob makes it possible to determine the viscosity (Lipt´ k. Surface tension In emulsion polymerizations.1 mm in diameter and 8 mm in length at a certain temperature and pressure (ASTM D1238). The Mooney a viscometer. but the spectra absorption bands obtained here are usually so broad that these devices are only of limited use. ionization methods (e. ﬁnished products. a 2.4. 2003). which restricts the sample to a disc-shaped cavity (ASTM D1646) (Lipt´ k. Among the different possibilities to measure viscosities in rotating viscometers. Examples of the latter are conductivity measurements (of ionic liquids.. and Marshall (2004). Fevotte. Leiza. 2003). Suitable devices for online control were developed from laboratory gas chromatographs and operate very reliably. sampling and analysis are time consuming and. Peycelon.. 1999). u Apart from optical methods. More recently the Fourier transform infrared technique (FTIR) has been used for faster data acquisition and handling than traditional IR spectrographic analysis. Kammona et al. copolymer composition. & Giudici.
7. for example. from analyzers. a As in the MWD techniques. 2003). and Mz ) during the polymerization process is of importance to ﬁnal polymer quality. (2) The trend towards shorter manufacturing campaigns for the different polymer grades manufactured in the same reactor or towards more frequent on-line product transitions to reduce product inventories and hence working capital. & Morbidelli.P. The chromatograms of these standards give narrow peaks and each standard is associated with the retention volume of the peak maximum. slurry containing the particles is forced through a capillary. Direct column calibration for a given polymer requires the use of narrow MWD samples of that polymer. but the digital controller has now become commonplace due to the widespread use of computers and distributed control systems. This can be used to calibrate the GPC/SEC.2.J. Traditionally gel permeation chromatography (GPC) or size-exclusion chromatography (SEC) have been used to determine MWD (Rodriguez et al.3 have been used as a substitute for molecular weight averages in online control. For online purposes. Advanced regulatory control 3. Acoustic attenuation measurements can be made without the need for sample dilution and can be used in the particle size range of 10 nm–100 m. 2002a. 2003). but many of these techniques still are practiced off-line in the process analytical laboratory. . For this purpose. optical diffraction and scattering. which are devices that are designed to keep a speciﬁc controlled variable constant despite outside disturbances. In GPC/SEC a polymer solution is injected into one or more columns in series packed with porous particles. The two principal light scattering technologies commercially available are light scattering intensity measurement (also known as static or Rayleigh scattering) and dynamic light scattering measurement (also known as quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS)). which is a measure of the attenuation of a beam of light passing through a suspended particle sample. electron imaging. For online control. For each type of polymer an empirical correlation exists between molecular weights and elution volumes. manufacturers are moving more towards online implementation of the more recent methods. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 1451 Deshpande. A calibration curve can be obtained from this arrangement as long as all signals are calibrated (Rodriguez et al.R. The measurement of just the average particle size may not be sufﬁcient. 1999). Molecular weight distribution (MWD) It is widely recognized that a reliable method of monitoring molecular weight distribution. J. 1993). These form the basis to control the process and to keep conditions constant so that the optimal quality results are obtained. 2. has been used traditionally in industry to obtain a measure of average particle size and even the entire PSD (Kammona et al. As sound travels through a slurry or colloid. the presence of different size populations resulting in a multimodal distribution could have a strong inﬂuence on ﬁnal properties and may need to be controlled.1. 2003.. Capillary hydrodynamic fractionation (CHDF) is a hydrodynamic method for measurement of nanometer-sized particles. Mw . penetrate into the pores. and the various molecular weight averages (Mn . electrical resistance changes. 2003). and a differential refractometer that monitors the column efﬂuent. For example. The measurable particle size range for CHDF is about 15 nm–2 m. which include a differential viscometer. There are a number of polymers for which narrow MWD standards are commercially available. 1999).. 1999).6. Some vendors are commercializing more rapid GPC/SEC instruments for online control with some instruments already available. Controllers and actuators Measurement instruments supply information on the current operating conditions of a plant. a Optical (larger than 1 m) and scanning electron microscopy (SEM) techniques literally give the clearest picture of a PSD. In this method. the viscosity measures previously mentioned in Section 2. sedimentation.. The following factors have contributed to the industrial signiﬁcance of polymer reactor control: (1) The need to improve ﬁxed asset productivity by optimizing reactor yield and uptime. and ultrasonic attenuation (Lipt´ k. 3. which allows the evaluation of average molecular weights and molecular weight distributions. The level of attenuation is related to the particle size distribution (Hipp. Kammona et al. and the chains elute in a decreasing order of molecular weights. Polymer reactor control issues The polymerization reactor is usually at the heart of the manufacturing process impacting both downstream processing and ﬁnal customer related polymer properties.2002b). sieving.. A more extensive discussion can be found in Richards and Congalidis (2005). Storti. Richards. controllers are used. a light-scattering instrument. these techniques must be evaluated for speed. More recently triple-detector instruments have been designed. The online method used is usually the bubble pressure method (Schork et al. reliability and sample dead time (Lipt´ k. Turbidimetry. 2. smaller molecules have access to a larger fraction of pores compared to the larger ones. the large majority of controllers were continuous controllers. it is attenuated.. depending on their size. There are several particle size measurement techniques used such as optical imaging.. Dynamic light scattering provides a relatively fast and simple method for submicron particle sizing (Kammona et al. In the past. Therefore. Digital signals are discrete in nature and arise from sampling continuous measurements at equal time intervals or they may arise from naturally discrete signals as. Particle size distribution (PSD) The particle size distribution can have a fundamental effect on the physical properties of dispersions that are common polymer products. 1993). 3. & Leffew. The packing has small pores and during elution the polymer molecules may or may not.
the ﬁnal polymer may not process satisfactorily when delivered to the customer. Doyle. homogeneous versus multiphase) have a direct bearing on the distribution of the ﬁnal polymer properties as shown by Ray (2003). 2003. Parker. 1998. 1988). Heemstra. In our experience several issues speciﬁc to polymer reactors are: (1) Polymerization reactors are known both theoretically and experimentally to exhibit multiple steady states (Adebekun. temperature. In this case the design of an appropriate stabilizing closed loop reactor controller is essential to smooth reactor operation. adaptive control. Ozkan. J. e Embirucu. Soares. Doyle. Ogunnaike. some of which are known in the literature as advanced control. & Pearson. This process. Richards & Schnelle. In the case where multiple steady states are present. (4) Safety and environmental considerations regarding the stable operation of a potentially thermally unstable reaction. Ling & Rivera. Bindlish & Rawlings. Han. Ogunnaike. Ray & Villa. & McFarlane. 1995. 1997. A polymerization reactor often produces several grades (in terms of composition and viscosity) of the same polymer and therefore the control strategy must be easily adapted to a multi-product plant and in some cases to on-line grade transitions. It may be therefore necessary to choose the unstable steady state at intermediate conversion as the reactor operating point. Kwalik. In most cases. it may be necessary to operate the reactor in terms of rather short campaigns in order to minimize ﬁnished product inventory and thus working capital. 1993. Lima. 1981). The special focus in the Embirucu et al. are not always adequate to meet practical considerations speciﬁc to a polymerization reactor. residence time. (2005). These disturbances typically result either from trace amount of polymerization inhibitors left over after monomer puriﬁcation prior to the polymerization reaction or from trace amounts of other compounds which may be present in a typical polymerization recipe and which may be affecting the reaction. Dimitratos et al. which pose additional challenges to the successful application of a control strategy. Harris & Palazo˘ lu. The discussion will be facilitated by focusing on the copolymerization process shown in Fig. & Ogunnaike. progress has been slow. 1989. These techniques have been extensively discussed in literature reviews (Congalidis & Richards. (2) As discussed previously. Doyle. which are designed for speciﬁc applications. Kothare. Lee. 1998. 2003. For example. the composition and molecular weight reactor (3) (4) (5) (6) control speciﬁcations may not be immediately available and are usually determined by lengthy trial and error processes involving product trials at the ﬁnal customer as discussed by Leffew et al. hence its similarity to an industrial problem.P. & Vidal. A good understanding of the polymerization kinetics is essential in designing a robust and effective reactor control strategy. ﬁrst discussed by Congalidis et al. Caralp. and processibility in an injection molding machine may not always be well deﬁned. which not only imposes tough requirements for polymer grade uniformity. ¸ and in books (Schork. 1996. In the case of a multi-product plant. 1993).R. & Ray (1998). on-line measurements of polymer architecture such as composition. 1996. & Hamielec. Furthermore. Pearson. & Chang. 2004. The ﬂowsheet captures many of the elements of actual free radical copolymerization reactor installations. & Georgakis. & Pinto. 1996. & Schork. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 (3) Global competition. For new specialty polymer types.1452 J. (1989). 2000)and in some cases may also exhibit oscillations in terms of monomer conversion and polymer particle diameter (Meira. polymer composition. 2003. ¨ Ogunnaike & Ray. but also requires that for new polymer types the time to commercialization be as short as possible. The . or for safety reasons. Lewin & Bogle. The relationship between reactor operating conditions such as monomer conversion. the reactor control system must be designed in such a way as to achieve fast startups while minimizing off-speciﬁcation polymer formation. Dihora. We will highlight several control engineering techniques. economic. has as of the time of this paper resulted in over 60 citations. polymerization reactors can be highly exothermic and may result in reactor thermal runaway unless an effective control strategy is implemented. many of which are generic in nature.. & Pearson. g 1997. The main motivation stated by ¨ Ozkan et al. Elicabe. Schork et al. the two stable steady states at very low and very high monomer conversion respectively cannot be chosen as the reactor operating point either for practical. The measurement and control techniques discussed in the previous sections. as shown for example in the case of polyethylene reactors by Villa. Dub´ . which impact polymer reactor operation. molecular weight and degree of branching are not always available and for some polymer systems may be simply unavailable. The authors point out that although emulsion polymerization has been studied and used for several decades. (2003) in selecting this process as a benchmark is its complexity. the nature of the kinetics (free radical versus condensation versus living polymerization) and the choice of reactor type (batch versus CSTR. and has been used as a benchmark to test various control and estimation schemes (BenAmor. 1994. & ¸ Georgakis. In these cases. Dimitratos. ¸ nonlinear control. Doyle. Maner. Regnier. 1999. which can be deployed to meet some of the challenging aspects of polymer reactor control. 1997. (1994) reviewed the major issues related to control of emulsion polymerization. and viscosity and the customer related ﬁnal properties such as tensile strength. 1996). Richards. 2001. The control system for a polymerization reactor must be sufﬁciently robust to handle unmeasured disturbances. 1998. 1994. Penlidis. 2. Maner & Doyle. and predictive control. (1996) survey was optimal control theory. Variability in the polymer isolation process and long term polymer structure changes such as “aging” may result in the fact that although in some cases the reactor may be operating “on-aim” within well deﬁned manufacturing speciﬁcations. In many cases the control engineer may have to rely on polymer properties inferred from infrequent laboratory analysis of reactor samples or from laboratory analysis of the ﬁnal polymer after it has experienced signiﬁcant post reactor processing thus introducing large dead times in the control loop. elongation at break. Defaye.
3 is very similar to the solution polymerization process of Fig. (1989) the performance of the feedforward control allows for the perfect compensation of disturbances that can for example arise from a step change in the purge ratio so that the reactor polymer characteristics (e. composition and molecular weight) are unaffected. For example for monomer A ﬂow this balance is: qna3 = qna1 + ya2 qn2 (1) Eq. Feedforward control of the recycle allows the designer to separate the control of the reactor from the rest of the process. solvent. which are widely used in polymer reactor control. The emulsion polymerization process ﬂowsheet of Fig. the monomers and solvent (stream 9) are stored in the recycle hold tank. which are discussed in subsequent sections.J. Fig. perfect control is not possible. is highly nonlinear. However. Two implementations of feedforward control will be discussed. which is particularly important for polymer reactor control. feedback control fails to provide predictive control action to compensate for the effects of known disturbances. J. since control action can only occur if a deviation occurs between the set point and the measured variable.3. if process conditions change. 3.3. These feed streams are combined (stream 1) with the recycle (stream 2) and ﬂow to the reactor (stream 3).g. as well as composition and viscosity feedback control. Its basic premise is to measure the important disturbance variables and then take corrective compensatory action based on a process model. Richards. A coolant ﬂows through the jacket to remove the heat of polymerization. is that the controlled variable cannot always be measured online. the PID controller can be retuned to maintain satisfactory performance. residual initiator. 2. Therefore. As will be discussed in the subsequent sections. Feedforward control The traditional PID feedback controller is very widely used. Furthermore. which acts as a surge capacity to smooth out variations in the recycle ﬂow and composition. and chain transfer agent.1. ratio and cascade control. and chain transfer agent are removed. Furthermore. (1) is then solved for the fresh feed of monomer A since it is desired to keep the target ﬂow of monomer A to the reactor (qna3 ) constant: qna1 = qna3 − ya2 qn2 (2) The recycle composition (ya2 ) is typically measured by online gas chromatographs. Similar feedforward controllers are implemented for monomers B and C. because it utilizes the best of both approaches since feedforward control works by reducing the effects of measured disturbances and feedback control provides the necessary compensation for the effects of model and measurement inaccuracies as well as unmeasured disturbances. the implementation of feedforward control does have the advantage that the reactor is decoupled from the 3. initiator and chain transfer agent ﬂow out of the reactor to the separator (stream 4) where polymer. As shown in Fig. In addition. However.P. Unreacted monomers and solvent (stream 7) then continue on to a purge point (stream 8). with the exception that water replaces the solvent and the reactor operates adiabatically. The feedforward control Eqs. where the techniques of feedforward control.R. and involves multiple sensor issues such as the necessity of online molecular weight and composition measurements or their estimates and dead-time issues such as gas chromatograph delays. solvent. the implementation of various control algorithms using multiple models on this process has proven very relevant in the area of polymerization reactor control. because it requires minimal process knowledge for its design. the powerful combination of feedforward and feedback control will be discussed. 3 represents an actual industrial emulsion terpolymerization process described by Congalidis and Richards (1998). The efﬂuent (stream 2) recycle is then added to the fresh feeds. 3). an inhibitor may enter with the fresh feeds as an impurity. were successfully implemented by the authors. a mathematical model of the process is not required although it can be quite useful for appropriate tuning. which represents venting and other losses and is required to prevent accumulation of inerts in the system. In particular. . A properly tuned PID controller can be quite robust in maintaining good steady state operation in the face of unmeasured disturbances. Naturally. 2. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 1453 characteristics of this reactor that are most relevant and interesting are that it is representative of a wide class of free radical polymer reactors with recycle. The quality of control is directly related to the ﬁdelity and accuracy of the process model. unreacted monomers. is MIMO. perfect feedforward control will typically not be possible unless the recycle composition measurement is instantaneous (or the holdup in the recycle tank is signiﬁcantly larger than that of the reactor) and all other measurements are perfect. exhibits multiple steady states. the problem achieves all this without being overly complex. The presence of the recycle stream introduces disturbances in the reactor feed which perturb the polymer properties. However. monomers A and B are continuously added with initiator. Recycle ﬂow is typically measured and controlled by manipulating the recycle valve to maintain the desired inventory in the hold tank. an Infrared or Raman spectroscopy probe may be used. After the purge. Steady state model feedforward control To illustrate this approach the polymerization process described by Congalidis and Richards (1998) is considered (see Fig. (1) and (2) were obtained by writing component material balances around the recycle addition point. A more serious limitation. Any disturbances in the recycle composition or ﬂow will cause variations in the fresh feed in order to keep the reactor feed constant. which is assumed to be a jacketed well-mixed tank. namely feedforward control design based on steady state models and ratio control. The objective of the feedforward control is to compensate for these disturbances by manipulating the fresh feeds in order to maintain constant feed composition and ﬂow to the reactor. As shown in Ogunnaike and Ray (1994) and Congalidis et al. If a faster response time of the analyzer is required. Feedforward control was developed to counter some of these limitations. Polymer. which may have signiﬁcant time delays.
which multiplies the signal by the desired ratio (typically determined by the polymer chemist) to calculate the set point for the ﬂow controller of monomer B. operators were making adjustments of monomer fresh feed ﬂows based on feedback from laboratory polymer composition measurements resulting in poor performance of the unit.g. online SEC/GPC is not routinely avail- . it is still difﬁcult to have online direct measurements of polymer composition. Fig. ﬂow controllers are designed for each of the reactor feed streams (e. its purpose is to keep the ratio of two process variables at a given value and hence it can be deployed when the objective is to maintain a certain proportion. Polymer properties are very sensitive to temperature excursions and in many cases. so the control design has to incorporate the available off line reactor sample composition measurements obtained at the laboratory typically using Infrared or nuclear magnetic resonance techniques. or stoichiometry. 3. one of the reactor feed streams (monomer A in this case) is chosen as the reference stream. of reactants to the reactor. The measured ﬂow rate of monomer A is then transmitted to the ratio station RC. 2 and 3 where.R. This conventional scheme may do a satisfactory job of regulating reactor temperature but disturbances that occur in the feed line may result in a rather sluggish response of the temperature controller. 4. initiator. this sluggish response of the temperature control loop may not be acceptable. in the absence of feedforward control. recycle stream and thus reduces the control problem to just that of controlling the reactor. 4. In the case shown in Fig. when ratio control is implemented as shown in Fig. 2005). Richards. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 Fig. monomer. However. Cascade control as shown in Fig. 3. we have seen continuous polymerization installations similar to the one shown in Figs. which is dependent on the particular polymer being made. 6 resolves the problem by introducing an additional measurement namely the temperature of the reactor feed and an additional controller. especially in the case of reactors producing specialty polymers with complex polymerization recipes. The concept of cascade control has been used extensively for effective reactor temperature control. 5 and in which only traditional feedback control is used. Ratio control Ratio control is a form of feedforward control. Although the concept is fairly obvious.4. Typically.1. J. measurement of the reactor temperature is used to manipulate the heat exchanger ﬂow to cool the reactor feed so that the reactor adiabatic temperature rise is adequate to remove the heat of polymerization. 5. Similarly. Cascade control Cascade control is also widely used in the chemical process industries and especially in cases where there may be nonlinear behavior in the dynamics of the control loop.P. Conventional temperature control of an adiabatic polymerizer (Richards & Congalidis. 4.3. Advanced supervisory control 4. in our experience we have seen that it has not been as extensively used in polymer reactor control. cascade control introduces an additional measurement and an additional feedback controller. In many instances polymerization reactors are operated adiabatically. Typically. Unlike feedforward control. The secondary measurement is typically located so that it recognizes the upset conditions sooner than the controlled variable. which requires that disturbances be explicitly measured and a model be available to calculate controller output. Ratio control of monomer feeds (Richards & Congalidis. 2005). chain transfer agent) and each one of these controllers has a set point. Feedforward-feedback control The combination of feedforward and feedback control provides a very powerful practical strategy for the control of polymer properties such as composition and molecular weight. despite advances in size exclusion chromatography/gel permeation chromatography technology (SEC/GPC). As is evident from its name. In our experience.1454 J.2. It also addresses the main drawback of conventional feedback control namely the fact that control action only occurs where the controlled variable deviates from the set point. which is widely used in the chemical industry and has proven very useful in reactor control.
Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 1455 able for most industrial polymer reactor control applications. (2004)) to determine the best pairings of controlled and manipulated variables for robust multi loop control. . Khare. and the polymer composition provided by laboratory analysis of reactor samples. As discussed in Congalidis et al. Adaptive control strategies were discussed by Tyner. that the reactor temperature control is crucial because inherent viscosity is extremely sensitive to temperature variations.J. is illustrated in Fig. a nonlinear input-output linearizing geometric approach was then applied to control the polymer molecular weight by manipulating the inlet ﬂow rate of the monomer. It consists of creating an approximate linear multivariable model from the nonlinear polymer reactor model using step test data and then using the techniques of relative gain array (RGA) and singular value decomposition analysis (SVD) (as described for example in Seborg et al. The feedforward controller can be easily extended to many monomers by specifying the total Fig. provide the capability of continuous measurement of melt index and viscosity during polymer production using on-line or at-line instrumentation. 2004) or model based control can be effectively used as shown for example by Chylla and Haase (1993) for an industrial reactor and by Defaye. for the polymerization reactor shown in Fig. An additional difﬁculty in the control of polymer properties is that in some cases the control problem is multivariable in the sense that there are interactions between the molecular weight and composition loops and therefore when a manipulated variable is chosen to control molecular weight it may affect composition. (1989) there exists a much more formal approach for feedback control system design. Another example of model based control is given by Othman et al. Typically. and Vidal (1993) for a laboratory scale one. It is very important to use process understanding (typically captured in dynamic simulations using experimentally validated models) in the design of the control system for polymer composition and molecular weight.R. which maintains total monomer feed rate and monomer A feed composition at the appropriate set points for the speciﬁc polymer grade being produced. (2004) where a model for the monitoring of both the average polymer molecular weight and the concentration of monomer in the reactor was developed with the partial least-squares calibration technique applied to NIR spectra. 1.P. It is important to use process knowledge to validate the selection of manipulated variables. The measurements used are the ﬂows of the fresh monomer feeds. the recycle ﬂow. because physical properties of the reactor contents vary from run to run and within a run and the standard PID controllers used in a cascade design may not be able to perform satisfactorily over the entire range of operation required. Soroush. and Chen (2003).. 3 and follow the discussion in Congalidis and Richards (1998) as well as the concept of the process control hierarchy shown in Fig. We may return to the polymerization process shown in Fig. which has been successfully implemented for the reactor shown in Fig. 6. 3 process simulations showed that one way to decouple polymer quality control is to take advantage of the fact that polymer composition is naturally very sensitive to changes in reactor feed composition but inherent viscosity is relatively insensitive to reactor feed composition changes. in many cases the control engineer has to rely on offline measurements of molecular weight and incorporate them in the control strategy. Chabanon. the latter being very common in polyoleﬁn production. as reported in the vendor literature. On the basis of a process model. Richards. measures of molecular weight used in control applications are the inherent viscosity and/or the melt index. Recent advances in capillary rheometry. Bremner. Regnier. 2005). the monomer composition of the recycle feed and the total monomer reactor feed provided by two on-line gas chromatographs. Therefore. A typical control strategy for polymer composition. adaptive cascade control strategies can provide better temperature control performance without the need for retuning versus a traditional PI cascade control system. which is however typical of a wide class of continuous polymer reactors in practice. and Grady (1999) for jacketed stirred tank reactors in which multiple products are produced and the overall heat-transfer coefﬁcient is unknown and can vary signiﬁcantly as a result of fouling. At-line instrumentation refers to a manual measurement of a sample at the process line by using for example a portable instrument as contrasted with automatic on-line sampling and off-line measurement at the laboratory. J. previously discussed. The supervisory control consists of three levels implemented in a cascade fashion: (1) Feedforward controller. It is also very important to establish appropriate set points and speciﬁcations for the inherent viscosity and melt index by relating them to the underlying molecular weight distribution as shown for example in Seavey. For example. Achieving good reactor temperature control can become particularly challenging in multi product semibatch polymerization reactors. In these cases more advanced temperature control strategies based on adaptive control (Seborg et al. 3. Cascade temperature control of an adiabatic polymerizer (Richards & Congalidis. Moreover. Liu. Polymerization reaction modeling showed for this speciﬁc case. Caralp. As discussed in the preceding section cascade control can be effectively deployed to control reactor temperature within very tight speciﬁcation limits. 7.
1). Copolymer composition control strategy. extensive data and controller output checks have been incorporated in the practical implementation to provide robust performance. J. is minimized. Usually. to calculate ﬂow correction factors for the monomers from the gas chromatograph measurement of the actual monomer feed composition. An inherent viscosity feedback controller adjusts automatically the set point of the monomer to transfer agent ratio controller based on the measured viscosity value and provides the necessary integral action so that the difference between the reactor inherent viscosity and the polymer grade inherent viscosity speciﬁcation is minimized. Richards. in practice extensive data validation checks must be incorporated so that robust performance can be assured even when the gas chromatograph or laboratory analysis measurements may be unavailable or faulty. 4. monomer reactor feed rate and the feed composition for the monomers. 7. The choice of sampling frequency balances the requirements for good quality control versus the need to minimize analytical costs. (2) Gas chromatograph feedback controller.R. The control of inherent viscosity shown in Fig. (3) Polymer composition feedback controller. because the interval of time between measurements is usually sufﬁcient for the effect of an adjustment to a process variable set point to be complete within this interval of time.2. which uses the velocity algorithm for digital PID control. Depending on the polymer grade being manufactured the initiator or the chain transfer agent may be used to control emulsion viscosity.1456 J. This controller provides the necessary integral action so that the offset between the actual reactor monomer feed composition and its set point.P. State estimation techniques In the design of the composition and viscosity feedback controllers it is very important to establish whether the polymer reactor dynamics need to be taken explicitly into account. Furthermore. integral control is appropriate. when the reactor residence time is much shorter than the sampling frequency. 8 uses the same approach as the composition control. In other cases the sampling dead time introduced by the periodic . which updates the set points for the reactor monomer feed composition based on the laboratory analysis of a reactor sample. which may be caused by ﬂowmeter inaccuracies or other unmeasured disturbances. It is important to note that these feedforward and feedback controllers have been designed hierarchically in the sense that each level in the structure will not activate unless the levels below it are functioning properly (as in Fig. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 Fig. As in the case of composition control. This controller thus provides the necessary integral action so that the offset between the measured composition of the reactor sample and the polymer grade composition is minimized.
As reported in a recent survey (Qin & Badgwell.R. Othman. BenAmor et al. Park. 4. Fevotte. Inherent viscosity control strategy. Hur. It should be pointed out that the choice of techniques for online estimation of polymer properties is still an active area of research and is very much dependent on the speciﬁcs of the polymer chemistry and available online and ofﬂine instrumentation. 1991. and molecular weight may necessitate the incorporation of on-line state estimators of polymer properties.P. polymer composition. 1999. (2004) estimated the reaction rate and molecular weight using a NIR in-line measurement of the monomer concentration. A receding horizon estimation scheme and. 1989) was used. inferential control. the process model (Congalidis et al. analysis of polymer concentration. and adaptive control that have been developed by the academic process control community for these tough multivariable control problems. 2003). Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 1457 Fig. McAuley & MacGregor.J. mainly in oil reﬁneries and petrochemical plants. Othman et al. Kammona et al. For example. Reaction calorimetry aims to measure heat released from a polymerization in order to infer monomer conversion and polymerization rate (as reviewed for example in Kammona et al. Linear MPC algorithms are rapidly becoming imbedded in the Distributed Control System software libraries. 8.. Taylor. and transport data. (2004) applied an industrial real-time optimization package for the nonlinear model predictive control (NLMPC) of a simu- lated polymer grade transition. 2004. polymerization heat generation. a Luenberger observer were designed to reconstruct unmeasured states. Careful measurement and balancing of mass and energy ﬂows are necessary for success of this technique. From the advanced process control techniques such as internal model control (IMC). the commercial Mettler-Toledo RC1 jacketed reactor acts as a calorimeter supplying mass balance. 2002).. and Hammouri (2000)). (1999). In another example. . In the study by Bindlish and Rawlings (2003). which facilitates their use. On-line estimation may also be accomplished using ﬁrst principles polymerization kinetic models implemented online in the form of an extended Kalman ﬁlter (EKF) as illustrated for example in (Ellis. & Jensen. Moritz (1989) and McKenna. separately. Santos. by the end of 1999 there were at least 4500 industrial MPC applications worldwide. Model predictive control (MPC) The previously discussed single loop and appropriately chosen multi loop feedforward and PID feedback control strategies may not be adequate for the effective control of polymer properties particularly in the case when the polymerization reactor exhibits strongly nonlinear dynamic behavior or when there are strong interactions between the controlled variables or when there are constraints on the manipulated variables. where the process model (Congalidis et al. J.. 1989) was again used to develop an extended Kalman ﬁlter for state estimation. Richards.3. 1994. Othman et al.. model predictive control has reached the stage where it is having a signiﬁcant impact on industrial practice. & Rhee. For example.
output. ¨ Ozkan et al. (2004). Material used by permission of John Wiley & Sons. production rate. 1989) demonstrated the ability of the algorithm to rapidly transition the process between different operating points. namely set point calculations and control calculations. The NLMPC algorithm was formulated by using orthogonal collocation to integrate the model equations and sequential quadratic programming to solve the resulting nonlinear programming problem. which resulted in a reduction of off-speciﬁcation product produced during the grade transition. 2004). several academic researchers as for example in Maner and Doyle (1997). However. academic researchers have been prominent in the application of nonlinear MPC in polymer reactors. Inc. BenAmor et al. The set points for the control calculations are typically calculated from an economic optimization of the process based on a steady state process. The residuals (i. It was observed that the transition period decreased as the number of linear models increased. The structure of MPC is shown in the block diagram Fig...1458 J. 2004). (2003) the authors studied the control of the solution copolymerization reactor proposed by Congalidis et al. inequality constraints arise as a result of physical limitations on plant equipment such as pumps. control valves. MPC block diagram (Seborg et al. (2004) described the application of an industrial real-time optimization package to the nonlinear model predictive control of a simulated polymer grade transition. (1989) was used to develop a target linearization and model predictive controller . 9 (Seborg et al. Cozewith. they were not able to get a signiﬁcantly better performance than that obtained from a multiloop PI control strategy. The control algorithm was a receding horizon scheme with an objective function. 2 and discussed in Congalidis et al. One of the earlier implementations of MPC is linear dynamic matrix control (DMC). For example. One of the difﬁculties for the widespread use of MPC control in polymer reactors could be that the embedded MPC modules inside the major DCS packages are variants of the linear MPC algorithm. and catalyst activity. ¨ As an additional example in the paper by Ozkan et al. As an example. Typical optimization objectives can include maximizing a process function. minimization of off grade product during grade transitions and regulation around a set point. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 Fig. Deshpande. These controllers were used successfully for plant startup. However. The objective of the control calculations in the control block is to determine a sequence of control moves (changes in the manipulated variables) so that the predicted response moves to the set point in an optimal manner for example by following a reference trajectory. The model is usually implemented in the form of a multivariable linear or nonlinear difference equation. A multivariable nonlinear MPC scheme was implemented and performance improvement was observed compared to a multiloop PI control strategy and a multivariable linear MPC structure. Silverman. (1989) using an MPC algorithm based on multiple piecewise linear models. or maximizing a production rate. which has ﬁnite and inﬁnite horizon cost components and uses multiple linear models in its predictions. As expected. They then proposed to close the dominant loop with a PI controller and identiﬁed Autoregressive plus Volterra models for the other loops. The calculated control actions are implemented as set points to regulatory control loops. Although MPC control has become an established technology for tough control problems in petrochemical plants its application in polymer reactor control is currently transitioning from purely academic studies using simulated examples to applications in industrial reactors.P. In practice. and disturbance variables. It is typically developed from data collected during special plant tests consisting of changing an input variable or a disturbance variable from one value to another using a series of step changes with different durations or more advanced protocols such as the pseudorandom-binary sequence described in Seborg et al.e. A mathematical model of the process is used to predict the current values of the output (controlled) variables. A simulation study was carried out by Meziou. Furthermore. J. For a detailed explanation of the different design choices that are necessary for the effective implementation of design of the MPC controller the reader is referred to Seborg et al. (2003). It is also essential to point out that the quality of MPC is very strongly dependent on the availability of a reasonably accurate process model that can capture the interactions between input. A unique feature of MPC is that inequality constraints can be incorporated in both the set point and control calculations.. in the study by Bindlish and Rawlings (2003). Richards. and Bindlish and Rawlings (2003) have designed and implemented nonlinear MPC controllers. (1989). Maner and Doyle (1997) implemented linear MPC using the same transfer functions as were identiﬁed by step tests by Congalidis et al. the difference between the predicted and actual output variables) serve as a feedback signal to the prediction block and are used in two types of control calculations that are performed at each sampling instant. and heat exchangers.R. (2004) and Ogunnaike and Ray (1994). Closed-loop simulation results conﬁrmed the potential of the multivariable DMC technique to reduce off-speciﬁcations during changes in EPDM product quality setpoints. referring to the polymerization process previously described in Fig. and Morrison (1996) to assess the performance of DMC for an ethylene-propylenediene polymerization reactor. 9. Simulation results on the model (Congalidis et al. minimizing a cost function. the most signiﬁcant beneﬁts from MPC for polymer reactors would be derived from applying nonlinear MPC due to severe process nonlinearities exhibited for example during product transitions. the process model proposed by Congalidis et al. For example. (1989).
In this case the monomer feed rate is automatically adjusted to maintain a constant rate of reaction as inferred for example by reactor pressure. This is typically accomplished by solving off line an optimization problem using a kinetic model of the process as shown for example in Maschio. In this application. 4. and then used to get the correct linearized model. Fontaine. A nong g linear control design strategy was proposed based on functional expansion (FEx) models. J. Typically. Bello. product grade transitions. The authors claim that the resulting TLMPC controller does not have the computational burdens associated with a full nonlinear model predictive controller (NMPC) but shows a performance similar to a NMPC. The TLMPC shows optimal plant startup.4. (2005) recently demonstrated a different approach to maintain polymer compositional uniformity in a pilot scale semibatch reactor used to produce specialty copolymers containing up to four monomers for electronic applications. namely variability within a batch and/or variability from batch to batch. However. Therefore. where the growth time of an individual chain is approximately the batch time. 1993). maximize productivity. batch and semibatch. They may vary in size from a ﬁve-gallon pilot unit to a 30. which are always operated dynamically. Process control of batch reactors must address the main disadvantage of batch reactors versus continuous ones. polymer chains formed early in the reaction may contain a higher fraction of the more reactive monomer than the chains formed later in the reaction (i. Now we will discuss an even more common class of reactors. The linearized model is utilized to calculate the actual control moves for dynamic regulation and develop an extended Kalman ﬁlter for state estimation. 1993). minimize settling time after rate changes or process upsets. Richards. and Asua (1997). The main advantage of batch reactors is the ﬂexi- bility to accommodate multiple products. and Gomatam (2003) have focused on the transition control requirements.P. internal model control (IMC). 1989). Arzamendi & Asua. unless special control strategies are deployed.g. was tested on the Congalidis et al.000 gallon (or greater) production size (Schork. a cost penalty may occur because of unacceptably long batch times for slow reactions. Recent reported industrial application of MPC in polymer reactors as for example by Seki et al. Depending on the speciﬁc process. since all chains will see the same changing environment (Schork. compensate for signiﬁcant multivariable interactions and unusual process dynamics).g. polyamides and polyesters). Armitage. the effects of the changing reaction environment and hence within batch inhomogeneities are much less of an issue. a Raman spectrometer was used on line to . Removal of the heat of polymerization is accomplished by circulating coolant through a jacket or by reﬂuxing monomer and solvent. Operation and variability Batch reactors are the most common reactor used in polymerization engineering. one way to address the issue of compositional drift in free radical batch copolymerization is to operate the reactor under the so-called starved feed policy (e. Doyle. They are well suited for low-volume products and for products for which there are numerous grades (as in specialty polymers). A review of the application of linear MPC tools to a prototype continuous polymerization (CP) process was given by Schnelle and Rollins (1998) where the authors discuss in general why the MPC technology may be a good ﬁt for CP control problems (e.4. Richards. 4. compositional drift).1. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 1459 (TLMPC) that separates the target calculations from dynamic regulation. which often translates into aggressive manipulated variable moves often against manipulated variable limits or plant constraints. Grady.R. Operation in semibatch reactor mode is very common in polymer reaction engineering practice. IMC was also used by Mahadevan.e. (1989) problem by Harris and Palazo˘ lu (1998) and Harris and Palazo˘ lu (2003). and/or reactor temperature to achieve desired polymer properties in minimum time. Leiza. This is especially signiﬁcant for composition control in a free radical batch copolymerization reactor where. Saenz de Buruaga. Soroush.J. (2001) and Bartusiak. The proposed controller targets are calculated from the nonlinear model. As pointed out by Takeda and Ray (1999).g. and Scali (1992. it is also possible to implement more sophisticated control strategies during the batch by establishing operating trajectories for initiator addition. and Congalidis (2001). On the contrary. and regulation around a set point for the polymerization process in comparison to a ﬁxed linear model predictive controller (LMPC). and Tyner. and Allcock (2002) on the problem of scheduling grade transitions in an isothermal methyl methacrylate polymerization reactor. Thomas and Kiparissides (1984). reported beneﬁts have also been achieved in product consistency or increased production rate. A related control technique. Batch and semibatch control Previous sections focused on continuous reactor control. where the time of formation of a single chain is only a very small fraction of the batch time and therefore inhomogeneity results from the fact that polymer chains can be formed under very different conditions during the course of the batch. in step growth polymerization (e. Schwanke. MPC is well suited to the grade transition problem. These essentially open loop trajectories constitute a form of feedforward control and are then implemented as part of the batch sequential logic and recipe management system using ladder logic and binary logic diagrams as shown in Seborg et al. because each batch can be made according to its own recipe and operating conditions without the costs incurred when a continuous reactor is shut down and restarted. Leffew et al. The controller was formulated as a linear controller with a series of correction terms to account for nonlinearities in the system. monomer addition.. This variability is particularly important in batch free radical polymerization. which typically consist in completing the transition in either a minimum amount of time or with minimum amount off-speciﬁcation product. They found that TLMPC performs better than a ﬁxed linear model predictive controller for different operating conditions. 1994). In this starved feed operation the reaction environment is maintained constant during the batch and therefore the monomer composition in the reactor feed is equal to the desired polymer composition. or tailor the polymer molecular weight distribution. (2004).
Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 measure the monomer composition in the reactor. & MacGregor. Although the use of tendency models in polymer reactors. This approach was also described by Peterson. It may be therefore possible to detect a potential bad batch before the run is over and take corrective action during the batch in order to bring it on aim. (1986). Nomikos. The authors claim that the proposed MDE algorithm offers faster speed. During start-up or grade-change operation of the reactor described by Congalidis et al. Richards. Statistical process control In many cases of batch and semi batch polymerization control there are no online measurements of polymer quality (e. Nomikos & MacGregor. control moves during the batch can be calculated by solving a nonlinear dynamic optimization problem within the context of the previously discussed model predictive control to account for the wide variety of constraints typically encountered in batch systems. and higher robustness to ﬁnd the global optimum than differential evolution algorithms.P. increasing the transition time required to reach the desired steady state from the initial state. For example. and Schork (1992) and applied recently by Wassick. since the polymer quality variable (for example the Mooney viscosity in elastomers manufacture) can be plotted for each successive batch on a Shewhart (x-bar) chart with the upper and lower control limits placed at three standard deviations above and below the target. no control action is taken to prevent manipulations of the batch process based on stochastic variations within it. increases the amount of off-speciﬁcation polymer product. which approximates the stoichiometric and kinetic models of a process using available plant data along with fundamental knowledge of the process characteristics. has been limited. Kourti.R. energy balance estimation. Fotopoulos et al. Very often in DCS operated batch polymer reactors the primary process variables such as pressure. An alternate technique to the purely statistical estimation and control methodologies has been used by Fotopoulos. Coffey. The philosophy of statistical process control can be very useful in this case. In addition.4. 2003. (2004). consists in the development of a low order nonlinear dynamic model. Arkun. (1998) explored the effect of process-model mismatch associated with tendency models on the state estimation of a batch processes consisting of eight individual reaction steps and showed how these models could be used in an extended Kalman ﬁlter and to tune the model covariance matrix. 4. J. this model can be as simple as a steady state (constant) gain relationship or a nonlinear model that includes the effects of different initial conditions and the batch time. Wang. 1995).g. or online gel permeation chromatography) it can be incorporated as part of a feedback adaptive predictive control strategy. polymer composition and molecular weight) during the batch and these measures of end use properties are only available at the end of the batch. In this case. and Callihan (2003) to a set of commercial polymerization reactors exhibiting challenging dynamic behavior that prevented conventional control from delivering optimum manufacturing performance. (1989) problem. they proposed a modiﬁed differential evolution (MDE) algorithm for the Congalidis et al. Pla. 1999). This technique known as “tendency modeling”. The minimal information needed to carry out this type of batch-to-batch control is a static model relating the manipulated variable to the quality variables at the end of the batch. The tendency model is evolutionary since it is updated as new process data become available. originally proposed by Filippi et al. As pointed out in Seborg et al. This closed loop policy resulted in better polymer compositional uniformity versus a simpler open loop starved feed approach. . it is possible to use advanced statistical techniques such as multi-way principal component analysis (PCA) and multiway partial least squares (PLS) along with an historical database of past successful batches to construct an empirical model of the batch (Clarke-Pringle & MacGregor. In this case recipe modiﬁcations from one run to the next are common. which was then used by an advanced feedback controller to manipulate monomer feeds and maintain the monomer reactor composition within tight limits. Lee et al. This empirical model is used to monitor the evolution of future batch runs. (1989). while bringing the reaction to a speciﬁed monomer conversion in minimum time by manipulating initiator feed rate and coolant jacket temperature. Improved polymer compositional uniformity resulted in substantially improved performance of the polymers in the end-use application. ﬂexible implementation. In a subsequent paper (Lee et al. Subsequent future unusual events can be detected during the course of the batch by referencing the measured process behavior against this “incontrol” model and its statistical properties. which is frequently encountered in the batch manufacture of specialty polymers. If the quality variable for the batch is within the control limits. If monomer conversion and molecular weight information is available during the batch (for example through online densitometry. level and ﬂow are recorded during the batch as well as the quality variables at the end of the batch. in the work of Houston and Schork (1987). Flores-Cerrillo & MacGregor. temperature. where the number of individual reactions is much higher.1460 J. (1997) calculated the minimum transition time and subsequently determined optimal control input trajectories using genetic algorithms combined with heuristic constraints. However. and Corriou (1995) constructed a tendency model and used it as an open loop predictor of product quality (molecular weight and polydispersity) for the control of a batch styrene polymerization reactor. Stenger. and Georgakis (1998) for the modeling and optimization of batch reactor processes when a detailed understanding based on a fundamental principles and detailed kinetic studies are not available.2. The proposed methodology was shown to have better performance than iterative dynamic programming (IDP) or sequential quadratic programming (SQP) in terms of accuracy and efﬁciency. it may be very difﬁcult to obtain a kinetic model of the polymerization process due to the complexity of the reaction mechanism. Hernandez. 1995.. if a fundamental model of the process is available including reaction kinetics and an energy balance. the objective was to maintain the molecular weight at a desired value. 1998. The likelihood of a point outside the control limits means that the batch is out-of-control and the batch recipe and possibly the sequence logic must be adjusted for the next batch.
It is almost a given that deployment of more accurate robust measurements will increase the performance of the control system. (2) The development of process models appropriate for control design is challenging. 1988) who concluded that there is a gap between industry and research practices. Part of the challenge. (4) Trends in the polymer industry. At the same time it is a challenge to develop sophisticated algorithms in a way that their implementation and maintenance would be relatively transparent to a process control engineer familiar only with the basics of regulatory control. Corripio. so that the controllability of the polymer reactor can be established before it is actually constructed and costly process control problems after startup can be avoided. Zhuang. For example Li. 2005) will ı become increasingly important in practice. Fruitful areas of research would include the combination of validated mathematical models with existing on-line sensors to obtain a continuous estimation of the PSD and to detect particle nucleation. Embirucu et al. it is expected that the on-line control not only of average polymer properties but also of polymer distributions such as the particle size distribution and the branching distribution will become important. because of the complexity of the polymerization kinetics and the reaction environment which may be homogeneous or heterogeneous or characterized by zones of poor mixing. Mueller. (3) Some of the newer multivariable control techniques such as linear MPC as illustrated by Schnelle and Rollins (1998) or ¨ nonlinear MPC as illustrated by Ozkan et al. to use supercritical carbon dioxide as the reaction medium as recently reviewed in Kemmere and Meyer (2005)) or as new specialty polymers are designed for speciﬁc end-use applications where time to market is of essence. 1996. and Kurtz (2004) have recently proposed a hierarchical extended Kalman ﬁlter (EKF) to estimate unreacted state variables and key kinetic parameters in a ﬁrst principles model of a continuous ethylene-propylene-diene polymer reactor and used simulation tests to show that the hierarchical EKF generates satisfactory estimates even in the presence of measurement noise and plant/model mismatch. It may not always be obvious what is the appropriate level of model complexity or how best to identify model parameters or how to integrate available measurements in these models in order to estimate unmeasured states related to ﬁnal product properties. (6) Furthermore. This is an area where the major DCS vendors have a signiﬁcant role to play in the development of hardware/software solutions. (1996) found ¸ that actual implementation of advanced control theory in the polymerization area requires the improvement of measurement and state estimation techniques. such as capillary hydrodynamic fractionation. Richards & Schnelle. Richards. which therefore become motivators for new research are: (1) Whereas off line or on line measurements of polymer architecture such as composition. Litvinenko. and Dong (1995b). molecular weight and degree of branching are available for commodity polymers. include the increasing emphasis by customers on receiving a uniform product with desired property speciﬁcations from their polymer suppliers. production scheduling. they are not always available for specialized polymers. We agree with the authors of previous reviews (Embirucu et ¸ al. and Litvinenko (1995a). which reinforce the importance of measurement and reactor process control. Henson.P. usually require taking samples and the analysis time is still too long for control. Harrison. The formulation and practical implementation of a control strategy is also an important area of research for some of the newer polymer processes such as the manufacture of polymers with tailor-made properties using novel metallocene catalysts or living radical polymerizations systems by means of radical addition and fragmentation transfer (RAFT) agents or degenerative chain transfer agents as described in Matyjaszewski and Davis (2002). on-line sensors used to measure the PSD. It is certain that the instrumentation and control methodologies that will be needed to be deployed to meet the evolving needs of polymer producers are a challenging and vibrant area . Yan. and Crowley (2003) as well as Edouard. and Hammouri (2005). In our assessment the reasons for this lag. Zhuang. the increasing computing power provided by DCS manufacturers and the availability of powerful supervisory computers interfaced with the DCS can make the implementation of model based control and especially nonlinear MPC much easier and faster. It is encouraging that the level of process control education of the engineers working in the polymer industries has been steadily increasing thus facilitating the technology transfer from academia. (2003) require specialized knowledge in the ﬁeld that may not always be available. which are increasingly becoming important in high value applications such as electronics. and Mueller. and at the same time the opportunity.R. In addition. & Sald´var-Guerra.J.. Congalidis / Computers and Chemical Engineering 30 (2006) 1447–1463 1461 5. As polymer reactors are tasked to produce several grades of a polymer recipe management. Future trends In discussing future trends it may be useful to reﬂect why the plethora of advanced process control techniques developed by academic researchers is not as widely practiced in polymer reactor control as in other parts of the chemical process industries for example distillation or more broadly petrochemical reﬁnery control. Yan. Biegler. (5) As new polymer reactors are designed (e. Sheibat-Othman.g.. it would be beneﬁcial to incorporate process control considerations in the process design phase. J. As shown in recent work by Doyle. This is a powerful economic incentive for reactor control especially when it is coupled with the need to operate the unit safely without in-line rework of material and with the objective to minimize yield losses during product transitions. and production optimization (Flores-Tlacuahuac. would be that some of these process modeling and control solutions tend to be polymer platform speciﬁc and must be validated in a laboratory or at least a pilot plant before their deployment in a large scale plant.
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