Computers &em. Engng, Vol. 17, No. 3, pp. 257-244. 1993 Printed in Great Britain.

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TEMPERATURE CONTROL POLYMERIZATION

R. W..
CHYLLA

OF SEMIBATCH REACTORS
U.S.A.
16 June 1992)

and D. RANDALL W

S. C. Johnson and Son, Inc., 1525 Howe St, M. S. 305, Racine, WI 53403-5011,
(Received 3 October 1991;fiMI revison received II May 1992; received for publication

Abstract-An industrial case study appropriate for process control studies is presented. The control problem focuses on the temperature control of a multiproduct semibatch polymerization reactor. Achieving good temperature control in these reactors is often difficult he=xuse physical properties of the contents, such as mass, heat capacity and heat transfer coefticient vary from run to run and within a run. Standard PID controllers are unable to perform satisfactorily over the entire range of operation required. Physical data and modeling equations are provided so that process control -chers may test various control strategies. This control problem is representative of those found in the speciality chemical

processingindustry.

INTRODUCTION The purpose of this article is to provide a realistic open-end control problem which researchers in the process control community can use to test the product of their research. This control problem wncems the temperature control of a reactor used to make specialty emulsion polymers. Data supplied for the reactor system describe a pilot plant reactor in the process development area. The dynamics of this are known to be consistent with the manufacturing-scale reactor system. Data for the pilot plant reactor is supplied for two reasons:

Gattu and Zamou (1991) describe the application of a nonlinear QDMC with state estimation to a reactor system based on an earlier version of this manuscript (Chylla and Haase, 1990) which was based on simpler kinetics and first-order plus deadtime transfer function descriptions of the reactor jacket dynamics.
PROCESS DESCRIPTION

1. Manufacturing equipment capacity is considered proprietary information. 2. All new control strategies are first tested in the pilot plant. This reactor control configuration is quite simple compared to many plant-wide or distributed parameter control problems. However, the many complications, nonlinearities and constraints that exist transform the control problem into quite a challenging one. The problem becomes difficult to formulate succinctly and does not lend itself to mathematical formalism. Data and equations are provided for process hardware, reaction kinetics, heat transfer and reaction viscosity. Several researchers have addressed control problems in reactor systems of this type. Juba and Hamer (1986) provide an excellent overview on the challenges in batch reactor control and suggest several control strategies. Davidson (1987) proposes a control algorithm which combines knowledge of the process with the logic used by a skilled operator and compares the results with standard PI controllers.
257

A stirred tank reactor is used to make specialty emulsion polymers in semi-batch processes. As is typical in the specialty chemicals industry, the same reactor equipment is used to produce a wide variety of products. Each product is characterized by unique polymer chemistry, reaction kinetics, product viscosity, reactor temperatures, feedrates, addition times, etc. Most processes consist of the following steps. An initial charge of prepolymer, surfactants and water is made to the reactor. After this initial charge reaches reaction temperature, a monomer mix is added to the reactor at a designated feedrate for a specified feed time. This addition period is often followed by a specified hold period. For some products, a secondary feed period may follow. The transient nature of these processes results in reactor heat loads that change continuously with time as depicted in Fig. 1 below. The reaction temperature determines the chemical composition and particle size distribution of the emulsion polymer_ Precise control of the reaction temperature is required throughout the batch to produce an acceptable product. Reaction temperature is controlled by manipulating the temperature of water which is mcirculated through the jacket of the reactor. A control scheme is required to manipulate

258

R. W. CHYLLA

andD. RMGDALL

HAAS

process data for Product A and Product B in Tables 3 and 4.

CONTROL CONFIGURATION

Time
Fig. 1. Reactor heat load vs batch time.

the jacket temperature in the face of the continuously changing reactor heat load. During typical reactor operation, four or five batches of a particular product would be made in succession. Afterwards, the reactor would be cleaned before changing to a new product. In this case study, data are provided for two products and processes that are representative of the large variety of products made. For this problem, complete data are given on the reactor and control system and product and

The control configuration is summarized in Fig. 2. The reactor temperature is maintained at its desired value by adjusting the temperature setpoint for water recirculating through the reactor jacket. This is accomplished by the master controller. The temperature of the water recirculating through the reactor jacket is controlled to the setpoint using a single-input/dualoutput controller (slave controller). When the slave controller output is between 0 and 49%, the controller is in cooling mode. In cooling mode, the controller output is used to throttle a control valve referred to as the dump valve. While the dump valve is open, hot water is discharged out of the recirculating loop and cold water enters through a pressure regulator. Thus the volumetric flow of the cold water entering exactly balances the volumetric flow of the hot water which is dumped and heat is removed.

Monomer Feed

r
I
I Distance

1
I I

DUMP
VALVE

from jacket exit to dump valve : 15 ft

Distance from steam valve to jacket inlet: 10 ft Distance from cold water inlet to jacket inlet: 15 ft
Total piping

: 35 ft of l-1/4

xhed

40 pipe.

Fig. 2. Reactor schematic.

Temperature control of semibatchpolymerization reactors For slave controller outputs between 51 and lOO%, the controller is in heating mode. The controller is used to throttle a control valve referred to as the steam vdve. While the steam valve is open, mediumpressure steam is injected directly into the recirculating water stream, thereby adding heat. At 50% control output, both the steam valve and the dump valve are closed. In the absence of system heat losses, the recirculation loop would be either heated or cooled by the contents of the reactor. Based on actual operating experience, heat losses in the recirculation loop are negligible.
CONTROL PROBLEM

259

4. Reactive

5. 6.

7. 8.

Objectives The control problem is to design a controller capable of maintaining the desired reaction temperature throughout the batch. Deviations in reactor temperature of less than 1 F are considered satisfactory. PID controllers are currently employed on both the master and slave loops. The new control design may replace one or both of these controllers. The structure of the controller (i.e. the algorithm) must remain the same for each product and succeeding batch; the tuning parameters can be different for each product but must remain the same from batch to batch of the same product. Automatic adjustments of parameters in the algorithm that are made transparent to the user are permissible. The only information available to the control algorithm is the product being made, and temperature measurements of the reactor, the inlet water to the jacket, the exit water from the jacket and the monomer feed. All other information is unknown. The controller must work over a series of 5 consecutive batches for both of the sample products under both winter and summer operation. Complications The and constraints

impurities result in batch-to-batch variation in the heat load curves. This makes jacket temperature scheduling practices impractical. Reaction kinetics are nonlinear and subject to a gel-effect. There is a practical minimum on the jacket temperature. Lowering the jacket temperature any further results in polymer freezing on the reactor walls and a complete loss of convective heat transfer. Process parameters change with season (winter/summer plant). Other operating conditions (feedrates, agitation, etc.) cannot be changed.
RBACTION KINETICS

control problem is complicated considerably by several features and constraints. These are summarized briefly in this section. Details are provided in the following 4 sections. All of the problem data given are summarized in the final section of the paper: 1. The reactor produces a large variety of products each with unique heat load-time curves. (Different reaction kinetics and heats of polymerization.) 2. The heat transfer coefficient falls sharply during the batch because of increasing batch viscosity as polymerization proceeds. 3. Temperature control of each succeeding batch of a particular product becomes more difficult because of heat transfer surface fouling.

Emulsion polymerization reactions are among the least understood polymerization processes. Complex chemical and physical phenomena govern the mechanisms taking place in an emulsion system. Accurate detailed modeling of simple emulsion polymer processes can be challenging. An excellent review article by Penlidis et al. (1985) discusses many of these modeling issues. In many industrial emulsion polymers, modeling becomes even more difficult. Industrial emulsion polymers can have many monomers, multiple surfactants and complex reactor feeding policies. Since the purpose of this problem is to consider the temperature dynamics of the system, an extremely oversimplified kinetic model can be used. This model will fairly describe the conversion vs time behavior in the reactor. This in turn can be used to model the energy balance about the reactor and the recirculation loop. This model description makes no attempt to describe the chemical composition, particle size distribution, nucleation or initiation mechanism. Because volume of the reacting mixture is a function of time in the semi-batch system, it is easier to model the material balance in terms of the moles of monomer, rather than concentration:

dn,=F Mdt

R
P

(1)

where of monomer in the reactor (lb-mol), FM = molar flowrate of monomer into the reactor (lb-mol/min), 4 = rate of polymerization (lb-m01 mm-),
nm = number of moles

FhlL3L

MW,

260 where

R. W. CINLLA and D. RUILMU HAME the feed mixture, heat generation due to reaction, heat transfer through the jacket and heat loss to the environment, respectively.
VISCOSITY RELATIONSHIPS

tiM = mass flowrate of monomer (lb/min), MW, = molecular weight of the monomer mix (lb/lb-mol), % = where
i = impurity factor (dimensionless), k = first-order kinetic constant @in-): i&n,),

(3)

k = k, exp[ - 6400/(T + 460)]#., where k, = preexponential factor (mm-), T = reactor temperature (OF), p = batch viscosity (cP).

(4)

Conversion is modeled using first-order kinetics. The only modification is the impurity factor i preceding the kinetic constant. The impurity factor takes on a random value between 0.8 and 1.2 for any particular batch. This is an attempt to model, in a simple way, the apparent fluctuations in monomer kinetics caused by batch-to-batch variation in reactive impurities. Note in equation (4) the influence of the batch viscosity on the Arrhenius expression. This crudely models the change in reaction kinetics due to the gel effect. The energy balance around the reactor is described in equation (5):

As the reaction proceeds, the viscosity of the reacting mixture builds sharply. This is shown in Fig. 3. The viscosity of the reactor contents is a function of the solids fraction in the reacting mixture. Experimental viscosity data taken at various levels of solids is shown below in Fig. 4 for both Product A and Product B. Not only is the viscosity a function of solids, it is a function of temperature as well. Equations (6) and (7) are viscosity correlations for Product A and Product B which have been determined empirically from experimental data.
Product

A p s 0.052 .eU6.4f,,oMA - l.-=Ncp, _

(6)

Product B p = 0 032 . e(19-U).1OP.YA where p= product f = fraction A = lOOO/(T T = product viscosity (cP), solids, + 460), temperature (OF).
cp 1.%311 *

(7)

d(~-Jf+T)
dz

= &, C

(Tunb- T)

The fraction solids can be computed at any time in the reactor using equations (g-10): solids( t ) f(r) = batch weight(t) solids(t) = solids(t = 0)

+R&-AH,,)--UA(T---)

where mass of component I in the reactor (lb), specific heat of component 2(B.t.u./lb-F), M for monomer, W for water, S for solids, ambient temperature (OF), heat of polymerization (B.t.u./lb-mol), overall heat transfer coefficient (B.t.u./ft2rain-F), A = jacket heat transfer area (ftq, 7 = average jacket temperature (OF), (UA),, = heat loss to environment per unit temperature (B.t.u./min-F). The enthalpy term on the left-hand side of the equation must be summed over the three components (monomer, water, solids) in the reactor. The terms on the right-hand side account for the sensible heat of m= Cp = I= Tpmb = -AI+ = U =

+ X(t)- total monomer added(z). batch weight(t) = solids(t) + total monomer added(t) *[ 1 - X(t)] + initial water,

(9)

(10)

Batch

Viscosity

Profile

Temperature control of semibatchpolymerization reactors

261

(a)

1000

Viscosity

vs.

Solids

Heat Transfer

at the WalI

IO0

CP
10

Fig. 5. Heat transfervs viscosity.

Viscosity vs. ----Y- o.ce2272 - eyls.o5*x)

100

Solids
R0.99722

(6) or (7) evaluated at the wall temperature estimated by (13). The overall heat transfer coefficient is a function of the film coelEcient given by (11) and a fouling factor. During successive batches of the same product, a polymer film forms on the reactor walls which gets thicker with each batch. This is modeled using the following fouling factors: 1 -= hr Batch

CP
10

Fig. 4. Viscosity vs solids. where X = monomer conversion. These viscosity relationships are required to compute the heat transfer coefficient as shown in the following section.
HEAT TRANSFER
RELATIONSHIPS

(0.000, T I

0.001,

0.002,

0.003,

0.004)

t
2

t
3

t
4

t
5 (14)

where l/h, = fouling factor (h-ftZ-OF)/B.t.u. The overall heat transfer coefficient is then given by equation (15):

Overall heat transfer coefficients for the reactor system were estimated from an online energy balance in a clean reactor. The film heat transfer coefficient falls drastically during the batch, as the viscosity builds at the reactor wall. This is shown in Fig. 5 below. An empirical equation describing the film heat transfer coefFicient as a function of viscosity at the wall is given below: h = 143.4~exp(-S.13~10-3~~1)r where h = film heat transfer coefficient (B.t.u./ft2-h-OF), AWlI= ~(~Wan), (12) (13) (11)

Table 1. Reactor and recirculation Descripti0n Reactor diameter Reactor tight Working volume Jacket volume Jacket bottoms area Jacket sidfil area Water recirculation rate Steam pressure Water inlet pressure Pump discbarge pressure Water inlet temperature (Winter) Water inlet temperature (Summer) Ambient air temperature (Winter) Ambient air temperature (Summer) c-nha Units in. in. gal 5

loopdata
Value 19.5 21.0 30.0 5.7 1.8 5.23 . he&In IS.0 150 75 60 42 70 45 90

psig F F OF F

psis psis

ft gal/min

T,,=

T+Tj.
2

Thus, the film heat transfer coefficient is computed using the viscosity of the reactor contents near the wall. This viscosity is determined by using equations

Dump valve: equal percentage C, - 0.42 2% hysteresis Steam valve: equal percentage C, = 0.42 2% hysteresis

RNctorbeatloml ((IA x, 10.74 B.t.u./(h-F)

262

R. W. CHnu

and D. Wn

Hm

The overall heat transfer coefhcient computed in (15) is used to model the heat transfer through the jacket, described in (5).
REACTOR AND RRCIRCULATION MOP

ture adjusted by the cooling or heating regulated by the controller: dTjP(r) _ dT,o(t - 6,) dt dt
+ (T,O(Z El,) 7-p(t)) +5 c(t) (18)

DESCRIPTION

The geometry of the reactor and reactor jacket is given in Table 1. Recirculated water is used as the heat transfer medium in the jacket. A centrifugal booster pump recirculates the water at 15.0 gal/min at a pressure of 60 psig. Recirculating water is cooled by discharging the water out of the loop through a control valve while replenishing it with ambient water available at 75 psig and ambient temperature (42F winter/70F summer) through a pressure regulator.

where 0, = K, = z,, = c(t) = transport delay in recirculation loop @in), heating/cooling process gain (OF/%), heating/cooling time constant (min), slave controller output (O-100%).

Using the data given in Table 1, one obtains the following expression for the process gain:

xa=

-3.21 x 10-3(30)(-~)/ZO(7~ z-met) 0 0.511(30)-2

OF/% cooling 0 < c(z) < 49 c = 50

OF/% heating 51 < c(t) < 100

, II

(19)

where Ttiti = water inlet temperature.

This control valve is an equal-percentage control valve with a C, = 0.42. Heating of the recirculating water is accomplished by throttling medium-pressure saturated steam available at 150 psig through an equal-percentage control valve with a C, = 0.42. Both valves typically experience valve hysteresis of about 2%. A minimum change in controller output of 1% (100% valve travel = 50% control output) is required in order to overcome friction in the valve stem and hence, change the valve position. The Ioop piping is sufficiently insulated such that heat losses are considered negligible. The exit temperature of the jacket fluid at time (t) can be described by:
m, Cpc J

Because equal-percentage valves are used, the process gain is a function of the valve lift as given by the controller output. In cooling mode, the gain is also determined by the temperature difference between the water in the recirculating loop and the water inlet temperature which varies depending on winter/ summer operation. The process time constant which accounts for the measurement element and valve dynamics is the same for both heating and cooling modes. The recirculation loop modeling data are summarized in Table 2. A Fortran subroutine which models the reactor system can be obtained by contacting the author.
EXISTING CONTROL STRUCTIJRR

dTP(t) = ti=Cpc[Tjn(r dt

- 19,) -

y(r)]

+ UA(T where

Tj),

(16)

r=(T+T)
J

(17)

where 0, = transport delay in jacket (min),

m, = mass of coolant in jacket (lb),

The inlet jacket temperature of the recirculating water is currently controlled via a PI controller. These were tuned by performing simple open-loop step tests on the controller output with the reactor filled with water. The responses were fit to either simple firstorder plus deadtime or integrator plus deadtime transfer functions and tuned using PID-IMC rules Table 2. Recirculation loop data Description MC CPC mc 0, 6 ZP Units lb B.t.u./lb-F Ib/min min min min VdUC 41.3 1.0 124.5 0.38 0.25 0.67

Cpc = heat capacity of coolant in jacket (B.t.u./ lb-OF). Since the jacket fluid is recirculated, the inlet jacket temperature is the time-delayed exit jacket tempera-

Temperature control of semibatchpolymerization reactors Temperature output

263

-.

2.5

7.5

10

Time Fig. 6. Typical servo response.

(Rivera et al., 1986). These were the transfer functions used by Gattu and Zafiriou (1991) in their nonlinear QDMC work. A detailed model has been provided in this paper, eliminating the need for these approximations. A typical closed-loop response to a +5F setpoint change is shown in Fig. 6.

While the jacket process is actually an integrating process, satisfactory tuning can be obtained by modeling as a first-order system. The master loop controller provides the inlet jacket temperature setpoint to the slave loop. Currently, a PID controller is used; tuning constants were chosen

Table 3. Product A data Arrhenious preexponential factor Heat of polymerization Monomer molecular weight Monomer spccitic heat Water specific heat Solids specific heat Monomer specific gravity Solids specific gravity water specific gravity Initial reactor charge Initial fraction solids Initial fraction water Initial fraction monomer Reaction temperature setpoint &,, -AF& MWM CPM CPW CPS Phi
PS

min- B.t.u./lb-mol lb/lb-mol B.t.u./lb-F B.t.u./lb-F B.t.u./lb-F

3300 30,160 0.4 0.4 1.0 0.75 0.9

1.04

%ids(r &i, g

= 0)

lb

F . product A recipe: (1) place initial charge of solids and water into the reactor at ambient temperature; (2) raise temperature of the initial charge to the reaction tempcraturc setpoint; (3) feed pure monomer into the reactor at 1.0 Ib/min for 70 min: and (4) after the feed addition period is complete. hold at reaction temperature for 60 min. Table 4. Product B data 1200 28,200 106 0.4 1.0 0.75 0.9 1.04 1.0 lb %ids(, = 0) 93.3 0.204 0.796 0 OF 17a.o Product B tip: (I) place initial charge of solids and water into the reactor at ambient tempcratun: (2) raise temperature of the initial charge to the reaction temperature setpoint; (3) feed pure monomer into the reactor at 0.8 Ib/min for 60 mitt; (4) after the feed addition period is complete. hold at reaction tcmpcraturc for 30 min; (5) fzed pure monomer into the reactor at 0.8 lb/min for 40 min; and (6) atkr tbc second feed addition period is complete, hold at reaction temperature for 4Smin. Arrhenious preexponential factor Heat of polymerization Monomer molecular weight Monomer spe&c heat Water specific beat Solids specific heat Monomer specjfic gravity Solids spccitic gravity Water specific gravity Initial reactor chaqte Initial fraction solids Initial fraction water Initial fraction monomer Reaction temperature setpoint /co -AH, MWM CPU CPW CPS PM Ps min- B.t.u./lb-mol lb/lb-mol B.t.u./lb-F B.t.u./lb-F B.t.u./lb-F

1.0 119.0 0.208 0.792 0 180.0

264

R. W.

CHYLLA

and D.

RANIMLLHMSE

through experience accumulated over time. Skilled operators will control the reactor temperature loop manually for some products. Less skilled operators rely exclusively on the controllers. There are several deficiencies with the existing control scheme:

(1) The same PID settings are used regardless

of product, batch number or winter/summer operation. The controller settings were chosen to exhibit robust behavior for all conditions, thus sacrificing performance. Deviations in reactor temperature of 5 F are not uncommon. (2) There is much variation in the regulation of the reactor temperature to setpoint based on the experience level of the operator. (3) No knowledge of the system is used. Thus, discontinuities in the overall energy balance caused by starting or stopping the monomer feed cause sharp disturbances in the reactor temperature.
CONCLUSIONS AND GUIDELINES

recirculating loop in the reactor jacket may be included in model-based control algorithms. These algorithms should be tested with plant-model mismatch. Changes in the nominal values of delay times and time constants of 25% are typical. Researchers are encouraged to add white noise to any measurement vector provided to the controller. Algorithms are permitted to contain product-specific tuning parameters but some guidance should be provided as to their selection when the controller is designed. Automatic adjustments in any of the controller parameters are permitted provided they are not based on any information which is not available to the control system (e.g. heat transfer coefficients, batch number). The problem is simple in the respect that there is only one variable (reactor temperature) that must be controlled. The stochastic elements of the process and the nonlinear kinetics provide challenges that standard PID controllers are not capable of meeting. This control problem is very representative of the types of control problems found in the specialty chemicals processing industry.
REFERENCES

An industrial case study for process control has been described. The control problem describes a multiproduct batch reactor and its temperature control system. Standard PID controllers are currently used despite their deficiencies in performance. A superior control algorithm is desired to replace one or both of the existing PID controllers. The controllers designed should not include any of the models of the kinetics, viscosity or heat transfer relationships. These models are only crude descriptions of actual reactor behavior provided solely for the purpose of simulating the reactor in controller simulations. However, one could use the model simulations to provide data for fitting empirical models, in the same way that one would perform identification experiments in a process plant. Models for the

Chylla R. W. and D. R. Haase, Temperaturecontrol of se&batch polymerization reactors.Paperpresented the at 1990 AIChE Annual Meeting, Chicago, IL (1990). Davidson R. S., An intelligent temperature controller for jacketed reactors. Proc. 1987 Am. Control Conf., Minr~+~lis. MN (1987).

Gattu G. and E. ZafZou, Nonlinear QDMC with state estimation-formulation and application to an industrial challenge semi batch process. Proc. 1991 Am. Control Co& Boston, MA (1391). Juba M. R. and J. W. Hamer. Progressand challenges in batch process control. Proc. CPC III. CACHE, Elsevier. Amsterdam (1986). Penlidis A., J. F. MacGregor and A. E. Hamielec, Dynamic modeling of emulsion polymerization reactors. AIChE J1

31, 881489 (1985). Rivera D. E., M. Morari and S. Skogzstad,Internal model control,4. PID controller design. Ind. Engng Process. Des.
Dev. 25, 252 (1986).