82 Optimization of A ComplexChemProcess Using An EquationOrientedModel

Mathematical Programming Study 20 (1982) 113-160 North-Holland Publishing Company
O P T I M I Z A T I O N OF A C O M P L E X C H E M I C A L P R O C E S S USING AN EQUATION O R I E N T E D M O D E L P.V.L.N. SARMA

E. I. Du Pont de Nemours & Co., Wilmington, DE 19898, U.S.A.
G.V. REKLAITIS
School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, U.S.A.
Received 4 January 1980 Revised manuscript received 26 May 1981 Meaningful evaluation of the utility and performance of available nonlinear programming techniques for engineering design optimization requires the availability of realistic design models. Such models have been notably lacking in the process design area. In this paper a detailed equation oriented model of a process for the production of ethylene oxide and ethylene glycol is developed to fill this void. The model involves a large number of variables and equality constraints which are by equation sequencing reduced to 22 independent variables, nineteen constraints, as well as bounds. The salient features of such models, their usefulness and limitations are presented. The applicability of available NLP algorithms and inherent difficulties in their application are discussed. Test results are reported with representative codes. GRG codes are found to provide the only practical approach to large scale design optimization.
Key words: Nonlinear Programming, Design Optimization, Process Modelling, Code Evaluation.
1. Introduction
Optimization of the complete integrated design of engineering systems is the ultimate goal of the design engineer. In order to achieve this goal using conventional NLP techniques, the engineer must (i) formulate the design model, (ii) prepare the model for optimization, (iii) select the appropriate optimization technique, (iv) execute the optimization runs. Each of the steps leading up to the final optimization runs constitute difficult and time consuming activities whose complexity are often not fully appreciated. In this paper we discuss these steps in the context of chemical process design. We develop a reasonably realistic model of a representative chemical process and use it as a benchmark problem to evaluate the applicability of readily available NLP codes and to elucidate the difficulties inherent in their application. In the next several subsections we commence with a review of steps (i) through (iii). In Sections 2 and 3, the process under consideration is described and a design model is developed. Finally, the results obtained using several NLP codes are discussed in Section 4. The complete problem is listed as a FORTRAN
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P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process
subroutine in the appendix. Copies of the problem in card or tape form are available from the authors upon request.
I.I. Process design model f o r m u l a t i o n
There are generally two types of models used in computer aided chemical process design: simulation or procedure oriented models and equation oriented models. Computer simulation models are typically assembled by using process simulation packages such as FLOWTRAN [36]. These consist of an executive, a library of process equipment modules, and libraries of physical properties as well as capital cost estimation routines and their associated data banks [23]. The equipment modules are self-contained models of various types of process equipment, for instance, compressor, distillation tower, heat exchanger, pump, and so on. The calculations executed within a module may involve solution of linear or nonlinear equation sets, integration of differential equations, and iterative calculations involving branching to physical properties estimation procedures. Regardless of the internal calculation details, however,, the user sees each module as simply a black box procedure, which given the input flows and the design parameters associated with that piece of equipmen L will predict the output flows and certain additional performance parameters of the unit. The module thus typically operates in the simulation or rating mode. The user assembles a process model by linking together the equipment modules very nearly as they would be connected in the actual process. One very important consequence of this mode of model assembly is that whenever recycles occur in the process, then starting with some initial guess of the recycle stream the entire sequence of module calculations must be repeated until convergence in the recycle stream parameters (flows, composition, temperatures, etc.) is attained. For instance, in the simple flowsheet shown in Fig. l, the feed streams FA and FB will normally be specified as part of the design but
FA FB REACTOR 9 HEAT E X C H A N G E R DECANTER FP
DISTILLATION
I FRC ] FRE
FRP FG COOLANT
rFD
Fig. 1. The Williams and Otto process.
P.V.L.N. Sarma and G.V. Reklaitis[ Optimization of a chemical process
115
the feedback or recycle stream R will not be known since its properties will be fixed by the outputs of the upstream process units. Thus in executing a simulation of this flowsheet, the properties of stream R must be estimated and then the unit models executed repeatedly in sequence until all of the properties of the recycle stream are converged to their steady state values. A process model assembled in this fashion using an available process simulation package can of course be used for optimization purposes. The process simulation is simply treated as a function subroutine which, for design values selected by the optimization algorithm, will simulate the entire process and calculate the value of some cost or profit function. Unfortunately because of the recycle iterations as well as the iterative calculations performed within many of the individual unit modules, evaluation of even a single design can be very time consuming, perhaps 20 to 500CPU secs on a reasonably large machine (CDC6600). Design optimization involving even as few as six or eight variables can thus require hours of CPU time [11, 2]. An alternate approach to process model development is to formulate the model directly in terms of the individual equations which describe the various process entities. The advantages of this formulation is that the iterative calculations required to converge recycle streams or to solve internal module equations are eliminated. Instead the complete set of equations is handled explicitly. The disadvantages are that the complete set of equations which must be solved generally becomes very large and that more complex unit models, such as those involving differential equations, must be replaced by algebraic approximations. Assembly of an equation oriented model can be carried out using manual methods, a subroutine library of modular equation generators, or automated approximations to simulation models. In the manual approach, the material, energy, design, physical properties and costing equations required to represent the given process are written out and coded by the engineer ab initio for each application. Most of the process optimization applications reported in the literature use models developed in this fashion (see for example, [38, 4] and all of the applications references listed in [29]. Because of the difficulty of manual assembly, all of the reported models consider only limited process subsections involving one or two equipment items or else grossly simplified models of small recycle systems such as that of Fig. 1. Computer aided approaches to generating equation oriented process models have been under development by Sargent [34, 15] and others [12, 43]. In these approaches, a library of unit modules is again used to assemble a process model but the modules serve primarily as equation generators. Solution (and presumably optimization) of the complete equation set for the process is controlled by an equation solving executive. Because of the large and, generally, sparse equation sets which must be processed, it is expedient in such methods to decompose the equation set by partitioning and sequencing into irreducible
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equation blocks and tearing of coupling equations [15]. Although partitioning and tearing techniques are well developed [33] the available equation oriented process modelling systems are still in the experimental stage. Use of these systems for optimization is being considered [43] but no results have yet appeared. In principle, automated equation generation coupled with equation sequencing and tearing techniques offer the best prospects for application of NLP methodology. An alternate approach to computerized process model generation has involved the automatic development of approximating models directly from the detailed simulation models. Both linear [31, 22] and quadratic approximations [25] have been considered. In the former case the periodically updated linearized model is used to speed the convergence of the simulation. Hence, optimization has to be controlled at the simulation model level. In the latter case, the unit quadratic response surface models are used to carry out successive optimization passes. The success of the latter method seems to hinge on the ability of the NLP code to handle large quadratically constrained quadratic programs and on the degree to which instabilities caused by successive model updating can be eliminated. Only limited success has been reported to date [25].
1.2. M o d e l p r e p a r a t i o n f o r o p t i m i z a t i o n
Whether the process design model is formulated using a simulation package or written, manually or automatically, in an equation oriented form, there are a number of modifications which must generally be made to adopt it for use in optimization. In the case of a process simulation model it is usually necessary to add two types of equality or inequality constraints: explicit constraints on the independent design variables which the optimization algorithm will be allowed to manipulate directly and implicit constraints which will disallow those independent design variable values that would cause certain internal module variables to take on physically unacceptable values. The former type of constraint is, of course, easily formulated. The implicit type of constraint is more awkward to handle. In general it is necessary to carefully examine each module to identify conditions which would either cause internal variables to take on unacceptable values or cause the model to abort because of arithmetic errors or illegal arguments. If all of the constraints required to avoid such conditions are assembled, their number is often so large as to make optimization too difficult. Instead, the need for such constraints is typically determined by trial and error during the course of the optimization: a constraint is added whenever an infeasible unit design or program abort is generated. Most commonly such constraints are added by inserting checks and resetting internal variables directly within the unit models. This, of course, will cause discontinuities in any numerically generated model derivative values and thus forces the use of direct search techniques for the optimization.
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In the case of equation oriented models it is also necessary to add inequality constraints to the model prior to optimization. These constraints will generally be of three types: (i) those which are required for the model to describe physically realistic situations (e.g. the outlet pressure must be greater than the inlet pressure in a compressor, flows must be nonnegative); (ii) those which are required so that all function values can be evaluated (e.g. arguments of log and power functions must not be negative); (iii) those that are required to restrict variable values to ranges of interest in the given application of the model. In general the resulting set of linear and nonlinear equalities and inequalities will be large, sparse and highly structured. The latter two properties arise because each equation in the subset used to model a particular unit in the process typically involves only a few variables belonging to that unit and its connecting streams. In addition the model will be underspecified, that is, the number of variables N will be larger than the number of equations (equality constraints) M. Given these features the design optimization problem can be handled in several ways: direct solution of the full model, elimination of model equations, implicit solution of model equations, and mixed equation processing. Direct solution of the full model would, of course, be the preferred mode since it would involve minimal preprocessing of the process model. However, because of the hundreds of equations and inequalities which will be involved this is at present infeasible. Direct solution therefore awaits the development of efficient optimization codes for processing large, sparse, nonlinear programs. Elimination of model equations amounts to reducing the dimensionality of the problem from N to N - M independent variables by using the equations to eliminate variables. This can be done either directly, by algebraic substitution, or else indirectly, by sequencing the equations so that each equation serves to define one of the M dependent variables. Sequencing can be carried out automatically using simple algorithms reviewed in [23]. However, care must be exercised to insure that all of the inequality constraints involving the eliminated M dependent variables are explicitly retained. The major disadvantage of the approach is that generally all of the model equations cannot be completely sequenced for direct evaluation. Instead, individual equations or sets of equations will have to be solved simultaneously. One approach to accommodating equations which cannot be sequenced for solution is the implicit elimination strategy. In this approach, any such equations are solved numerically each time the model must be evaluated for given values of the N - M independent variables. In effect, this is what is done when a simulation model is optimized. The recycle iterations and all internal module calculations are fully converged at each new trial point in the space of the independent design variables. For this strategy to be effective the model iterations must be carried out with relatively tight tolerance since inaccurate evalua-
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tions will cause the optimization algorithm to be misled. However, the tighter tolerances will require even more computational effort for each model evaluation. Because of this large computational overhead, this strategy is generally not to be preferred. An alternate strategy, which we call mixed constraint processing, involves eliminating directly or by sequencing all equations that can be solved for a single variable. The remaining model equations are explicitly treated as equality constraints. As in the elimination strategy, care must of course be taken to insure that all inequality constraints on the dependent variables are retained. This strategy is preferable to the former because both constraint satisfaction and objective improvement will be handled simultaneously by the optimization algorithms with properly balanced tolerances. The mixed processing strategy has the additional advantage that the required model rearrangement can be easily automated by using the partitioning and tearing strategies as reported by Sargent [15, 33]. By way of illustrating these various strategies, consider the simple Williams and Otto process [44] of Fig. 1. The full model as solved by Jung, et al. [16], contained twelve variables and eight equality constraints. Sriram and Stevens [38] eliminated seven of the equality constraints and reduced the problem to one in four variables and a simple cubic equation which was solved iteratively for each objective function evaluation (implicit elimination). If this equation had been treated as an explicit equality constraint, a five variable problem would have been obtained (mixing processing). Finally, Luus and Jaakola [19] after presumably much trial and error manipulation, reported a way of grouping variables so that even the last equality could be explicitly eliminated to result in a totally unconstrained problem (explicit elimination). If, as in this case, all modes are feasible then the solution strategies could be ranked in decreasing difficulty as follows: full model, implicit elimination, mixed processing, and explicit elimination.
1.3. Selection o f optimization technique
Once the model has been formulated and prepared for optimization, the problem of algorithm and code selection remain to be addressed. In general, the N L P methods available for optimizing process design problems can be divided into six categories: (i) search methods, (ii) small step gradient methods, (iii) large step gradient methods, (iv) penalty function methods, (v) successive quadratic programming methods, (vi) special structure methods. As surveyed in [42], a number of studies have been published on the comparative performance of these categories of algorithms in solving general
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NLP problems. The most recent of these in that of Sandgren [32], who tested a wide range of NLP codes on a battery of thirty test problems. Although these problems were generally low in dimensionality and not particularly representative of process design problems, the general conclusion favoring large step gradient methods would probably apply as well to process design applications. A number of smaller scale studies which have involved design problems have also been reported (for example, [3] and [9]). However, the conclusions of these studies are of limited applicability because of the nature of the test problems used: low in dimensionality and number of equality constraints. There simply are very few, if any, realistically formulated process design problems used in these studies or, for that matter, reported in the applications literature. A case in point is the Williams and Otto process shown in Fig. 1. Although the flowsheet contains several units, the model, as used by numerous authors, focused primarily on the reactor. The distillation column, for instance, is approximated as a simple flow splitter. Since the publication of the model in 1960, many studies have been reported which used it as a benchmark problem for comparing optimization algorithms. The scope of these studies is summarized in Table 1. Table 2 shows the optimal solutions computed by various workers. The results show a remarkable lack of uniformity. This can be attributed to the different assumptions/modifications made to the original model by individual workers. Note, for instance, the work of Jaakola and Luus [19] who rearranged the equality constraints, so that the problem became unconstrained and then applied their technique which employs random search with interval contraction. Such modifications to the original problem alter the characteristics of the problem to such an extent that comparison of the effectiveness of various algorithms is meaningless. Based on this state of knowledge, the design engineer can, in fact, find very little guidance in selecting among the large number of alternate algorithms and codes reported in the literature. In this paper we seek to rectify this situation in part by presenting a fairly realistic, although nonetheless simplified, equation oriented model for a representative chemical process. We will use this model as a benchmark problem to evaluate the performance of a representative collection of NLP codes. We commence in the next section with a description of the process and continue in Section 3 with the model development.
2. Process description The manufacture of ethylene oxide by partial oxidation of ethylene and subsequent hydration to ethylene glycol was chosen as a representative chemical process. The reasons for selecting this process are: (i) It contains a broad selection of common chemical process equipment:
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tubular reactor, stirred tank reactor, absorber-stripper combination, distillation columns, evaporator, compressor, and heat exchangers. (ii) It has the characteristic recycle streams. (iii) The number of species in the system, ten, is moderate but fairly representative. (iv) Physical property data can be readily obtained. (v) Kinetic and phase equilibrium relations are also available. Ethylene oxide is produced by direct oxidation of ethylene with either air or oxygen. The flowsheet for the variant using oxygen is shown in Fig. 2. This flowsheet is a slightly modified version of the flow sheet given by Considine [6]. In this process, ethylene, oxygen, nitrogen and recycle gases are mixed and fed to a tubular reactor packed with silver catalyst. Nitrogen is used as a diluent to keep the mixture outside of the flammability limits. The oxidation reactions
C2H4 + 102 --~C2H40 C2H4 + 302 --~2CO2 + 2H20
are highly exothermic and thus the temperature is controlled by transferring heat from the reactants to a Dowtherm utility stream. The reactor effluent gases containing ethylene oxide are fed to an absorber, in which water is used as an absorbent. Except for a small vent the residual gases are sent to a carbon dioxide removal system. Here gases are scrubbed with a suitable solvent to remove carbon dioxide and then compressed to the operating pressure of the reactor. The rich solution from the ethylene oxide absorber is fed to a stripping column where live steam is used to strip ethylene oxide. The bottoms stream from the stripper is split into two parts. Most of it is returned to the top of the absorber and the remainder is sent to the glycol reactor. The aqueous ethylene oxide stream from the top of the stripper is compressed and condensed and sent to a light ends removal column. In this column the absorbed carbon dioxide and other light ends products like formaldehyde are removed. The bottoms of this column now contain only ethylene oxide and water. A fraction of this stream is sent to the final purification column where pure ethylene oxide is recovered as overhead product. The streams from the stripper and the light ends column are mixed with makeup water and fed to a stirred tank reactor. Here ethylene oxide is hydrated to form mono-, di-, tri-, and higher polyglycols in the presence of sulfuric acid. The reactor conditions are adjusted to favor monoglycol production. The reactor effluent is passed through a sulfuric acid removal system in which the acid is neutralized and then fed to an evaporator. The bulk of the water is removed in the evaporator, and the remaining water is removed in a distillation column. The mixture is then fed to a purification column where monoglycol is recovered as overhead product.
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3. Model development
The equation oriented model for this process will consist of several general types of equations: material balances, energy balances, physical property correlations, equipment design equations, and inequality constraints associated with each of the processing units. For brevity's sake, we will not enumerate and derive the equations for all the units. Instead we will present an example of each type of equation as it occurs in the process. The complete model derivation can be found in [35]. The computer program for the model is shown in the appendix. The following symbols will be used in the model development. E O TN CO EO EG1 EG2 W L G ethylene, oxygen, nitrogen, carbon dioxide, ethylene oxide, monoglycol, diglycol, water, total liquid, total gas.
The above symbol followed by a stream number will be used to indicate the flow in (lb mol/hr) of that quantity in the corresponding stream. For instance, E5 will denote the flow rate of ethylene in stream 5. The above symbol preceded by a Y and followed by a stream number will be used to indicate a vapor mole fraction in the corresponding stream. If X is used, it will indicate a liquid mole fraction. For instance, XEO8 will denote the liquid mole fraction of ethylene oxide in stream 8.
3.1. Material b a l a n c e equations
The simplest of the model equations will usually be the material balance equations. They will typically be linear in the species flows and, in general, one balance equation can be written for each species processed in a unit. For example in the case of the absorber, the balance equations consist of: E6 = E5, 06 = 05, TN6 = TN5, CO6 + CO9 = CO5, EO6 + EO9 = EO5 + EO8, W6 + W9 = W5 + W8,
125
If required b y the equipment sizing equations, the individual species flows can be expressed in terms of mole fractions and total flows. For instance, in the case of the absorber, compositions and flows are required, hence, the relations given below must be included. EO6 = YEO6 G6, CO6 = YCO6 x G6, W6 = YW6 x G6, EO8 = XEO8 L8, W8 = (1 - XEO8) x L8.
3.2. Energy b a l a n c e equations
The energy balance equations in chemical process applications typically exclude mechanical energy flows and therefore consider only enthalpy changes. In cases in which thermal properties can be assumed to be constant with temperature, the balance equations thus will be quite straightforward. For example, in the case of the evaporator, the evaporator heat load can be calculated from, 0 = W16 x X + L 1 5 C p A T where )t = heat of vaporization of water, Cp = molar heat capacity of liquid water, AT = temperature difference. In other cases, constant properties m a y not be assumed and then the balance equation will include nonlinear temperature dependent terms. For instance, in the ethylene oxide reactor, the isothermal heat load will be given by
T
Q = AH0 + ~ (N5 - N4), f Cp, dt

all i J 77 ~
where AH0 = ((EO5 - EO4)45300) + ((CO5 - CO4)284000) = the heat of reaction at the reference temperature of 77~ and where the second term corresponds to the difference in the sensible heat of products and reactants. If the gas heat capacity of species i is given by
Cpi = ai + BiT + ~/iT 2
where ai,/31 and ~/i are empirical constants, then the reactor balance becomes Q = AH0 + A a ( T - 77) + A-tiff (T2 - (77) 2) + A-47-7 (T 3 - (77)3).
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In this equation, zla = ~ (N5 - N4)ioti

all i
where i is summed over all species i in the reactor. Similar definitions apply for A/3 and Av.
3.3. Equilibrium relations
In addition to the thermal properties, chemical process models also require vapor-liquid equilibrium distribution coefficients. These can be complex empirical expressions such as the following expression for the Henry's law constant for CO2, kco:, [40] ln(kc~ = [(16"43-2~---9---~8) -P/203"14R\ T /P~2[119.76 552 22 9"756x 10 2' - O ' 0 0 6 6 2 R ) T
3.964x 107_t _9.518x 108)]
\--T- + T -
T3
T"
where T = temperature in ~ P = pressure in atm, R = universal gas constant = 82.0053 cm 3 atm/gmol ~ Alternatively they may involve simple functions such as the Antoine vapor pressure equation, log(p H20/760) = 7.96681 1668.21 T + 228
where pH20 is the vapor pressure of water in atm.

3.4. Equipment design equations
The equipment sizing or design equations can range from algebraic equations to complex sets of differential equations. The former can either be expressions in which design variables can be explicitly evaluated given the other unit parameters or else may involve implicit expressions which would require iterative solution for their evaluation. Absorber. The design of the ethylene oxide absorber can be modeled in a straightforward manner assuming constant pressure, isothermal operation and using the Kremser equation [37] to calculate the number of theoretical stages. With ethylene oxide as the key species, this equation takes the form, / f/YEO6-mXEO8, 1 / A ] ) / ( I n A) N = ~ln[~y---E-~_ m---~X--g~)(1 - I/A)+ where m = the equilibrium constant for ethylene oxide in water, a function of temperature and pressure; L/G = the ratio of liquid to gas molar flows in the absorber; A = L [ m G and as design specifications, YEO6 = 0.0001 and XEO8 = 0.0005.
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Using N as defined above, the K r e m s e r equation is used in reverse to predict the CO2 mole fraction in the outlet gas. Thus, YCO6 = m X C O 8 + (1 - 1 / A ' ) ( Y C 0 5 - m ' X C O 8 ) (A') N - I/A'
where m' = the equilibrium constant for CO: in water, a function of temperature and pressure; A ' = L / m ' G and as a design specification X C O 8 = 0.0. The diameter of the column is calculated by using a flooding correlation to estimate the flooding velocity [37]. Thus, D = ~ where
0.5
1 4 G' ]112 ~ P~ V--~660]
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Cf=[0.1191og[(G)(~)
+0.1808]](~)
r = surface tension of the liquid (dynes/cm), pc, OL = gas, liquid mass densities, L', G' = liquid, gas mass flow rates. With a stage efficiency of 50% and a typical tray spacing of 18" selected as design specifications, the column height can be calculated as, H = 1.5 x N/0.5 ft. Once H and D for the column are known, its cost can be estimated using available equations. Distillation column. The design equations for the water removal column, on the other hand, although also algebraic are more complex because this unit involves at least three chemical species. For multi-component distillation column design, the short cut design procedure consisting of the Fenske equation, the Underwood equations, and the Gilliland correlation are often r e c o m m e n d e d [41]. In the present case, the column will be designed with water and monoglycol as the key components, assuming 99.9% r e c o v e r y of water and 0.1% of monoglycol in the column overhead. Using the Fenske equation, the minimum number of theoretical separation stages, Nm, is calculated as follows, , I- W18 EGll9-1. NM = l o g [ ~ x ~_]/log where
b ",112 O~wl = (Ottwl X O/wl J ,
_ Otwl
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P . V . L . N . S a r m a and G.V. Reklaitis[ Optimization o[ a chemical process
awl = Pw(Tt)/PEGI(Tt), b Otwl = Pw(Tb)/PE~I(Tb),
Tb = temperature at the bottom of the column, Tt = temperature at the top of the column, P~(T) = partial pressure of species i at temperature T. The split of the diglycol component resulting from Nm stages of separation is calculated using the Fenske equation in reverse, EG218 = EG217(caN~)/(1 + CaNto), C = E G l l 8 I E G l l 9 where
~,,=
= (~,h ~ 9 'I=,
h = PEGI(T,)/P~o2(T,),
ab2 = PEc,( Tb)/ PEc2(Tb). The temperatures at the top and bottom of the column are related to the compositions at the corresponding locations by assuming that stream 18 is at its dew point and stream 19 at its bubble point temperature. This gives rise to two equations with implicit temperature dependence, lIP ~ Pi(TOXi 17 = 1.0, P ~, Yi 18[P,(Tt)= 1.0
i
(1) (2)
where i = water, monoglycol, diglycol, P = total column pressure. The mole fractions in the above equations are of course related to the species flows appearing in the Fenske equation via material balance equation. The minimum reflux ratio is calculated using the Underwood equation. Assuming saturated liquid feed, the first equation, aiXi 17 -~i- ~ = 0 (3)
with awl-< 0-< t~2~ fixes the value of the Underwood parameter 0. The second equation,
R~+ 1 = ~ ~-~_--~-
ai~Xil8
(4)
serves to define the minimum reflux ratio Rm. The actual reflux is usually
129
selected as a design multiple of Rm or can itself be selected by optimization. In the present case we will fix R at 2 x Rm. With R known, the total condenser cooling duty can be calculated from,
Qc= L18(R + I)(~ XilSAi)

where Xi is the heat of vaporization of species i. The reboiler heating duty can next be calculated from the overall column energy balance. With both duties known and assuming suitable values for heat transfer coefficients and utilities stream temperatures, the condenser and reboiler heat transfer surfaces can be established. With Nm, Rm, and R determined, the actual number of stages can be established using Eduljee's analytical expression [10] for the Gilliland correlation.
Finally the column diameter and height can be determined using the estimation equations presented for the absorber design model. Tubular reactors. The design equations for the tubular ethylene reactor with external wall cooling consists of the differential equations,
dNEo d W = rEO,
dNco2 d W = rco2,
dH dNEo dNco UAs (T - Tc), d W - d W (AHEo) + ~ (AHco2) -- pbA

dP = l . 0 4 8 1 x 1 0 - 7 ( l _ ~ ) . P _ 1 Q2 1 d-W pb" P--d"A-~ " 14.7 where flow rate of ethylene oxide, lb mol/hr, NCO 2 flow rate of carbon dioxide, lb mol/hr, H = enthalpy, Btu/lb mol, A H E o = heat of reaction for ethylene oxide reaction, AHco, = heat of reaction for carbon dioxide reaction, U = overall heat transfer coefficient, Btu/hr ft2~ As = surface area of tube per unit length, ft2/ft, Yc= temperature of coolant, ~ porosity of bed, p = density of gas mixture, lb/ft 3,
]~EO
130
Pb = A = P = Pa = Q=
density of bed, lb/ft 3, cross sectional area of tube, ft 2, pressure, atm, particle diameter, ft, volumetric flow rate of gas, ft3/min
and rEO and rco2 are the rate equations reported by Buntin [5] and given by: k l ~O t E J tol/2 0 2 " F(Pr) rEo = 1 + 24.55PE
I L
lb mol of EO hr (lb of catalyst)' lb mol of CO2 hr (lb of catalyst)
k2~ O 1/2 tE D x 0 2 " F(Pr) rco2 = (1 + 24.55PE)(1 + 1.71749Pg~)
where F(Pr) represents the effect of products on the reaction rate and is given by,
1
F(Pr) = 1 + 30.63PH~o + 7.68(Pco2 + PEO) and the constants kl and k2 are the temperature dependent rate constants,
,-0094 8ox ( 41(

PE, Po, PH2o, Pco2, PEO are partial pressures of ethylene, oxygen, water, carbon dioxide and ethylene oxide respectively. T is temperature in degrees Rankine. These differential equations must of course be converted to algebraic form for use with conventional N L P algorithms. This can be done quite readily if the equations are analytically integrable. Unfortunately this is not the case in the present instance. As an approximation, the reactor can be assumed to operate isothermally and at essentially constant pressure. This allows the last two differential equations to be replaced by algebraic equations. The remaining, however, can neither be further reduced nor integrated analytically. Since these equations are required to yield the total catalyst weight and selectivity between the two reactions, they must be considered in the model. To convert them to an algebraic form, tractable by N L P methodology, approximate response surfaces had to be fit to the numerical solutions generated over a range of anticipated operating conditions. The result was an equation of the form
W = AO Y E 4 Al
YO4 A2X
A3 pA4(e-r)A~
In(2-- X) A6
for the catalyst weight, and equation of the form

1
S = 1 + ATYO4 ~8
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for the selectivity. The constants A0 through A8 are evaluated by least squares regression of the numerical integration results. X is the overall conversion of ethylene in the reactor. The response surfaces inherently have only a limited range of validity and hence may need to be refitted if their limits are exceeded during use of the model. S u m m a r y o f other unit models. The remaining key process units were modelled as follows: Recycle compressor: adiabatic compression formula [7]. Stripper: same as EO absorber except energy balance included to calculate amount of condensed steam. Light ends column: Fenske binary minimum reflux equation, Gilliland correlation, flooding correlation. EO purification column: same as light ends column. Glycol reactor: isothermal CSTR reactor model using two consecutive reactions and the kinetics of Parker and Prados [26]. Evaporator: conventional algebraic steady state model [21] with fitted boiling point elevation correlation. Glycol purification column: same as light ends column. Heat exchangers: log mean temperature driving force design formulas with specified heat transfer coefficients. Two process units, the CO2 removal unit and the acid neutralization unit were not designed as part of this model. Miscellaneous pumps and trim heat exchangers were also not included in the model.
3.5. Inequality constraints
In addition to the large number of nonlinear and linear equations, the process model also has associated with it a number of inequalities. These can be grouped into three classes: (i) the explicit constraints which are an integral part of the model; (ii) the implicit constraints which are required to avoid numerical difficulties during optimization; (iii) upper and lower bounds on key variables which are imposed to restrict the model to a given domain for a particular application. In the present formulation in addition to the nonnegativity conditions on the variables, the most important explicit constraints are the flammability limits on the ethylene oxide reactor feed, YE -< 0.3, YO4 -< 0.2, (5) (6)
the bounds in the Underwood parameter 0 which arises in the water removal column design equations, 0 -< a~2, (7)
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P . V . L N . Sarma and G.V. Reklaitis] Optimization of a chemical process
o~wl-< 0,
(8)
and the requirement that the saturated temperature of the stripping steam be above the stripper feed temperature to avoid excessive steam condensation, STEMT - T9A -> 0. (9)
The implicit constraints consist of the arguments of various logarithmic and power functions. In principle all such arguments should be bounded to avoid possible arithmetic errors or undefined function values. However, in practice the majority of the resulting large number of inequality constraints can be deleted during initial model runs since the argument values may be very far from the critical values. In the present case the following were found to be important: the argument of one of the log terms in the Kremser equation for the EO stripper,
mGIL > - 1.1;
(10)
the argument of the second log term in the Kremser equation for the EO stripper, XEO9 XEO9 x--E--0-23 XEO2------3X(~m)+~m] - 1.11; (11)
the argument of the corresponding term in the Kremser equation for the EO absorber, Y E O 6 - mXEO8\ YEO5_ ~ ) ( 1 l/A)+ 1/A-> 1.1, (12)
the argument of the Gilliland correlation in the case of the glycol purification column, since the argument is raised to a fractional power,
R~+-~m ~ 0;
the minimum reflux for the glycol water column,
(13)
~a,Yil8
"
1 > 0.001;
(14)
O~il - - 0
the temperature difference in the returned absorber liquid across the heat exchanger, STEMT - T8 -> 0; (15)
the temperature difference between the steam and the boiling solution in the evaporator, TST - TDEW - BPE -- 0. (16)
The latter two temperature constraints are necessary to avoid calculation of negative heat transfers and, thus, negative heat transfer areas.
P.V.L.N. Sarma and G.V. Reklaitis[ Optimization of a chemical process
133
The third type of inequality constraint is the set of upper and lower bounds on various model variables which will be specific for a given application. These consist of bounds on: (1) the ethylene oxide reactor design, dictated by the catalyst used and the limitations of the heat transfer fluid, reactor temperature _ 242~ reactor pressure -< 14.5 atm, ethylene conversion -< 0.3; (2) the glycol reactor design variables 20 - reactor temperature - 75~ 10-3 - acid normality -< 0.16, 500 - molar ratio of water to ethylene oxide x 100 -< 6000; (3) the absorber design variables absorber temperature -< 200~ absorber L/G ratio -> 0.5; (4) the stripper design variables stripper feed inlet temperature _< 200~ 0.2 -< stripper pressure -< 100 psia; (5) the glycol column pressure pressure -< 0.5263 atm; (6) the evaporator water removal fraction 0.5 -< water removal -< 0.9; (7) the percentage of ethylene oxide sent directly to final purification 30% -< percentage sent to purification <- 80%.
3.6. Objective functions

For process design optimization purposes, the objective function normally consists of maximizations of either return on investment or hourly net profit, where return on investment, ROI, is computed from, ROI Annual net profit (before taxes) total capital investment
134
and hourly net profit is computed from, net profit = sales $ / h r - t o t a l cost/hr total cost/hr = investment costs/hr investment cost/hr = Lf D x total installed cost. cost/hr + utility costs/hr + raw material
where LF and D are the Lang plant factor and the depreciation rate respectively. The installed cost is the sum of the costs of EO reactor, EO absorber, EO stripper, recycle gas compressor, light ends column, E O purification column, glycol reactor, water evaporator, water removal column, glycol purification column, and EO reactor effluent/recycle gas heat exchanger. These individual equipment costs are estimated from cost capacity data for various equipment types reported by Guthrie [14] fitted to power function. For example, the installed cost of a tower of stainless steel clad construction with stainless steel bubble cap trays is given by:
PF{(674 + 4.63P)(DI"~176 + (88.42DI"454H H3(D + H)-~ where P = operating pressure, atm, D = tower diameter, ft, H = tower height, ft, P r = vacuum factor = ~1.0 t 2.0 for P > 1 atm, for P < 1 atm.
+
H) -0"175)
The utility costs include cost of steam for E O stripping and water evaporation, cost of electricity to drive the recycle gas compressor, cost of process water for glycol reactor, and cost of sulfuric acid. The credit for steam generated from heat liberated in the E O reactor is subtracted from utility costs. The assumed utility costs are: cost of cooling water cost of process water cost of steam cost of electricity cost of sulfuric acid = 1.07 10-5 $/lb, = 4.8 x 10-5 $/lb, = 0.001 $/lb, =.0.03 S/kw-hr, = 0.05 S/lb.
credit for generated heat = 1.17 x 10-6 $/Btu,
The raw material costs consist of the costs of ethylene, oxygen, and nitrogen: 0.10 $/lb, 0.02 $/lb and 0.02 $/lb, respectively. The product selling prices assumed are: ethylene oxide 0.15 $/lb and e t h y l e n e glycol 0.19 S/lb.
P, V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process
135
The following economic factors are assumed: number of hours of operation in a year = 8000, depreciation rate = 10% and overall Lang factor = 3.0. 3.7. N L P f o r m u l a t i o n The complete equation oriented flowsheet model will consist of more than one hundred equations and an even larger number of bounds and inequalities. As noted in Section 1, because of the network structure of the underlying physical problem, the problem variables and equations can be sequenced for solution so that only a much reduced set of independent variables and constraints needs to be explicitly considered. In the present case, sequencing reduces the problem to the following twenty-two independent variables: X(1) = flow rate of ethylene in feed stream 4, lb mol/hr, X(2) = ratio of oxygen to ethylene in feed, X(3) = reactor temperature, ~ X(4) = conversion of ethylene in reactor, X(5) = flow rate of ethylene oxide in feed, lb mol/hr, X(6) = fraction of ethylene oxide sent to purification column, X(7) = flow rate of carbon dioxide in feed, lb mol/hr, X(8) = flow rate of nitrogen in feed, lb mol/hr, X(9) = reactor pressure, atm, X(10) = absorber temperature, ~ X ( l l ) = pressure in stripper, psia, X(12) = L/G ratio for stripper, X(13) = L/G ratio for absorber, X(14) = temperature of exit stream of recycle exchanger, stream 9, ~ X(15) = molar ratio of water and ethylene oxide in glycol reactor feed, stream 15, X(16) = temperature of glycol reactor, ~ X(17) = normality of sulfuric acid, X(18) = fraction of water removed in evaporator, X(19) = bubble point temperature of bottoms stream of glycol column, ~ X(20) = dew point temperature of overhead stream of glycol column, ~ X(21) = Underwood parameter for glycol column, X(22) = pressure in glycol column, atm. Further as noted in Section 1, only two types of equations will normally resist sequencing: the material and energy balance equations required to close key recycle loops and subsets of the individual equipment design equations which cannot be explicitly solved for one or more of the design variables. In the present case, the recycle equations which cannot be sequenced without tearing are the balances associated with the ethylene oxide loop, E4 - (El + E3) = 0, (17)
136
P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process C O 4 - CO3 = 0, E O 4 - EO3 = 0, (18) (19)
and the energy balance associated with the absorber-stripper loop, expressed in terms of the single temperature equation, T 9 - T9A = 0 (20)
where T9A is the assumed and T9 the calculated temperature of the stripper feed stream. The internal equipment equations which cannot be sequenced are those associated with the glycol-water column, namely; the bubble and dew point equations, (1) and (2), as well as the Underwood equation (3). The resulting NLP problem takes the standard form, Maximize subject to F(X), Hi(X)=0, Gi(X)-0,
Xi>-Li, Xi<-Ui,
i = l ..... NEQ, i = I + N E Q ..... M, i = 1 ..... N, i = l ..... N,
where X is a twenty-two component vector of independent variables. The problem has seven equality constraints (equations 1, 2, 3, 17, 18, 19, 20), twelve inequality constraints (equations 5 through 16) and a virtually complete set of upper and lower bounds. For a complete formulation of the above model, the reader is directed to the appendix in which a listing is given of a subroutine suitable for execution with most NLP solution codes. Both the ROI and net profit objective functions are evaluated hence either can be returned to the calling program subject to the user's choice. The routine listed provides objective function and constraint function values. If derivatives are required by the NLP code these must be evaluated by first order finite differencing.
4. Optimization trials
The equation oriented model presented in the previous section was optimized using several nonlinear programming codes selected from the various NLP algorithm categories. To be applicable to the problem at hand the algorithm must of course be able to accommodate both equality and inequality constraints. Since none of the available direct search methods (Complex, etc.) can handle nonlinear equality constraints, this class of algorithms was excluded from consideration. Similarly, no geometric programming codes such as GGP [7] or other specialized structure algorithms were considered because of the enormous
137
amount of algebraic manipulation which would be required to convert the EOM to posynomial or other specialized form. The list of candidates is thus reduced to the large and small step gradient methods, penalty function methods and successive quadratic approximation methods. As surveyed in [42] numerous codes implementing these categories of algorithms are available. Based on Sandgren's study [32] the following codes were selected: (i) GRG [17], a generalized reduced gradient; (ii) RALP [32], a modified repetitive linear programming method; (iii) SUMT4 [24], a mixed penalty function; (iv) EXPEN [32], an exterior penalty function method; (v) BIAS [30], a method of multipliers method. A good successive quadratic programming code was not available to us at the time the study was conducted. However, we expect that difficulties similar to those encountered with BIAS would have been found with such a code. All computational results reported were obtained using the Purdue University CDC 6500 computer, the MNF compiler (revision 5.3) and the MACE operating system.
4.1. O p t i m i z a t i o n with G R G
The initial runs with GRG using the original model were unsuccessful, often resulting in negative arguments for power and logarithmic functions and premature termination because of scaling difficulties. These problems were remedied in part by imposing the class (ii) inequality constraints discussed in Section 3.5. Also the following three variables were scaled as shown, TN4 = X(8) x 10 3, RATW = X(15) x 10 -2, FREO = X(23) x 10-2.
With these changes difficulties were still encountered with arithmetic errors and invalid arguments during the constraint adjustment phases of the algorithm. Apparently, the modest constraint infeasibilities permitted by the algorithm during this phase were sufficient to cause abortion of the run. To surmount this type of difficulty, the model was modified by adding checks of function arguments and resetting these arguments to acceptable lower bounds if invalid arguments were encountered. (See statements A2020, 3120, 3660, 4150, 4530, 6100, and 7680 in the Appendix). Such resetting in principle introduces derivative discontinuities at the reset points; however, since the optimal solution was sufficiently far from the reset points, difficulties with discontinuities were not observed in our runs. The modified model was successfully optimized using the GRG code from four different points. Upper and lower bounds on the independent variables were set as shown in Table 3a. The code parameters were set to values shown in Table 3b. The results are shown in Tables 4a and 4b for four and three different
138
P.V.L.N. Sarma and G.V. Reklaitisl Optimization o[ a chemical process
Table 3a Variable bounds Lower bound X(1) = E4 X(2) = RAT X(3) = RTEMP X(4) = CONV X(5) = EO4 X(6) -- FREO X(7) = CO4 X(8) = TN4 X(9) = RPRES X(10) = ATEMP X(11) = STPR X(12) = RLGS X(13) = RLGA X(14) = T9A X(15) = RATW X(16) = TC X(17) = RON X (18) = FRWE X(19) = BBL1 X(20) = DEW1 X(21) = THETA X(22) = PT 0 0 0 0 0 30.0 0 0 0 0 0.2 0 0.5 0 500.0 20.0 0.001 0.5 30.0 30.0 0.001 0.001 Upper bound 105 300.0 242.0 0.3 2000.0 80.0 105
103
14.5 200.0 100.0 100.0 100.0 200.0 6000.0 75.0 0.16 0,9 300.0 300,0 100,0 0.5263
Table 3b GRG code parameters Parameter EPNEWT EPBOUND EPSTOP NSTOP Value 10-4 l0 4 l0 -3 Significance constraint tolerance (plus and minus) variable bound tolerance relative objective fraction value convergence criterion number of consecutive convergence tolerance successes before run terminated
starting points, respectively. The optimal solutions obtained f r o m these respect i v e starting p o i n t s ar e listed in c o r r e s p o n d i n g o r d e r . T h e m o d e l p a r a m e t e r s w e r e t h e s a m e f o r all of t h e starting points. In t h r e e o u t of f o u r c a s e s t h e o b j e c t i v e f u n c t i o n a t t a i n e d t h e s a m e v a l u e , 2928.43, a n d in t h e f o u r t h it d i f f e r e d o n l y slightly. H e n c e , t h e o b j e c t i v e v a l u e o f 2938.43 is p r o b a b l y t h e d e s i r e d l o cal optimum. T h r e e v a r i a b l e s - - t h e f r a c t i o n of e t h y l e n e o x i d e s e n t to t h e final p u r i f i c a t i o n c o l u m n , the o p e r a t i n g p r e s s u r e in th e E O s t r i p p e r an d t h e L / G r at i o in t h e E O a b s o r b e r - - r e a c h e d t h e i r l o w e r b o u n d s . F o u r v a r i a b l e s - - c o n v e r s i o n in t h e E O
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reactor, the temperatures in both the reactors and the fraction of water removed in the evaporator--reached their upper bounds. Fifteen variables are within their bounds. The constraints on the flammability limits (5), (6), and two secondary constraints (9), (16) are binding at the optimum. The temperatures in the reactors and the conversion of ethylene are expected to reach their upper bounds, because higher values of these variables favor higher production of EO and EG, which in turn increases the profit. The upper bound value for the fraction of water removed in the evaporator suggests that at that upper bound value it is still cheaper to remove water in the evaporator rather than in a distillation column. The flow split, FREO, determines the fraction of ethylene oxide purified and sold as ethylene oxide product, the remainder being converted to ethylene glycol. Its optimum value reached the lower bound of 0.3, which implies that it is more profitable to sell ethylene oxide as ethylene glycol instead of pure ethylene oxide. This can be expected in view of the higher price of 19r of ethylene glycol compared to that of 15r for ethylene oxide. A run was made with an artificial price of ethylene oxide set at 15r and that of ethylene glycol set at 14C/lb. As expected, FREO reached the upper bound of 0.8, indicating that it is more profitable to produce EO than ethylene glycol. The L/G ratio of the ethylene oxide absorber reached the lower bound of 0.5. In general, as L/G ratio decreases the operating costs (the cost of removing the solvent subsequently) will be lower, but the fixed cost of the absorber will increase. In the case of the EO absorber, the fixed cost is negligible compared to the savings in operating expenses because of low theoretical plate requirements. To further test the consistency of the model the following additional studies were made. The objective function was changed in order to maximize the return on investment (ROI) instead of maximizing the profit per hour. The ROI reflects the effect of fixed charges to a larger degree than does the profit. This effect is clearly evident from the results of Table 4b. The amounts of EO and glycol produced have decreased by about 1.5% and 4% respectively, but the ROI increased from 96.44%. This can be attributed to lower fixed costs, especially that of reactors. (Note the reductions in volumes of both the reactors). The lower bound on the L/G ratio for EO absorber was changed to 0.05 to reduce the operating expenses if possible. The optimum values are shown in Table 5. The L/G ratio attained a value of 0.062 (not the lower bound). This resulted in an increase of ROI to 111.58%. These studies supported the credibility of the model by yielding design changes which agree qualitatively with trends predictable from engineering judgment.
4.2. O p t i m i z a t i o n with R A L P
RALP was used to optimize the EOM with profit/hr as the objective. Initial runs with suggested values of R = 50, SIZE = 0.001, end constraint tolerance =
142
P. V.L.N. Sarma and G. V. Reklaitis/ Optimization o[ a chemical process
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P. V.L.N. Sarma and G, V. Reklaitis[ Optimization of a chemical process
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0.001 (the product of R and SIZE determines the maximum change in independent variables during the LP phase to ensure that the linearization is valid) showed very slow progress towards the optimum as shown below. Starting points Initial objective value Objective value after 1000 seconds of computation 1 2964.9 2 3 2700.083 2111.6 4 2785.063
2969.43 2858.81 2858.81 2794.26
in case of point 1 the objective function reached the optimum value of 2969.43 in 788 seconds. In all other cases the program was terminated after 1000 seconds. In order to improve the rate of convergence, various values for R were tested. The improvements in the computation times are shown below for starting point 1. R 50 1000 2000 5000 CPU time (seconds) 788 768 734 654
For values of R greater than 1000 additional scaling of variables was needed to avoid numerical errors. A value of R = 5000 was then chosen as the best value and the optimization attempted from the four different points. Again, only in the case of the first starting point did the program terminate after finding the optimum. The results of two selected cases are shown in Table 6 along with the values computed by the GRG code. The RALP optimum has a slightly higher objective function value because of the looser constraint tolerances which had to be permitted in order for this code to make any progress. From these results it can be concluded that, although RALP can solve process optimization problems its rate of convergence towards the optimum is very slow. This undoubtedly is due to the high nonlinearity of the objective function and the presence of too many constraints.
4.3. O p t i m i z a t i o n with p e n a l t y f u n c t i o n m e t h o d s
The mixed penalty function, exterior penalty function and multiplier methods were next tested on the EOM. Initial runs with the mixed penalty function method SUMT4 were unsuccessful during phase I. During this phase the program finds a feasible point by minimizing the sum of squares of the violated constraints. Even from feasible points numerical errors halted the computation. After extensive trials involving scaling of variables and constraints the computations entered phase II in which the true objective is minimized. This phase of calculations also encountered numerical problems very quickly. Many trials involving adjustment of the penalty factor and the reduction factor proved futile. The presence of equality
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P.V.L.N. Sarma and G.V. Reklaitis] Optimization of a chemical process
Table 6 Optimization results with
RALP
Starting points
1 2
Corresponding optimal points

1 2b GRG
optimum
X(1) = E4 X(2) = RAT X(3) = RTEMP X(4) = CONV/100 X(5) = EO4 X(6) = FREO X(7) = CO4 X(8) = TN4 X(9) = RPRES X(10) = ATEMP X(11) = STPR X(12) = RLGS X(13) = RLGA X(14) = T9A X(15) = RATW X(16) = TC X(17) = RON X(18) = FRWE/1000 X(19) = BBL1 X(20) = DEW1 X(21) = THETA X(22) = PT/100 F = PROF C P U time (seconds) V E O (ft 3) V G L (ft 3) NST NGL E O lb m o l / h r G L lb m o l / h r 32.5733 0.6667 242.0 30.0 1.0362 30.0 0.3849 5.4275 9.6592 28.471 2.0 2.4235 0.5 39.62 2798.85 75.0 0.0524 980.0 176.46 83.67 0.143 49.29 2964.94 4952.8 1.094 240.0 19.38 2.4 34.0 0.37 14.1 14.0 44.4 2.1 2.42 0.55 44.4 2410.0 74.0 0.067 890 159.0 68.0 1.36 27.6 2700.8 3257.33 0.6668 242.0 30.0 1.0358 30.0 0.3851 5.4235 14.5 57.514 2.0 2.4235 0.5 48.24 2712.9 75.0 0.0538 980.0 176.33 83.58 0.1431 48.978 2969.42 654 15084 29357 12 16 234.09 471.03 4836.6 0.6668 242.0 19.87 1.5557 30.0 0.3788 8.0532 14.5 57.64 2.0 2.4235 0.5 47.15 2513.08 75.0 0.0535 980.0 159.58 70.22 2.6737 27.168 2860.02 I000 3257.33 0.6667 242.0 0.3 a 1.0362 30.0 0.385 5.4275 12.73 44.41 2.0 2.4235 0.5 44.41 2712.9 75.0 0.0528 0.98 a 176.33 83.58 0.1431 0.4898 a 2968.56 85 15055 29907 12 16 233.96 471.11
aUnscaled values. bOptimum not reached.
constraints and too many inequality constraints are again the likely reasons for the failure of the mixed penalty function method. Optimization of the EOM with the exterior penalty function EXPEN was next attempted. Five different starting points were tried. In all cases the program failed at the very first iteration because of negative arguments for log and power function. No additional attempts were made to scale the variables or the constraints. The problems of scaling and the numerical ill conditioning of the Hessian matrix known to be inherent to conventional penalty function methods ought in
P.V.L.N. Sarma and G.V. Reklaitis/ Optimization o[ a chemical process
145
principle, to be avoided by using a method of multipliers. Hence BIAS was tried. However, the runs with BIAS were no more successful then those with EXPEN. After a few iterations the runs terminated because of negative arguments for logarithmic and power functions. The failure of BIAS and EXPEN can be attributed to the exterior nature of the penalty function they incorporate. In an exterior penalty function method excursion into the infeasible region is permitted. This does not hamper optimization in principle. However, evaluation of objective function or constraints may not be possible because the points selected may result in negative arguments for logarithmic and power functions. Recall that secondary constraints were added to the model to preclude such combinations of independent variables. EXPEN and BIAS defeated the purpose of these constraints by allowing these constraints to be violated and therefore encountered numerical difficulties. The only way to circumvent these difficulties is to design a method of multipliers with interior penalty function. No such method is available at the present time. We expect that similar difficulties will be encountered with the recent quadratic programming based methods, since these too allow generation of infeasible points.
5. Conclusions
In this paper we have reviewed the problems associated with the development and optimization of process models. It appears that equation oriented models incorporating judicious approximations and simplifications are the appropriate model form with which to carry out process design optimization studies. An EOM of a reasonably realistic although still simplified chemical process was developed. The model included most of the common types of process equipment and involved both algebraic and differential equations. The model was prepared for optimization by restructuring it into the mixed equation form and by adding the necessary inequality constraints. It was then used as a bench mark problem for evaluating the effectiveness of NLP codes in solving process design problems. Tests showed that algorithms which allowed inequality constraint infeasibilities during the computations (exterior penalty functions, methods of multipliers, and Lagrangian based variants such as successive approximate quadratic program solutions) were generally unsuitable for process design optimization. The algorithms which generally maintained constraint feasibility but did allow small excursions outside the constraints during the constraint adjustment phases (generalized reduced gradient and modified successive LP) were suitable for use. However, checks had to be inserted into the model subroutine to avoid fatal arithmetic errors and invalid arguments during the adjustment calculations. Even with these modifications, the successive LP code, RALP, proved very slow in
146
convergence. The GRG code quite clearly was shown to be the most effective optimization code for use with this class of problems.
Appendix. Computer program for the equation oriented model The computer program for the EOM is listed in this Appendix. This subroutine calls only one another subroutine PRINTX to print varriables with titles. Equipment data such as heat transfer coefficients and splits are set through Fortran DATA statement. Hence, no further input data are required.
SUBROUTINE GCOMP (QX,X) C O M M O N /FLAGS/ IFLAQ IFLAG=I TRIGGERS PRINTING O F ~EPERDEMT VARIABLES. C O N T R O L THIS FROM OPT. P R O G R A M C O M M O N ICONSTI A(I5),B(15) A,B ARRAYS CONTAIN FIXED P A R A M E T E R S LIKE HEAT TRANSFER COEFF.
DIMENSION X ( 2 3 ) , OX(22) DIMENSION N(4),NI(4) THESE VARIABLES ARE TO TRANSFER TITLES ONLY, DATA MI/IOH C, IOH ,tOH ,iOH
X IS INDEPENDENT UARIABLES UECTOR , Q CONTAINS EQUALITY , INEQUALITY AND OBJECTIUE FUNCTIONS IN THAT ORDER REAL MEO, MCO,LS,MEOS,L20, LPA, LPS,L24 REAL K W i , K i I , K 2 1 , K W 2 , K I 2 , K22 REAL LP REAL KWE,KIE,K2E
V A P O R PRESSURE FUNCTIONS, A T M
UAPEO(T)=EXP(2.303*(S.B39-1410.I(T+273.13)))/76.
UAPCO(T)=G94.+33.55*T UAPN(T)=E UAP1(T)=EXP(2.303*(8.09083-20BS.936/(T+203.454)))/760. UAP2(T)=EXP(2,303*(?.63666-1939.35S/(T+I62,?14)))/760.
MOLAR HEAT CAPACITIES FUNCTIONS , DTU/LB MOL OF CPE(T)=2.B3+28.60IE-3*T-8.Z26E-6*T*T CPO(T)=6.148+3.tO2E-3*T-O.923E-6*T*T CPCO(T)=S.214+tO.39SE-3*T-3.S45E-S*T*T CPEO(T)=-.ZSS296+4S.T83E-3~T-tS.E-6*T*T CPN(T)=?.256+2.298E-3*T-O.283E-6*T*T CPM(T)=6.524+1.25E-3*T-.OOtE-6*T*T HLATN(T)=18614.*((3?4.-T)/334.)**0.38 MOLAR HEATS OF VAPORIZATION , BTU/LB MOL
HLATI(T)=28825.*((374.-T)I334.)**0.38 HLAT2(T)=39158.*((407.-T)/367.)**0.38 H E M R Y S CONSTANTS FOR EO, AND C02
QMI(T)=EXP(lB2.33-2S.163*ALOG(273.+T)-IIOI2.57/(T+273.))/ZS. OM2(T,P)=EXP(16.43-2698./(T+273.)-2.477*P/(T+273.)+I18S.S*P/(T+273EOM I.)**2+.O178*P**2/(T+273.)+.O8EI*P**2/(T+273.)**2) EOM

EOM
E O M E O M E O M E O M E O M EOM E O M EOM E O M EOM EOM E O M EOM EOM EOM EOM EOM EOM E6I EOM EOM EOM EON EOM EOM E O M EOM ECM EOM EOM EOM EOM EOM EOM EOM EOM EOM ECM EOM EOM EOM EOM EOil EOM ECM EOM EOM EOM ECM ECM EOM EOM
10 20 30 40 50 60 70 80 90 100 Ii0 120 130 140 150 160 170 180 150 200 210 220 230 2qO 250 2]0 270 2SO 250 300 310 320 330 $40 350 3S0 370 $50 330 400 4!0 4~0 430 440 450 4S0 47'(, 480 430 500 510 530 5S0 540 55O
147
SATURATION TEMP OF STEAM GIUEM PRESSURE
EOM EOM
5S0 570
530 600 6LO 6R9 CSO 640 6.50 650 6?0 ~SO 630 7O0 710 7~0 COSTCOL(B,H,P, PF)=PF*((SZ4.+4.S3*P)*D**I.O21*H**.SSS*(B+H)**(-.IZSEOM ?30 I)+88.42*D**I.4S4*H**I.13*(D+H)**(-.275)) EOM 740 BATA A/2.0,1.S,.OI,.999, IOOO.,O.,O.,30.,.OOOI,.SSS,.S~9,.OOI,O.,O.EOM ZSO i,I./ EOM 7S0 DATA B/0.,.28,0.,0.,0.,300.,5.,9S8.,.88,225.,.99,.001,50.,0.,I./ EOM 770 JPR=IFLAG EOM 780 EOM 7~0 SET IMDEPEMDEHT UARIABLES FOR EO SECTION OF THE PROCESS EOM 800 ERM 8i0 E4=X(1) EOM 6{0 RAT=X(2) EOM 830 RTEMP=X(3) EOM 840 COMV=X(4) EOM 8~0 EO4=X(5) EOM 8S0 W4=O. EOM 870 XOEO=5./IO00. EOM S~O FREO=X(6)/IO0. EOM 890 C04=X(T) EOM SCO TM4=X(8)*IO00. EOM B!O RPRES=X(9) EOM 5~0 ATEMP=X(IO) E O M S30 STP~=X(tl) EOM 540 RLGS=X(12) EOM s RLGA=X(13) EOM 950 Ts EOM 970 M(1)=IOHIMBEPEMBEN EOM $30 M(e)=IOHT UARIABLE EOM 950 M(3)=IOHS FOR EO EOM 1000 M(4)=IOHSECTIOM EOM 1010 CALL FRIMTX(M,S, IOHETHY. IM 4 ,E4,1OHOXY/ETHRAT ,RAT, EOM 10~0 CIOHEOR TEMP ,RTEMP, IOHCOMUERSIOM ,CO'U, EOM 1030 CIOHEO IM 4 ,E04) EOM 1040 CALL PRINTX(MI,5,1OHCO IM 4 ,C04,10HM2 IN 4 ,TM4, EOM 1050 CIOHEOR PRES ,RPRES, IOHABSB TEMP ,ATEMP, EOM 10SO CIOHSTRP PRES ,STPR) E O M 1070 CALL PRIMTX(MI,3,1OHL/Q ABSB ,RLGA, tOHL/G STRP ,RLGS, EOM IOSO CIOHTSASSUME ,TSA) EOM 1090 PI=3.1415 EOM II00 XMP=XOEO EGM 1110 YIEO=I.E-4 EOM i120 EOM 1130 BESIGM EO REACTOR EOM 1140 EOM IIEO 04=RAT*E4 EOM IISO G4=E4+O4+EO4+W4+CO4+TN4 EOM i!?0 XE=E4/Q4 EOM II~0 XO=O4/Q4 9 EOM 1190 TR=RTEMP*I.8+4~2. EOM IRO0 W=4.534328E+8*(EXP((-273.-RTEMP)/273.))**T.2SOI52B?*ALOQ(2.-COMU)*EOM IEIO I*(-I.716403)*COMU**I.39?OI4S*XE**I.530602S*XO**(-.SSSO9423)*RPRES*EOM 1220 2-~ EOM 1230 H = W * Q 4 EOM 12~0 EPS=.4 EOM ~e50 S=I./(I.+.132114" EOM 12S0 EOM 1270 EO=S*COMU*E4 CO=(I.-S)*CONU*E4*2. EOM 1280 UOLTOT=N/85.3 EOM 12S0 U O L B E B = U O L T O T EOM 1300 EOM ISlO CATCOST=W*A(1)
STEAMT(P)=8576.65/(15.4TSSS-ALOG(P))-459.21B+P*(-O.O2371g+P*(O.S42EOM IiSE-O4+P*(-O.?O854E-OT))) EOM EOM LMTD FUNCTION EOM EOM RLMTD(THI,THO, TCI,TCO)=((THI-TCO)-(THO-TCI))IALOG((THI-TCO)/(THO-TEOM iCI)) EOM EOM MINIMUM REFLUX RATIO FUNCTION FOR BINARY SYSTEM EOM E~II REMIM(A, XB,XF)=(XB/XF-A*(t.-XB)/(I.-XF))/(A-i.) EOM ESM COST OF A TOWER WITH BUBBLE CAP TRAYS. EOM EOM
148
P.V.L.N. Sanna and G.V. Reklaitis/ Optimization of a chemical process
C C C
C C C
EOM 13:30 EOM 1330 EOM 1340 E5=(I.-CONU)*E4 EOM 1350 05=04-(.5-E0+1.5-C0) EOM 1350 EO5=EO+E04 EOM 1370 N5=N4+CO EOM 13~0 005=004+C0 EOM 1330 TN5=TN4 EOM Iq00 GS=E5+OS+WS+COS+TM5+E05 EOM 141!' TP=RTEMP+273. EOM 1420 E54=ES-E4 EOM 1430 054=05-04 EOM 1440 EO54=EOS-E04 EOM 1450 H54=W5-N4 EOM 1460 C054=C05-C04 EOM 1470 TN54=TNS-TM4 EOM 1460 EOM 14S0 STAM~ARD HEATS OF REACTIOM5 EOM 1530 EOM 1510 STDHR=-(EO*45300.+CO*284000.) EOM 1520 CI=E54*2,83+O54*8.148+EO54*(-.789298)+W54*7.258+CO54*G.214+TN54*S,EOM 1530 1524 EOM 1540 C2=ES4~2~.60I+O54*3.102+EO54*46.783+N54*2.298+CO54*IO.396+TM54*I.2EOM 1550 15 EOM 1580 02=C2"1.E-3 EOM 1570 EOM 15~0 C3=E54*B.728+O54*.923+EO54*IS.+N54*,283+COSq*3.S45+TM54*.O01 C3=-C3-I.E-6 EOM 1550 EOM 1600 DHO=STOHR-CI*537,-C2*2.OSE+5-C3*t.548E+8 EOM ISI0 HRXM=DHO+CI*TR+C2*TR**2+C3*TR**3 EOM 1820 AUMWR=(E5*2G. EOM 1830 HUUOL=359.*(TP/273.)/RPRES AUD=AUMNR/AUUOL EOM 1640 EOM 1850 EOM 1880 DESIGN EXCHANGER REACTOR EOM 1870 TL=30. EOM 1830 TB=I. EOM 1830 TAX=.ZB54*TD**2/144. EOM 1700 TUOL=TL*TAX EOM iZlO EOM 1720 TMUM=UCLTOT/TUOL TPT=I.25~TD EOM 1730 EOM 1740 SDIR=IoI5*TPT*SORT(TNUM) EOM 1750 RAPEA=PI*TD/12.~30.*TMUM EOM IF@O RCOST=I266.12*RAREA**.5778 GI=CS/TMUM EOM 1770 UZ=GI*AUMNR/(AUD*TAX*3600,) EOM 17aO DP=I./64. EOM 1790 EOM 1800 DELTAP=.OI215*(I.-EPS)/EPS**3*(UZ**2/BP)*(AUD*TL/32.2) EOM 1810 M(1)=IOHEO REACTOR M(2)=iOH DESIGN EOM 1820 N(3)=IOH EOM 1830 M(4)=IOH EOM 1840 EOM 1850 CALL PRIMTX(M,5,1OHCAT (LB) ,N, IOHUOL FT3 ,UOLSED, CIOHCAT COST ,CATCOST,IOHNOS TUBES ,TMUM, EOM 1880 CIOHSHEL DIA ,SDIA) EOM 1870 CALL PRIMTX(MI,q,4HCOST ,RCOST,IOHEO P R O D M ,EO, EOM 1880 CIOHCO PROem ,CO, IOHSELECTUTY ,5) EOM iBgo PABS=RPRES-DELTAP/14.7 EOM 1300 AAUOL=35s EOM 1910 AAU~=AUMWR/AAUOL EOM 1920 EOM 1530 INLET LIQUID COMPOSITION TO EO ABSORBER EOM 1940 EOM 1950 A L = Q S * R L G A EOII 1980 EOB=AL*XOEO EOM 1970 HB=AL-EOB EOM 1980 MEO:QMI(ATEMP)/PABS EOM 1990 AEO=AL/(MEO*65) EOM 20JO E8=E5 EOM 2010 O6=05 EOM 2020 TM6=TM5 E O M 2030 YMEC=E05/G5 EOM 2040 YNCO=COS/Q5 EOM 2050 EOM 2080 FFAC=(YMEO-MEO*XOEO)I(YIEO-MEO*XOEO)*(I.-I./AEO)+I.IAEO IF(FFAC.LT.I.I) 35,38 EOM 2070 OUTPUT STREAM COMPOSITION
P.V.L.N, Sarma and G.V. Reklaitisl Optimization of a chemical process

35 TPA=2. G OT O 37 36 C O N T I N U E TPA=ALOG(FFAC)/ALOG(AEO) 3T CONTINUE
149
E OA B S O R B E R DIAMETER STNA=70. G P A = G 5 * A U M W R LPA=AL*I8. CFA=(.II2*ALOGlO(GPA/LPA*SQRT(S2.0/AAUB))+.IBOS)*(STMA/20.)**.2 UFA=CFA*SORT((SS.O-AAUD)/AAUD) UFAD=UFA*.T5 AXR=G5/3800.*AAUOL/UFAD/.88 ADIA=SORT(4.*AXA/PI) APA=TPA/.50 ABHT=APA*I.5 ABCOST=COSTCOL(ADIA,ABHT, PABS, I.) M(1)=IOHEO A B S O R B E M N(2)=IOHR DESIGN CALL PRIMTX(M,5,1OHOP PRES ,PABS, IOHTH.PLATES ,TPA, CIOHDIA FT , A D I AIOHHEIT , FT ,ABHT, C I O H C O S T ,ABCOST) EXIT GAS COMPOSITION MCO=OM2(ATEMP,PABS)/PABS ~CO=AL/(MCO*G5) YICO=YMCO*(I.-I./ACO)/(ACO**TPA-I./ACO) YIW=UAPW(ATEMP)/PABS YI=I.-YICO-YIW-YIEO G I = E G + O G + T M 6 66::65 EO6=YIEO*G6 C06=YICO~G6 N6=YIW~66 EXIT LIOUID COMPOSITIONS NS=W8+W5-WS C09=C05-C06 PURGE FRRCTIOM AND PURGE COMPOSITION PFR=A(3) EOS=EOS-EOT+EO8 PFRI=I.-PFR ET=FFRI*E6 E28=ES-ET 07=PFRI*06 028=06-07 TNT=PFRI~TM8 I'N2S=T~6-TM7 NT=FFRI*~!6 W20=I-!G-WY EOT=PFRI~E06 EOs CO?=PFR!*C06 C028=C06-C07 GT=PFRI*G6
CO2 REMOVED
FRCO=A(4) COS=(I.-FRCO)~COZ E3=E7 03=07 I'NS=TN7 EOZ=EOT W3=W7 63=E3+O3+TM3+EO3+CO3+W3 C030=C07-C03
COMPRESSOR
BESIGM
E O M 2080 E O M 2080 E O M 2100 E O M 2110 EOM 2120 E O M 2130 E O M 2140 E O M 2150 E O M 2160 E O M 2170 E O M 2180 E O M 2150 E O M 2200 EOM 2210 EOM 2220 EOM 2230 E O M 2240 EOM 2250 EOM 2250 E O M 2270 E O M 2280 E O M 2230 E O M 2300 E O M 2310 EOM 2520 E O M 2330 EOM E340 EOM 2850 EOM 2360 EOM 2370 EOM 23S0 EOM 2330 EOM 2400 EOM 2410 E O M 2420 EOM 2430 EOM 2440 EOM 2430 EOM 2450 EON 24?0 EOM 2480 EOM 2430 EOM 2500 EOM 2510 EOM 2520 EOM 2530 EO!I 2540 ECM 2550 EJM 2ESO EO,I 2570 EOM 2530 EOM 2590 EOM 2600 EOM 2610 EOM 2620 EDM 2630 E O M 2640 E~il 2650 EGM 2660 EOM 26?0 EOM 2890 EOM 2690 EOM 2700 EOM 2710 EOM 2790 EOM 2730 EOM 2740 EOM 2750 EON 27~0 EOM 2770 EOM 8T~O EOM 2780 E O M 2800 E O M 2810 E O M 2820 E O M 2830
150

P R A T = R P R E S / P A B S GAMA=I.35 C U F = Q 3 * A U U O L CHP=.OOIOSBB*QAMA/(QAMA-I.)*PABS*CUF*(PRAT**((QAMA-I.)/~AMA)-I.) CSHP=CHP/.75 CRCOST=3709.2*CSHP**.796 M(1)=IOHCOMPRESSOR M(2)=IOH DESIGN CALL PRIMTX(M,3,1OHSHAFT P I P ,CSHP,IOHPRESR A T ,PRAT, C4HCOST ,CRCOST)
SET EOUALITY CONSTRAINTS FOR RECYCLE LOOP EI:A(5) 02:04-03 EQI=E4-(EI+E3) TN2=TN4-TM3 E02=004-C03 EO3=W4-W3 EO4=E04-E03 STRIPPER DESIGN
0010~009 LB:COg+NB+EO9 GST=Lg/RLGS STEMT=(STEAMT(STPR)-32.)/I.8 OMEOI=OMt(STEMT+20.)/STPR*I4.T MEOS=OMEOI XO=EOB/L~ SS=MEOS*GST/L9 FACI=XO/XMP-XO/(XNP*SS)+I,/SS SSX=SS IF(SS.LT.I.I)SS=I.I TPS=RLOC(FACI)/ALOG(SS) RPS=TPS/,5 SHT=APS*I.5 STRIPPER DIAMETER STHS=60, RHCGS=I3.BB8*STPR/(2F3.+STEMT) AUMWS=COS/LS*44.+EOS/LS*44.+WS/LS*I8. GPS=GST*IB. LPS=LS*AUMW9 CFS=(.II2*ALOGIO(GPS/LPS*SORT(62.0/RHOGS))+.ISOS)*(STM5/~O.)**.2 UFS=CFS*SQRT((62,0-RHOGS)/RHOGS) UFSD=UFS*.T5 AXS=I8.*GST/3GOO./RHOGS/UFSD/.88 STDIA=SQRT(4.*AXS/PI) STPI=I.+STPR/14.7 STCOST=COSTCOL(STDIA, SHT, STPI,2.) OSTR=L9*AUMNS*(STEMT-TSA) N(1)=IOHEO STRIPPE M(2)=IOHR DESIGM CALL PRIHTX(N,5,1OHTH.PLATES ,TPS, IOHHEIGHT ,SHT, CIOHDIA FT ,STDIA, 4HCOST ,STCOST, CIOHFLO0~ F ,CFS) SCOM=OSTR/HLATW(STEMT)
EXIT LIOUID COMPOSITION FROM STRIPPER
N20=NS+SCOM L20=W20/(t.-XMP) EO20=L20-W20

EXIT UAPOR COMPOSITION F R O M STRIPPER
NIO=GST-SCON EOIO=EOg-EO20 G!G=EOIO+WIO+COIO

LIGHT ENDS COLUMN EOII=A(9)*EOIO COI~=A(IO)~COIO
E O M 2840 E O M 2850 E O M 2860 E O M 2870 E O M 2880 E O M e890 E O M ~900 E O M 2910 EOM2920 E O M 2930 E O M 2940 E O M 2550 E O M 2960 E O M 2570 E O M 2980 E O M 2990 E O M 3000 EOM 3010 EOM 3020 EOM 3030 EOM 3040 EOM 3050 EOM 3080 EOM 3070 EOM 3080 EOM 3090 EOM 3100 EOM 3110 EOM 3120 EOM 3130 EOM 3140 E O M 3130 EOM 3180 E O M 3170 EOM3180 E O M 3190 E O M 32O0 E O M 3210 EOM 3220 EOM 3230 EOM 3240 EOM 3250 EOM 3250 EOM 327'0 EOM 3280 EOM 3290 EOM 3300 EGM 3310 EOM 3320 EOM 3330 EOM 3340 EOM 3330 EOM 3350 EOM 3370 EOM 3380 EOM 3390 EOM 3400 EOM 3410 EOM 3420 EOM 3430 EOM 3440 E O M 3450 E O M 3450 EOM 34Z0 EOM 3480 EOM 3450 EOM 3500 EOM 3510 EGM 3520 EOM 3530 EOM 3540 EOM 3530 EOM 3560 EOM 35TC EOM 3550 EOM 3590

BII=EOII+COII EOlS=EOIO-EOII COiE=C010-COII NI2=NIO PLE=5. TLE=85. ALFALE=OM2(TLE,PLE)/UAPEO(TLE) TPLE=ALOC(COII/COI2*EOI2/EOIIJ/ALOC(ALFALE) XFCO=COIO/GIO XBCO=COII/BII MMLE=REMIM(ALFALE,XOCO, XFCO) RMLEI=RMLE IF" (RMLE.LT.O.) RMLE=.OI RLE=3.~RMLE NMWII=(EOII*44.+COII*44.)/BII GPLP=RLE/(I.+RLE) RHOG=AIIWil/(359.*(TLE+273.)/273./PLE) RHOL=40. ST~I=25. CF=(.I12~ALOGIO(GPLP*SORT(RHOL/RHOG?)+.1808)~(STN/20.)**.2 DUF=CF*SORT((RHOL-RHOG)/RHOG)*.T5 AXLE=(I.+RLE)*BII/3600.*(RMNII/RHOG)/DUF/.88 BLE=SORT(4.*RXLE/PI) XRAT=(PLE-RMLE)/(I.+RLE) YR~T=.T5-.Z5~XRAT*~.58~ TPLEA=(-TPLE-YRAT)/(YRAT-1.) RPLE=TPLEA/.5 HTLE=APLE~I.5 COSTLE=COSTCOL(BLE, HTLE,PLE, 1 . ) M ( i ) = ! O H L I C H T EHOS M(2)=IOH COLUMit M(3)=IOHDESIGH M(~)=IOH CALL PRIMTX(H,5,4HALFA, ALFALE ,IOHTH.PLATES ,TPLEA, CIhHDZA FT ,BLE, IOHHEIGHT ,HTLE, CIOHCOST oCOSTLE) FRACTIOM SEMT TO EO PURiFICATIOM COLUMM E087=FREO~EOI~ E028=E012-E027 N8?=FREO~WI2 q2s FIMNL PURIFICATION COLUMN FOR EO TFC=35. PFC=I. ALFAFC=UAPEO(TFC)/UAPW(TFC) E013=A(11)~E027 E014=E027-E013 WIS=W2?~A(12) Nt4=W27-NI3 TPLF=ALDG(EOI3/EO14*W14/W13)/ALOG(ALFAFC) C013=C012 F27=EO27+W27 D12=E013+W13 XEF=EO27/F27 XED=EOI3/Bt3 AMNI3=(EOI3*44.+WI3*I8.)/BI3 RMF'C=REMIM(ALFAFC, XEB,XEF) R M F C I = R M F C IF (RMFC.LT.O.) R M F C = . 0 1 RFC=2.*RMFC QPLP=RFC/(I.+RFC)
151
RHOG=AMWIS/(358.*(TFC+273.)/273./PFC)
R H O L = 4 0 . 5TN=22. CF=(.II2*ALOGIO(GPLP*SORT(RHOL/RHOG))+.I808)*(STM/20.)**.2 D U F = C F * S Q R T ( ( R H O L R H O G ) / R H O G ) * . 7 5 AXFC=(t.+RFC)*DI3/3600.*(AMWI3/RHOG)/BUF/.88 BFC=SORT(4.*AXFC/PI) XRAT=(RFC-RMFC)/(RFC+I.) YRAT=.75-.75*XRAT**.5668 TPLAF=(-TPLF-YRAT)/(YRAT-I.) APLF=TPLAF/.5
EOM 3800 EOM 3810 ECM 382C EOM 3930 ESM 3540 EOM 3850 EOM 3880 EZOM 3870 EOM 3880 EOM 3630 EOM 3700 EOM 3710 EOM 3720 EOM 3730 EOM 3740 EOM 3?50 EOM 3750 EOM 3770 EOM 3780 EOM 3720 EOM 3800 EOM 35i0 EOM 3820 EOM 3830 EOM 3840 EOM 3850 EOM 3850 EOM 3870 EOM 3820 KOM 3850 EOM 3200 EOM 3810 EOM 3820 EOM 3530 EOM 3s LOH 3550 EOM 3550 EOM 3970 EOM 3920 EOM 3580 EOrl 4030 EOM 4010 EOM 4020 EOM 4030 EOM 4040 EOM 4050 EOM 4050 EOM 4070 EOM 4080 EOM 4090 EOM 4100 EOM 4110 EOM 4120 EOM 4130 EOM 4140 EOM 4 1 5 0 EOM 4160 EOM 4170 EOM 418(I EOM 4150 EOM 4200 EOM 4210 EOM 4220 EOM 4230 EOM 4240 EOM 4250 EOM 4260 EOM 4270 EOM 4280 EOM 4890 EOM 4300 EOM 4310 EOM 4320 EOM 4330 EOM 4340 EOM 4350
152
P.V.L.N. Sarma and G.V. Reklaitisl Optimization o[ a chemical process

EOM 4SSO EOM 4370 EOM 4380 EOM 4350 EOM 4400 EOM 4410 EOM 4420 ,TPLAF, EOf! 4430 EOM 4440 EOM 4450 EOM 4450 FR~CTIOM OF STRIPPER BOTTOMS SENT TO GLYCOL REACTOR EOM 4470 RCF2=AL/L20 EOM 4450 EO24=EQ8 EOM 4489 W24=RCFe*N20 EOM 4500 N25=N20-W24 EOM 45!0 EO25=EO20-E024 EOM 4520 L24=EO24+W24 EOM 4530 AUMW20=EO20/LSO*44.+N20/LSO*lS. EOM 4540 TS=RTEMP+5. EOM 4550 OE2=L24*AUMW20*(STEMT-T8)*!.8 EOM 4560 BTS=OE2/(LS*AUMWS) EOM 4570 TS=ATEMP+DTS/I.8 EOM 4550 RTDS=RLMTO(STEMT+20.,T8,ATEMP,TS) EJM 45~0 AREA2=OE2/(RTD2*I.8*I50.) E3M 4600 IF (AREA2,LT.O~) AREA2=O. EQM 4 B i 0 X2COST=I2GG.12*AREA2**.5T?8 EO!I 4520 EQS=TSA-T9 EOM 4~?0 CP5=E5/G5*CPE(TP)+O5/G5*CPO(TP)+EOS/GS*CPEO(TP)+N5/GS*CPW(TP)+COS/EOM 4943 IGS*CPCO(TP)+TMS/GS*CPM(TP) E3M 46~8 QI=CPS*G5*(RTEMP-ATEMP)*I.8 EOM 4650 TINI=(ATEMP+5.+RTEMP)/2.+2?3. EOM 46~0 CP4=(E4*CPE(TIMI)+O4*CPO(TINI)+EO4*CPEO(TIMI)+W4*CPN(TIMI)+CO4*CPCEQM 4650 IO(T!MI)+TM4*CPM(TIMI))/G4 "EOM 4ESO TRISE=QI/(G4*CP5)/I.8 EOM 4700 T4=TRISE+ATEMP-5. EOM 47[C RTBI=RLMTD(RTEMP,ATEMP, ATEMP-5.,T4) EOM 4720 AREAI=QI/(RTBI*A(8)*I.8) EOM 4730 XICOST=I256.12*ARERI**.5778 EOM 4740 II(1)=!OHRECYCLE GA EOM 4730 M(2)=IOHS/EFFLUENT EQM 4760 M(3)=lOM EXCHAHOR EOM 4770 M(4)=!OHDESIGM EGM 47C0 CALL PRIMTX(N,4, IOHLOAB BTU/H ,QI,IOHLOO DT ,RTOI, EOM 4ZOO CIOHAREA FTs ,RREAI, IOHCOST ,XICOST) EOM 4500 EGil 4810 UTILITY COSTS EOM 4 8 ) 0 EOM 4870 POCOST=CSHP/.8*.7455*.03 EQM 4540 STMCST=GST*IS.*.O01 EOM 4830 QGAIN=-HR EOM 4850 RAW=EI*eG.*.l+O2*32.*.Oe+TM2*28.*.02 EOM 4870 UTILI=POCOST+STMCST -OGAiN EOll ~880 M(1)=IOHUTILITY EOM 4~S0 M(2)=IOHCOSTS EOM 4900 M(3)=IOHFOR EO EOM 4~I0 M(#)=IOHSECTIOM EOM 4920 CALL PRIHTX(M,4,1OHELEC COST ,POCOST, IOHSTEAM COST 9STMCST, EOM 4530 I IOHSTEM CRDT ,OGAIM, iOHTOTAL UTIL ,UTILI) EOIt 4940 SALESI=EOI3*44.*.I5 ESM 4850 FIXCSTI=RCOST+RBCOST+STCOST+XiCOST+CRCOST+X2COST+CRTCOST+COSTLE+COEOM 4s ISTF EGM 4970 FIXHRI=FIXCSTI/80000.*3. EOM 4980 TTLCSTI=FIXHRI+RAW+UTILI EJM 42:30 M(1)=IOHTOTAI_ EOM 5000 M(2)=IOHCOSTS FOR EOM 5010 H(3)=IOHETH OXID EOM 50~0 M(4)=IOHSECTIOM EOM 5030 CALL PRIMTX(M,4,10HFIXCOST ,FIXCSTI,IOHRAW MAT ,RAW, EQM 5040 CIOHFIX/HR ,FIXHRI,IOHSALES $ ,5~LESI) EOM 5[50 COSTLBE=TTLCSTI/(EO12*44.)*lO0. EOM 5080 EQM 55;'0 PROFIT/HR FROM EO EOM 5070 EOM 5050 PRCFI=SALESI-TTLCSTI EOM 5100 EOI! 5ii0 HTFC=APLF*I.5 COSTF=COSTCOL(DFC,HTFC,PFC, I.) M(1)=IOHFIMNL PURI N(2)=IOHIFICATIOM M(3)=IOHCOLUMM M(4)=IOHDESIGM CALL PRINTX(M,S,4HALFA, ALFAFC, IOHTH.PLATES CIOHBIA FT ,BFC, IOHHEIGHT FT ,HTFCp C I O H C O S T ,COSTF)
153
C C C C C
END EO SECTION. BEGIN GLYCOL SECTION EOTOT=EO25+(I.-FREO)*EOI2 SET INDEPENDENT VARIABLES FOR GLYCOL SECTION RATN=X(15)/100, TC=X(16) ROM=X(17) FRWE=X(18) BBLI=X(19) BEWI=X(20) THETA=X(21) PT=X(22) FENC=,SS5 C014=,999 COH=.98 TK=TC+s M(1)=IOHIMBEPE'I'IBNT H(2)=IOH VARIABLS M(3)=IOHFOR GLYCOL M(4)=IOH SECTION CALL PRINTX(M,5,1OHHSO/EO RAT ,RATW, IOHGLYR TEMP ,TC, CIOHNORMAL!TY ,RON, 1OHFR N EUPTD ,FRWE, CIOHBPT, G-WCOL ,BBLI ) CALL PRIMTX(MI,3,1OHBPT, G-WCOL ,DENI,iOHUMDER4OOB ,THETA, CtOHOP.PRES ,PT)
C C C
GLYCOL REACTOR
W R E Q = E O T O T * R A T N FF=NREQ+EOTOT WMAK=WREQ-W25-W26 AUhN=EOTOT/FF*44,+WREQ/FF*I8, FLB=FF*AUMW FVOL=FLB/68.4 C A O = W R E Q / F U O L C B O = E O T O T / F U O L A L F R X = 2 . 1 CB=CBO*(I.-COM) S6=CBO-CB SI=2.*ALFAX-t. Ss S 3 = 2 . * A L F A X * C A O * C A O A L F A X * C A O ~ S 6 S4=SQRT(S2*S2-4,*SI*S3) CA=(-82-$4)/(2.*$I) CR=CA*(CAO-CA)/(CA+ALFAX*(CAO-CA)) C S = C A O C R C A PHI=EXP(30.163-10583./TK) RKI=PHI*ROM*~61.135 R A T E = R K I * C A * C B T A U = ( C A O ~ C A ) / R A T E U O L = T A U * F V O L A C I D P = R O M * 4 . 4 5 COSTI=S633.T8*UOL**.5822+I52.32*UOL**.626 M(t)=IOHGLYCOL M ( 2 ) = I O H R E A C T O R M(3)=IOHDESIGM M(4)=IOH C A L L PRINTX(M,3,1OHTAU MR ,TAU, I O H U O L U M E FT3 C I O H C O S T ,COST1) C C C EXIT LIQUID F R O MR E A C T O R
EOIS=FUOL*CB W15=FUOL*CA EGI15=FUOL*CR EG215=FVOL*C5 C C C
,UOL,
EXIT V A P O RF R O ME V A P O R A T O R
NEVAP=IJ15*FRWE N16=WEVAP E016=E015 NTP=EGII5*S2./(FLB-WEUAP~IB.-E6215*I06,)*IO0. PE=B(7)
ESK 51~0 EOM 5139 E8M 51~0 ESM 5_fO EOH 5130 ES~I 5!70 EO'~ 5 ! 8 0 EOd 5 i S 0 E3M 5230 EOM 5SIO EOH 5223 EOrl 5230 Et]'1 52.~0 23~I 5250 ECN 52F0 EOM 5270 EOh 5280 EOM 5s EOH 53u0 EOiq 5310 E~h 52]0 EOM 5330 EOM 5340 EOM 5350 EGO 5SSO E(]: ~ 537[ EOh 5230 EOM 5~SO ESM 5400 EOM 5410 EC~I 5 4 : ; EOM 5430 EOM 54~0 EOM 5450 EOM 5~$0 EOM 5~70 LOll 5430 EOM 5450 EOM 5500 EOPi 55!0 EOM 5520 EOM 5530 EO~ 55~0 EOM 5550 ~ O M 5530 EOM 5570 EOM 55~0 EOM 5~90 EOM 5600 E O M 5610 E O M 5620 E O M 5630 E O M 5640 E O M 5650 E O M 56~0 E O M 5670 E O M 5680 EOM 5890 EOM 5700 EOM 5710 EOM 5720 EOM 5730 EOM 5740 EOM 5?50 EOM 5760 EOM 5770 EOM 5780 EOM 5750 EOM 5800 EOM 5810 EOM 5820 EOM 5830 EOM 5840 E O M 5850 EOM 5860 EOM 5870
154
P. V.L.N. Sarma and G. V. Reklaitisl Optimization of a chemical process

EOM 5889 EOM 5890 EOM 5800 EOM 5810 BOILING POINT ELEUATION OF GLYCOL-WATER SOLUTION EOM 5820 E@M 5530 BPE=6804oe31555-6873.445341*NLOG+2584.536349*WLOG**2-433.7"8406*NLOEOII 5840 EOM 5350 IG**3+27.116801*WL08**4 EOM 5980 BPE=EXP(BPE) EOM 5~TO B(8)=HLATW(TDEWC)/18. EGH 5380 EOd 55~0 LO~BS ON EUAPORATOR AND CONBENSER EOM 83&0 EOM 5010 QLOAD=I8.*WEUAP*B(8)+FLB~B(9)*(TBEWF-(TC*I.8+32.)) EOM 8020 OSURF=I8.*WEURP*B(8) EOM 8030 TW!=25. TWO=30. EOM 6GqO EOM 80~0 CWLB=I.OZE-5 EOM 60~0 RWC=QSUPF/((TNO-TWI)*I.8)*CWLB EOd 8070 ~TSURF=((TBEWC-TWO)-(TDEWC-TWI))/s EOM 8030 DTSURF=DTSURF~I.8 USRF=IO0. EOM 8050 EOM 8100 ASURF=CSURF/(LISRF*DTSURF) EOM 8110 CSLB=.O01 TST=I50. EOM 61~0 STL=HLAT!4(TST)/18. EOM 8130 EOM 8140 DELTAT=TST~l.8+32.-TDENF-BPE EOM S150 STMRQ=GLOAD/STL EOM 8130 STNCST=STMRO*CSLB EOM 8170 AEUAP=QLORD/(B(IO)*DELTAT) EOM 8 ] ~ q IF ( R E U ~ . L T . O o ) CO TO 101 GO TO 102 EOM 81JO I01COSTE=O. EOM 6200 GO TO !03 EO~! B~lO 102 COSTE=EO3.74*AEUAP**.579 EOM E2EO 103 CONTINUE EOil 6230 EOM 6240 COSTF=@05.Z4*ASURF*~.579 COST~=CD3TE+COSTF EOM 8230 EOM 8230 N(!)=IONEURPORRTR M(2)=IOHDESIGH EOM 8270 N(3)=lOh EOM 8~S0 M(4)=IOH EOM 6230 CALL PRIHTX(N,5, tOHLGAB ,BLOAD, IOHBP ELEU ,BPE, EOM 8300 CIOHTEMP BIF ,BELTAT, IONSTEAM RQ ,STMRO, EOM 8210 CIOKRRER FT2 ,REUAP) EOM 8380 H(1)=IOHCOMBENSER EOM 8230 N(2)=IOHBESIGH EOM 8340 CALL PRINTX(N,4,1OHLOAB ,~SURF, IOMDELTAT ,DELTAT, EOM 835U CIOHRREA FT2 ,ASURF, 1OHCOST ,COSTF) EOM 6230 EOM 8370 BULLET LIOUID COMPOSITION FROM EUAPORATOR EOM BSSO EOM 8330 WIT=WIS-~EUAP EOM 6~00 EGII7=ECII5 EOM 8410 E8217=EC~15 EOM 8450 WIB=FRLC~WI7 EOM 64Z0 Wl =WIF-Wl8 EOM 8440 EOM 8450 WATER REMOUAL COLUMN EOM 8480 EOM 8470 EGI!8=R(i2)*EGII7 EOM 6430 EG!~8=EGII7-EGII8 EOM q4~O ALFATI=UAPW(DEWI)/UAPI(BEWI) EOM 85C0 ALFABI=UAPW(BBLI)/UAPI(BBLI) EON 8510 ALFA=SORT(ALFATI~ALFABI) EOM 85~0 TPL=ALOC(WIB/EGIIB*EGII /WI )/ALOG(ALFA) EOM 8530 FF=NI7+EGII?+EG217 EOM 85J0 AG2T=UAP2(DEWt)/URPI(DEWI) EOM 8580 AG2B=UAP2(BBLI)/UAPI(BBL!) EOII 85s AG2=SORT(AG2T*AG2B) ElM 8STO CC=EGIIB/EGII9 EOM 85~0 EG218=EC217*AG2**TPL*CC/(I.+AG2**TPL*CC) E0;1 8~50 EG219=EC217-E8218 EOM 8300 EOM 8810 OUERHERB STREAM EONBs EOM 8830 TBEWF=STEAMT(PE) TOEWC=(TDEWF-32.)/I.8 WLOG=ALOG(WTP)
C C C
C C C
C C C

DI=EGll8+W1B+EG2IB YN=I418/DI YI=CG!18/DI Y2=EG21S/ul FFI=EGIlT+WI7+EG217 ZN=W!Z/FFI ZI=EGIIZ/FFI Z2=EG217/FFI
155
EOM 6~40 EOM 6650 EOM 68S0 EOM 6670 EOM 6680 EOM 6630 EOM G?O0 EOM G7!O EOM B720 BOTTOMS STREAM EOM 6730 EOM 6740 BI=EGIIs163 EOM 6750 XBW=WIS/BI EOM 67E0 XBI=EGIlS/BI EOM 6270 XB2=EG2I~/BI EOM g7~O AG~=!. ECM 67S0 RMIII=ALFAeYW/(ALFA-THETA)+AGI*YI/(AGI-THETA)+AG2*Y2/(AG2-THETA)-I.EOM 6800 EOM 6SlO MINIMUM REFLUX COMSTRAIMT EOM 68E0 EOM 6830 COMi=ALFA*ZW*(AGI-THETA)*(AG2-THETA)+AGI*Zl*(ALFA-THETA)*(AG2-THETEOM 6840 IA)+AG2*Z2*(ALFA-THETA)*(AGI-THETA) EOM 68E0 KWI=UAPW(DEW1)/PT EOM 68s KWE=UAPW(BBL1)/PT EOM GOZO Kll=UAPI(DEW1)/PT EOM 6S30 KI2=UAPI(BBL1)/PT EOM 6890 Kel=UAP2(DEW1)/PT EQM 6S00 K22=UAP2rBBL1)/PT EOM 6910 EOM 69~0 BENPOIMT ANB BUBBLE POINT CONSTRAINTS EOM 6930 EOM 6940 BEWPT=YW/KWI+YI/KII+Y2/K21 EOM 6S50 BBLPT=XBN*KN2+XBI*KI2+XB2*K22 EOM GSGO R=2.*RMIN EOM 6970 EOM ~380 CONDENSER AND REBOILER LOADS AND AREAS EOM 6950 EOM ?000 OC=(I.+R)*DI*(YN*HLATW(DEWI)+YI*HLATI(~EWI)+Y2*HLAT2(DEWI)) EOM 70!0 XRAT=(R-RKIM~/(R+I.) EOM TO20 YRAT=O.75-O.ZS*XRAT**O.5668 ES!I 7CZO TAPL=(-TPL-YRAT)/(YRAT-I.) E~M 70~? APL=TAPL/.5 E~M 7050 00=I. EOM 70S0 UB!=FFI~CQ+R O l - B I E2M T07'r OB=UBI*(XBW*HLATW(BBL1)+XBI*HLATI(BBL1)+XB2*HLAT2(BBLI)) EOM TOSO TDI=((BEWI-TWO)-(BEWI-TWI))/ALOG((BEWI-TWO)/(SENI-TWI)) EOM 7CEO UCi=75. E3PI 7i00 ACI=QC/(UCI*TBI*I.8) EOM 7~10 UBI=50. EOM 71~0 DEHT=OC/((I.+R)*BI) E]ifl 7120 BEHT=QB/UBI EOM 71~0 TSTI=220. E~1'1 ?i]0 STLI=HLATW(TSTI)/IS. E~M 71~0 TBD!=TSTI-BBLI E3?] 7170 STERMR=QB/STLI E,SM 7160 ABI=QB/(UBI*TBBI*I.8) E3!1TISO CWR=OC/(].8*(TNO-TW!)) EOM 72}0 E ~ I 72~0 DIAMETER OF WATER REMOUAL COLUMN EOII 7~PO EOM 7220 RHOL=70. EOM 7240 AUMOLNT=YN*IO.+YI*62.02+Y2*I06. EGM TESO AUUOL=359.*(BEWI+273.)/273./PT EOM 7E?O RMOG=AUMOLWT/AUUOL ESM 7270 GP=(I.+R)*BI*AUMOLWT ESM 72S0 LP=R*BI*AUMOLWT EO?I 7EEO STN=50. EOd TEeD CF=(O.II2*ALOGIO(GP/LP*S~RT(RHOL/RHOG))+O.18OO)*(STM/20.}*~0.2 EGM 73!0 UF=CF*SQRT((RHOL-RHOG)/RHOG) EOM 73~0 UFB=.ZS*UF EOM 72~0 AX=(I.+R)*D1/3BOO.*AUUOL/UFB/o~8 EOM 72140 DIA=SQRT(4.*AX/PI) ESd 72~0 HEIT=APL*I.5 ZOM 7350 COST3=COSTCOL(DIA, MEIT,PT+I.,2.) EOM T270 COSTS=II31.1*ACI**.5778 EOd 7SEO COST6=I454.95*ABI**.5778 EOM 7279
[56
P, V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process
COSTST=STEAMR*CSLB COSTCN=CNR~CNLB COST7=COSTST+COSTCW TTL!=COST3+COSTS+COST6 N(1)=IOHGLYCOL M(2)=IOHHRTER COL M(3)=IOHUMN M(4)=IOHDESIGM CALL PRINTX(M,5,1OHTH.PLATES ,TAPL, IOHREFLUX CIOHBIA FT ,BIA, IOHHEIGHT FT ,HEIT, CIOHCOST ,COST3) N(1)=IOHREBOILER N(2)=IOHDESIGM
,R,
N(S)=IOH
N(4)=IOH CALL PRIMT C I O F I A R E A FT2 ,ABI,1OHCOST N(1)=IOHCONBEMSER M(2)=IOHBESIGN CALL PRINTX(N,4,1oHLOAB CIOHAREA FTe ,ACI,1OHCOST T2=120. PTG=.3 ALFA2=UAPI(T2)/UAP2(TS) A15=0.99 A16=O.O1 EGI20=EGIIs EG220=EG219*A16 WSO=W19 EG!21:EGIIg-EGI20 EG221=EG219-EG280 ,O8,10HTEMP BIF ,COST6) ,OC, IOHTEMP DIF ,COSTS) ,TBDI~
,TDI,
XD:E~I20/(EGI20+EG220)
XB=EGI21/(EGI21+EG281)
TPL2=ALOG(XB/(1.-XD)*(I,-XB)/XB)/ALOQ(ALFA2)
FF2=EGIIg+EG219 XF=EGIIg/FF2
820:E0120+EG220
RMGL=REMIN(ALFA2, XB,XF) RMGLI=RMGL IF (RNGL.LT.O.) RMGL=.OI
RGL=2.*RMGL
AMW20=(EGI20*G2.+EG220*I06.)/D20 RHOL=70. STN=40. RHDG=AMW20/(359.*(T2+273.)/273./PTG)
GPLP=RQL/(I,+RGL) CF=(.II2*ALOGIO(GPLP*SORT(RHOL/RHOG))+.ISOS)*(STM/20.)**.2 UFB=CF*SQRT((RHOL-RHOG)/RHOG)*.75 AXGL=(I.+RGL)*D20/3600.*(AMWs DGL=SORT(4.*A XRAT=(RQL-RMQL)/(RGL+I.) YRAT=,FS-.TS*XRAT**.5668 TPLAG=(-TPLS-YRAT)/(YRAT-I,) APL2=TPLAG/.5 HTG=APL2*I.5 C O S T G L = C O S T C O L ( D G L , HTG,PTG+I,,2.)
N(1)=IOHFIMAL PURI N(2)=IOHFICATIOM M(3)=IOHCOLUMM N(4)=IOHDESIGN
CALL PRINTX(M,5,1OHALFA
CIOHBIA FT ,~GL, IOHHEIGHT CIOHCOST ,COSTGL) FIXCST2=COSTI+COST2+TTLI+COSTGL COSTS FOR GLYCOL SECTION
,ALFA2,1OHTH.PLATES
,HTG,
,TPLAG,
PRWC=WMAK*I8.*4.8E-5 H2SO4C=ACIBP/IOO.*FLB*O.05 UTILB=COSTST+COSTCN+STMCST+PRNC+RWC+H2S04C RAW2=EOTOT*44,*COSTLBE/IO0. FIXHR2=FIXCBT2/80000.*3.
SALES2=EgI20*62.*.I9 TTLCST2=FIXHR2+UTIL2+RAW2 P R O F S = S A L E S S ~ T T L C S T 2 COSTLBG:TTLCST2/(EGI20*S8.)*IO0.
ECM 7400 EOM 74 10 E2M 7<EC ECM 7<39 EOil 7440 E:]M 7450 E~]il 7450 EL]M 7~70 EOH 74~0 EOd 745 ["~ EOM 7500 E0~I 7510 EOM 75L0 EJId 7520 ECM TSCO EOM 7550 E0;I 7560 ESM 7570 ElM 7580 ESH 75 b.rJ EOM 7609 EOM 7610 EOM 7620 EOI~ 7~39 EOM 7E:gO EOI1 7G50 EOf! 76~0 EOM 7570 ECd 7880 Eg','1 7220 EOM 7700 EOM 7710 EOM 7 7 2 0 EOM 7730 EOM 7740 EOM 7750 EOM 7760 EOM 7770 EOM 7780 EOM 7790 EOII 7800 EOM 7610 EOM 7EEO EOM 7830 EOM 7840 EOM 76:5C EOM 7860 EOM 7870 E0['I 7880 EOM 7E,SO EOM 7900 EOM 7210 EOM 7950 EOM 753-0 EOM 7540 EOH 7550 ECM 7580 EOM 7570 EOM 75~0 EOM 75S0 EOM 8,000 EOM 8010 EOM 8080 EOM 8030 E011 8040 E:]M 8050 EOM 8050 EOM 80:'0 EOM 8~,s EOM 8060 EOM 8100 EOM 8110 EJM 8] ~ ; EOM 8130 EOM 8150 EOM 8150
P. V.L.N. Sarma and G. V. Reklaitis/ Optimization of a chemicat process
157
C C C
C C C
C C C C C
C C C
C C C C
EOM 2150 EOM 8170 EOM 3150 EOd 8!~9 ,UTIL2, EOM 82:10 EOM 8610 EOld 8220 TOTAL PROFIT AND RETURN ON IMUESTMEHT ESM 8889 EOI1 8240 PPROF=SALESI+SALES2-TTLCSTI-FiXHRS-UTIL2 E]M 8250 RDI=PPROF*8OOO./(3.*FIXCSTI+3.*FIXCST2) EOM B2SO RDI=ROI*IO0. EOM 86i~0 M(1)=IOHFIMAL UALU E9,1 823S M(2)=IOHS FOR THE E!3X SE?O M(3)=IOHEMTIRE EOil 83C0 M(4)=IOHPROCESS EOM 8ZIO ,PPROF, CALL PRIMTX(M,4,1OHROI ,ROI,IOHPROFIT/HR EOM 8220 CIOHEO PRODM ,EOI3,10HGLY PRODM ,EGI20) EQ;1 2320 EOM 8340 SET EOUALITY CONSTRAINTS 8 IM HUMBER EG! 8350 E:]h 8ZSO QX(1)=EQI EOM 8~?0 8X(2)=E02 EOM 8330 0X(4)=E04 E~3 82G0 QX(5)=E05 Et]M 8 4 ] 0 EOM 84!0 OX(G)=COMI ESM 8~E0 OX(7)=DEWPT-I. EOM 8430 QX(3)=BBLPT-I. EOM S~LO OX(8)=FACI-I.II E3M 84!50 EJM 8460 SET IMEOUALITY CONSTRAINTS ii IH HUMBER EOM 8476 FOR XO AND XE THE UPPER BOUNDS ARE SUPPLIED BY GRG EOM 8C80 THEY ARE 0.2 AHD 0.3 RESPECTIUELY E8;1 8488 EOM 8880 OX(g):XO ECM 8510 OX(IO)=XE EOM 8~E0 QX(!I)=SSX -!.i E8~ 8530 QX(12)=ALFA-THETA EOM 86~[, QX(13)=THETA-AG2 EGK 8550 OX(14)=BELTAT EGM 85~6 OX(~S)=XRAT EOM 8570 QX(!G)=STEMT-TgA EOM 8 ~ 9 QX(!7)=~MIM-.O01 EOM 8~SL QX(18)=STEMT-T8 EGM 8CbC OX(19)=FFAC-I.I EOM 8319 EOM $6~0 SET OBJECTIUE FUNCTION. CHOOSE ONE EOM 8639 EOM 8640 QX(20)=-PPROF EOM 8650 OX(20)=-ROI EOM 86~8 IF (IFLAS.ME.I) RETURN EGA 8~70 EOM 8230 HERE ATOM BALANCES ARE MADE. THESE SERUE TO CHECK EOM 8680 IF AMY GROSS ERRORS PRESENT IH MATERIAL BALANCING. EOM 8TO0 EOM 8TIO CIM=EI*2. EOM 8780 HIM=EI*4.+GST*2.+NMAK*2. OIM=O2*8.+GST+NMAK EOM 8730 C O U T = E S B * 2 . + C O 2 8 + E O I I * 2 . + C O I ! + E O I 3 * 2 . + E O I 4 * 2 . + E O I ~ * 2 . + E G l I 8 * 2 . + E G 2 E O M 8T40 I18*4.+E8220*4.+EG121*8.+E8221*4.+E028*2.+EG120*2.+C013+0030 EOM 8750 87~0 HOUT=E28*4.+EO28*4.+W28*2.+EO!I*4.+EOI3*4.+WI3*2.+EOI4*4.+WI4*2o+EEOM 8770 I016*4.+NIB*2.+WI8*2.+EG118*G.+EG218*IO.+EG120~B.+EG220*IO.+EGI21*BEOM 2.+EG221*10.+W20*8. EOM 87'80 OOUT=CO28*2.+O28*2.+EO23+N28+EOII+COII*2.+EOI3+WI3+EOI4+WI4+WIT+EOEOM 8780 IIB+WIS+EQII8*2.+EQ218*3.+EQIeO*2.+EG2eo*3.+EGI21*2.+EG221*3.+COI3*EOM 8800 28.+W20+C030-8. EOM 8s EOM 8820 TMIM=TM2*2. EOM 8830 TMOUT=TM28*2. EOM 8840 M(1)=IOHATOM BALAM ECM 8850 M(2)=IOHCES EOM 8680 M(3)=IOH EOM 8870 H(4)=IOH EOM 8830 ,CIM, IOHCARBOM OUT ,COUT) CALL PRIMTX(M,2,1OHCARBOM IM ,H!M, IOHHYBRO ObT ,HOUT) EOM 8880 CALL PRIMTX(MI,e,I O H H Y D R O IN ,OIM, IOHOXY OUT ,0OUT) EOM 8800 CALL PRIMTX(MI,2~IOHOXY IM ,TMIM,!OHMITRO OUT ,TMOUT) EOM 8Si0 CALL PRIMTX(MI,2,1OHMITRO IM
M(1)=IOHTOTAL M(2)=IOHCOSTS FOR M(S)=IOHGLYCOL M(4)=IOHSECTIOM CALL PRIMTX(M,4,1OHFIX CST ,FIXCST2,1OHUT[LITIES CIOHTTLCST/HR ,TTLCST2,1OHSALES $ ,SALESS)
158
P.V.L.N. Sarma and G.V. Reklaitis[ Optimization o[ a chemical process
15 14 13 12 Ii I i0
RETURN EMD SUFROUTINE PRINTX(L,N, NAMI,XI,MAM2,X2,NAM3, XS, MAM4,X4, NAMS, N5) COMMOM/FLAGS/ IFLRG DIMENSION MAM(5),X(5),L(4) IF(IFLAG.NE.I) RETURN IF(M.EQ.O)GO TO 1 GO TO (Ii,12,13,14,15) N X(5)=X5 NAM(5)=MAM5 215 NAM(4)=NRM4 215 NAM(3)=MAM3 X(2)=X2 MAM(2)=MRM2 X(1)=XI MAM(1)=MAMI PRIMT IO,L,(MAM(I),X(I),I=I,M) FORMAT(IX,4AIO/ IH=,EI2.S,3X)) RETURM END
EOM EOM EOM EOM E3M EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM EOM
8920 ~$30 8~40 ~5~C 85~0
$57'0
85E0 8ESO ~OOO 9010 B020 ~030 S040 5050 90@0 3570 SOS0 9OS8 9100 9110 ~!20 9130
A.1. Explanation of A and B arrays

A(1) A(2) A(3) A(4) A(5) A(6) A(7) A(8) A(9) A(10) A(11) A(12) = = = = = = = = = = = = cost of catalyst for E O reactor $1b/Lang factor, not used, purge fraction, fraction of CO2 r e m o v e d in the CO2 removal system, feed rate of ethylene, lb mol/hr, not used, not used, heat transfer coefficient for recycle/feed exchanger, Btu/hr/ft2/~ fraction of ethylene oxide r e m o v e d in the light ends column, fraction of carbon dioxide r e m o v e d in the light ends column, fraction of ethylene oxide r e m o v e d in the final purification column, fraction of w a t e r removed in the final purification column and also fraction of m o n o e t h y l e n e glycol r e m o v e d in the water removal column, not used, not used, not used, not used, not used, not used, not used, not used, not used, pressure in evaporator, psia, heat of vaporization of water corresponding to pressure in evaporator, Btu/lb (calculated in the program), not used, heat transfer coefficient for e v a p o r a t o r , Btu/hr/ft2/~
A(13) A(14) A(15) B(1) B(2) B(3) B(4) B(5) B(6) B(7) B(8)
= = = = = = = = = = =
B(9) = B(10) =
P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process B(11) = n o t u s e d , B(12) = n o t u s e d , B(13) = n o t u s e d , B(14) = n o t u s e d , B(15) = n o t u s e d .
159
Acknowledgment
T h e first a u t h o r g r a t e f u l l y a c k n o w l e d g e s the e n c o u r a g e m e n t a n d s u p p o r t of the Selas C o r p o r a t i o n of A m e r i c a d u r i n g the p r e p a r a t i o n of this p a p e r a n d the partial s u p p o r t of the P u r d u e R e s e a r c h F o u n d a t i o n d u r i n g the m o d e l d e v e l o p m e n t phase.
References
[1] A. Adelman and W.F. Stevens, "Process optimization by the complex method", AIChE Journal 18 (1972) 20-27. [2] S.H. Ballman and J.L. Gaddy, "Optimization of methanol process by flowsheet simulation", Industrial and Engineering Chemistry Process Design and Development 16 (1977) 337-344. [3] R.A. Barneson, "Picking optimization methods", Chemical Engineering 77 (1970) 132-136. [4] J. Bracken and G.P. McCormick, Selected applications of nonlinear programming (Wiley, New York, 1968). [5] R.R. Buntin, "A kinetic study of oxidation of ethylene on a silver catalyst", Ph.D. thesis, Purdue University, W. Lafayette, IN (1961). [6] D.M. Considine, ed., Chemical and process technology encyclopedia (McGraw-Hill, New York, 1974). [7] R.S. Dembo, "GGP: A computer program for the solution of generalized geometric programming problems: Users manual", McMaster University, Hamilton, Canada (1975). [8] C.W. Dibella and W.F. Stevens, "Process optimization by nonlinear programming", Industrial and Engineering Chemistry Process Design and Development 4 (1965) 16-24. [9] E.D. Eason and R.G. Fenton, "Testing and evaluation of numerical methods for design optimization", UTME-TP 720,1, University of Toronto, Toronto, Canada (1972). [10] H.E. Eduljee, "Equations replace Gilliland plot", Hydrocarbon Processing 54 (1975) 120-123. [lll L.D. Gaines and J.L. Gaddy, "Process optimization by flowsheet simulation", Industrial and Engineering Chemistry Process Design and Development 15 (1976) 208-217. [12] E.W. Gorczynski, H.P. Hutchinson, and A.R.M. Wajih, "Development of a modularly original equation oriented process simulator", CACE 79, Montreux, Switzerland (April 1979). [13] B.S. Gottfried, "Nonlinear process optimization by a Monte Carlo simulation technique", personal communication. [14] K.M. Guthrie, "Data and techniques for preliminary capital cost estimating", in: H. Popper, ed., Modern cost engineering techniques (McGraw-Hill, New York, 1970). [15] R. Hernandez and R.W.H. Sargent, "A new algorithm for process flowsheeting", CACE 79, 12th Symposium on Computer Applications in Chemical Engineering, Montreux, Switzerland (April 1979). [16] B.S. Jung, W. Mirosh and W.H. Ray, "A study of large scale optimization techniques", AIChE 71st National Meeting, Dallas, TX (1972). [17] L.S. Lasdon, A.D. Warren, A. Jain and M.W. Ratner, "Design and testing of a generalized reduced gradient code for nonlinear programming", ACM Transactions on Mathematical Software 4 (1978) 34--50.
160
[18] R. Luus and T.H.I. Jaakola, "Optimization by direct search and systematic reduction of the size of search region", AIChE Journal 19 (1973) 760-766. [19] R. Luus and T.H.I. Jaakola, "A note on the application of nonlinear programming to chemical process optimization", Operations Research 22 (1974) 415--418. [20] J.T. Mason and O.K. Crosser, "Optimal search on the return on investment surface of a small chemical plant", paper presented at AIChE 71st National Meeting, Dallas, TX (1972). [21] W. McCabe and J.C. Smith, Unit operations of chemical engineering (McGraw-Hill, New York, 1972). [22] M, McLane, M.K. Sood and G.V. Reklaitis, "A hierarchical strategy for large scale process calculations", CACE 79, Montreux, Switzerland (April 1979). [23] R.L. Motard, M. Shacham and E.M. Rosen, "Steady state chemical process simulation", AIChE Journal 21 (1975) 417--438. [24] W.C. Mylander, R.L. Holmes and G.P. McCormick, "A guide to SUMT-version 4: The computer program implementing the sequential unconstrained minimization technique for nonlinear programming", Paper RAC-P-63, Research Analysis Corporation, McLean, VA (1974). [25] A,L. Parker and R.R. Hughes, "Computational problems in the implementation of quadratic approximation programming", paper presented at the AIChE Meeting, Houston, TX (April 1979). [26] W.A. Parker and J.W. Prados, "Analog computer design of an ethylene glycol system", Chemical Engineering Progress 60 (1964) 74-83. [27] M.S. Peters and K.D. Timmerhaus, Plant design and economics for chemical engineers (McGraw-Hill, New York, 1968). [28] M.J. Rijckaert and X.M. Martens, "Analysis and optimization of the Williams-Otto process by geometric programming", AIChE Journal 20 (1974) 742-747. [29] M.J. Rijckaert and X.M. Martens, "Biographical note on geometric programming", Journal of Optimization Theory and Applications 26 (1978) 325-329. [30] R.R. Root, "An investigation of method of multipliers", Ph.D, thesis, Purdue University, W. Lafayette, IN (1977). [31] E.M. Rose, "A machine computation method for performing material balances", Chemical Engineering Progress 58 (1962) 69-75. [32] E. Sandgren, "The utility of nonlinear programming algorithms", Ph.D. thesis, Purdue University, W. Lafayette, IN (1977). [33] R.W.H. Sargent, "The decomposition of systems of procedures and algebraic equations", in: Lecture Notes in Mathematics 630 (Springer, Berlin, 1978) pp. 158-178. [34] R.W.H. Sargent and A.W. Westerberg, "Speed-up in chemical engineering design", Transactions of the Institutions of Chemical Engineers 42 (1964) 190-197. [35] P.V.L.N. Sarma, "Strategy of modeling and optimization in chemical process design", Ph.D. thesis, Purdue University, W. Lafayette, IN (1978). [36] J.D. Seader, W.D. Seider and A.C. Pauls, "FLOWTRAN simulation--Anintroduction", 2nd ed. (Ulrich's Bookstore, Ann Arbor, MI, 1977). [37] B.D. Smith, Design of equilibrium state processes, (McGraw-Hill, New York, 1963). [38] M. Sriram and W.F. Stevens, "An example of the application of nonlinear programming to chemical-process optimization", Operations Research 21 (1973) 296--302. [39] W.F. Stevens, "Applications of nonlinear programming to chemical engineering process optimization", paper presented at the ORSA Meeting, New Orleans, LA (1972). [40] P.B. Stewart and P. Mungal, "Correlation equation for solubility of carbon dioxide in water, seawater, and seawater concentrates", Journal of Chemical and Engineering Data 2 (1971) 170-178. [41] R.E. Treybal, Mass transfer operations, (McGraw-Hill, New York, 1968). [42] A.D. Warren and L.S. Lasdon, "The status of nonlinear programming software", Operations Research 27 (1979) 431-448. [43] A.W. Westerberg, Carnegie-Mellon University, Pittsburgh, private communication. [44] T.J. Williams and R.E. Otto, "A generalized chemical processing model for the investigation of computer control", AIEE Transactions Part 1, Communications and Electronics 79 (1960) 458--471.

82 Optimization of A ComplexChemProcess Using An EquationOrientedModel

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82 Optimization of A ComplexChemProcess Using An EquationOrientedModel

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Mathematical Programming Study 20 (1982) 113-160 North-Holland Publishing Company

O P T I M I Z A T I O N OF A C O M P L E X C H E M I C A L P R O C E S S USING AN EQUATION O R I E N T E D M O D E L P.V.L.N. SARMA

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

FA FB REACTOR 9 HEAT E X C H A N G E R DECANTER FP

Fig. 1. The Williams and Otto process.

P.V.L.N. Sarma and G.V. Reklaitis[ Optimization of a chemical process

P. V.L.N. Sarma and G. V. Reklaitis/ Optimization of a chemical process

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

P. V,L.N. Sarma a n d G.V. Rekiaitis/ Optimization of a chemicat process

P. V.L.N. Sarma and G. V. Reklaitis/ Optimization of a chemical process

P. V.L.N. Sarma and G. V. Reklaitis[ Optimization of a chemical process

P. V.L.N. Sarma and G. V. Reklaitis[ Optimization of a chemical process

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

P. V.L.N. Sarma and G. V. Reklaitis/ Optimization of a chemical process

3.2. Energy b a l a n c e equations

Q = AH0 + ~ (N5 - N4), f Cp, dt

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

In this equation, zla = ~ (N5 - N4)ioti

3.964x 107_t _9.518x 108)]

where pH20 is the vapor pressure of water in atm.

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

1 4 G' ]112 ~ P~ V--~660]

P . V . L . N . S a r m a and G.V. Reklaitis[ Optimization o[ a chemical process

awl = Pw(Tt)/PEGI(Tt), b Otwl = Pw(Tb)/PE~I(Tb),

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

Qc= L18(R + I)(~ XilSAi)

dH dNEo dNco UAs (T - Tc), d W - d W (AHEo) + ~ (AHco2) -- pbA

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

lb mol of EO hr (lb of catalyst)' lb mol of CO2 hr (lb of catalyst)

k2~ O 1/2 tE D x 0 2 " F(Pr) rco2 = (1 + 24.55PE)(1 + 1.71749Pg~)

,-0094 8ox ( 41(

for the catalyst weight, and equation of the form

P. V.L.N. Sarma and G. V. Reklaitis/ Optimization of a chemical process

P . V . L N . Sarma and G.V. Reklaitis] Optimization of a chemical process

mGIL > - 1.1;

P.V.L.N. Sarma and G.V. Reklaitis[ Optimization of a chemical process

3.6. Objective functions

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

credit for generated heat = 1.17 x 10-6 $/Btu,

P, V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

i = l ..... NEQ, i = I + N E Q ..... M, i = 1 ..... N, i = l ..... N,

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

P.V.L.N. Sarma and G.V. Reklaitisl Optimization o[ a chemical process

P. V.L.N. Sarrna and G. V. Reklaitis/ Optimization o[ a chemical process

P.V.L,N. Sarma and G.V. Reklaitis! Optimization o~ a chemical process

P.V.LN. Sarma and G.V. Reklaitis/ Optimization of a chemical process

P. V.L.N. Sarma and G. V. Reklaitis/ Optimization o[ a chemical process

P. V.L.N. Sarma and G, V. Reklaitis[ Optimization of a chemical process

2969.43 2858.81 2858.81 2794.26

P.V.L.N. Sarma and G.V. Reklaitis] Optimization of a chemical process

Table 6 Optimization results with

Corresponding optimal points

aUnscaled values. bOptimum not reached.

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization o[ a chemical process

P.V.L.N. Sarma and G.V. Reklaitis/ Optimization of a chemical process

HLATI(T)=28825.*((374.-T)I334.)**0.38 HLAT2(T)=39158.*((407.-T)/367.)**0.38 H E M R Y S CONSTANTS FOR EO, AND C02

QMI(T)=EXP(lB2.33-2S.163*ALOG(273.+T)-IIOI2.57/(T+273.))/ZS. OM2(T,P)=EXP(16.43-2698./(T+273.)-2.477*P/(T+273.)+I18S.S*P/(T+273EOM I.)**2+.O178*P**2/(T+273.)+.O8EI*P**2/(T+273.)**2) EOM

P. V.L.N. Sarma and G. V. Reklaitis[ Optimization of a chemical process

SATURATION TEMP OF STEAM GIUEM PRESSURE

P.V.L.N. Sanna and G.V. Reklaitis/ Optimization of a chemical process

QMI(T)=EXP(lB2.33-2S.163ALOG(273.+T)-IIOI2.57/(T+273.))/ZS. OM2(T,P)=EXP(16.43-2698./(T+273.)-2.477P/(T+273.)+I18S.S*P/(T+273EOM I.)**2+.O178*P**2/(T+273.)+.O8EI*P2/(T+273.)2) EOM

PRWC=WMAKI8.4.8E-5 H2SO4C=ACIBP/IOO.FLBO.05 UTILB=COSTST+COSTCN+STMCST+PRNC+RWC+H2S04C RAW2=EOTOT44,COSTLBE/IO0. FIXHR2=FIXCBT2/80000.*3.

SALES2=EgI2062..I9 TTLCST2=FIXHR2+UTIL2+RAW2 P R O F S = S A L E S S ~ T T L C S T 2 COSTLBG:TTLCST2/(EGI20S8.)IO0.