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Journal of Food Engineering 69 (2005) 207215 www.elsevier.

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Operation planning in the rectication of essential oils


Silvina D. Zamar a, Hector E. Salomone b, Oscar A. Iribarren
a

a,b,*

Unidad Academica Reconquista, Universidad Tecnologica Nacional, Roca 1250 (3560) Reconquista, Argentina b Instituto de Desarrollo y Diseno, INGAR, Conicet Avellaneda 3657 (3000) Santa Fe, Argentina Received 1 March 2000; revised 2 February 2004; accepted 14 July 2004

Abstract This paper proposes a methodology that uses a recently developed shortcut model to represent each individual separation task, for planning the operation of a batch distillation column. For a given column and recycle policy, optimization of the recoveries of two key components at each separation renders the set of optimal reux ratios and advances in each separation. The methodology is specially expedite for systems with a large number of components and whose performance can be upgraded by recycling intermediate cuts, as is the case in the rectication of essential oils. We illustrate the methodology by planning the rectication of crude orange oil to produce an oil essence depleted from light terpenes, which are responsible for rancidity of oils. 2004 Elsevier Ltd. All rights reserved.
Keywords: Essential oils processing; Batch rectication; Operation planning

1. Introduction Crude essential oils are processed in batch distillation columns in order to enrich the product in some components while decreasing the amount of another components. Even if complete elimination of a component is not physically possible, any desired extent of separation is theoretically attainable by adding more separation stages and increasing the reux ratio. For existing columns, the number of stages places a limitation on the sharpness of the separation, which is the one attainable if the column were operated at total reux. Therefore, the more rigorous is the specication for a separation, the larger is the reux ratio required and the longer is the operation time needed to perform the separation. In practice, if the desired separation demands very large reux ratios, it may be convenient to operate the column at a lower reux, producing cuts
Corresponding author. Tel.: +54 342 4555229; fax: +54 342 4553439. E-mail address: iribarr@ceride.gov.ar (O.A. Iribarren). 0260-8774/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2004.07.019
*

out of specication and re-processing these cuts afterwards. This operation strategy often leads to shorter total operation time than that of the single step separation. Once admitted the possibility for multiple step operations, there is a number of alternative strategies. For instance, a rst step may produce a distillate cut on spec and a sloppy residue that is processed in a second step in order to achieve the specications for the nal residue. The distillate obtained on this second step has to be re-processed and therefore is normally recycled and mixed in a subsequent batch. Choices on which sloppy cuts are generated, and how they are recycled for re-processing gives raise to the different alternatives. In general, any of these alternatives can be represented as a network of single step separations connected by material balance constraints, known as a state task network STN after Kondili, Pantelides, and Sargent (1993), which is equivalent to the process ow sheet of continuous processes. In the context of this work, we use the term operation planning meaning the decision problem of selecting

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Nomenclature b C d f F MW N N Nmin Ph Pl R moles in bottom after the separation [kg mol] number of components moles in distillate after the separation [kg mol] feed: moles in still before separation [kg mol] feed to separation network [kg mol] or [kg] molecular weight [kg/kg mol] moles in still during the separation number of separation stages of the column minimum number of separation stages to perform a given separation task heavy product exiting the network [kg mol] or [kg] light product exiting the network [kg mol] or [kg] reux ratio Rmin x minimum reux ratio to perform a given separation task composition [molar fraction]

Greek symbols a relative volatility g recovery dened as d/b Subscripts b bottom of the column f feed i component k separation task lk light key hk heavy key r reference component t top of the column

a particular sequence of separations (i.e. the STN), determining the size and composition of the sloppy cuts to be re-processed and choosing the operation conditions for each single separation, for a given existing batch distillation column. The optimization of a performance indicator for the whole network will typically drive the decision process. Any suitable indicator will require the estimation of the performance of each individual separation task. The resulting optimization problem is very hard to solve if it is approached with rigorous models for the distillation operations. Unlike what happens for continuous processes, for which there are commercial simulators that permit to implement rigorous distillation models, batch process owsheeting must still resort to simplied models. On one hand dynamic models are computationally much more expensive than steady state models, but also batch processes need to be scheduled so that all the required batch tasks are performed within the available time horizon. For example Hysys does provide a rigorous batch distillation block, but this block cannot be a node inside a STN that includes other separation blocks: the simulation package lacks the interfaces to interconnect blocks, there is no provision for implementing scheduling constraints, nor a block to drive the convergence of mass balances of the STN and by no means a block for optimizing the process variables at each separation. Writing an ad hoc program to do the job is possible, for example Salomone, Montagna, and Iribarren (1997) use a simulation approach for the design and operation of a batch plant, but as they report it is a very time consuming task, both for setting up the problem and for solving it.

So for example, to optimize a process including reaction and distillation stages with the recycle of intermediate cuts, Bhatia and Biegler (1996) resort to a simplied Fenske Underwood Gilliland FUG model for the distillation tasks, developed by Logsdon, Diwekar, and Biegler (1990). In this way they were able to optimize the molar conversions at the reaction steps and the reux ratios at the distillation steps, satisfying both the scheduling and mass balances constraints. Models even simpler than FUG may be used, as the constant size factor model used by Quesada and Grossmann (1995) to solve a problem of synthesis of the separation network, which is more complex than the sizing problem solved by Bhatia and Biegler (1996): There is a tradeo between the complexity of the problem to be solved and the level of detail of the operation unit model that can be aorded. Therefore, in this paper we use a simplied model for the batch distillations, to screen the structural alternatives (the recycling alternatives), optimizing the operation conditions of each separation task: reux ratio and extent of separation. The simplied batch distillation model is also of the FUG type, but has a smaller computational demand than the model of Logsdon et al. (1990). We will briey introduce the model here but is described in detail in Zamar, Salomone, and Iribarren (1998). Based on this model we propose a methodology for the operation-planning problem above described. We illustrate its implementation with an example of rectifying a crude essential oil of orange, where operation strategies based on sloppy cut recycling prove to be better options than the single step separation.

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2. Shortcut method for multiple task batch rectication The shortcut model used in this work allows the estimation of the separation performance of a given network of batch distillation tasks without resorting to dynamic multistage models. Unlike the simulation approaches that take as data the feed, the number of stages, and the reux ratio, giving the extent of separation as a result; the model that we describe here takes as data the feed and a specied extent of separation, giving the minimum number of stages Nmin and reux ratio Rmin as a result. The method uses partition functions to estimate the nal distribution of components for each individual separation task in the network. These distributions are obtained as product quantities relative to feed quantities and are used to solve the material balances for the whole network. With all the intermediate compositions already dened, it is possible to predict the reux ratio needed for each separation task by using a Gilliland-like correlation developed by Salomone, Chiotti, and Iribarren (1997) for batch rectication. 2.1. Minimum number of stages With the same simplifying assumptions needed to arrive to Fenske equation in continuous distillation, Zamar et al. (1998) derived an equivalent expression valid for batch rectication, to predict the minimum number of stages needed to perform a separation task: h i ln1glk ln ln1ghk N min 1 ln alk;hk where gi are the recoveries of product i, i.e. the amount of product i in the distillate after the separation, divided by the amount of product i in the feed before the separation. If the recoveries of two key components light key (lk) and heavy key (hk) are set and replaced in Eq. (1) one gets the value of Nmin. 2.2. Partition functions Geddes (1958) rst realized that the distribution of components in actual continuous distillation columns could be approximated by straight lines in plots of the logarithm of a fractional index dened as (xi,t/xi,b)/ (xk,t/xk,b) vs. the logarithm of their relative volatility ai,k. Further work by other authors, reviewed in King (1980) showed that this distribution can be rigorously predicted for total reux, and is a good approximation to the actual distributions in a range of reux ratios around 1.2 the minimum. For batch distillation Zamar et al. (1998) rearranged Eq. (1) to get: 1 gi 1 gr ai;r
N min

and showed that it can be used as a partition function to reasonably approximate the distribution of non-key components, given the recovery of a reference product r, where r can be any of the keys. So, if a value is set for the recoveries of two key components one can get Nmin from Eq. (1) and then use Eq. (2) to get the recoveries of the remaining components. 2.3. Computation of material balances Using recovery fractions as variables, the material balances at each separation task k can be written: d i;k gi;k fi;k bi;k 1 gi;k fi;k 3

where fi,k are the moles of component i fed to separation k, di,k are the moles of component i collected in the distillate after separation k, and bi,k are the moles of component i that remain in the still after separation k. So, the material balances for the network consist of as many Eq. (3) as separation tasks are contained in the network, plus the equations that connect tasks, for example: bi;k fi;k1 fi;k bi;k1 d i;k1 4

The rst is a simple connection: the bottom collected after performing task k is going to be the feed for task k + 1. The second represents a recycle: the distillate of task k + 1 is going to be added to the bottom of task k 1 to conform the feed of task k. Finally, we compute the equations that connect the distillation network with the environment, i.e. the denition of feeds and products of the network. For example: F i fi;1 ; P li d i;k ; P hi bi;k1 5 for a network with just one feed that enters to separation 1, a light product which is the distillate produced after separation k and a heavy product which is the bottom produced after separation k + 1. By inspection of the form of Eqs. (3)(5), the reader may verify that the whole system of equations representing the mass balances, becomes linear when the gi,k are set. 2.4. Computation of the minimum reux ratio By solving the material balances given by Eqs. (3)(5) provides all the information needed by the methodology proposed by Salomone, Chiotti, et al. (1997) to get the reux ratios Rmin needed to achieve these separations. The minimum reux to perform a separation task is dened as the reux required by a hypothetical batch distillation column having an innite number of separation stages, so its instantaneous separation performance is given by Underwood equations. At each step of the integration one must compute the C 1 roots hm of

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iC X ai xi;b 0 ai hm i1

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Each of these roots is located between the consecutive ai and is readily found by an area elimination method. Then one nds the top compositions by solving:
iC X ai xi;t 1R ai hm i1

m 1; . . . ; C 1

There are C 1 independent equations like (7) and the required extra equation is that the summation of xi,t equals unity. This easy to solve linear system of equations provides the top compositions at each integration step of the mass balance equations for the still. The integration is performed for a guessed value of R starting from feed composition and stops when the recovery of the light key component reaches glk Then, depending on the recovery obtained for the heavy key component being smaller or larger than ghk dictates the next trial of R being smaller or larger than the value at the previous iteration, till convergence. A more detailed description of the procedure is presented by Salomone, Chiotti, et al. (1997). 2.5. Correlation between number of stages and reux ratio After getting Nmin and Rmin, these values can be related to the actual number of stages N and reux ratio R by using a Gilliland-like correlation that was constructed for batch distillation by Salomone, Chiotti, et al. (1997):    0:34 ! N N min R Rmin 8 0:62 1 N 1 R1

3. Methodology for planning the separation Following we present the contribution of the present paper, which is a strategy for solving the operation planning problem that uses the described shortcut model. First we analyze the degrees of freedom and tradeos involved, then we address the objective function and constraints, and nally we outline the proposed methodology. 3.1. Analysis of degrees of freedom and tradeos It is well established in the relevant literature that any proposed network of distillation tasks has two degrees of freedom per each separation (Mujtaba & Macchietto, 1993). Thus, in order to ll these degrees of freedom, it is usual to specify two compositions (distillate and residue), or one composition (usually the distillate) and the recovery of some component.

Another way to fully dene a separation is to specify the recoveries of two key components, namely the light and the heavy keys. Thus, the separation task to be achieved consists in recovering at least glk of the light key and no more than ghk of the heavy key. Using fractional recoveries in the distillate for specifying a given separation has some advantages against using compositions. Along the batch distillation, the recoveries are monotonically increasing quantities while compositions are not. The recovery of any component increases from 0 to 1 with the advance of the rectication. At the beginning of the distillation, the recovery of all components is zero, while if the operation were continued until all the feed is collected as distillate, at this point the recoveries of all components would be equal to one. For any given advance of the rectication the recovery of each component is dierent from the recoveries of the other components, and for mixtures with constant relative volatilities, the value of these recoveries are ordered in the same order as their relative volatilities. As the separation capacity of the column increases (larger N, R), the trajectories for the recoveries of individual components become steeper and separates one from each other. If just one degree of freedom is used by specifying the recovery of one component, for example the recovery of a light key component glk = 0.95, then this specication can be satised with any pair (N, R) by just stopping the operation when 95% of the light component present in the feed is collected as distillate. If the second degree of freedom is given by specifying a value for the recovery of a heavy key component, for example ghk = 0.05 then, for a given number of stages N there exists one (and only one) value of R that permits to simultaneously satisfy both specications. For example if for a trial R and stopping the advance of the rectication when glk = 0.95 it happens that the recovery of the heavy key is larger than specied i.e. ghk > 0.05 then a larger R is needed to get a sharper separation. Also, once the recoveries of two components are set, it is not possible to set the recovery of any of the remaining components: they will be distributed between the distillate and the still according to their relative volatilities with respect to the pair light keyheavy key. If the number of stages were not xed but were a decision variable (i.e. in the design problem), then there exist innite pairs (N, R) able to meet the specication on the recoveries (glk, ghk). Should be observed that for systems with constant volatilities, given any specication in terms of two recoveries it will be always possible to nd a design (Number of Stages, Reux Ratio) that produces that separation (i.e. the trajectories of the recoveries for the two components specied, reach the target value simultaneously). The previous assertion is only

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limited to the fact that a separation worse than the simple distillation (one stage, no reux) cannot be obtained. The specication of two recoveries unambiguously denes the separation and provides two bounds on (N, R) which are the minimum number of stages Nmin and minimum reux ratio Rmin Then, there still exist an innite number of pairs (N, R) with N > Nmin and R > Rmin that can satisfy the separation. The linking between an N and its corresponding R is given by Eq. (8). And the innite number of pairs (N, R) range from N innite (corresponding to R = Rmin) and N = Nmin (corresponding to R innite, i.e. total reux). If the number of design specications were such that it included all the degrees of freedom (glk, ghk), then the design problem would consist in selecting the sets (N, Rk) that optimize an objective function that will depend on N and Rk. If the number of design specications were smaller than two times the number of separations (the original number of degrees of freedom), then the optimization problem would have more degrees of freedom including variables g. This is the typical case when some of the streams are not nal products but are recycled within the process (switching to a recycle policy increases the degrees of freedom, usually without changing the number of design specications). The production-planning problem that we address in this paper is just a particular case of the scenario described above, where the number of stages N is xed which reduces the feasible region of (glk, ghk). Here we propose to take the recoveries of two key components per separation as the independent variables and get a value for them by optimizing a proper objective function. Specications other than recoveries can be handled as constraints at the optimization, while specications given as recoveries reduce by one the degrees of freedom simplifying the problem. 3.2. Objective functions and constraints The choice of the objective function is dierent if the methodology is applied to design a new column or to plan operations in an existing one. In the rst case, the objective function will usually be a combination of capital and operating costs. Capital costs are those depending on N (costs associated with the height of the column and packing or number of trays) and the boilup rate (costs associated with the diameter of the column and the heat exchange area of boiler and condenser). Operating costs are those associated to the energy costs for boiling and condensing as well as labor costs depending on the operating time. In the case of operation planning, a performance indicator such as total operating time, value of products obtained, etc., may be used. In addition, the problem will have dierent constraints such us specications of

purity, maximum boilup, time horizon, number of stages, etc. The boilup determines the design of a column (the size required) or the operating time required by an existing column and is related to the amounts of distillate obtained and the reux ratios: Boilup X
k

d k Rk 1

where dk is the distillate produced at each step k, P d k i d i;k and Rk is the reux ratio used at each step. The purity specications are given as constraints on the components molar ow rates, e.g. d i;k X
i

d i;k P xspec i

10

is constraining the molar fraction of component i in the distillate collected in separation k to be larger than or equal to the specication xspec . i The other general constraint in the case of production planning is concerned with the minimum number of stages required by each separation task being smaller than the actual number of stages of the column: N min k < N 3.3. Outline of the methodology By selecting recoveries as the independent variables the shortcut model for the single separations can be readily incorporated into a methodology for solving the operation-planning problem. Given an alternative network structure, the goodness of the alternative can be assessed by the value of the objective function once all the non-specied recoveries have been set to its optimal value. Within this optimization, the shortcut method is used to evaluate the objective function through the following steps: Step 1 Given a value for the two key recoveries for each separation task. Step 2 For each separation: Compute the Nmin with Eq. (1). Check feasibility. If unfeasible, penalize Objective Function. Go to Step 5. Use Eq. (2) to predict the recoveries of non-key components. Step 3 Solve the mass balances for the network equations (3) (5): Check feasibility. If unfeasible, penalize Objective Function. Go to Step 5. 11

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Step 4 For each separation: Compute Rmin by the procedure outlined in Section 2.4. Compute the actual R with Eq. (8). Step 5 Evaluate the objective function. Given the procedural nature of the computation, handling of constraints is done through penalties in the objective function. A term depending on the magnitude of the violation is added to the objective function at the end of the computation. Thus, any unconstrained non-linear optimization algorithm can be used for driving the search of the decision variables, generating a new set of recoveries for the key components of each separation. Observe that the procedure checks for feasibility as soon as they may be generated, thus avoiding unnecessary computations.

4. The rectication of essential oil of orange Consider the case of removing the light terpenes from a crude oil of orange with the composition in Table 1. Unlike literature examples that rarely exceed three or four components of quite balanced (equimolar) feeds, this highly unbalanced mixture of 8 components is representative of the avors and fragrances industry. The terpenes lighter than limonene are present in a small amount and are responsible for rancidity of the essential oil. While the price of the crude oil is about $18 kg1, a cut containing limonene and heavier components with less than 500 ppm of myrcene and lighter components has a price of $30 kg1 and the byproduct containing the light terpenes has a much lower price of $8 kg1. If the rectication is done without producing and recycling intermediate cuts out of specication, then even with very large reux ratios a lot of limonene is lost into the light product. There are only two possible recycle schemes here, because the end products are two. So the cuts to be produced are three: a light end product, a heavy end product and an intermediate cut to be recyTable 1 Composition of essential oil of orange Name a-Pinene b-Pinene Myrcene d-Limonene Linalool Decanal Citral Valencene Molar fraction 0.004 0.004 0.018 0.952 0.004 0.005 0.001 0.012 Volatility 1.9854 1.7094 1.0770 1.0000 0.2886 0.1827 0.1016 0.0617 Molar weight 136.24 163.24 136.24 136.24 154.25 156.27 152.24 204.36

cled. The alternatives arise from the possible sequences for producing the splits: rst split the light cut from the intermediate plus heavy cut, or rst split the heavy cut from the intermediate plus light cut, a more detailed description about the generation of these alternatives is given by Chiotti, Salomone, and Iribarren (1993). The rst recycling strategy consists in producing the light product cut at a large (but not so large as in the case with no recycle) reux ratio to minimize the amount of limonene in this cut, and afterwards collect an intermediate cut (to be re-processed) until the stringent specication of light terpenes in the bottom is reached. With this recycle strategy, the light product will contain a smaller amount of limonene, which in turn increases the amount of valuable heavy product. The other alternative is to rst proceed with the rectication at a lower reux ratio until getting the bottom product specication and afterwards re-distill the rst distillate to produce the light product with a larger concentration of light components and a bottom (where most of the limonene in the rst distillate is recovered) which is recycled to be processed with the next fresh feed. In any case, there is a set of reux ratios and termination criteria for each of the two consecutive steps that optimize the performance of the separation. To illustrate the implementation of the methodology proposed here for solving multiple task batch distillation problems, we will optimize the rectication of batches of 10 kg of this essential oil in an existing glass laboratory column, which has 40 separation stages provided by three meters of regular packing of Teon. Heating is provided by a 5 kW electric pad. This feed is processed under vacuum at decreasing absolute pressure to maintain the temperature below a threshold of 70 C. Electrical power in the heater is regulated to maximize heat input without ooding the column. This results in an average power consumption of 4.8 kW. We assumed that an operating time of 15 h (two shifts) was available to do this processing. With an average heat of vaporization of 69 kcal/kg, it accounts for a maximum Boilup available of 900 kg. 4.1. Single pass processing We rst considered the single pass separation schematized in Fig. 1. The problem has two constraints: P3 bi Purity Pi1 6 0:0005 12 8 i1 bi X 13 Boilup R 1 d i MWi 6 900 where the MWi are the molecular weights of the components. The objective function is to maximize the selling price: Objective Max OF 8P l 30P h 14

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Fig. 2. Two steps distillation, with recycle of intermediate cut.

Fig. 1. Single pass distillation, no recycle.

Table 2 Single pass distillation, no recycle Mass balances # 1 2 3 4 5 6 7 8 Total Base 1 mol feed F 0.004 0.004 0.018 0.952 0.004 0.005 0.001 0.012 1 d 0.004 0.004 0.01763 0.23326 0 0 0 0 0.25889 b 0 0 0.00037 0.71874 0.004 0.005 0.001 0.012 0.74111

time (allowing even larger reux ratios). Instead, we kept the same constraints and tried the strategy of recycling an intermediate slop cut. The strategy is schematized in Fig. 2. The optimization program consists of two sets of Eq. (3) and the connecting equations are: fi;2 bi;1 fi;1 F i d i;2 15

The equations that dene the Boilup and end products are now: Boilup
8 X i1 8 X i1 8 X i1

d i;1 R1 1 d i;2 R2 1MWi

16

glk = 0.97947, ghk = 0.24502, objective function = 243.05$, Nmin = 35, Rmin = 152.2, R = 345.3.

P P where P l 8 d i MWi and P h 8 bi MWi are the i1 i1 light and heavy products in kg. The degrees of freedom for a single pass are two. The key components are myrcene and d-limonene so their recoveries were selected as optimization variables. The optimal solution and corresponding mass balances are presented in Table 2. As could be expected by simple analysis, the constraints are active. The reux ratio should be such that the purity constraint is satised at Boilup = 900 kg. Such huge values for the reux ratio are not uncommon in essential oils processing. Even so, the amount of valuable product is about 75% of the feed while the light cut contains more than 90% of limonene. An important amount of the total limonene is in the lower price product in order to strip-o the light components from the bottom. 4.2. Recycle of an intermediate slop cut The single pass separation considered in the last section could be made sharper assigning more operating

Pl

d i;1 MWi

and

Ph

bi;2 MWi

17

The optimal solution and corresponding mass balances are presented in Table 3. The intermediate cut that is recycled amounts to almost 60% of the fresh feed and this permitted to increase the valuable product to almost 90% of the feed with the light product composition of limonene dropping to about 75%. 4.3. Re-distilling the distillate The separation task that we took as an example is the typical case of removing a small quantity of light components. It is a common practice in industry in this case, to obtain a rst distillate such to remove the light components from the bottom and afterwards re-distill the distillate to recover the main product in it. The bottom of this second separation is then added to the next fresh feed. We tried this strategy next, which is schematized in Fig. 3, with the optimal solution presented in Table 4. The connecting equations changed to

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Table 3 Two steps distillation, with recycle of intermediate cut Mass balances # 1 2 3 4 5 6 7 8 Total Base 1 mol feed Fi 0.004 0.004 0.018 0.952 0.004 0.005 0.001 0.012 1 fi,1 0.004 0.004 0.032515 1.521793 0.004 0.005 0.001 0.012 1.584308 di,1 0.004 0.004 0.017552 0.077413 0 0 0 0 0.102965 bi,1 0 0 0.014963 1.444379 0.004 0.005 0.001 0.012 1.481342 di,2 0 0 0.014515 0.569793 0 0 0 0 0.584308 bi,2 0 0 0.000447 0.874586 0.004 0.005 0.001 0.012 0.897033

glk(I) = 0.53982, glk (II) = 0.97010, objective function = 277.35$, ghk (I) = 0.05087, ghk (II) = 0.39449, Nmin (I) = 36, Nmin (II) = 26, Rmin (I) = 135.7, Rmin (II) = 74.7, R (I) = 367.5, R (II) = 88.0.

with the rest of the program remaining the same. This alternative recycles a large amount of material: the bottom of the second distillation is even larger than the fresh feed, but anyway it turned out to be the best, increasing the valuable product to 91.5% of the fresh feed with a light product composition of limonene of 70%.

5. Discussion and conclusions A methodology for supporting the decision problem of planning separations using batch distillation is presented. The methodology allows the rapid screening of intermediate cut recycling alternatives using simplied models. The suitability of the approach is illustrated with an example where operation strategies other than single step rectication proved to be more convenient. The models were implemented in Visual Basic and the optimization algorithm used was Simplex. The optimization runs demanded in the order of 15 min or less in a PC Pentium 2333 MHz.

Fig. 3. Two steps distillation, re-distilling the distillate.

fi;2 d i;1 fi;1 F i bi;2

18

while the assignment of end products equations changed to Pl


8 X i1

d i;2 MWi

and P h

8 X i1

bi;1 MWi

19

Table 4 Two steps distillation, re-distilling the distillate Mass balances # 1 2 3 4 5 6 7 8 Total Base 1 mol feed Fi 0.004 0.004 0.018 0.952 0.004 0.005 0.001 0.012 1 fi,1 0.004 0.004 0.036497 2.089093 0.004 0.005 0.001 0.012 2.15559 di,1 0.004 0.004 0.036041 1.197217 0 0 0 0 1.241258 bi,1 0 0 0.000457 0.891875 0.004 0.005 0.001 0.012 0.914332 di,2 0.004 0.004 0.017543 0.060124 0 0 0 0 0.085667 bi,2 0 0 0.018498 1.137093 0 0 0 0 1.155591

glk (I) = 0.98749, ghk (I) = 0.57308, objective function = 281.15$, glk (II) = 0.48676, ghk (II) = 0.05022, Nmin (I) = 22, Nmin (II) = 34, Rmin (I) = 52.4, Rmin (II) = 109.8, R (I) = 56.4, R (II) = 220.1.

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Depending on the problem, a model with this intermediate level of detail can suce, or otherwise will provide a good starting point for the next, more rigorous level. This is the hierarchical approach introduced by Douglas (1988) and it is applicable for this kind of processes as well. In the particular case of the separation approached here, the strongest simplifying assumptions of the short cut model do apply. If a suitable relative volatility is estimated for a dilute solution of myrcene in limonene at 70 C it will remain nearly constant because these process conditions do not change. The simplifying assumption of negligible column hold-up was appropriate for our application because regular packing have very little hold-up. Also constant molar overow is here a good approximation because most of the components are isomers that have very similar heats of vaporization. The simplied distillation model allowed a rapid comparison of alternative processing schemes and a rst estimation of good operation conditions. In a general case, the next step would be a rened design using models that are more rigorous. However, as solving this problem with rigorous distillation models proves to be a formidable task, few publications approached the problem of optimizing the recycle of intermediate cuts. Luyben (1988), Mujtaba and Macchietto (1992) and Bonny, Domenech, Floquet, and Pibouleau (1994) did solve this problem, with varying degrees of detail for the column model but in all cases handling mixtures of at most three components. The present paper is to our knowledge the rst report solving a problem with a large number of components. Finally, we would like to note that the approach proposed here is also expedite in terms of programming eort. Setting the problem for dierent recycling alternatives is straightforward when posing the material balances in terms of recoveries. Using two recoveries per separation as the decision variables, allows the estimation of all other recoveries and operating conditions with a simple shortcut method. For an application in operation planning, like the one described here, simplicity for setting up the optimization problems and a rapid resolution of them become desirable features.

Acknowledgements Founding for this work by CONICET through Project PIP 02706 and FONCYT through Project PICT 14-08752, is gratefully acknowledged.

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