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Introduction to

Multicomponent Distillation

1

Calculation difficulties

Binary

problems:

straightforward

solution

**using stage-by-stage calculation
**

Use graphical approach with the McCabe &

Thiele diagram or computer calculation

Multicomponent problem: is significantly more

difficult

2

**Consider distillation column and assume CMO,
**

constant pressure and adiabatic column

3

**Number of degrees of freedom = C+6
**

Binary mixture C=2

Degrees of freedom=8

Specify 8 variables: F, z, feed quality q, distillate

composition xD, distillate temperature TD

(saturated liquid), xB, L/D (R), NF (optimal feed

location)

Operating lines are fully defined and one can step

off stages using the McCabe & Thiele graphical

4

method

Also assume column pressure is fixed and the column is adiabatic 5 . Degrees of freedom=9 Number of variables Variable 1 Feed rate.bot (or x3. q (or hF or TF) 1 Distillate. x2.z1 -z2) 1 Feed quality.dist (or x3. x1. z2 (z3 = 1 .bot or one fractional recovery) 1 L0/D or V/B or QR 1 Saturated liquid reflux or Treflux 1 Optimum feed plate location 9 Column pressure and Qcol = 0 are already specified. z1.dist or D or one fractional recovery) 1 Bottoms. F 2 Feed composition.Ternary mixture C=3.

For C=3. Thus. neither bottom nor distillate composition is completely specified. the extra degree of freedom is used to specify the feed composition. 6 .

Consequently. However. for multi-component systems. 7 . it is also possible to do a complete analytical solution using mass and energy balances with the equilibrium relationship. one would find that the number of equations obtained from mass and energy balances with the equilibrium relationship will always be one less than the number of unknowns. C > 2.Multi-Component Distillation (MCD) – The Problem While we can graphically solve a binary component distillation system using the McCabe-Thiele method. as well as special considerations as to enhancing convergence of the solution. one cannot do a complete analytical solution for multi-component distillation – it requires a trial-and-error solution with the additional unknown assumed to be known.

one always needs to know the underlying theory and methods of calculation to enable one to make decisions about the validity of these “off–the– shelf” packages and to verify the results. 8 . Aspen Hysys /UniSim have been developed to perform the rigorous solution of multi-component distillation systems. as a design engineer.“Off-the-Shelf” Solutions Fortunately. However. numerical design packages. such as Aspen Plus.

9 .MCD – Some Additional Terminology When dealing with multi-component systems. we introduce some new terminology in addition to the terms used in binary distillation: Fractional recoveries Key components Non-key components Splits – distributing and non-distributing systems Note that binary systems can be handled in the same terms.

MCD – Fractional Recoveries 10 .

i Fz F. i Bx i bot Fz F. i FR i dist 1 FR i bot FR i bot 1 FR i dist It is the simple relationships expressed by the right-hand-side equations that make the use of fractional recoveries useful. i Bx B. These are also often specified simply as % recovery. i Dx D. 11 .MCD – Fractional Recoveries Fractional recoveries are often specified in MCD. FRi. is the amount or flow rate of component i in the distillate or bottoms stream with respect to the amount or flow rate of component i in the feed stream: FR i dist FR i bot Dx i dist Fz F. i Fz F. A fractional recovery.

The most volatile of the key components is termed the light key (LK).MCD – Key Components The components that have their distillate and bottoms composition specified are known as the key components. 12 . The least volatile of the key components is termed the heavy key (HK).

13 . If a non-key component is less volatile than the heavy key. If a non-key component is more volatile than the light key. then it is termed a light non-key (LNK). it is a heavy non-key (HNK). then it is an intermediate non-key (INK) or simply NK. If a non-key component is neither a heavy non-key nor a light non-key.MCD – Non-Key Components All other components not specified in the distillate or botoms are termed non-key components (NK’s).

Decreasing volatility 1. LNKs: light non-keys 2. HNKs: heavy non-keys 14 . HK: heavy key 4. LK: light key 3.

MCD – Non-Key Component Splits The split of the non–key components is generally defined as to where the non–key components are obtained with respect to the distillate or bottoms stream. One can have two types of situations concerning the split of the non–key components: Sharp split – Non-distribution of non-keys Split – Distribution of non-keys 15 .

16 . We obtain a sharp split of the NK’s.MCD – Non-distribution of NK’s Non–distribution of non–keys means that essentially all of the non–keys are obtained in either the distillate stream or the bottoms stream. Non–distribution of non–keys can be assumed when: All of the non-keys are either HNK’s or LNK’s The fractional recoveries of the LK in the distillate and HK in the bottoms are relatively large.

The fractional recoveries of the LK in the distillate and HK in the bottoms are not relatively large. Distribution of non–keys occurs when: Not all of the non-keys are either HNK’s or LNK’s – we have NK’s.MCD – Distribution of NK’s Distribution of non–keys means that the non keys are not sharply split between the distillate stream or the bottoms stream. We obtain a split of the NK’s. 17 .

The relative volatility for the reference component. which is trivial for a binary system. from the DePriester charts for hydrocarbon systems.How do we determine the keys (LK and HK) and the non–keys (LNK’s. 18 .g. of course. will be 1. In order to use relative volatilities in MCD. HNK’s and NK’s) in MCD? The classification of components in MCD can be determined from their relative volatilities. but in general it will be the HK component since it is less volatile than the LK component. We can then define relative volatilities using equilibrium coefficient K values for each component. The choice of the reference component depends upon the problem. we choose a reference component and define all other component volatilities with respect to the reference component. Relative volatility is defined as the ratio of the K values for two components.. e.

What are the key and non–key designations for this separation? 19 .Key and Non-Key Example Consider a distillation column with the following feed components: propane n–butane n–pentane n–hexane The recoveries for n–butane and n–pentane are specified for the distillation.

From the DePriester charts.Key and Non-Key Example Component volatilities can be determined from the K values. the order of volatility is: propane > n–butane > n–pentane > n–hexane Since the recoveries of n–butane and n– pentane are specified… 20 .

Key and Non-Key Example We have: Volatilities propane > n–butane > n–pentane > n–hexane Component Propane n–butane n–pentane n–hexane Designation Light Non–Key Light Key Heavy Key Heavy Non–Key 21 .

Key and Non-Key Example If the recoveries of n-butane and nhexane are specified: Volatilities propane > n-butane > n-pentane > n-hexane Component Propane Light n-butane n-pentane n-hexane Designation Non-Key Light Key Non-Key Heavy Key 22 .

Key and Non-Key Example If only the recovery of n–butane is specified: Volatilities propane > n–butane > n–pentane > n–hexane Component Propane n–butane n–pentane n–hexane Designation Light Non–Key Key Non–Key Non–Key 23 .

one specifies the LK and the HK recoveries. but it must be estimated since not enough information is typically given in the problem to determine it directly. One way to estimate the fractional recovery of the missing key component is to do an external mass balance based upon a binary system comprised of the LK and HK.Missing Keys In typical MCD problems. 24 . This fractional recovery is then used in the MCD solution. – usually the non-key component with the greatest feed composition. The fractional recovery of the missing key needs to be determined. respectively. A trail–and– error solution may be required to determine the actual fractional recovery. one typically chooses one of the non-key components to be the HK or LK. If only the LK or the HK recovery is specified.

xD. What are the key and non-key designations for this separation? 25 . for ethylene is required.Key and Non-Key Example Consider a distillation column with the following feed components: Methane Ethane Ethylene Propylene Propane It is specified that a distillate concentration.

which can be found from the DePriester charts.Key and Non-Key Example One source for determining the order of the component volatilities can be determined from the K values. The order of volatility is: methane > ethylene > ethane > propylene > propane Since xD for ethylene is specified it is a key component. 26 . for example.

What if an xD for ethylene and an xB for propylene are specified? 27 .Key and Non-Key Example Component Designation Methane Light Non-Key Ethylene Light Key Ethane Non-Key Propylene Non-Key Propane Non-Key There is no heavy key specified for this problem.

Key and Non-Key Example Component Designation Methane Ethylene Ethane Propylene Propane Light Non-Key Light Key Non-Key Heavy Key Heavy Non-Key 28 .

Note that in multicomponent distillation neither the distillate nor the bottoms composition is completely specified because there are not enough variables to allow complete specification The external balance equations for the column shown in Figure 5-1 are easily developed. Distillation column 29 . Figure 5-1.

(5-2) For a ternary system. but these equations must add to give Eq. (5-1). only two of Eqs. Thus. (5-1) are independent Summation rules 30 . (5-2) plus Eq. Eqs.The external balance equations for the column shown in Figure 5-1 Eq. (5-1) Eqs. (5-2) can be written three times.

we only have xi.dist .Solve mass balances to get D and B For any components. but not both. we cannot compute D and B 31 . Thus.bot or xi.

For stage-by-stage calculation. x3. x2.dist.bot 5 equations only: 3 mass balances and 2 summation rules Energy balance and equilibrium relationships will add extra variables (vapor mole fractions. D. 32 .Ternary mixture 6 unknowns: B. one cannot start out by solving external mass and energy balance equations. x1. need to know all compositions at one end of the column.bot and x3.dist. condenser and reboiler duties) Thus.

If sharp separation (split of the NK components) then one can solve external mass balances LNK appear only in the distillate HNK appear only in the bottoms Need only fractional recoveries to completely specify Bottom and distillate compositions 33 .

Profiles for Multicomponent Distillation Flow rates and temperature profiles are similar to binary distillation case Composition profiles look different from binary distillation 34 .

Profiles for Multicomponent Distillation If CMO valid Vapor and liquid flow rates will be constant in each section They change at withdrawals stage each feed stage or side-stream Non CMO case Vapor and liquid flow rates will vary from plate to plate The ratio L/V varies less significantly 35 .

434 mole frac similar to the behavior of binary systems Saturated liquid. Total liquid and vapor flow rates 36 .21. αtol = 1. and there are 19 equilibrium stages plus a partial reboiler. Figure 5-2.0 kmol/h. Toluene= 0.3 kPa.Simulation for distillation of benzene-toluene-cumene Feed condition Benzene= 0. Feed stage is number 10 above the partial reboiler.233 mole frac. F = 1.333 mole frac.0. A total condenser is used. Desire 99% recovery of benzene Cumene= 0. αcum = 0. L/D = 1.0. p = 101.25. Relative volatilities: αben = 2.

37 . same problem as in Figures 5-2 and 5-4.Temperature profile Temperature profile decreases monotonically from reboiler to condenser Behavior similar to binary distillation case If temperature plateaus then there is a pinch point in the column Figure 5-3. Temperature profile for benzene-toluene-cumene distillation.

same conditions as Figures 5-2 and 5-3 for nonconstant molal overflow benzene mole fraction is very low in the reboiler and increases monotonically to a high value in the total condenser. and there is no LNK Figure 5-4. Thus. This is essentially the same behavior as that of the more volatile component in binary distillation. Liquid-phase composition profiles for distillation for benzenetoluene-cumene. cumene is the HNK. so its behavior is simple 38 . and toluene is the HK.Stage 10 is the feed stage. Composition profiles benzene recovery in the distillate was specified as 99% Benzene is the LK. In this problem benzene is always most volatile.

and cumene (HK). toluene (LK). same problem as in Figure 5-2 to 5-4 except that a 99% recovery of toluene in the distillate is specified 39 . toluene (LK). Liquid phase composition profiles for distillation of benzene (LNK). the HK concentration does not have any maxima Figure 5-5.Composition profiles benzene (LNK). and cumene (HK) 99% recovery of toluene in the distillate is specified Note that with no HNKs.

αcum = 0. 0.33. Liquid composition profiles for distillation of benzene (LNK). toluene (LK).0.Composition profiles Recovery of toluene in distillate 99%. αxy = 0. and cumene (HNK).275 cumene. Feed is 0. we would expect the LK curve to show maxima. and since there is an HNK.125 benzene. 0. and 0. we would expect maxima in the HK concentration profile Figure 5-6. Relative volatilities: α ben = 2. primary maxima secondary maxima Since there is an LNK.21 40 . αtol = 1. xylene (HK).375 xylene.225 toluene.25.

Sandwich component: Tend to accumulate in the middle section of the distillation column Can cause column flooding and/or development of a second liquid phase the Happens when one separates ethanol/water mixture: trace components such as butanol are partially miscible with water Solution: use sidestream withdrawal to remove intermediate boiling components 41 .

all component must be present at feed stage but at that stage a discontinuity in the composition profile is present 42 .NK usually do not distribute HNKs present only in the bottoms LNKs present only in the distillate 3.key component concentration can have maxima 2.NK often go through plateau region 4.Differences between binary and multicomponent distillation 1.

The feed is 0. Reflux ratio is L0/D = 3.Example 5-1. 43 . 0.482 n-pentane.7% of the n-pentane in the bottoms. External mass balances using fractional recoveries We wish to distill 2000 kmol/h of a saturated liquid feed. The optimum feed stage is to be used.056 mole fraction propane.3 kPa. 0. A fractional recovery of 99. Estimate distillate and bottoms compositions and flow rates.4% n-butane is desired in the distillate and 99. and reflux is a saturated liquid.5. The column operates at 101.321 n-butane. The column has a total condenser and a partial reboiler. and the remainder nhexane.

and npentane is the HK.The order of volatilities is: propane > n-butane > n-pentane > n-hexane quite high Thus. xi.dist.bot. n-butane is the LK. We will estimate distillate and bottoms based on these assumptions 44 . and B Assumption: Since the recoveries of the keys are quite high. quite high Find xi. This automatically makes propane the LNK and n-hexane the HNK. D. it is reasonable to assume that all of the LNK collects in the distillate and all of the HNK collects in the bottoms.

which we will write as Eq. 5-11 Eq. 5-10 Note that this also implies For n-pentane the equations are Eq. 5-8a. 5-14a Eq. 5-9a. (5-8) to (5-13) represent eight equations with ten unknowns (four compositions in both distillate and bottoms plus D and B). 5-13 Eqs. 5-14b 45 .assumptions of the NK splits can be written either as Eq.b or The fractional recovery of n-butane in the distillate can be used to write Eq.b Eq. Equations (5-4) give two additional equations. 5-12 Eq.

9940)(2000)(0. (5-11). and B = 1246.89 Then Now the individual distillate mole fractions are Equation 5-15 Check: Bottoms can be found from Eqs.bot = 0.6.dist DxC6. and (5-14b). (5-12). xC4. Start with the distillate DxC3.bot = 0. (5-9a).056) = 112 0 (0.003)(2000)(0. xC6. xC5.5 (0.dist = = = = FzC3 = (2000)(0.dist DxC5.0031.7708.These ten equations can easily be solved.dist DxC4.bot = 0.2260.482) = 2. Remember that these are estimates based on our assumptions for the splits of the NK 46 .bot = 0.321) = 638. (5-8b). The results are xC3. since distillate and bottoms calculations can be done separately Do it.

8% recovery of methanol in the distillate and a methanol mole fraction in the distillate of 0.Chapter:3. and F = 10. Feed is a saturated liquid. We have a feed mixture of 22 mol% methanol. We desire a 99. and 13 mol% n-butanol. 18 mol% n-propanol.99.000 kmol/day. Find compositions of distillate and bottoms. Problem D3. 47 . Find D and B. 47 mol% ethanol.

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