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You are on page 1of 47

Introduction to

Multicomponent Distillation

1

Calculation difficulties

Binary

problems:

straightforward

solution

Use graphical approach with the McCabe &

Thiele diagram or computer calculation

Multicomponent problem: is significantly more

difficult

2

constant pressure and adiabatic column

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

Number of variables

Variable

Feed rate, F

fractional recovery)

recovery)

L0/D or V/B or QR

9

Column pressure and Qcol = 0 are already specified.

Also assume column pressure is fixed and the column is adiabatic

used to specify the feed composition.

Thus,

neither

bottom

nor

distillate

system using the McCabe-Thiele method, it is also possible to

do a complete analytical solution using mass and energy

balances with the equilibrium relationship.

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.

multi-component distillation it requires a trial-and-error

solution with the additional unknown assumed to be known, as

well as special considerations as to enhancing convergence of

the solution.

Off-the-Shelf Solutions

Fortunately, numerical design packages, such

as Aspen Plus, Aspen Hysys /UniSim have been

developed to perform the rigorous solution of

multi-component distillation systems.

However, as a design engineer, one always

needs to know the underlying theory and

methods of calculation to enable one to make

decisions about the validity of these offthe

shelf packages and to verify the results.

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

terms.

9

10

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

Bx i bot

Fz F, i

Dx D, i

Fz F, i

Bx B, i

Fz F, i

FR i dist

1 FR i bot

FR i bot

1 FR i dist

that make the use of fractional recoveries useful.

11

The components that have their distillate and

bottoms composition specified are known as the

key components.

The most volatile of the key components is

termed the light key (LK).

The least volatile of the key components is

termed the heavy key (HK).

12

botoms are termed non-key components (NKs).

then it is termed a light non-key (LNK).

it is a heavy non-key (HNK).

light non-key, then it is an intermediate non-key (INK) or

simply NK.

13

Decreasing volatility

2. LK: light key

3. HK: heavy key

4. HNKs: heavy non-keys

14

The split of the nonkey components is

generally defined as to where the nonkey

components are obtained with respect to the

distillate or bottoms stream.

One can have two types of situations

concerning the split of the nonkey

components:

Sharp split Non-distribution of non-keys

Split Distribution of non-keys

15

Nondistribution of nonkeys means that

essentially all of the nonkeys are obtained in

either the distillate stream or the bottoms

stream. We obtain a sharp split of the NKs.

Nondistribution of nonkeys can be assumed

when:

All of the non-keys are either HNKs or LNKs

The fractional recoveries of the LK in the

distillate and HK in the bottoms are relatively

large.

16

Distribution of nonkeys means that the non keys are not sharply split between the distillate

stream or the bottoms stream. We obtain a

split of the NKs.

Distribution of nonkeys occurs when:

Not all of the non-keys are either HNKs or

LNKs we have NKs.

The fractional recoveries of the LK in the

distillate and HK in the bottoms are not

relatively large.

17

the nonkeys (LNKs, HNKs and NKs) in MCD?

volatilities.

Relative volatility is defined as the ratio of the K values for two components,

which is trivial for a binary system.

and define all other component volatilities with respect to the reference

component.

for each component, e.g., from the DePriester charts for hydrocarbon

systems.

The choice of the reference component depends upon the problem, but in

general it will be the HK component since it is less volatile than the LK

component.

18

Consider a distillation column with the following feed

components:

propane

nbutane

npentane

nhexane

for the distillation.

What are the key and nonkey designations for this

separation?

19

Component volatilities can be determined

from the K values.

From the DePriester charts, the order of

volatility is:

propane > nbutane > npentane > nhexane

pentane are specified

20

We have:

Volatilities

propane > nbutane > npentane > nhexane

Component

Propane

nbutane

npentane

nhexane

Designation

Light NonKey

Light Key

Heavy Key

Heavy NonKey

21

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

If only the recovery of nbutane is

specified:

Volatilities

propane > nbutane > npentane > nhexane

Component

Propane

nbutane

npentane

nhexane

Designation

Light NonKey

Key

NonKey

NonKey

23

Missing Keys

of the non-key components to be the HK or LK, respectively, usually

the non-key component with the greatest feed composition.

it must be estimated since not enough information is typically given in

the problem to determine it directly.

component is to do an external mass balance based upon a binary

system comprised of the LK and HK.

error solution may be required to determine the actual fractional

recovery.

24

Consider a distillation column with the

following feed components:

Methane

Ethane

Ethylene

Propylene

Propane

xD, for ethylene is required.

What are the key and non-key designations

for this separation?

25

One source for determining the order of the

component volatilities can be determined

from the K values, which can be found from

the DePriester charts, for example.

The order of volatility is:

methane > ethylene > ethane >

propylene > propane

Since xD for ethylene is specified it is a key

component.

26

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.

What if an xD for ethylene and an xB for

propylene are specified?

27

Component

Designation

Methane

Ethylene

Ethane

Propylene

Propane

Light Non-Key

Light Key

Non-Key

Heavy Key

Heavy Non-Key

28

neither the distillate nor the bottoms

composition is completely specified

because there are not enough variables

to allow complete specification

shown in Figure 5-1 are easily developed.

29

shown in Figure 5-1

Eq. (5-1)

Eqs. (5-2)

For a ternary system, Eqs. (5-2) can be written three times, but these

equations must add to give Eq. (5-1). Thus, only two of Eqs. (5-2) plus

Eq. (5-1) are independent

Summation rules

30

not both.

Thus, we cannot compute D and B

31

Ternary mixture

6 unknowns: B, D, x2,dist, x3,dist, x1,bot and x3,bot

5 equations only: 3 mass balances and 2 summation

rules

Energy balance and equilibrium relationships will add

extra variables (vapor mole fractions, condenser and

reboiler duties)

Thus, one cannot start out by solving external mass and

energy balance equations.

For stage-by-stage calculation, need to know all

compositions at one end of the column.

32

then one can solve external mass balances

LNK appear only in the distillate

HNK appear only in the bottoms

specify Bottom and distillate compositions

33

Distillation

Flow rates and temperature profiles are similar to

binary distillation case

Composition profiles look different from binary

distillation

34

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

Vapor and liquid flow rates will vary from plate to plate

The ratio L/V varies less significantly

35

Feed condition

Benzene= 0.233 mole frac,

Toluene= 0.333 mole frac,

Desire 99% recovery of benzene Cumene= 0.434 mole frac

similar to the behavior of binary systems

Saturated liquid. F =

1.0 kmol/h. Feed stage

is number 10 above

the partial reboiler, and

there are 19

equilibrium stages plus

a partial reboiler. A

total condenser is

used. p = 101.3 kPa.

Relative volatilities: ben

= 2.25, tol = 1.0, cum = 0.21.

L/D = 1.0.

36

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

benzene-toluene-cumene distillation;

same problem as in Figures 5-2 and 5-4.

37

Composition profiles

benzene recovery in the

distillate was specified as

99%

Benzene is the LK, and

toluene is the HK.

Thus, cumene is the HNK,

and there is no LNK

profiles for distillation for benzenetoluene-cumene; same conditions as

Figures 5-2 and 5-3 for nonconstant

molal overflow

low in the reboiler and

increases monotonically to a

high value in the total

condenser. This is essentially

the same behavior as that of

the more volatile component

in binary distillation. In this

problem benzene is always

most volatile, so its behavior

is simple

38

Composition profiles

and cumene (HK)

in the distillate is

specified

HK concentration does not

have any maxima

benzene (LNK), toluene (LK), and cumene (HK); same problem

as in Figure 5-2 to 5-4 except that a 99% recovery of toluene in

the distillate is specified

39

Composition profiles

Recovery of toluene in distillate 99%.

primary maxima

secondary maxima

Since there is an LNK, we would expect

the LK curve to show maxima; and

since there is an HNK, we would expect

maxima in the HK concentration profile

Figure 5-6. Liquid composition profiles for distillation of benzene (LNK), toluene (LK),

xylene (HK), and cumene (HNK). Feed is 0.125 benzene, 0.225 toluene, 0.375 xylene,

and 0.275 cumene. Relative volatilities: ben = 2.25, tol = 1.0, xy = 0.33, cum = 0.21

40

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

mixture: trace components such as butanol are

partially miscible with water

Solution: use sidestream withdrawal to remove

intermediate boiling components

41

multicomponent distillation

1.key component concentration can have maxima

2.NK usually do not distribute

HNKs present only in the bottoms

LNKs present only in the distillate

3.NK often go through plateau region

4.all component must be present at feed stage but at

that stage a discontinuity in the composition profile is

present

42

fractional recoveries

We wish to distill 2000 kmol/h of a saturated liquid

feed. The feed is 0.056 mole fraction propane, 0.321

n-butane, 0.482 n-pentane, and the remainder nhexane. The column operates at 101.3 kPa. The

column has a total condenser and a partial reboiler.

Reflux ratio is L0/D = 3.5, and reflux is a saturated

liquid. The optimum feed stage is to be used. A

fractional recovery of 99.4% n-butane is desired in

the distillate and 99.7% of the n-pentane in the

bottoms. Estimate distillate and bottoms

compositions and flow rates.

43

The order of volatilities is: propane > n-butane > n-pentane > n-hexane

quite high

This automatically makes

propane the LNK and n-hexane

the HNK.

quite high

Assumption: Since the recoveries of the keys are quite high,

it is reasonable to assume that all of the LNK collects in the

distillate and all of the HNK collects in the bottoms. We will

estimate distillate and bottoms based on these assumptions

44

Eq. 5-8a,b

Eq. 5-9a,b

or

The fractional recovery of n-butane in the distillate can be used to

write

Eq. 5-10

For n-pentane the equations are

Eq. 5-11

Eq. 5-12

Eq. 5-13

unknowns (four compositions in both distillate and bottoms

plus D and B). Equations (5-4) give two additional equations,

which we will write as

Eq. 5-14a

Eq. 5-14b

45

bottoms calculations can be done separately

Do it. Start with the distillate

DxC3,dist

DxC6,dist

DxC4,dist

DxC5,dist

=

=

=

=

0

(0.9940)(2000)(0.321) = 638.5

(0.003)(2000)(0.482) = 2.89

Then

Now the individual distillate mole

fractions are

Equation 5-15

Check:

Bottoms can be found from Eqs. (5-8b), (5-9a), (5-11), (5-12), and (5-14b). The results are

xC3,bot = 0, xC4,bot = 0.0031, xC5,bot = 0.7708, xC6,bot = 0.2260, and B = 1246.6. Remember that

these are estimates based on our assumptions for the splits of the NK

46

We have a feed mixture of 22 mol% methanol, 47

mol% ethanol, 18 mol% n-propanol, and 13 mol%

n-butanol. Feed is a saturated liquid, and F =

10,000 kmol/day. We desire a 99.8% recovery of

methanol in the distillate and a methanol mole

fraction in the distillate of 0.99.

Find D and B.

Find compositions of distillate and bottoms.

47

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