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Multi-component distillation

Prof. S. Scott, ChE 128, UC Santa Barbara

How many distillation columns are required?

One distillation column can be optimized to separate one pair of volatile components.
D, xD,1

F zF,1 zF,2

We can specify two fractional recoveries: FR1 = (DxD,1)/(FzF,1) = 0.95 FR2 = (BxB,2)/(FzF,2) = 0.98 If the feed contains more than two volatile components, we cannot specify the recoveries of the additional components. However, we can add more distillation columns.

B, xB,1

Distillation of multicomponent mixtures


Alternative? 1

1, 2


F zF,1 zF,2 zF,3 zF,4



3, 4

III Separation of C components requires (C1) distillation columns.


Key components
Each column is designed to separate two components of adjacent relative volatility. These components are the keys. All other components are non-keys.
1 design for separation 2 3 4 5

1.5 1.4 1.3 1.2 1.0

Light non-key (LNK) Light key (LK) Heavy key (HK) Heavy non-key (HNK) Heavy non-key (HNK) assume exclusively in distillate specify recovery in distillate specify recovery in bottoms assume exclusively in bottoms

Distributions in the distillate and bottoms streams are specified for the two key components. If we assume that the non-keys do not distribute, the overall mass balance is easily solved.

Overall mass balance

with non-distribution of non-keys
If non-keys do not distribute, then LNK: Dxi,D = Fzi,F HNK: Bxi,B = Fzi,F

Define fi, di, and bi as molar flow rates of component i in feed, distillate and bottoms, respectively.
Ex.: 100 mol/h of an equimolar mixture of four components. Assume 80 % recovery of LK in D, and 80 % recovery of HK in B. component i zF,i fi = F zF,i di xD,i = di/D bi LNK LK HK HNK 0.25 0.25 0.25 0.25 25 25 25 25 25 20 5 0 di = D = 50 0.50 0.40 0.10 0 xD,i = 1 0 5 20 25 bi = B = 50

xB,i = bi/B 0 0.10 0.40 0.50 xB,i = 1

Stage-by-stage calculations
For a specified external reflux ratio R = L0/D and feed quality q, and assuming constant molal overflow (CMO), first perform the overall column balance to obtain D. Then, L = (L0/D) D V=L+D


L = L + q F V = V + (1 q) F
Algebraic solution, starting at top of column: 1. yi,1 = xi,D 2. xi,1 = yi,1 / Ki,1 3. yi,2 = (L/V) xi,1 + (1 L/V) xD section)


(total condensor) (VLE) (mass balance, rectifying

Repeat steps (2) and (3) down to feed stage. Then, change mass balance equation to yi,k+1 = (L/V ) xi,k + (1 L/V ) xB We just need to find Ki for each stage.

Obtaining Ki(T) for each stage

Consider a ternary system with components A, B, C Assume constant relative volatility Choose B as the reference compound

a AB

K A y A / xA = = K B y B / xB
y A, j K A, j = y A, j

a BB = 1
xA, j + xB, j + xC , j =

a CB =
y A, j +

y B, j + y C, j

xA, j =

a ABK B, j
y B, j yC, j

a ABK B, j

a BBK B, j
y A, j

a CBK B, j


K B, j =

y A, j

a AB

a BB

a CB

y i,j = a iB i

xA, j =

y i,j a iB i

a AB

IF relative volatility is not constant, use geometric average, (a1aN). Or, find Tj from dewpoint calculation (starting with xD,i), then find Ki(Tj) using VLE.

Trial-and-error solution
Perform stage-by-stage analysis, from top to bottom of column. xHK,N+1 xHK,B xLK,N+1 xLK,B

must be satisfied simultaneously

if not true, choose different starting concentrations at the top of the column, and repeat cannot assume xD,HNK = 0, but no way to guess works best if there are no HNKs. If there is no LNK, can start at bottom of column and work to the top

not obvious where the optimum feed stage is

very tedious, convergence is difficult

Approximate shortcut methods for multicomponent distillation

Suitable for preliminary designs Three-part F-U-G method: 1. Use Fenske equation to estimate Nmin (at total reflux) 2. Use Underwood equations (2) to estimate Rmin (with N = ) 3. Use Gilliland correlation to estimate Nactual and Nfeed (can also use Kirkbride equation)

Operating at total reflux

yi,1 1 xi,0

designate the keys A and B, and assume constant aAB according to the definition of equilibrium:

yA xA = a AB y B N +1 xB N +1

(even though there is no liquid stream with composition xi,N+1)

at total reflux, the operating line is y = x yi,j+1 = xi,j so yi,N+1 = xi,N


xi,N N+1

xA xA = a AB xB N xB N +1 move up to stage N: yA xA xA 2 = a AB = a AB y B N xB N xB N +1 continue to the top of the column

Estimating Nmin
at the top of the column

xA y A Nmin xA = = a AB xB 0 y B 1 xB N +1
x xA A ln xB 0 xB N +1 = lna AB

solve for Nmin

Fenske equation


can also write in terms of fractional recoveries (FR)


FR 1 - FRB A ln FR 1 FR A distillate B bottoms = ln a AB

Other uses of the Fenske equation

Once Nmin is known, check non-distribution of non-keys, or estimate their distribution:
N a CB

FRC,distillate =

FRB Nmin + a CB 1 - FR B bottoms

estimate optimum feed stage at total reflux:

NF ,min

x zA A ln z x B 0 B F = lna AB

Pinch points in binary distillation

Recall for binary distillation: Rmin pinch point x zF xD Binary composition profile


plateau of constant composition feed stage number reboiler



Using Rmin generates a pinch point at the feed stage

xB condensor

near the pinch point, composition changes little from stage to stage - passing streams are very close to equilibrium - no change in temperature between stages

Behavior in ternary systems

in the presence of a third component whose composition does change through the feed stage, the pinch point moves 1 Ternary composition profile LK-HK-HNK rectifying stripping

Consider LK
LK is the most volatile component in the system on every stage there is almost no LK at the reboiler stage xi

Consider HNK
HNK is the least volatile component in the system on every stage almost all HNK is found at the reboiler stage finite HNK at feed stage, drops off rapidly above 0 C F stage number R

Behavior of HK
1 Ternary composition profile LK-HK-HNK pinch point ~binary

Consider HK:
HK behavior is most complex above feed stage, distillation is almost binary

near reboiler, distillation is almost binary (HNK-HK), but HK is the more volatile component HNK goes through a maximum in the stripping section, creating a pinch point there 0 C

F stage number


(HK-LK), with HK the less volatile component xi

Pinch points in multicomponent distillation

pinch F LK, HK, HNK F LNK, LK, HK F LNK, LK, HK, HNK pinch



LK-HK-HNK system
has a pinch point in the stripping section

LNK-LK-HK system has a pinch point in the rectifying section

LNK-LK-HK-HNK has pinch points in both sections

Graphical methods are not helpful in finding these pinch points.

Second Underwood equation

CMB in rectifying section at minimum reflux: at the pinch point: VLE: relative volatility:

xi , j = xi , j +1 y i , j +1 = K i xi , j +1

Vmin y i , j +1 = Lmin xi , j + Dxi ,D

a i = K i Kref

y i , j +1 = a i Kref xi , j +1
Lmin Vmin y i , j +1 1= Dxi ,D a iVminK ref
define: f =

Lmin Vmin y i , j +1 = y i , j +1 + Dxi ,D a i Kref

Vmin y i , j +1 =

a i Dxi ,D
Lmin ai VminK ref

Lmin VminK ref

a i Dxi ,D 2nd Underwood equation: Vmin = Vmin y i , j +1 = ai - f i i

First Underwood equation

in the stripping section: assume

a i Bxi ,B -Vmin = Vmin y i ,k +1 = i i ai - f

f =f
DVfeed a i Dxi ,D a i Bxi ,B = Vmin - Vmin = + a f a f i i i a i Fzi ,F = i ai -f

1st Underwood equation: feed quality definition:


DVfeed = F (1- q)

searching for: with C components, the 1st Underwood equation has C roots, one between each adjacent pair of a-values, and one between 0 and the smallest a-value. We need the root aHK < < aLK binary system: use quadratic equation to solve for trial-and-error: use (aHK + aLK) as initial guess

Estimating Rmin
Onceis known, obtain Vmin using the 2nd Underwood equation.

a i Dxi ,D Vmin = Vmin y i , j +1 = ai - f i i

To get xi,D values for non-keys: assume non-distribution OR assume distribution is the same at minimum reflux and total reflux i.e., use Fenske equation

Lmin = Vmin D Rmin = Lmin/D

Gilliland correlation
We have Nmin (Fenske) and Rmin (Underwood). R is often specified as a multiple of Rmin, e.g., R = 1.5 Rmin


y = 1- e

1+54.4 x x -1 0.5 11 + 117.2 x x

Figure 7-3 Gilliland correlation as modified by Liddle (1968);
Reprinted with permission from Chemical Engineering, 75(23), 137 (1968), copyright 1968, McGraw-Hill.

From Separation Process Engineering, Third Edition by Phillip C. Wankat (ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.

Optimum feed stage

obtain Nmin and NF,min from Fenske eqn obtain N from Gilliland correlation

Assume relative position of the feed stage is the same as it was at total reflux:

F NF,min F NF

NF ,min Nmin


Remember! Nmin and N include partial reboiler (and partial condensor). Works well for symmetrical columns (feed stage close to middle).

Kirkbride equation
Better feed stage estimation for unsymmetrical columns:

Nrectifying Nstripping

z x 2 B = HK LK ,B zLK xHK ,D D F

where Nrect and Nstrip do not include the feed stage:


N = Nrect + Nstrip + 1

Sandwich components
At the beginning of this section, we specified that the key components should have adjacent relative volatilities. What if there is a non-key with intermediate volatility (i.e., between the two key components)? This component is called a sandwich component.
component 1 2 3 4 5 a 1.5 1.4 1.3 1.2 1.0 designation Light non-key (LNK) Light key (LK) Sandwich non-key Heavy key (HK) Heavy non-key (HNK) F S D

Sandwich components tend to concentrate in the middle of the column, and can cause flooding even when present at trace concentrations. If unavoidable, use side-streams to withdraw them.