Sep-tek.

Ch.11 (continued)
Distillation (Multistage with reflux)
Sigurd Skogestad

Distillation
• Separation of liquid mixtures by
repeated evaporation
– multi-stage with reflux
– Old name: ”Rectification”
• Basis: Components have
different boiling points (different
volatility)
• Most common separation
process in industry
– Chemicals
– Oil and gas
• ”Separating agent” = heat
(thermal energy)
• 3% of world energy
consumption is for distillation

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 When use distillation?
• Liquid mixtures (with difference in boiling point)
• Unbeatable for high-purity separations because
• Essentially same energy usage independent of (im)purity!
» Going from 1% to 0.0001% (1 ppm) impurity in one product
increases energy usage only by about 1%
• Number of stages increases only as log of impurity!
» Going from 1% to 0.0001% (1 ppm) impurity in one product
increases required number of stages only by factor 3 (Proof using Fenske:
ln(1.e-6)/ln(1.e-2)=3)

• Well suited for scale-up

» Columns with diameters over 18 m
• Examples of unlikely uses of distillation:
» High-purity silicon for computers (via SiCl3 distillation)
» Water – heavy-water separation (boiling point difference only 1.4C)

Sigurd and distillation

• 1980-83 (Norsk Hydro): Steady-state design and simulation
– Crude oil, Mongstad refinery
– Petrochemicals, VCM
– Methanol-water, formic acid-water
– Mostly thermodynamics
• 1983-rest of life: Control and dynamics
• 1995-2000: Optimal batch (multivessel)
• 1997-present: Optimal integrated continuous distillation
columns (Petlyuk, Kaibel)
• http://www.nt.ntnu.no/users/skoge/distillation/

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 CONTINOUS DISTILLATION

Top section

L D
F

Bottom section
V

I prefer to number the stages

from the bottom (with reboiler=1),
BUT the book does it from the top.

(I prefer numbering from bottom, like in a building, because this makes more sense if the
equlibrium stage is a physical tray)

3
 Trayed column:

Alternative: Packed column

Both cases: Want intensive mixing and large surface area between phases

Lab

Packed Tray Tray

4
 Distillation column modeling
• Equlibrium stage concept: Many flashes on top of each other!
• Each stage is an adiabatic flash:
– Component balance
– Energy balance
– Vapor-liquid equilibrium (VLE), y = K x

1. Detailed numerical solution is straightforward but requires computer

• Commercial: Unisim / Hysys, Aspen
• Free software (very nice!): ChemSep.org
2. Analytical solution
– Possible is certain cases
– Most common assumption: Constant molar flows (simplified energy balance)

• Constant K (VLE) + constant molar flows: Kremser-equations

• Constant relative volatility (VLE) + constant molar flows: Fenske, Underwood.

3. Graphical solution
• Graphical solution of component balances + VLE
• Any VLE + Constant molar flows: McCabe-Thiele

The equilibrium stage concept

Vn-1
yn-1

Stage n-1
Material balance stage i (out=in)*:
Ln-1 Ln xn + Vn yn = Ln-1xn-1 + Vn+1yn+1
Vn Xn-1
yn

Stage n Equilibrium (VLE): yn = fn(xn,…)

Ln
Vn+1 xn
yn+1

Stage n+1
* We usually make balances to end of column.
Gives same result!

Note: Numbering is here from top (as in book).

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 Top section

Btm section
B, xB

Top operating line:

y and x
between stages
in top section

x y

VT LT

y x

Top operating line. Goes through point (xD,XD) and has slope LT/VT<1.
Proof: x=xD gives: y = (LT+D)xD/VT = xD

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Bottom operating line:
y and x
between stages
in bottom section

yB

B, xB

LB VB

y x

Bottom operating line. Goes through point (xB,xB) and has slope LB/VB>1.

y and x for
intersection of
operating lines T=top section

B=btm section

LB = LT + qF
VT = VB+ (1-q)F
q = Fraction of liquid in feed

Subcooled liquid feed

4. Feed line (crossing of operating lines): Liquid feed

Proof:
Top: VT y = L T x + D x D Vapor feed
Bot t om: VB y = L B x ¡ B x B
At crossing of t hese lines, y and x are same. Subt ract :
y (VT ¡ VB ) = x (L T ¡ L B ) + F x F
| {z } | {z }
( 1¡ q) F ¡ qF
) y= ¡ q
1¡ q
x + xF
1¡ q
(feed line)

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 Usually: Constant molar flows
assumption
• Each section: Constant molar flows of liquid L
and vapor V:
– VT = V1 = V2 = Vn =Vn+1
– LT = L1 = L2 = Ln = Ln+1 = L
– VB = VN = Vm =Vm+1
– LB = LN = Lm =Lm+1

• Replaces energy balance

– Holds for components with similar heat of
vaporization

Summary operating lines for

Constant molar flows
" Operat ing line" = Relat ionship between y and x between st ages (from mat erial
balance).

Top sect ion: y = LVTT x + VDT x D Goes through (y,x)=(xD,xD) + (y,x)=(DxD/VT,0)=(xD/(R+1),0)

Bt m sect ion: y = LVBB x ¡ VBB x B Goes through (y,x)=(xB,xB) + crossing of top/feed-lines

Crossing (feed line): y = q¡q 1 x ¡ xF

q¡ 1
Goes through (y,x)=(xF,xF) + has slope q/(q-1)

, Tot al balance at feed: L B = L T + qF , VT = VB + (1 ¡ q)F

cooling
D
Top LT VT
F q = Fraction liquid in feed
Btm LB VB

heating B

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McCabe-Thiele graphical method
Example: Benzene-Toluene continuous distillation
• F = 100 kmol/h
• xF = 0.45, qF =1.19 (subcooled liquid)
• Desired products: xD=0.95, xB=0.1
• Given: R= LT/D = 4
• How many stages are required?

• x,y – mole fractions bemzene (light component)

VT
Top section
LT

LB
VB

VB
Btm section
B, xB

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0.
McCabe-Thiele graphical solution
Use overall mass balances to find product compositions, product flows and flows inside column.
1. Draw equilibrium curve: (x,y) on stages.
2. Draw upper operating line: (x,y) between stages.
Starts in (xD,xD) and has slope LT/VT = R/(R+1) where R=L/D. Goes through (x,y)=(0,xD/(R+1))=(0, 0.19)
3. Draw feed lines (goes through (xF,xF) and has slope –q/(1-q).
• Feed sat. liquid (q=1): Vertical.
• Feed sat. vapor (q=0): Horizontal
• Partly vapor (0<q<1): Between (negative slope)
• Feed subcooled (q>1): Positive slope (see Figure below)
4. Draw lower operating line : (x,y) between stages. Starts in (xB,xB) and goes through crossing of feed line and upper operating line
5. Graphical solution to find number of stages: Start from product and switch between on stages (xn,yn) and between stages (xn,yn+1) by making staircase.
6. Optimal feed location (design): Switch between operating lines at feed line (=crossing of operating lines)
7. Given N and NF (more difficult): Need to guess product composition and iterate to fit in N stages

(x1,y1)
(x2,y2) (xD,y1) = (xD,xD) tot. condenser

(x1,y2)
(x2,y3)

(0,0.19)

xB

Note: This feed (q) line is for subcooled liquid feed (q>1)

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 No. of stages in each section

Previous slide:
Counting from top to btm: 7.6 stages

3.6 (xF*,yF*) = crossing = optimal feed stage composition

3
To find no. of stages in each section:
Often easier to start from both ends.
2 Let final stairs reach crossing (xF*,yF*)

1 Counting from top to feed: 4.1 stages

Counting from btm to feed: 3.6 stages
Total: 7.7 stages

Some comments on distillation and McCabe-Thiele

1. Nonoptimal feed stage location

If “too many” stages in top section:

Get “pinch zone” above feed

“Pinch zone” = zone with small change in composition

Comments:
1. Exact location of feed stage is not critical unless the column is poorly designed
with “too few” stages
2. Existing column: During operation, one may get non-optimal feed location (with
pinch) because of changes in feed composition and product purities.

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 2. Reboiler and condenser duty
• Reflux: L = LT
• Assuming constant molar flows:
LB = L + qF
VB = LB – B = L + qF – B
VT = VB + (1-q)F = L + D
• Reboiler and condenser duty
• QB [J/s]= VB [mol/s] ·ΔHBvap [J/mol]
• QC [J/s]= VT [mol/s] ·ΔHDvap [J/mol] (total condenser)
• Note: If feed is liquid & total condenser: QB ¼ QC.
Example: L=LT=(L/D)*D=4*41.17 = 164.68 kmol/h,
VB = L + qF – B = 164.68 + 1.19*100 – 58.83 = 224.85 kmol/h
QB = VB ·ΔHBvap = 224.85*(1000/3600)*32.1*1000 J/s = 2.0 e6 J/s = 2.0 MW

3. Minimum number of stages, Nmin

(with total reflux, that is, infinite energy)
A. Graphical

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3. Minimum no. of stages, Nmin ( with total reflux)
B. Analytical (constant )
• Assumption VLE: Constant relative volatility.
Stage i (L=light component, H = heavy component):
Stage i+1
Total reflux: Li+1
Vi = Li+1 Vi xi+1
yi = xi+1
• Repeat for all N stages
yi
Stage i
Li • Fenske’s formula for minimum no. of stages
Vi-1 xi
yi-1

• Applies also to column sections

• Example. Benzene-Toluene.

Number of stages increases only as

log of impurity!

• Example: α=2. Binary separation with purities: 90%

light in top and 90% heavy in bottom:

• Example: α=2. Binary separation with purities: 99.9%

light in top and 98% heavy in bottom:

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 Comments
Number of stages
• Reboiler (“partial reboiler”): Gives 1 theoretical stage
• Total condenser: 0 stage
• Partial condenser: 1 theoretical stage
• N is usually (e.g., in Fenske’s fomula, N = lnS/lnα) the total no. of theoretical
stages including reboiler and partial condenser
• Thus: Nstages inside column = N-1 (or N-2 for partial condenser)

“Total reflux” vs. “Total condenser”

We use "total" with (at least) two different meanings:
1."Total condenser" = all is condensed (so D is liquid)
2."Total reflux" = (all is condensed and) all is send back as reflux (so
D=0 or more generally L>>D)

4. Minimum reflux (minimum energy)

(with infinite number of stages)
A. Graphical
Nonideal mixture:

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NOT IN BOOK

4. Minimum reflux (minimum energy)

(with infinite number of stages)
B. Analytical (constant )
• King’s formula, assuming pinch at feed (not in book):

•Note: Essentially same energy usage independent of (im)purity!

Pure products:

Easy to remember!

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 5. Design: “Optimum” reflux or
How many stages (N)?
5A. Energy (V) vs. number of stages (N)

• Trade-off between number of stages and

Number of stages

energy
• Actual V approaches Vmin for N
approximately 2 x Nmin or larger,
typically:
Nmin N=2Nmin  Vmin + 25%
Vmin N=3Nmin  Vmin + 3 %
Energy N=4Nmin  Vmin + 0.3 %

Conclusion:
Recommend N= 2.5 Nmin (use higher value to save energy and simplify operation).
Gives actual boilup (energy) V ¼ 1.1 Vmin

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10.6B Equipment for absorption
and distillation

Random/dumped packings

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Structured packing (1970’s)

Structured packings (today)

Koch-Glitsch Mellapak (Sulzer)

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6. Height of real columns (section 11.5)
• N = no. of theoretical stages (total)
• Ninside = no. of theoretical stages inside column
= N - 1 (total condenser, assuming reboiler gives 1 theoretical stage)
= N – 2 (partial condenser)

– Tray columns:
• Ntrays = Actual number of trays inside column
• Eo=overall tray efficiency (typical 0.7)
• Ntrays = Ninside / Eo
Comment: Sigurd does not recommend using Murphy or Point efficiency

– Packed columns:
• H = height of packings [m] = Ninside* HETP
• HETP = height equivalent to 1 theoretical plate
• Estimation of HETP:
1. Mass transfer model
HETP ¼ H0G * f = f * V / (Ky a S) (10.6-55) (not very reliable, f = ln(1/A)/(1/A-1))
2. Rule of thumb (recommended in practice)
– Random packing: HETP [m] = 18 Dp [m] (equation 11.5-11)
Dp = diameter of each packing element
3. (Best) Data from packing manufacturer

7. Column operation and diameter

Gas load

Packed:
Channeling /
packing not wetted Liquid buildup

flooding

Liquid load

Similar for packed column

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 Column diameter
• In many cases the diameter is determined by the
(superficial) gas velocity v [m/s]
v[m/s] = V[m3/s] / A[m2]
Where for ideal gas: V[m3/s] = V[mol/s] · RT/p

• Example. Column at 2 bar with V = 50 mol/s and given vmax = 1.5 m/s.
Temperature bottom (highest) = 400K.
– Then V [m3/s] = 50 mol/s · 8.31 J/K,mol · 400K /2.e5 Pa = 0.83 m3/s
– A [m2] = V[m3/s] / vmax [m/s] = 0.83 / 1.5 = 0.553 m2
– Column area A = (π/4) D2
– Conclusion: Diameter D = √(4A/π) = √(4· 0.553 / 3.14) = 0.84 m

Trayed column
• Maximum vapor velocity is limited by entrainment
• Tray column. Fair correlation:

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 Packed column
• Maximum gas load limited by flooding

Flooding, gives vmax

8. Trays vs. packings

• Packings:
+ Much smaller pressure drop (typically 1/10)
+ Usually: More stages for given column height
- Problems with liquid distribution in larger columns (can use structured
packings, but more expensive)

• Trays:
+ More easy to clean
+ Better for large capacity columns
+ Larger holdup (typically, 2 times larger): Advantage for control (“have
more time”)
- Can have inverse response in bottom of column (- effect - difficult to
predict)

• Overall: Differences are surprisingly small – also for process control

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 9. Special cases of distillation
1. Stripping column (no top part)
2. Enriching column (no btm part)
3. Stripper / absorber (no condenser or reboiler)
4. ”Direct” steam injection (instead of heat)
5. Column with side stream
6. Partial condenser (gives 1 extra eq. stage)
7. More than one feed

• All cases: Exactly same principles (can use McCabe-Thiele)

• Start with material balances to derive operating lines
• Need equilibrium data!

10. Multicomponent mixtures

• Most of the derivations apply to the
multicomponent case
• Identify ”key components” (light and heavy, L-H)
for split
• McCabe-Thiele: Plot xy-diagram for pseudo-
binary, x = xL/(xL+xH)
• Fenske’s formula OK: Nmin = lnS / ln .
 = relative volatility between L and H
S = separation factor between L and H

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 11. Shortcut: ”How to design a
distillation column in 5 min”
1. Multicomponent: Identify key components (LH)
2. Estimate relative volatility . Can use Sigurd’s formula*
3. Find split (D/F) from desired product purities
4. Stages (height of column): Find Separation
factor S and Nmin = lnS / ln . Select N = 2.5 Nmin
5. Feed stage: Can use another Sigurd-formula (last slide)
6. Reflux / Energy usage: Find Lmin=F/(-1) (feed
liquid) and Vmin/F. Real V is about 10% higher
7. Diameter: A = (V[mol/s]RT/p ) / vmax. D = √(4A/π).
Typical value: vmax= 2m/s.
*Sigurd’s formula

IDEAL VLE
MIXTURE
(constant α)

Example: “5 min column design”

• Design a column for separating air
• Feed: 80 mol-% N2 (L) and 20% O2 (H)
• Products: Distillate is 99% N2 and bottoms is
99.998% O2
• Component data
– Nitrogen: Tb = 77.4 K,  Hvap=5.57 kJ/mol
– Oxygen: Tb = 90.2 K,  Hvap=6.82 kJ/mol
• Problem: 1) Estimate . 2) Find split D/F. 3)
Stages: Find Nmin and 4) suggest values for N and
NF. 5) Energy usage: Find Vmin/F for a) vapor feed
and b) liquid feed.

• Given: For vapor feed and sharp sep. of binary mixture: Vmin/F =
1/(-1)

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IDEAL VLE
MIXTURE
(constant α)

Solution “5-min design”

Also see paper (“Theory of distillation”)

IDEAL VLE
MIXTURE
(constant α)

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IDEAL VLE
MIXTURE
(constant α)

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11. Distillation design in practice: Numerical solution using
“simulators”.
Example using Chemsep
• http://www.chemsep.org/
• Written by Ross Taylor, Clarkson University
• Lite version:
– max 50 stages and 5 components
– free and extremely simple to use
• Example 11.4-2: Benzene-Toluene
– Specify 8 stages, feed on stage 5 from top
– Specify product compositions, xD=0.95, xB=0.10
– Find: Reflux ratio L/D (was 4 but then we needed
only 7.6 stages)

Enter title….
Use arrow to go through menus

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Data input... components

... column configuration

Note: Program counts condenser as stage 1

even if it is not an equlibrium stage

27
 ... thermodynamics

Here: Raoults law + idea enthalpy

Normally use:
- Soave-RK equation of state (EOS) for relatively ideal mixtures like hydrocarbons
- Gamma-Phi (UNIQUAC, SRK) for non-ideal components

... feed data

Normally choose “Split”, but does not matter here

since the feed is subcooled

Can write 1atm and program converts automatically

Note: Use 55 mol/s (instead og 55 kmol/h)

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 Assume constant pressure (1 atm) in column
(Normally the pressure drop is about 0.1 bar
from the bottom to the top)

Assume no heat loss

Assume 100% stage efficiency

TOP: Specify xD=0.95

BTM: Specify xB=0.1

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 Press solve…

… results… Streams

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McCabe-Thiele diagram

2
3
4
5
6

8
9
=reboiler

Profiles

Before R= 4. Now we need less reflux (and less energy)

because we have more stages (increased from 7.6 to 8)

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 Liquid phase composition

TOP
benzene

Stage

toluene

BTM
x

Vapor phase composition

TOP

benzene
Stage

BTM toluene

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 Flow profiles
Note: Not quite constant molar flows
because dHvap is different for components
TOP

L V

Stage

BTM
Flows

Temperature profile

TOP

Stage

BTM

Temperature [K]

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 Log (xL/xH)-plot (“key ratio profile”):
Use to check feed location
TOP

Stage

log(xL/xH) straight line:

Feed placement OK

BTM

Relative volatility

2.4 2.5 2.6

TOP

Stage

BTM

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 1. More literature on distillation
• King (Wiley, 1980) on distillation design
• Shinskey (McGraw-Hill, 1984) on distillation control
• Kister (McGraw-Hill, 1990) on distillation operation

• General info: http://lorien.ncl.ac.uk/ming/distil/distil0.htm

• I.J. Halvorsen and S. Skogestad, ``Distillation Theory'', In: Encyclopedia of

Separation Science. Ian D. Wilson (Editor-in-chief), Academic Press, 2000, pp.
1117-1134.

• S. Skogestad, Dynamics and control of distillation columns - A tutorial

introduction., Trans IChemE (UK), Vol. 75, Part A, Sept. 1997, 539-562
(Presented at Distillation and Absorbtion 97, Maastricht, Netherlands, 8-10
Sept. 1997).
• More: see home page Sigurd Skogestad http://www.nt.ntnu.no/users/skoge/
http://www.nt.ntnu.no/users/skoge/distillation
• Free steady-state distillation software with thermo package :
http://www.chemsep.org/

Extra slides

35
 Simple formula for feed stage
IDEAL VLE
MIXTURE
(constant α)

location (Skogestad, 1987)

Example. C3-splitter. zFL=0.65, xDH= 0.005, xBL=0.1, =1.12.

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