SHR Chapter 7

Binary Distillation

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 SHR §7.1

Introduction
st
Dates back to 1 century AD

• first used in a batch mode (distillate changes in time)

Goal: separate “heavy key” (less volatile) from
“light key” (more volatile) by exploiting α≠1.

• for α≫1 or α≪1, this can be done very effectively
unless an azeotrope exists (where α=1).

‣ then we recover the azeotrope and the light or heavy key,
depending on which side the feed lies.

th
• By 16 century, multiple stages were in use to
improve separation.

By 1976, distillation accounted for nearly 3% of
the US energy consumption!

• mostly in petroleum refineries

Binary distillation is simplest & most well-
understood.

• we will limit our discussion to binary distillation

Third Law of Thermo - typically low
thermodynamic efficiency.

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 Design Considerations
Operating pressure - “knob 1”

• below ambient pressure requires vacuum operation
D
• many things may influence choice of operating pressure
V
‣ Thermo: azeotrope formation, α, etc.

L
‣ Column operating temperature range (avoiding reactions,
corrosion, etc.)

F
• most analyses do not account for pressure variation
through the column

V
Operating temperature - “knob 2”

B
• Reboiler & Condenser:
L
‣ Bottoms above ambient requires additional energy input to the
reboiler

‣ Distillate below ambient requires energy removal from the
condenser.

• Thermodynamics: critical points of fluids

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 Batch Distillation

Conceptually, follows
the T-x-y diagram.

More rigorous analysis
in SHR chapter 13

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 SHR §7.2

The McCabe-Thiele
Graphical Method
1925

Continuous (staged) distillation

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 Nomenclature
Specifications
F total (molar) feed rate
z LK mole fraction in feed
P Column operating pressure
x LK mole fraction in distillate
x LK mole fraction in bottoms
R/R reflux ratio
Feed phase condition
VLE data (y/x plot)
Type of condenser (partial/total)
Type of reboiler (partial/total)
Results
D Distillate (molar) flow rate
B Bottoms (molar) flow rate
N minimum number of stages
R minimum reflux flow rate
V Boilup ratio
N Number of equilibrium stages
Feed stage location
Stage compositions (

• “Light Key” (LK) - more volatile component

• “Heavy Key” (HK) - less volatile component

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Preliminaries
Rectifying section - like an absorber

• Feed & reboiler supply vapor

• Condenser supplies liquid

Stripping section - like a stripper

• Feed & condenser supply liquid

• Reboiler supplies vapor

overall mole balance: F = D + B

light-key mole balance: F zF = xD D + xB B
✓ ◆
combine to eliminate zF xB
D=F
B & solve for D: xD xB

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 SHR §7.2.1

Rectifying Section Operating Line

Overall mole balance: V = L + D
Light key mole balance: V yn+1 = Lxn + DxD

L D relates light-key compositions in passing streams

yn+1 = xn + xD (streams on a stage are assumed to be in equilibrium)
V V
If L and V are constant, then this is a straight line.

The “McCabe-Thiele Assumptions”

• Both components have equal and constant molar
enthalpies of vaporization (latent heats).

• Sensible heat, CpΔT, is negligible compared to latent heat.

• Column is insulated (no heat loss on each stage).

• Column pressure is constant (thermodynamics can be ne
done at a single pressure). li
ing
erat
Big assumptions, but allow for simple analysis, since op
L and V are constant under these assumptions.

L L L/D R L reflux
= =L = R⌘
V L+D /D + D/D R+1 D ratio
D 1 ✓ ◆ ✓ ◆
= R 1
V R+1 y= x+ xD
R+1 R+1

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 Range of Reflux Ratios
L D L
y= x + xD R=
V V D
✓ ◆
L R
0 =  1 because 0  R  1
V R+1

• What happens at R = 0?

• What happens at R = ∞?

What is the minimum R that allows separation?

(We will answer this question shortly)

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 SHR §7.2.2

Stripping Section Operating Line

Overall mole balance: L = V + D
McCabe-Thiele assumptions
Light key mole balance: Lxm = V ym+1 + BxB have been applied.

The feed stage material balance relates L and V to L and V

L B relates light-key compositions in passing streams

ym+1 = xm xB (streams on a stage are assumed to be in equilibrium)
V V

✓ ◆ ✓ ◆
VB + 1 1
y= x xB
VB VB

e
V boilup

lin
VB ⌘
ing
B ratio
rat
e
op

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 SHR §7.2.3

Feed Stage & the “q-Line”

rectifying
section

stripping
section
subcooled liquid saturated liquid partially vaporized saturated vapor superheated vapor
q>1 q=1 q = LF/F q=0 q<0

L L V V liquid flow increase across feed

q= =1+ rate normalized by feed rate.
F F
hsat.
F
vapor
hF
q=
hsat.
F
vapor
hsat.
F
liquid
Operating lines & q-
line must intersect at
a single point.

∴ cannot specify q, VB
and R independently.

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 More on the q-line
rectifying section: stripping section: q=
L L
=1+
V V
F F
L D L B
y = x + xD y= x xB
V V V V
subtract

y V V =x L L + DxD + BxB
| {z }
F zF

✓ ◆ ✓ ◆
V V L L
y = x + zF
F F
y (1 q) = qx + zF
✓ ◆
q zF
y = x
q 1 q 1

Typically the feed condition is

known (specifying q).

Then we can choose VB or R.
Note: specifying R implies VB.

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 SHR §7.2.4

Feed Stage & Number of Stages

too low

just right

too high

Locate feed stage nearest to the intersection of

the operating lines & q-line as possible (just after
the horizontal line on the staircase passes “P”

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Partial Reboilers & Condensers
Total Reboiler:

D
• all liquid is turned back to vapor
V

Partial reboiler:

L
• bottoms product is liquid, boilup is vapor

• This is another equilibrium stage! F

• very common...

V
Total condenser:

B
• all vapor is condensed back to liquid
L
Partial condenser:

• distillate is vapor, reflux is liquid

• This is another equilibrium stage!

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 SHR §7.2.4

Limiting Cases: Rmin, Nmin.

D
V “Minimum reflux”

“Total reflux”
• N = ∞.
L
Rmin
• R = ∞, VB = ∞.
(L/V )min =
• L = V, D = B = F = 0.
F Rmin + 1
• F = 0, N = Nmin.
(L/V )min
Rmin =
• y = x is operating line.
V 1 (L/V )min
• No product... ⇥ ⇤ 1
B (VB )min = L/V max 1
L
1.0 1.0 1.0

1
“pinch
point”
2
ve

ve
cur

cur
ium

ium
ilibr

ilibr
y

y
equ

equ
3
y y y
x= x= x=
x = zF
x = zF
x = xD x = xB x = xD x = xD
x = xB x = xB
0 0 0
x 1.0 x 1.0 x 1.0

higher operating costs higher capital costs

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 SHR §7.2.4

Perfect Separation - Another “Limiting Case”

Perfect separation: xB = 0, xD = 1.

1.0
Pinch points form in each section
of the column.

Theoretical value for minimum
reflux ratio and boilup to achieve
perfect separation.

To find this:

y
• Obtain x-y data from thermo.
y
x=
• Determine q-line

• Determine slope of rectifying x = zF
operating line = Rmin/(Rmin+1).
0
x 1.0

1
For saturated liquid feed, Rmin =
zF (↵ 1)

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 Example
We want to separate a mixture of n-heptane and n-octane using distillation at
atmospheric pressure.

If the feed is 40 mole% n-heptane as a saturated vapor, determine the
minimum reflux ratio and minimum number of stages required to obtain
product streams with 95% and 5% n-heptane.

D
V
Known:
Needed:

L • xD = 0.95
• K-values (equilibrium curve)

• xB = 0.05
• q-line

F
• zF = 0.4, saturated vapor
• operating lines
V

B
L

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