SHR Chapter 7

Binary Distillation

BinaryDistillation.key - March 28, 2014

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 1.

for 1 or 1, this can be done very effectively
unless an azeotrope exists (where =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 wellunderstood.

we will limit our discussion to binary distillation

Third Law of Thermo - typically low
thermodynamic efficiency.

BinaryDistillation.key - March 28, 2014

Design Considerations
Operating pressure - knob 1

below ambient pressure requires vacuum operation

many things may influence choice of operating pressure

Thermo: azeotrope formation, , etc.

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

most analyses do not account for pressure variation

V
L

through the column

Operating temperature - knob 2

Reboiler & Condenser:

Bottoms above ambient requires additional energy input to the

reboiler

Distillate below ambient requires energy removal from the
condenser.

Thermodynamics: critical points of fluids

3

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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
Results

Specifications
F

total (molar) feed rate

Distillate (molar) flow rate

LK mole fraction in feed

Bottoms (molar) flow rate

Column operating pressure

minimum number of stages

LK mole fraction in distillate

minimum reflux flow rate

LK mole fraction in bottoms

Boilup ratio

reflux ratio

Number of equilibrium stages

R/R

Feed phase condition

Feed stage location

VLE data (y/x plot)

Type of condenser (partial/total)

Stage compositions (

Type of reboiler (partial/total)

Light Key (LK) - more volatile component

Heavy Key (HK) - less volatile component

BinaryDistillation.key - March 28, 2014

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
D=F
B & solve for D:

zF
xD

xB
xB

BinaryDistillation.key - March 28, 2014

SHR 7.2.1

Rectifying Section Operating Line

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

yn+1 =

L
D
xn + xD
V
V

relates light-key compositions in passing streams

(streams on a stage are assumed to be in equilibrium)

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, CpT, is negligible compared to latent heat.

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

Column pressure is constant (thermodynamics can be
done at a single pressure).

Big assumptions, but allow for simple analysis, since

L and V are constant under these assumptions.

li
ing

ne

rat

e
op

L/D
L
L
R
L reflux
R
=
=L
=
D ratio
V
L+D
/D + D/D
R+1
D
1

=
1
R
V
R+1
x+
xD
y=

R+1

R+1
8

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Range of Reflux Ratios

y=

L
D
x + xD
V
V

L
R
=
V
R+1

R=

L
D

1 because 0 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)

BinaryDistillation.key - March 28, 2014

SHR 7.2.2

Stripping Section Operating Line

Overall mole balance: L = V + D
Light key mole balance: Lxm = V ym+1 + BxB

McCabe-Thiele assumptions
have been applied.

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

1
VB

xB
lin

V boilup
B ratio

ing

VB

relates light-key compositions in passing streams

(streams on a stage are assumed to be in equilibrium)

VB + 1
VB

B
xB
V

rat

y=

L
xm
V

op
e

ym+1 =

10

BinaryDistillation.key - March 28, 2014

SHR 7.2.3

Feed Stage & the q-Line

rectifying
section
stripping
section

q=

q=

subcooled liquid

saturated liquid

q>1

q=1

L
F

vapor
hsat.
F
vapor
hsat.
F

saturated vapor

superheated vapor

q=0

q<0

V liquid flow increase across feed

=1+

partially vaporized
q = LF/F

rate normalized by feed rate.

hF

liquid
hsat.
F

Operating lines & qline 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:
L
y= x
V

L
D
y = x + xD
V
V

B
xB
V

q=

L
F

=1+

V
F

subtract

y V

V =x L

L + DxD + BxB
|
{z
}
F zF

V
F
y (1

x + zF
F
q) =
qx + zF

q
zF
x
y =
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
13

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Partial Reboilers & Condensers

Total Reboiler:

all liquid is turned back to vapor

Partial reboiler:

bottoms product is liquid, boilup is vapor

This is another equilibrium stage!
very common...

Total condenser:

all vapor is condensed back to liquid

Partial condenser:

distillate is vapor, reflux is liquid

This is another equilibrium stage!

14

V
L
F
V

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SHR 7.2.4

Limiting Cases: Rmin, Nmin.

D

Total reflux

Minimum reflux

N = .

R = , VB = .

L = V, D = B = F = 0.

F = 0, N = Nmin.

y = x is operating line.

No product...

Rmin
Rmin + 1
(L/V )min
Rmin =
1 (L/V )min

L
(VB )min =
/V max 1
(L/V )min =

F
V

L
1.0

1.0

1.0
1

pinch
point
ve
cur

y
3

x=

x=

x = zF

x = xD

x = xB

x = xB
1.0

ilibr

ium

x=

equ

equ

ilibr

ium

cur

ve

higher operating costs

x = zF
x = xD

x = xD

x = xB
1.0

1.0

higher capital costs

15

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SHR 7.2.4

Perfect Separation - Another Limiting Case

operating line = Rmin/(Rmin+1).

1.0

Perfect separation: xB = 0, xD = 1.

Pinch points form in each section
of the column.

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

To find this:

Obtain x-y data from thermo.

Determine q-line

Determine slope of rectifying

x=

x = zF
0

For saturated liquid feed, Rmin =

16

1.0

1
zF ( 1)
BinaryDistillation.key - March 28, 2014

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

Known:

Needed:

xD = 0.95

K-values (equilibrium curve)

xB = 0.05

q-line

zF = 0.4, saturated vapor
operating lines

L
F
V

17

BinaryDistillation.key - March 28, 2014