Binary Distillation

SHR Chapter 7
Binary Distillation
Tuesday, April 2, 13
Introduction
Dates back to 1st century AD rst used in a batch mode (distillate changes in
time)
SHR 7.1
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.
By 16th century, multiple stages were in use to

improve separation.
By 1976, distillation accounted for nearly 3% of the US energy consumption! mostly in petroleum reneries Binary distillation is simplest & most wellunderstood. we will limit our discussion to binary distillation Third Law of Thermo - typically low thermodynamic efciency.
Design Considerations
Operating pressure - knob 1
below ambient pressure requires vacuum operation many things may inuence choice of operating pressure
Thermo: azeotrope formation, , etc. Column operating temperature range (avoiding reactions, corrosion, etc.)
most analyses do not account for pressure variation through the column
Operating temperature - knob 2

Reboiler & Condenser:
Bottoms above ambient requires additional energy input to the reboiler Distillate below ambient requires energy input to the condenser.
Thermodynamics: critical points of uids
Batch Distillation
Conceptually, follows the T-x-y diagram. More rigorous analysis in SHR chapter 13
SHR 7.2
The McCabe-Thiele Graphical Method

1925 Continuous (staged) distillation
Nomenclature
Specications
F zF P xD xB total (molar) feed rate LK mole fraction in feed Column operating pressure LK mole fraction in distillate LK mole fraction in bottoms D B
Results
Distillate (molar) ow rate Bottoms (molar) ow rate Nmin minimum number of stages Rmin minimum reux ow rate VB N Boilup ratio Number of equilibrium stages Feed stage location Stage compositions (xA,yA)
R/Rmin reux ratio Feed phase condition VLE data (y/x plot) Type of condenser (partial/total) Type of reboiler (partial/total)
Light Key (LK) - more volatile component Heavy Key (HK) - less volatile component
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
Rectifying Section Operating Line

Overall mole balance: V = L + D Light key mole balance: Vn+1 yn+1 = Ln xn + DxD
SHR 7.2.1
yn+1
Ln D = xn + xD Vn+1 Vn+1
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 equal (thermodynamics can be done at a single pressure).
Big assumptions, but allow for simple analysis, since L and V are constant under these assumptions.
L/D L L R L reux = =L = R D ratio V L+D /D + D/D R+1 D 1 = 1 R V R+1 x+ xD y=
op
in t a er
ne i l g
R+1
R+1
Range of Reux Ratios

L D y = x + xD V V
L R= D
1 because 0 R 1
L R = 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)
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.
SHR 7.2.2
The feed stage material balance relates L and V to L and V
ym+1
L = xm V
B xB V
relates light-key compositions in passing streams (streams on a stage are assumed to be in equilibrium)
y=
VB + 1 VB
1 VB
xB
ing op e rat lin e
VB
V boilup B ratio
10
Feed Stage & the q-Line

rectifying section stripping section subcooled liquid saturated liquid
SHR 7.2.3
q>1
q= L F L =1+ V F
q=1
partially vaporized q = LF/F
saturated vapor
superheated vapor
q=0
q<0
V liquid ow increase across feed

rate normalized by feed rate.
q=
. vapor hsat F . vapor hsat F
hF
. liquid hsat F
Operating lines & qline must intersect at a single point. cannot specify q, VB and R independently.
11
More on the q-line

rectifying section:
L D y = x + xD V V
subtract
stripping section:
L y= x V B xB V
q=
L F
=1+
V F
y V
V =x L
V F y (1
q) y
= = =
L + DxD + BxB | {z }
F zF
F qx + zF q x q 1
x + zF zF q 1
Typically the feed condition is known (specifying q). Then we can choose VB or R.
Note: specifying R implies VB.
Tuesday, April 2, 13 12
Feed Stage & Number of Stages

too low just right
SHR 7.2.4
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
Tuesday, April 2, 13 13
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, reux is liquid This is another equilibrium stage!
V L F
V
14
Limiting Cases: Rmin, Nmin.

V D
SHR 7.2.4
Minimum reux
N = .
Total reux

1.0
L F
V
R = , VB = . L = V, D = B = F = 0. F = 0, N = Nmin. y = x is operating line. No product...

1.0
L
1.0 1
Rmin min = Rmin + 1 (L/V )min Rmin = 1 (L/V )min (VB )min = L/V max 1 (L/V )
pinch point
cu r ve
ilibr ium
cu r
ve
equ
x=
x=
equ
ilibr ium
x=
x = xB
0
x = xD x
1.0 0
x = zF x = xB x
x = zF x = xD
1.0 0
x = xB x
x = xD
1.0
higher operating costs

higher capital costs

15
SHR 7.2.4
Perfect Separation - Another Limiting Case

Perfect separation: xB = 0, xD = 1. Pinch points form in each section of the column. Theoretical value for minimum reux ratio and boilup to achieve perfect separation. To nd this: Obtain x-y data from thermo. Determine q-line Determine slope of rectifying
operating line = Rmin/(Rmin+1).
1.0
x=
x = zF
0
x
1 = zF ( 1)
1.0
For saturated liquid feed, Rmin

16
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 reux ratio and minimum number of stages required to obtain product streams with 95% and 5% n-heptane.
V L F
V
Known: Needed: xD = 0.95 K-values (equilibrium curve) xB = 0.05 q-line zF = 0.4, saturated vapor operating lines
17

Binary Distillation

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SHR Chapter 7

By 16th century, multiple stages were in use to

Operating temperature - knob 2

Thermodynamics: critical points of uids

The McCabe-Thiele Graphical Method

Rectifying Section Operating Line

Range of Reux Ratios

What happens at R = 0? What happens at R = ?

Stripping Section Operating Line

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

Feed Stage & the q-Line

partially vaporized q = LF/F

V liquid ow increase across feed

. vapor hsat F . vapor hsat F

More on the q-line

Feed Stage & Number of Stages

Partial Reboilers & Condensers

Limiting Cases: Rmin, Nmin.

R = , VB = . L = V, D = B = F = 0. F = 0, N = Nmin. y = x is operating line. No product...

higher operating costs

higher capital costs

Perfect Separation - Another Limiting Case

For saturated liquid feed, Rmin

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