Separation Processes Examples:

defined as operations which transform a Gas Absorption

mixture of substances into two or more - Gas/liquid contact
product streams which differ from one - Liquid phase is separating agent

another in composition

i.e. they attempt to separate a mixture

Liquid Extraction
into its component parts.
- Liquid/liquid contact
- Liquid(solvent) phase is separating agent
almost always involve the contacting of
two immiscible phases and the transfer
of components from one phase to
another.
Leaching
"In most chemical, petroleum,
- Solid/liquid contact
petrochemical and pharmaceutical plants,
- Liquid phase is separating agent
separations account for 40% to 70% of
both capital and operating expenses"1
Distillation -
- Gas/liquid contact
-. Energy is separation agent
- Part of feed vaporised to generate the
1
Humphrey J.L., Keller G.E., II, Separation Process Technology, McGraw-Hill, New York second phase
(1997)
1-1 1-2
 1 DISTILLATION known as the relative volatility or the
selectivity.
REFERENCES: C&R Vol 2 Ch. 11, Treybal Ch. 9
y / xA
Distillation is the separation of liquid  BA = A
yB / xB .... 1.1
mixtures where all components are
appreciably volatile.
where all values are determined at
equilibrium. The larger the value of α above
Enthalpy is the separating agent i.e. if a
unity the greater the degree of separability.
single liquid phase undergoes partial
vaporisation then the new vapour phase is
For binary systems, where A and B are the
richer in the more volatile component. The
only components:
remaining liquid phase is richer in the less
y (1 - x A )
volatile component.  BA  A
x A (1 - y A ) .... 1.2

Equilibrium is generally complex. Use

graphical or computer database data. For ideal solutions (obeying Raoults Law):
sat
PA
Generally use constant pressure equilibrium  B = sat
A
.... 1.3
PB
data, temperature varies. Generally α varies less with composition than
m.
Relative Volatility For efficient separation
of a species A from another species B we This ratio is used extensively in
require the receiving phase to have a high multicomponent distillation problems.
selectivity towards A. This difference is
quantified by the separation factor, also
1-3 1-4
 Dew Point Curve A is the more volatile
T versus y component by
convention. Lever Arm Rule:
T
D F Horizontal tie lines D mols/hr, xD F mols/hr, zF D mols/hr, xD
E F mols/hr, zF
(constant T)
E mols/hr, yE E mols/hr, yE
Bubble Point Curve
T versus x
Lever Arm Rule applies

00 xD Mol fraction A yE 1
Overall mass balance:
.... 1.4
HG versus y Enthalpy Diagram
H L  xC pA (TL  T0 ) MWA 
H
J/kg B E (1  x )C pB (TL  T0 ) MWB  H solution Component A mass balance:
or .... 1.5
F
J/mol H G  H L  y A MWA  (1  y ) B MWB
D
A
HL versus x
Lever Arm Rule Applies
Enthalpy Balance:
... 1.6
00 xD Mol fraction A yE 1

x-y Diagram 
(D,E)
T varies continuously Lever Arm rule:
yE

along line
Mol fraction A in gas phase, y

Lever arms don't work

here.

0 xD Mol fraction A in liquid phase, x 1 1-5 1-6

1.1. Differential Distillation

An unsteady state process whereby a liquid T

is heated at a constant rate and the vapor is y
removed as rapidly as it forms. x

Constant Vapour Removal and 0

Condensation
0 Mol fraction A 1

L = mols of liquid remaining in the still pot at time t

x = mol fraction of component A in the still at time t
y = mol fraction of component A in the vapour
Constant Heat Input
Component mass balance in the still:
y dL = d(Lx) = xdL + Ldx mols .... 1.7
At any time, the vapor formed is in equilibrium with
the liquid in the still pot. ( y - x) dL = L dx mols .... 1.8
Total vapour removed is NOT in equilibrium with
the liquid remaining in the still pot after any given Integrate from (F, xF) to residual liquid
time. composition (W, xw):
W xw
dL W  dx
Initially we have F mols of a liquid of composition  L
= ln
F
= 
 xF y - x .... 1.9
xF. During any time interval dt, dL mols of liquid F
then evaporates into dD mols of distillate of
composition y. Finally, W mols of liquid of Solution requires a graphical or algebraic
composition xW remains. equilibrium relationship between y and x.
1-7 1-8
1.2. Equilibrium Flash - Single Stage Separation HG versus y
H
Distillate Vapor (J/mol)

D yD HD

Feed
P
F
zF HL versus x
HF (zF,HF)
HF
Q
Bottoms Liquid 0 xw zF yD 1

Mol fraction A
W xW HW

Overall Mass Balance: yD

.... 1.10

Mol fraction A in gas phase, y

Component Mass Balance:
Fz F = WxW + Dy D .... 1.11

Energy Balance:
F H F + Q = WH W + DH D .... 1.12
1
0
xw zF
1-9 Mol fraction A in liquid phase, x 1-10
Combining Equations 1.10 and 1.11 gives: 1.3. Fractionation - Multistage Countercurrent
W ( yD - zF ) Distillation
- = .... 1.13
D ( xW - z F ) - the most widely used method for separating liquid mixtures
This material balance can be shown on an
x-y diagram as an OPERATING LINE Distillate
D yD HD
For equilibrium flash separation, the Condenser Qc
saturated vapor is in equilibrium with the
saturated liquid and the two are related by a
TIE-LINE (isotherm) on the Enthalpy- G L
Reflux
concentration diagram. For this tie-line we
can similarly deduce from Equations 1.10 to Absorbing
1.12: or
Feed

Increasing A concentration
G L
enriching
W y D - z F H D - ( H F + Q/F) F section
- = =
D xW - z F H W - ( H F + Q/F) .... 1.14 zF Multiple
HF Stripping or Trays
exhausting G L
section
The vapor with the highest concentration of
A forms if D0 and the operating line is
vertical

The liquid with the lowest concentration of Bottoms

A forms if W0 and the operating line is W xW HW
horizontal.
1-11 1-12
 Schematic Diagram of a Cross-Flow Sieve Tray Tray Equilibrium
(Treybal Figure 6.15)
Gn Ln-1 Note:
yn xn-1 Subscript indicates
Stage the tray from which a
n stream originates.
Gn+1 Ln
yn+1 xn Contrary to C+R we
number trays from
the top down.
At each stage:
- some of the more volatile component is vaporised
- some of the less volatile component condenses
into the liquid stream.

If A  b mass transfer approaches ideal

equimolar counterdiffusion (NA = -NB)

The driving force is the non-equilibrium vapour

(from the tray below) and liquid (from the tray
above) streams arriving at plate n. These
streams mix and form new streams.
Initially we assume that each tray (plate) is an
equilibrium stage or an ideal plate. That is, we
assume that there is perfect mixing on the tray
and the exiting phases are at equilibrium
(yn=mxn)

1-13 1-14
 Condenser: Reboiler:

Overhead
Vapour G1 Qc Condenser
Tray NIP Total
Accumulator or Reboiler
reflux drum GNIP1
Tray 1 LNIP
Reflux Distillate
L0 D Bottoms
W xw Hw
Reflux Ratio:
QB
L
R= 0 .... 1.15
D
Partial
Total Condenser (shown) - If the distillate Reboiler
product is a liquid, the distillate and the reflux Tray NIP-1
are identical in composition. This is the normal
arrangement. GNIP
Bottoms
W xw Hw LNIP 1
Partial Condenser - If the distillate product is a
vapor, the distillate and the reflux will have
different compositions. If equilibrium
condensation occurs, the condenser acts as an QB
extra ideal stage. In practice, separation in the
condenser is less than ideal. Reboilers may be partial (most common) or
Partial condensers are used if a vapour product total, internal or external.
is required or the distillate boiling point is low. Note: Overbars indicate stripping section flows.
1-15 1-16
Reboiler Arrangements (Treybal Fig. 9.29) 1.4. Material and Energy Balances of a
Countercurrent Distillation Column
(Treybal Fig. 9.17)

xD

1-17 1-18
Balances over the Entire Tower (Region II) Stage Calculations – McCabe-Thiele Method

Overall mass balance: Approximate method only but does not require
mol/s .... 1.16 detailed enthalpy data.
Component mass balance:
Performed on y-x equilibrium curve rather
mol/s .... 1.17
than H-x curve
Energy Balance:
ℎ Requires EQUIMOLAL OVERFLOW i.e.
J/s .... 1.18 vaporisation of 1 mole of liquid is accompanied
by the condensation of 1 mole of vapor
Balances over the Condenser (Region I)
Overall Mass Balance: This is true if:
1. The molar heat of vaporisation is constant
G1 = L0 + D = D (R + 1) mol/s .... 1.19 and independent of composition
2. Heat losses are insignificant
Component Mass Balance: 3. Heats of solution are insignificant
G1 y1 = L0 x0 + Dx D mol/s .... 1.20 4. Changes in sensible heat with temperature
through the column are insignificant.
Energy Balance (assuming no losses):
If these four criteria can be assumed the vapor
G 1 H G 1 = L0 H L 0 + DH D + Q C J/s .... 1.21 and liquid lines on the H-x diagram are straight
and parallel.
or substituting in the Reflux ratio, R=L0/D:
QC = D[(R + 1) H G 1 - RH L 0 - H D ] J/s .... 1.22

1-19 1-20
HL1 = HL2 = .... = HL Balances over Enriching Section (Region III)
HG1 = HG2 = .... = HG
HG,n+1 - HLn = λav G
y1 Qc

Similarly, as 1 mol vapour condenses for Tray 1

every mol of liquid that evaporates: L,x0 D xD
G L
L1 = Ln = L = constant
G Tray n
G1 = Gn = G = constant
yn+1 xn
L D
and are also constant.
F
Overall Mass Balance:
L/G in each section is mol/s .... 1.23
constant
G Component Mass Balance:
N.B. Due to the feed flow: Gy n+1 = L x n + Dx D mol/s .... 1.24

!"# $ $ L W
Combining:
L xn D xD
y n+1 = +
N.B. Molar basis used – mass flowrates can (L + D) (L + D) .... 1.25
still change along column
L xD
y n +1 = xn + ... 1.26
These assumptions are reasonable for many G R +1
systems.
This is the equation of the OPERATING LINE for
the Enriching Section on the x-y diagram.

1-21 1-22
It defines the relationship between yn+1 and xn Balances over the Stripping Section
(Region IV)
If xn = xD Equation 1.24 gives yn+1 = xD, so the
operating line intersects the diagonal at Tray m
ym+1 .... 1.30
(xD, xD). xm

Tray NIP-1
When xn=0, yn+1 = xD/(R+1) so the y-intercept
of the operating line is xD/(R+1) Bottoms
W xw Hw

Q
(xD,xD)

Overall Mass Balance:

Mol fraction A in gas phase, y

.... 1.31
....
Component Mass Balance:
L xm = G y m+1 + Wx w .... 1.32

Combining:
L W xW
y m+1 = xm -
( L - W) ( L - W) .... 1.33

xD
Mol fraction A in liquid phase, x 1-23 1-24
 Balances around the feed point
This is the equation of the OPERATING
LINE for the Stripping Section on the x-y L G
diagram. F

When xm = xW, ym+1 = xW and the operating L G

line passes through (xW, xW). .... ....
Overall Balance:
.... 1.36

Enthalpy Balance:
FH F + LH L + G H G = L H L + GH G .... 1.37
Mol fraction A in gas phase, y

Define:
q = heat required to vaporise 1 mol of feed
molar latent heat of the feed
-
q= HG HF
HG - HL .... 1.38

So for liquid feeds:

 + C pL ( T Bubble - T F )
q=
(xw,xw)  .... 1.39
and for vapor feeds:
xw C pG ( T Dew - T F )
q= .... 1.40
Mol fraction A in liquid phase, x 
1-25 1-26
 Now combine this with the entire tower
Thermal Feed Conditions: component balance (Equation 1.17):
Cold liquid: Fz F = WxW + DxD .... 1.46
Saturated Liquid:
Partially Vapor: to give:
()( ,-
Saturated Vapor: '*)* + *)*
.... 1.47
Superheated Vapor:
Now incorporating Equations 1.40, 1.41:
Re-arranging Equations 1.35 to 1.37: qF F
y = x - zF
% .... 1.41 (q  1) F (q  1) F .... 1.48

% 1 .... 1.42 y=
q
x -
zF
q-1 q-1 .... 1.49
Intersection of Operating Lines:
This is a straight line with slope q/q-1 called
Enriching Section (Equation 1.23) the q-LINE.
Gy = L x + Dx D .... 1.43
The intersection of the operating lines for
Stripping Section (Equation 1.31) the enriching and stripping sections lies on
L x = G y + Wx w the q-line.
.... 1.44
Subtracting these equations from each other: When x=y , the equation yields x=y=zf so
( G - G) y = ( L - L) x - ( WxW + D x D ) .... 1.45 the q-line crosses the diagonal at (zF,zF)

1-27 1-28
q-line for different feed conditions McCabe-Thiele construction
(Treybal, Fig. 9.38)

(xD,xD)

Mol fraction A in gas phase, y

zF
xD
R 1
....

(xw,xw)

xw zF xD
Mol fraction A in liquid phase, x

1-29 1-30
General Procedure for McCabe Thiele Method : Other Issues

a) Feed Plate Location

It is the introduction of feed which governs
1. Complete the entire tower mass
the change from one operating line to the
balances in order to determine F,D,W and
other.
zF, xD, xW .
For optimum design of new columns, the
2. Locate the enriching section operating
minimum number of ideal plates results
line by the point (xD,xD) and the y-
when feed is introduced at the plate which
intercept xD/R+1
straddles the operating line intersection.
3. Calculate and locate the q-line by the
For an existing column, the feed location
point (zF ,zF) and the q-line equation.
may be fixed at a certain stage. In this
case, cross from the enriching section
4. Locate the stripping section operating
operating line to the stripping section
line through the point (xW,xW) and to
operating line at the feed plate stage, not at
intersect the enriching section line at the
the intersection of operating lines.
q-line.
Totally liquid feeds should be introduced to
5. Step off the ideal stages, starting on the
enter the feed tray with the liquid from the
top operating line and crossing to the
tray above.
bottom operating line when the feed point
Totally vapour feeds should be introduced
is passed.
to enter the feed tray with the vapour from
the tray below.
1-31 1-32
Location of Feed Tray c) Reflux Ratio
(Treybal Fig 9.39)
( (
. .... 1.51
*)(

- as R increases, L and G increase for a

given D, so the column diameter increases;

- the y-intercept of the top operating line

moves down, increasing the separation
driving force and thus decreasing the
number of trays required to achieve a
desired separation;

- but QC & QB also increase, so larger heat

transfer areas are required.

d) Total Reflux
At R = , the minimum number of trays is
required to achieve separation.
But no products are withdrawn from the
column!

1-33 1-34
At total reflux, L/G = L/G = 1. For the McCabe-Thiele method, the
 The slopes of the operating lines on minimum reflux occurs when an operating
the x-y diagram are both 1 i.e. coincident line first touches the equilibrium line
with the diagonal (Treybal, Fig. 9.41)

xw zF xD

e) Minimum Reflux
The minimum reflux ratio will result in:

- an infinite number of stages

- a minimum column diameter
- minimum QB & QC.

1-35 1-36
f) Optimum Reflux Ratio Economic decision must be made, trading
off fixed costs (construction of column) with
Tradeoff between the minimum number of operating costs (reboiler energy, etc.)
stages and the minimum reflux ratio. Typically, Ropt  1.2 to 1.5 Rmin
(Treybal, Fig. 9.25a)
(Treybal, Fig. 9.26)

1-37 1-38
 Efficiency Murphree Plate Efficiency:
These stage calculations assume that The efficiency will vary up the length of the
equilibrium is reached on each plate. In column as the proportions of liquid and vapor,
practice, this is not the case. and the fluid temperature changes.
The Murphree plate efficiency is the ratio of
Overall Efficiency: the actual change in composition across a
N IP plate to that which would occur if equilibrium
EO = .... 1.52
NP were achieved.
NIP = number of ideal plates y n - y n 1
N= number of actual plates E MG = .... 1.53
yne - yn1
Typically E0 is between 30 and 100% yne is the composition of the vapor that would
be in equilibrium with liquid xn actually leaving
Loss of efficiency can be due to: the plate.
- mass transfer rates between phases reducing
xn1 - xn
the rate of approach to equilibrium E ML = .... 1.54
xn1 - xne
- flow patterns on plates causing incomplete xne is the composition of the liquid that would
mixing be in equilibrium with liquid yn actually leaving
the plate.
Empirical equations have been developed to
predict efficiencies and these depend upon: Generally /* /(
- mixture physical properties
- column geometry
- phase flowrates
1-39 1-40
 Simulation Techniques
There are three levels of simulation available within
HYSYS for distillation:
The Splitter – solves the overall material and energy
balances.
yne Shortcut Distillation – uses simple techniques to
yn estimate the reflux ratio, number of trays and feed
tray position for the column. Comparable to McCabe-
Theile.
yn+1 Distillation Column – completes rigorous tray by
tray calculations comparable to Ponchon-Savarit.

xne xn xn-1

1-41 1-42
Open Steam Component Mass balance:

Can be used to split a more volatile component

L x m + S(0) = G y m+1 + W xW .... 1.59
from water. The supply of heat (reboiler) is
replaced by direct addition of steam at the L W
bottom of the column. y m+1 = x m - xW .... 1.60
G G

For a given reflux ratio and distillate

L
y m+1 = ( x m - xW )
composition, more trays are required. G .... 1.61

Stripping Section: This becomes the Stripping Section operating

line, which still intersects the enriching section
operating line at the
Tray m q-line. Also, when x= xW , y = 0
ym+1 ....
xm

Mol fraction A in gas phase, y

Tray NIP
(xD,xD)
S= steam flowrate
ys=0
zF
W, xw
....
For saturated steam and constant molal
overflow:
and 3 xw zF xD
.... 1.58
Mol fraction A in liquid phase, x
1-43 1-44
Sidestreams or:
L S xs + Dx D
y k+1 = xk + .... 1.65
G G
Products of intermediate composition are
withdrawn from intermediate trays
If S is a liquid sidestream (usual case):
4 4
e.g. consider a sidestream removed from plate p 3 56 .... 1.66
above the feed point: and:
L-S Sx S + D x D
y k+1 = xk + .... 1.67
G G G
y1 Qc
This is the operating line for the section of the
Tray 1 column between tray k and the feed point.
L,x0 D xD
G L
By simultaneous solution of the component
Tray p S xs balances for the top(Eqn 1.23) and middle(Eqn
G'k L'k 1.63) sections we can show that the top and the
yk+1 xk middle operating lines intersect at x=xs

Overall Mass Balance: Similarly combining component balances for the

′ ′ 3 .... 1.63
middle and bottom sections shows that these
lines intersect on the q-line.
Component Mass Balance:
G y k+1 = L xk + S x s + D x D .... 1.64

1-45 1-46
 The Ponchon-Savarit Method

Rigorous method, handles all situations

Requires detailed enthalpy data
Solution of the set of simultaneous equations:
(xD,xD)
1. between each of n stages:
a. overall mass balance
b. component mass balance
c. enthalpy balance
Mol fraction A in gas phase, y

2. For each of n stages:

a. Equilibrium relationship

3. For the entire tower:

a. Overall mass balance
b. Component mass balance
c. Enthalpy balance
(xw,xw)

xw zF xs xD

Mol fraction A in liquid phase, x

1-47 1-48