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Distillation
Distillation
DISTILLATION
9.1 Introduction
The method of separating the components from a solution depending on its
distribution between a liquid phase and vapour phase is termed distillation. This is
applied to mixtures which distribute in both the phases.
This can also be defined as an operation in which a liquid or vapour mixture
of two or more components is separated into its component fractions of desired
purity, by the application of heat. Thus, in this process, a vapor is obtained from a
boiling mixture which will be richer in components that have lower boiling points.
9.2 Vapour liquid Equilibria (VLE)
The vapor liquid equilibrium data is the basis for distillation operations.
9.2.1 Constant pressure Equilibria
A typical VLE at constant pressure is shown below in Fig. 9.1
B.P of B P
J
I H
G y vs. T
T F
E K
D
C
B.P of A
x vs. T
M
0 x, y 1.0
Fig.9.1: VLE diagram at constant pressure
The upper curve is the dew point curve which provides the relationship between
temperature and mole fraction of the more volatile component in vapor phase(y) and
the lower curve is the bubble point curve which gives the relationship between the
temperature and mole fraction of the more volatile component in liquid phase (x) at a
particular pressure. The horizontal tie lines CD, EF and GH at different temperatures
provide equilibrium compositions of liquid and vapour phase at each temperature.
Any mixture lying on the lower (bubble point) curve will be a saturated liquid and a
mixture lying on the (dew point) upper curve will be a saturated vapor. A mixture
located in between the two curves, say K, will be a two phase mixture of liquid and
vapour with compositions C and D respectively. Their relative amounts are given by
239
moles of C Length of line KD
moles of D Length of line KC
Consider a mixture at point M. It is only a liquid. If it is kept inside a cylinder fitted
with a frictionless piston and heated, its temperature will increase till it reaches „E‟
when it will become a saturated liquid. The vapour in equilibrium with it will have a
composition of F. As heating is further continued more vaporization takes place, the
liquid phase composition will move towards G and the associated vapour will have a
composition of H. The effective composition of the entire mass comprising both
liquid and vapour continues to remain at M. Finally, when the last droplet of liquid as
indicated at point „I‟ is vaporized, the vapour generated would have a composition of
„J‟. Further application of heat results in super heating of the vapor. During the entire
operation, the pressure is kept constant.
T B
0 1.0
x, y
Fig.9.2: Effect of pressure on VLE
240
pressures. A liquid defined at point M is a liquid below its bubble point and as the
pressure is reduced at constant temperature, at point „N‟ on the upper (bubble point)
curve, a saturated liquid is obtained. As the pressure is brought down further, at point
Q on the lower (dew point) curve, a saturated vapor forms and a further reduction in
pressure gives a fully superheated vapor as defined by R.
T: constant
Bubble point
Liquid curve
V.P of A
x vs. P
M G
H
E
F Dew
P point
N curve
O
C
D y vs. P
V.P of B Q
0 x, y 1.0
Raoult’s law states that when a gas and a liquid are in equilibrium, the partial
pressure of „A‟, „pA‟ is equal to the product of its vapor pressure, PA at that
temperature and its mole fraction „xA‟ in the liquid.
(i.e.) pA = PA. xA (9.2)
Similarly pB = PB. xB (9.3)
When the gas and liquid behave ideally, Raoult‟s law holds good.
241
We know that sum of the partial pressures of components in a gas mixture is
equal to the total pressure, PT. The composition of a component y, in gas phase is
given by Dalton‟s law,
pA p
yA and yB B (9.4)
PT PT
p A PT y A y A
PA x A x A y B
α AB
PB p B PT y B x A
xB xB xB
yA
α AB 1 yA (9.5)
xA
1 xA
Rearranging, we get
α AB x A
yA (9.6)
1 x A (α AB 1)
and more simply as
αx
y= (9.7)
1 x(α 1)
9.4 Computation of VLE data (Equilibrium data)
The vapour pressure of the components involved is the basis for the
computation of VLE data.
From Eq. (9.2) and (9.3) pA = xA PA
pB = xB PB = (1 – xA) PB (9.8)
For a binary system,
pA + pB = PT = xA PA + (1 – xA) PB = PB + xA (PA – PB) (9.9)
PT PB
xA (9.10)
PA PB
From the vapor pressure data at each temperature, xA can be computed using
Eq. (9.10). After computing xA, the partial pressure pA can be estimated by using
Eq.(9.2). The mole fraction of A in gas phase, yA is then determined by using Eq.
(9.4). Thus, for the whole range of boiling points of components involved, we can
compute VLE data.
Whenever α lies in a narrow range, y can be computed by assuming various
values of „x‟ using Eq. (9.7).
242
9.5 Deviation from ideality:
A mixture whose total pressure is either greater or lesser than that computed
using Raoult‟s law is said to exhibit either a positive deviation or a negative deviation
from ideality.
T: constant PT vs. x
PT vs. y PA
Pressure
PB
0 x, y 1.0
P: constant
BPA
y vs. T
T
BPB
x vs. T
0 x, y 1.0
243
1.0
P: constant
0 x 1.0
PA
Pressure
PT vs. x
PB
PT vs. y
0 x, y 1.0
244
y vs. T
A x vs. T
Temperature
B
0 x, y 1.0
0 x 1.0
245
The use of additional components in distillation
Extractive distillation – use of solvent
Azeotropic distillation – use of entrainer
The type of columns:
Tray columns – use of sieve plate columns/Bubble cap trays/Valve trays
for better vapour – liquid contacting
Packed towers – use of packings in columns for better vapor – liquid
contacting.
DISTILLATION
Batch Continuous
Simple/ Flash/
Differential Equilibrium Stage wise contact Differential
distillation distillation (Tray tower) contact
(Packed
tower)
246
mixture boils. With vapor pressure data of the individual components, one can also
estimate the temperature at which such distillations take place.
PT = P A + PB (9.11)
TB BP of A BP of B
Temperature
247
Fig.9.12: Differential Distillation
248
F xF
dx
ln (9.18)
W xw αx
x
1 α 1x
dx
RHS of Eq. (9.18) = (9.19)
αx
x
1 α 1x
On simplification,
1 α 1x dx 1 α 1x dx
αx x αx x xα 1 αx x
2 2
1 α 1x dx 1 α 1x dx
x1α 1 x α 1 [x1 - x α 1]
A B
dx ln 1 x
dx dx 1
x1 x α 1 1 x α 1 x 1 x
A1 x Bx 1 dx dx
ln 1 x
1
α 1 x1 x
dx ln 1 x
α 1 x 1 x
W 1 x
W F
1 x
W
F1 x F 1 x F 1 x W
ln ln
W1 x W α 1 1 - x F x W
α 1ln F1 x F ln x F 1 x W
W1 x W 1 - x F x W
xF
F1 x F x F1 x F
α ln ln W
ln
W 1 x W 1 x W W1 x W
1 x
F
F1 x F x F F
α ln ln
W 1 x
W W W
x
F1 x F Fx F
α ln ln
W1 x W Wx W
249
α
Fx F F(1 x F )
(i.e.) (9.20)
Wx W W(1 x W )
The above equation (9.20) is very useful in the estimation of the amount of residue
(alternatively the estimation of the quantity to b distilled) in the case of systems of
constant relative volatility. This is also used in the estimation of relative volatility
for such systems.
(HF + Q/F)
F, ZF, HF
Pressure
Reduction valve
Residue liquid
W, xW, HW
Q
W Z F y D
(9.27)
D Z F x W
Similarly from Eqs. (9.22) and (9.24) we get
250
Q
H F F H D
W
(9.28)
D Q
H F F H w
Dividing Eq. (9.26) by „F‟ we get,
W
Z F x W D Z F y D (9.29)
F F
Let „f‟ be the fraction of vapor that has been condensed and removed
(1 – f) is the fraction of residue left behind.
(1 – f) (ZF – x W ) = f (yD - ZF) (9.30)
ZF – x W = f (yD – x W )
ZF + x W (f – 1) = fyD
yD
ZF
xW
f 1 (9.31)
f f
So the Eq. (9.31) can be called as an operating line drawn with a slope of [(f – 1)/f]
and simplified as
ZF f 1
y x (9.32)
f f
The Feed point is x = y = ZF
Having seen the principles involved in flash distillation, let us now see how
compositions are estimated in flash distillation operation
9.9.1 Steps:
There are two methods available to estimate the composition of products.
They are explained in detail below.
9.9.1.1 Case I
When the equilibrium data and the quantity of distillate or residue and feed are
available, the following procedure shall be adopted :
Draw the equilibrium curve
Draw the diagonal.(x = y line)
Locate feed point corresponding to xF on the diagonal (xF = yF = ZF)
W
Draw the operating line with a slope of -
D
251
The intersection of this line with equilibrium curve gives xW and yD as shown in
Fig.9.14.
9.9.1.2 Case II
When the enthalpy – concentration data (HL vs x and HG vs y) and heat
added „Q‟ are available, the following procedure shall be adopted.
Plot the enthalpy concentration data and also equilibrium curve below it.
Locate the feed point corresponding to F‟ (ZF, HF + Q/F)
Draw a line by trial and error, passing through „ F‟ ‟ such that it will be a tie
line.
The points of intersection of this line with enthalpy – concentration. Plot gives
the enthalpy and concentration of both the distillate and residue.
Figures (9.14) and (9.15) represent the procedures followed to determine the product
concentrations through case I and case II respectively.
yD
y ZF
Slope = - W/D
xW ZF
x
Fig.9.14: Estimation of composition of products in Flash distillation
252
HG vs. y
HD HG vs. y
HF + Q/F
F‟ HL vs. x
HL
HL vs. x
H
F
ZF x, y 1.0
Slope = –W/D
ZF x
253
Subsequently using the total material balance equation, D can be calculated
and then the mole fraction of each component in the distillate phase (vapour phase)
can be evaluated by making a component balance.
However in cases where the „ α ‟ varies significantly, the Rayleigh‟s equation
xF
F dx
of the form ln has to be used taking two components at a time. Here
W xW y x
also one has to assume „W‟ and suitably estimate xW. The values of xW will have to
be determined for all the components and finally checked using Eq. (9.36). If Eq.
(9.36) is not satisfied, one has to make a fresh assumption of „W‟ and has to proceed
till Eq. (9.36) is satisfied.
9.11 Multicomponent flash distillation
At low pressures almost all systems behave ideally. As flash distillation
occurs at low pressures, ideal behavior can be expected and Raoult‟s law is
applicable. Hence the equilibrium relationship for any component may be expressed
as
yi = mixi (9.37)
where mi = vapor pressure of component/total pressure. Suffix i denotes the
component
(i.e.) yi,D = mi (xi,W) (9.38)
W y D Z F
We know that from Eq. (9.27)
D x W Z F
W y i,D Z i,F
D Z i,F x i,W
(9.39)
yi, D Zi, F (9.40)
yi, D
Zi, F mi
W y i,D
or i,F
Z y i,D Z i,F (9.41)
D mi
W 1 W
(i.e.) Z i,F 1 y i,D 1 (9.42)
D mi D
W
D 1
y i,D Z i,F (9.43)
1 W
1
m i D
254
W
D 1
and x i, W Z i,F (9.44)
W
m i D
255
G1, y1, HG1
I
QC
L0, x0 Distillate
G1, y1 D, ZD, HD
Reflux L0
1 x0
HL0
L1 G2
2
Heat L2
Loss
n III
Feed
Ln Gn+1
xn Yn+1
HLn HG, n+1
II
Gm+1
Lm
Ym+1
xm
Heat H IV
HLm G, m+1
Loss
Np
QB Reboiler
W, xW, HW
256
Let G be the molar flow rate of vapor in enriching section, G the molar flow
rate of vapor in stripping section, L the molar flow rate of liquid in enriching section,
L the molar flow rate of liquid in stripping section, HG the Enthalpy of vapor, HL the
Enthalpy of liquid, y the mole fraction of more volatile component in vapor and x the
mole fraction of more volatile component in liquid.
Let R be the external reflux ratio L0/D, QC the load on condenser, QB the heat
supplied in reboiler and QL the total heat loss.
Considering envelope I and making a mass balance,
G1 = D + L0 (9.45)
G1 = D + RD = D(R + 1) (9.46)
A component balance gives
G1y1 = DZD + L0x0 (9.47)
Making an energy balance gives,
G1HG1 = L0HL0 + DHD + QC (9.48)
QC = G1HG1 – L0HL0 – DHD (9.49)
Substituting for G1 from Eq. (9.46) get,
QC = [D(R + 1) HG1] – RDHL0 – DHD
= D [(R + 1) HG1 – RHL0 – HD] (9.50)
Considering envelope II and making an energy balance,
Heat in = Heat out
QB + FHF = DHD + WHW + QC + QL (9.51)
Heat added in reboiler „QB‟ = DHD + WHW + QC + QL – FHF (9.52)
Now, let us consider envelope III, the enriching section and make mass and energy
balance.
A total mass balance yields,
Gn + 1 = Ln + D (9.53)
A component balance gives,
Gn + 1 yn +1 = Lnxn + DZD (9.54)
An energy balance gives,
Gn + 1 HG, n + 1 = Ln.HLn + DHD + QC (9.55)
(Q DH D )
Let Q( = اNet heat out/Net moles out) = C (9.56)
D
Then, Eq. (9.55) becomes
Gn + 1 HG, n + 1 = Ln.HLn + D Qا (9.57)
257
Eliminating „D‟ in Eq. (9.54) using Eq. (9.53) gives,
Gn + 1.yn +1 −Lnxn = (Gn + 1 – Ln) ZD (9.58)
(Gn + 1)[ZD – yn +1] = Ln (ZD – xn)
Ln
ZD yn 1 (9.59)
Gn 1 ZD xn
where (Ln/Gn + 1) is defined as internal reflux ratio
Similarly Eq. (9.53) and (9.57) yields
Ln
Q'HG, n 1 (9.60)
Gn 1 Q'HLn
Equating Eq.(9.59) with Eq.(9.60) gives,
Ln
ZD yn 1 Q'HG, n 1 (9.61)
Gn 1 ZD xn Q'HLn
Eq. (9.61) represents a straight line passing through
(HG, n + 1, yn +1) at Gn + 1 (HLn, xn) at Ln and (Qا, ZD) at ∆D
where ∆D is called the difference point and it represents
Qا: Net heat, out/Net moles, out and
ZD: Net moles of more volatile component, out/Net moles, out
Let us consider Eq. (9.60)
Ln
Q'HG, n 1
Gn 1 Q'HLn
Substituting for Gn + 1 in the above expression from Eq. (9.53) gives us,
Ln
Q'HG, n 1 (9.62)
Ln D Q'HLn
(i.e.)
Ln D Q'HL, n
Ln Q'HG, n 1
D
(i.e.) 1
Q'HL, n
Ln Q'HG, n 1
D HG, n 1 HL, n
(9.63)
Ln Q'HG, n 1
Ln
Q'HG, n 1 (9.64)
D HG, n 1 HL, n
When n = 0, it indicates the condenser and then for n=0 we get,
L0
Q'HG,1 (9.65)
D HG,1 HL,0
258
L0 Lenth of line ΔD.G1
(i.e.) „R‟, the external reflux ratio = = (9.66)
D Lenth of line G1L0
as indicated in Fig. 9.17
Hence, if the reflux ratio „R‟ is known, then it will be easy for us to locate ∆D point
(ZD, Q‟)
Ln ZD yn 1
Also, from Eq.(9.59)
D yn 1 xn
Let us consider envelope IV, in the stripping section
A mass balance yields
Lm = Gm + 1 + W (9.67)
A component balance yields
Lmxm = Gm + 1ym + 1 + WxW (9.68)
Lm xm − Gm 1 ym + 1 = WxW (9.69)
An energy balance yields
Lm.HLm + QB = Gm + 1HGm + 1 +WHW (9.70)
Let Q"
WHW QB (9.71)
W
Lm.HLm − Gm + 1HG, m + 1 +WQاا (9.72)
Eliminating „W‟ from Eq. (9.67) and (9.69) yield
Lm
ym 1 xW (9.73)
Gm 1 xm xW
Similarly eliminating „W‟ from Eq. (9.67) and (9.72) gives us,
Lm
HG, m 1 Q" (9.74)
Gm 1 HL, m Q"
Hence from Eq. (9.73) and (9.74) we get
Lm
ym 1 xW HG, m 1 Q" (9.75)
Gm 1 xm xW HL, m Q"
From Eq. (9.67)
Lm W
1
Gm 1 m
G 1
Hence rearrangement of Eq. (9.75) using Eq.(9.67) gives,
W
ym 1 xW (9.76)
Gm 1 xm xW
259
Lm
HG, m 1 Q" ym 1 xW (9.77)
W HG, m 1 HL, m ym 1 xm
Eq. (9.77) represents a line passing through (xW, Q)اا, (xm, HL, m) and
(ym + 1, HG, m +1)
where Q" represents: Net heat, out /Net moles out and
xW: moles of A out/Net moles out. Now let us consider the fractionator as single unit
and make mass and energy balances;
Total mass balance gives,
F=D+W (9.78)
A component balance gives
F.ZF = DyD + WxW (9.79)
An enthalpy balance gives
F.HF = (DQ ا+ WQ)اا (9.80)
(Neglecting QL, the heat loss)
Eliminating „F‟ from Eqs. (9.78), (9.79) and (9.80) we get,
D ZF xW HF Q"
(9.81)
W ZD ZF Q'HF
Eq. (9.81) represents a line passing through (ZD, Q)ا, (ZF, HF) and (xW, Q)اا
In other words F = ΔD + ΔW (9.82)
The schematic representation of enthalpy concentration and distribution diagrams for
determination of number of stages is shown in Fig. 9.17.
260
Fig. 9.17 (a) : Determination of number of stages by Ponchon Savarit Method
261
Fig. 9.17 (b) : Determination of minimum reflux in Ponchon Savarit Method
262
9.12.1.1 Steps involved:
1) Draw the H vs x, y diagram and the equilibrium curve
2) Locate xF, yD and xW in both the diagrams and draw vertical lines from yD in
„+‟ve y axis direction and from xW in the „-„ve y axis direction.
3) Locate F (xF, HF) in the H – x, y diagram
263
G1, y1
L
x0 y1 D, yD
x0 = yD
1
x1
y2
2
x2
yn
n
L
xn yn+1
264
L
L
L
D
R
(9.87)
G L D L D R 1
D D
D D 1
(9.88)
G L D R 1
R 1
yn 1 xn yD (9.89)
R 1 R 1
The equation (9.89) represents the operating line for enriching section, which has
R 1
a slope of and an intercept of R 1 . If xn = xD= yD then substituting in the
R 1
above equation (9.89) gives,
1
yn 1 RyD yD y D (9.90)
R 1
(i.e.) when, xn = yD, yn + 1 = yD.
Hence, this line passes through x = y = yD. (i.e.) it lies on the diagonal. This point on
y
the diagonal and the y intercept D permit us the construction of operating line
R 1
for enriching section.
Let us consider the stripping section shown in Fig. 9.19
ym
m
L G
xm ym+1
m+1
xm+1
yNp
NP
xNP
W, xW
265
A component balance gives
L xm G y m1 Wx W (9.92)
L W
y m1 x m x W (9.93)
G G
L
x m
W
(i.e.) y m1 x W (9.94)
LW LW
The above equation (9.94) describes the operating line for stripping section. The
L
and an intercept of –
W
operating line has a slope of .
LW LW
Let us assume that xm = xW (Reboiler)
L
x W
W
y m1 x W xW (9.95)
LW LW
(i.e.) xm = ym + 1 = xW Hence, the operating line passes through the point x = y = x W
(i.e. it lies on the diagonal). Having seen the analysis of enriching section and
stripping section separately, let us analyze the feed plate, f, shown in Fig.9.20.
L G
H L, f -1 HG, f
Feed, F
f
GF, yF, HGF
F LF, xF, HLF
ZF, HF
L G
HL, f HG, f +1
(i.e.) L L G G F (9.98)
Enthalpy balance on feed plate gives,
F.HF L.HL, f 1 G.HG, f 1 G.HG, f L.HL, f (9.99)
266
As an approximation, HG, f HG, f + 1 = HG and HL, f – 1 HL, f =HL (9.100)
L L HL G G HG FHF (9.101)
i.e. L L HL G G HG HF (9.102)
F F
Substituting for L L from Eq. (9.98) we get
G G F
HL
GG
HG HF
(9.103)
F F
(i.e.)
G G H L HL
G G HG HF (9.104)
F F
G G H L HG HF HL (9.105)
F
G G HF HL
(9.106)
F HL HG
Substituting for G G from Eq. (9.98) we get,
L L F H H F L
(9.107)
F HL HG
(i.e.)
L L H H 1 F L
(9.108)
F HL HG
=
HG HF (9.109)
HG HL
Let us now, define
HG HF as q, where „q‟ is the quantity of heat required to
HG HL
convert one mole of feed at its thermal condition to a saturated vapor to the molal
latent heat of vaporization.
q
L L H HF
G
(9.110)
F HG HL
Similarly
G G L L 1 q 1 (9.111)
F F
(i.e.) G G Fq 1 (9.112)
A solute balance above feed plate gives,
Gy Lx DxD (9.113)
A solute balance below feed plate gives,
267
Gy Lx WxW (9.114)
Subtracting Eq. (9.113) from (9.114) gives,
G G y L L x Dx D Wx W (9.115)
Total component balance for the distillation column gives,
FZF = DxD + WxW (9.116)
Substituting Eqs. (9.110), (9.112) and (9.116) in Eq. (9.115) gives,
F (q – 1) y = Fq.x - FZF
q ZF
y x (9.117)
q 1 q 1
q
The above Eq.(9.117) is the equation for feed line. It has a slope of and passes
q 1
through y = x = ZF.
The various slope values obtained under different thermal conditions of feed are
given below and shown in Fig. 9.21.
1
2 1. Cold feed
3
2. Saturated liquid
4 3. Liquid + vapor
y 4. Saturated vapor
5 5. Super heated vapor
x
Fig.9.21: Feed line for different Thermal conditions of feed
268
Determination of „q‟ is as follows:
i) Cold feed
From Eq. (9.110)
q
HG HF
HG HL
Let Tb is boiling point of mixture and TF is feed temperature
λ is latent heat of vaporization, CP,L is the specific heat of feed liquid and T0 is the
reference temperature then,
HG CP, L Tb T0 λ, HF CP, LTF T0 and HG HL λ, (9.118)
q
CP, L Tb T0 λ CP, LTF T0 CP, L Tb T0 - TF - T0 λ (9.119)
λ λ
CP, L Tb TF
(i.e.) q 1 (9.120)
λ
ii) Saturated liquid
q
HG HF (9.121)
HG HL
For saturated liquid HF = HL q = 1.0
iii) Mixture of liquid and vapor
Let „x‟ be the mole fraction of liquid in feed in the case of liquid + vapor mixture
Then,
HF = xHL + (1 – x) HG (9.122)
Therefore, q
HG xH L HG xH G
HG HL
1.0
x HG HL
(9.123)
HG HL
iv) Saturated vapor
q
HG HF (9.124)
HG HL
For saturated vapor HF = HG q = 0
iv) Super heated vapor
Let CP,V is the specific heat of feed vapor
HG = HG
HF = HG + Cp, v (TF – Tb) (9.125)
269
HG HG CP, vTF Tb CP, vTF Tb
q (9.126)
λ λ
T
y F
S
yD
R+1 W
0 xw xF yD 1.0
x
270
Fig. 9.23 (a) Optimal feed location
271
Fig.9.23 (c) Early feed entry
The point of intersection of the two operating lines is generally believed to be the
point that demarcates enriching and exhausting sections. This normally occurs in the newly
designed columns fro a specific xw, yD, xF and condition of feed. However, in an existing
column, designed for a different utility, the feed point location is fixed and may not be at the
optimum location. Further, the feed entry point will not demarcate the enriching and
exhausting sections.
Generally when the reflux ratio and the yD values are fixed, the operating line for
enriching section is fixed. Further when the xw and the condition of the feed are fixed the
operating line for exhausting section is fixed.
Once a feed enters a specific plate, below the point of intersection of operating lines
and q-line (in an existing column), from the top plate to feed entry point, the operating line
for enriching section is to be used and subsequently the operating line for exhausting section.
Such an arrangement indicates a delayed feed entry. If the feed enters at a specific plate,
above the point of intersection of operating lines and q-line (in an existing column), from the
top plate to feed entry point, the operating line for enriching section is to be used and
subsequently the operating line for exhausting section . This arrangement indicates an early
feed entry. In both the cases the number of stages estimated will always be more compared
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to the number of stages estimated with feed entering exactly at the point of intersection of
operating lines and q-line.
Consider the above three figures,
Fig. (a): Optimal design 9 plates and 5th plate is feed plate.
Fig. (b): An existing column with 10 plates and feed enters at 7th plate.
Fig. (c): An existing column with 10 plates and feed is introduced at 3rd plate.
9.14 Reflux ratio
It is one of the important operating parameters in distillation, by which the
quality of the products can be changed. Let us deal with the relationship between
reflux ratio and number of trays in the tower.
9.14.1 Determination of minimum reflux ratio:
To determine the minimum reflux ratio, draw the q – line from F to cut the
equilibrium curve at Tا. Join DT اand extend it to intersect on y axis to meet at Sا. OSا
yD
gives from which Rmin is estimated as shown in Fig. 9.24. Normally at
Rmin 1
Rmin condition the number of stages will be infinity as the equilibrium curve and
operating line get pinched.
1.0
Tا D
ا q line
S
F
y
W
0 xw xF yD 1.0
x
Fig.9.24: Determination of minimum reflux ratio
9.14.1.1 Steps involved in the determination of minimum reflux:
1) Draw the equilibrium curve and diagonal.
2) Locate F, D and W corresponding to feed, distillate and residue compositions
based on more volatile component.
3) Draw the q line from F and allow it to intersect the equilibrium curve at T
4) Join T‟D and allow it to intersect the y – axis at S‟.
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yD
5) OS‟ corresponds to from which Rmin , the minimum reflux ratio is
Rmin 1
estimated.
9.14.2 Total reflux:
At total reflux, all the distillate is returned back to the column and no distillate
is taken out as distillate product.
(i.e) D = 0
L
R
D
Hence, the operating line [Eq.(9.89)] for enriching section which is,
R 1
yn 1 xn xD
R 1 R 1
becomes, yn +1 = xn (9.127)
(i.e) it merges with the diagonal (x = y line) for both enriching and stripping sections.
Under such circumstances, minimum number of theoretical stages can be estimated
by the same graphical procedure described in section 9.12.2.1.. For systems where the
relative volatility is constant and under total reflux conditions the theoretical number
of stages needed could be estimated analytically.
yA yA
A B
x y
We know that for a binary system, α AB
y x
B A
x B x B
yA x
α AB A
yB xB
yA xA
α AB
1 yA 1 xA
Let us apply this relationship to (n + 1)th plate
y n 1 x n 1
α (9.128)
1 y n 1 1 x n 1
L R
At total reflux D = 0 and 1.0 ,
G R 1
Hence, from Eq.. (9.27)
(yn + 1) = xn (9.129)
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When n = 0 (i.e) at the top of the column, xn = x0
y1 = x0 = yD , when total condenser is used
Substituting for yn +1 in terms of xn in Eq. (9.129) we get
xn x n 1
α AB (9.130)
1 x n 1 x n 1
x0 x1
When n = 0, α AB (9.131)
1 x 0 1 x 1
x1 x2
When n = 1, α AB (9.132)
1 x 1 1 x 2
x n -1 xn
When n = n -1, α AB (9.133)
1 x n-1 1 x n
(i.e) Substituting for x1, x2 … xn – 1 from Eqs. (9.132) and (9.133)
x0 xn
α AB
n
(9.134)
1 x 0 1 x n
When n = NP + 1, (Last stage, (i.e.) reboiler) we get,
x0 x NP 1
α
NP 1
(9.135)
1 x 0 1 x NP1
As (NP + 1)th stage accounts for reboiler, x NP 1 = xw
yD xW
α
NP 1
(i.e) (9.136)
1 y D 1 x W
Eq. (9.136) is called Fenske equation. To apply this equation, α , the relative
volatility must be fairly constant and the column has to be operated under total reflux
conditions. This may not be possible in industries, but has theoretical importance.
9.14.3 Optimum reflux ratio:
At minimum reflux ratio the column requires infinite number of stages or
trays. However, as reflux ratio increases from minimum, for a given feed and
specified quality of distillate and residue, the number of stages or trays decrease. At
minimum reflux ratio when the stages or trays are infinite, the fixed cost and
maintenance cost are also infinite. However, the operating cost for operating
condenser, reboiler etc is the least. When the reflux increases, the trays or stages
reduce but the column diameter is to be increased to handle larger capacities of liquid
being recycled. The size of other accessories like condenser and reboiler increase
which will result in a higher requirement of cooling water or heating. Ultimately this
will result in a higher operating cost. Thus, the total cost which includes both
275
operating cost and fixed cost, vary with reflux ratio and reach a minimum value for a
certain reflux ratio which is called the optimum or economic reflux ratio. This value
is normally in the range of 1.2 Rmin to 1.5 Rmin.
Total cost
Operating cost
Annual cost
Fixed cost
Ropt
Reflux ratio
Condensate
276
Condensate
Bottoms
Steam
Condensate
277
Vapor
Steam
Bottoms
Condensate
They are heat exchangers of different configurations used to supply the heat to
the liquid at the bottom of the column to vaporize them. In effect all the heat needed
is basically supplied at the reboiler only.
A simple Jacketed kettle is one such reboiler which has a low heat transfer
area and hence vapor generation capacity will also be poor.
Tubular heat exchangers (both of vertical and horizontal configurations)
provide larger area of heat transfer. They can be placed inside the column or outside
the column. When they are located inside, during cleaning of the exchanger, the
distillation operation has to be stopped. However, when external reboilers are used, a
standby exchanger is always kept which can be used during cleaning of the exchanger
attached to the column. Thus, the distillation operation will proceed without any
interruption.. The liquid can flow either through the tube side or shell side. Reboilers
can be heated by steam, oil or other hot fluids.
9.16 Condensers:
The condensers are generally heat exchangers of horizontal orientation with
coolant flowing through tube side. However, in rare instances vertical condensers are
used with the coolant flowing on either side of the tubes. They are placed above the
tower in the case of laboratory scale units for gravity flow of the condensed reflux to
278
the top most tray. Sometimes they are placed at ground level for easy maintenance, in
which case the liquid is pumped from accumulator to the top tray. The coolant is
normally water. The condensers may either be a total condenser or a partial
condenser. Whenever, a partial condenser is used, the condensate is returned as reflux
and the vapour from condenser is the main distillate product. The partial condenser
itself acts as one stage for separation. In an existing distillation column, if one desires
to have a highly enriched distillate (richer than the designed value) then one can
resort to partial condensation and obtain an enriched product. However, when a
column is being designed fresh it is always preferable to go for additional trays than
to depend on partial condensation for enrichment.
9.17 Use of open steam:
Normally the heat needed for distillation is supplied through (by heat
exchangers) reboilers. However, when an aqueous solution is fractionated to give non
aqueous solute as distillate and water as residue, the heat required may be supplied by
open steam in which case the reboiler is not required. The schematic arrangement is
shown in Fig. 9.27 and the overall material balance is given below.
G, yn D,yD
n
F, ZF
n I
L, xn
m
Lm, xm Gm +1, ym +1
NP - 1
NP
L=W G
xW y=0
Fig. 9.27 Open steam distillation
279
The equation for the operating line in enriching section is obtained as in the case of
McCabe – Thiele method.
L R y
(i.e.) Slope = and intercept = D (9.137)
G R 1 R 1
However, let us analyze the exhausting section
A component balance gives
Lxm G(0) Gym 1 LxW (9.138)
L y m 1 0
(i.e) (9.140)
G x m x W
(i.e.) The operating line for exhausting section passes through (x = x W and y = 0) and
(xm, ym + 1). Thus, the line passes through „xW‟, the point in x – axis as shown in Fig.
9.28. After constructing the equilibrium curve and operating lines, by step wise
construction the number of stages are determined as in the case of McCabe Thiele
method.
1.0
D
T
y
F
yD
R+1
0 W xF yD 1.0
xW x
280
If the steam entering the tower is superheated (HG, NP + 1), it will vaporize liquid on
tray “NP” to the extent such that the steam will reach saturation (HG, Sat). An energy
balance yields,
HG, NP 1 HG, Sat
G GNP 1 1 (9.141)
λM
Where λ M is molar latent heat of vaporization, and
L G GNP 1 LNP (9.142)
L
Using equations (9.141) and (9.142), the ratio is computed.
G
9.17.1 Determination of number of trays:
1) Draw the equilibrium curve and diagonal.
2) Locate F and D corresponding to the composition of feed and distillate respectively
on diagonal.
3) Locate W corresponding to the composition of xW on x – axis.
yD
4) Based on the reflux ratio and distillate composition, estimate and locate it
R 1
on y axis as „S‟.
5) Join SD this is the operating line for enriching section.
6) From „F‟ draw q – line depending on feed condition and allow it cut the
operating line for enriching section -„SD‟, and locate the point of intersection as
T.
7) Join TW. TW is the operating line for stripping section.
8) By stepwise construction starting from „D‟ upto „W‟, the number of stages by can
be determined.
9) The minimum reflux ratio needed is estimated in the same manner as in the case of
McCabe – Thiele method.
9.18 Continuous differential contact − Packed tower distillation
Whenever we have heat sensitive materials to be distilled which require less
contact time, packed towers are preferred. The pressure drop is also low and hence it
is suitable for low pressure distillation operations.
The height of column can be determined in the same way as for other mass
transfer operations using packed towers by making a material balance across a
differential section and integrating as indicated in Fig. 9.29.
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G2 L2, x2 D, yD
y2
2
G, y
Ze
dZ
L, x
F, ZF
G
L ZS
G1,y1
L1,x1
R.B
W, xW
282
Similarly, the stripping section can also be analysed and it can be shown that,
ZS = (HtG) (NtG) = (HtL) (NtL) (9.147)
Total height Z = Ze + ZS (9.148)
The determination of HtG or HtL can be done using the flow rates of vapour or
liquid and vapour or liquid mass transfer coefficients. However, to determine NtG or
NtL one needs to find interfacial compositions. If the film coefficients are known the
interfacial concentrations can be determined from the operating line and equilibrium
kx'
curve. These values are given by a line drawn with a slope of from the
ky'
operating line to the equilibrium curve. The point at which this line cuts operating
line gives x and y values and the point of intersection with the equilibrium curve
gives the interfacial compositions xi and yi. A number of such lines can be drawn
which will give various sets of (x – xi) and (yi – y) values as shown in Fig 9.30. Using
these values, NtL or NtG can be determined. One should use NtL or NtG (corresponding
to HtL or HtG) to determine the height depending on the resistance which is controlling
the mass transfer.
yi, 1e
-kx/ky D
y, 1e
2221e
yi, 2e -kx/ky
y, 2e
I
F
y
yD
R+1
W
xW xF x2e x1, e yD
x
283
x2
Ht0L Nt0L
dx
Ze Ht0L (9.150)
xa x x *
when liquid phase is controlling
In equations (9.149) and (9.150) , (y* − y) and (x – x*) are the overall driving forces
in terms of vapour and liquid phase composition respectively.
G L
Here, Ht0G and Ht0L
Ky' a Kx' a
1 1 m
We know that,
Ky' ky' kx'
1 1 1
Kx' kx' mky'
Similarly, HtoG and HtoL can also be written as
mG
Ht0G HtG HtL (9.151)
L
L
Ht0L HtL HtG (9.152)
mG
where „m‟ is the slope of equilibrium curve
284
dx dy dx dy
9) Evaluate x x
i
or y y
i
or x x * or y * y graphically to
This is a technique which is used for the separation of binary mixtures which
are either difficult or impossible to separate by ordinary fractionation. This happens
when either the mixture to be separated has a very low relative volatility, in which
case one may require high reflux ratio and more number of trays, or when the mixture
forms an azeotrope. Under such circumstances, a third component called an
„entrainer‟ is added to the binary mixture to form a new low boiling hetero azeotrope
with one of the components in the original mixture whose volatility is such that it can
be separated from the other original constituent.
A typical example for this operation is presented in the flow diagram of Fig.
9.31 where the separation of acetic acid (BP: 118.1°C) and water (BP: 100°C)
mixture. This mixture has a low relative volatility and hence separation by
conventional methods is not economical. Here Butyl acetate, which is slightly
soluble in water, is added to the mixture from the top of the column as an entrainer. It
forms a hetero − azeotrope with all the water in the feed and readily distills out from
the high boiling acetic acid and the acetic acid leaves as a residue product. The hetero
azeotrope on condensation forms two insoluble layers which can easily be separated.
The water layer obtained is saturated with ester and vice versa. The ester layer
saturated with water is returned back to the column as a source of entrainer for further
separation. The aqueous layer is also sent to another column to separate water and
ester. The separated ester is also sent back as entrainer.
Sometimes the new azeotrope formed contains all the three constituents. In the
dehydration of ethanol water mixture, benzene is added as an entrainer which gives a
ternary azeotrope containing benzene (53.9 mol %), water (3.3 mole %) and ethanol
(22.8 mol %) boiling at 64.9°C as distillate and ethanol (BP: 78.4°C) as residue.
285
Benzene is separated and sent back to the top of the column as entrainer. Since water
– ethanol are equally present in distillate, the mixture should be given a preliminary
rectification to produce an alcohol rich binary azeotrope.
286
One such example is the separation of toluene (BP: 110.8°C) from isooctane
(BP: 99.3°C). Their separation is relatively difficult. In the presence of Phenol (BP:
181.4°C), the relative volatility of isooctane increases, so that with increase in phenol
content, the separation becomes more and more easy. A typical flow diagram of the
process is shown in Fig. 9.32.
Here, the toluene – isooctane binary mixture is introduced in the middle of the
column and phenol near the top of the column. Isooctane is readily distilled as an
overhead product, while toluene and phenol are collected as residue. The residue from
the tower is rectified in the auxiliary tower to separate toluene and phenol as distillate
and residue respectively. Phenol is returned back to the main column as solvent.
Similarly a mixture of acetone (BP: 56.4°C) and methanol (BP: 64.7°C) can be
separated by using Butanol (BP: 117.8°C) solvent.
287
iv) Easy separability, for easier removal of solvent
v) Non corrosive
vi) Non toxic
vii) Cheap and easily available
viii) Low freezing point
ix) Low viscosity
x) Chemical stability and inertness towards the components to be separated.
9.21 Comparison of Azeotropic and extractive distillation
In both the processes an additional external agent is added, which is
undesirable. Solvent to feed ratio in extractive distillation greater than 3 or 4 is found
to be effective. Proper choice of material of construction and recovery technique are
to be examined. However, of the two, extractive distillation is said to be more
favoured than azeotropic distillation since i) there is a greater choice of solvent ii)
smaller quantity of solvent to be volatilized. In spite of the above advantages, the
azeotropic distillation is said to be more effective in the dehydration of ethanol from
an 85.6 mole% Ethanol – water solution. In this case water is azeotroped with n –
pentane and then separated rather than using extractive distillation with ethylene
glycol as solvent.
288
molecules will return to the liquid. The composition of the distillate will now be
different from that given by normal vaporization and the ratio of the constituents is
given by
pA
0.5
NA moles of A MA
(9.153)
NB moles of B pB
MB0.5
289