II.

DISTILLATION
Distillation is the separation of the components of a liquid mixture on the basis of the
volatility difference.
The volatility of a component can be characterised by the boiling point (TBP) and the
vapour pressure (p0(T)) of the component. The lower TBP, the more volatile is the component.

Vapour-liquid equilibrium conditions (VLE)

Basic notions and rules

1. Pure component vapour pressure (p0)
The Antoine equation describes the relation between vapour pressure and
temperature for pure components. It is derived from the Clausius-Clapeyron equation .

Antoine - equation

where - mmHg (torr)

T - ⁰C
A,B,C - Antoine constants

38
 Numerical example
a) Calculate the vapour pressure of water at 25⁰C.
b) Determine the boiling point of water for a pressure of 994 mbar

Antoine constants:A = 8.07131

B = 1730.63
C = 233.426

1 atm = 760 mmHg = 1013 mbar = 1.013·105 Pa

1 mmHg = 133.28 Pa
Solution
a) T = 25⁰C p0 = ?
1730.63
− 8.07131 − 1.3745
+ 25 + 233.426
10 . !"#
$%. & (()*
23.7 mmHg = 31.59 mbar = 3200 Pa
b) P = 994 mbar = 745.74 mmHg
T = Tbp = ?
The water boils if p0 = P
.
lg - − /01
.
− lg -
/01
. ! 6.7
2 34 5
− 8.6! 34 !"#.!"
− 233.426 99. :⁰<

2. Dalton’s Law
It is valid for ideal vapour phase (mixture of ideal (perfect) gases).
Ideal mixture: interactions between the same molecules (e.g. i and i) are equal with
those between the different (e. g. i and j) molecules. The mixture of the members of
the same homologous series (e.g. n – hexane – n – heptane, benzene – toluene) can be
considered ideal even in the liquid phase. At atmospheric distillations the vapour
phase is usually ideal (if there is no association in it) since the molecules are far from
each other.

39
 Dalton’s law:
= >= ? i = 1…NC
where pi partial pressure of component i
yi vapour mole fraction of comp. i
P total pressure
NC number of components

Partial pressure: the pressure which would be exerted by the given component if it
would be present at the same temperature in the same volumetric concentration alone
(without the other components of the mixture).
C1

@ AB - @ EB -
BD B

3. Raoult’s Law
For ideal liquid phase. = F= =

where xi mole fraction of component i in the liquid phase

The liquid phase is ideal less frequently than the vapour phase since the molecules are
much closer to each other therefore the interactions (attraction, repulsion (repelling))
are much stronger.

4. Vapour – liquid equilibrium (VLE) of ideal mixtures

(Raoult’s – Dalton’s Law)
Condition of equilibrium:
ABG ABH =pi i: 1…NC L
– liquid phase, V – vapour phase

AB IB AB6 EB -

>= =
F= Non-linear relationship (even for ideal mixtures!)
?

For binary mixtures (NC=2):

The more volatile component (MVC) is denoted by 1 (or A), the less volatile
component (LVC) is denoted by 2 (or B).
x1=x x2=1-x since x1+x2=1 and
y1=y y2=1-y since y1+y2=1

40
- VLE constant (VLE ratio)
KL NLO
JB ideal mixture: JB
ML 5

- Relative volatility:
JB AB6 ⁄- AB6
PB,R
JR AR6 ⁄- AR6
NVO
For a binary mixture: P ,T P U
NWO

The influence of the relative volatility on the equilibrium curve

The higher the value of α the further runs the equilibrium curve from the diagonal y=x.

41
Equilibrium relation for α = const. mixtures:
XL,Y ML
EB ∑]^
L_V[XL,Y ML \

where r - reference component, e.g. r = NC

PC1,C1 1
For a binary mixture:
XM
E
XM0 M

Numerical example
a) Determine the composition of the equilibrium vapour phase at 60 ⁰C for a liquid
mixture containing 40 mol% benzene and 60 mol% toluene.
b) Determine the composition of the equilibrium phases at atmospheric pressure at
90⁰C.
c) Calculate the relative volatilities for cases a and b.

The Antoine constants:

A B C
Benzene 6.90565 1211.033 220.790
Toluene 6.95464 1344.800 219.482

42
Solution
a) benzene (A) – toluene (B) t = 60 ⁰C
xA = x = 40 mol% = 0.4 (1-x) = 0.6
y=?
N`
t → A26 , A.6 → A2 , A. → P → E2 E
5
Antoine eq. Raoult’s law Dalton’s law

VWVV.Obb
A26 107.a6#7# cO WWO.dec =391.47 mmHg
A.6 138.95
A2 0.4 · 391.47 156.6
A. 0.6 · 138.95 83.4
P=156.6 + 83.4 = 240 mmHg
N` #7.7
E 0.653 (y>x)
5 T"6

b) P = 760 mmHg t = 90⁰C

x=? y=?
- A2 + A. IA26 + (1 − I)A.6
A26 (906 ) 1021jjkl
A.6 (906 ) 406.7jjkl
- − A. 760 − 406.7
I 0.575
A26 − A.6 1021 − 406.7
A26
E I 0.772
-
c) P2,. P ?
J2 A26
P
J. A.6
A26
J2
-
c.1) For case a T = 60⁰C

A26 (606 )
J2
-
A.6 (606 )
J.
-

43
 391.47
J2 1.63
240
J. 0.578
J2
n $. o$
J.

c.2) For case b T = 90⁰C

0.772
J2 1.342
0.572
0.228
J. 0.536
0.425
P2,. 2.5

44
5. Non-ideal Liquid Phase, Azeotropes
Raoult’s law is not valid more
AB pB IB AB6
where
pB q(I , … … . , IC1 , s) activity coefficient of component i

pB IB tB activity of component i

Models (equations) for calculating γi : UNIQAC, Wilson, NRTL, etc.

Highly non-ideal mixtures: they show strong deviation from the Raoult’s Law:
a. strong positive deviation : p2 ≫ 1 p. ≫ 1
These mixtures can form minimum boiling point azeotropes (e.g. ethanol (A) –
water (B)).
At the azeotropic point: T = Taz = Tmin
y=x
K⁄M
P 1
( K)⁄( M)

45
b. strong negative deviation: γA << 1 γB << 1
These mixtures form maximum boiling azeotropes (e.g Chloroform (A) – Acetone
(B)).
At the azeotropic point: T = Taz = Tmax

46
c. very strong positive deviation: limited miscibility:
(Minimum boiling) heteroazeotropes (e.g. Water (A) – n-Butanol (B)).
heteroazeotrope: The condensate of the azeotrope splits into 2 liquid phases.

47
 Distillation Methods
1. Flash Distillation
2. Rectification
3. Batch Distillation (Differential Distillation)
4. Batch Rectification

1. Flash distillation
For binary mixture (NC = 2)

a: pump b:heater c:valve d:separator

F, V, L molar flow rates (mol/s)

xF, y, x mole fraction of the more volatile component in the feed, vapour and liquid
respectively
The vapour and liquid leaving the drum are in equilibrium
y = f(x)

48
 Total material Balance (TMB)

“ in = out “
F=V+L

Component Material balance (CMB)

vIw xE + yI
y v
E − I + Iw
x x

H
By introducing z fraction vaporized
w

{ F|
> − F+ Operating Line Equation
{ {

Straight line:
z−1
tanP
z
It passes through (xF, yF).
Proof:
z−1 Iw z−1+1
Iw Iw + Iw Iw
z z z

49
 Known: F, xF, β, (P), (y=f(x) equil. diag.)
Unknown: y, x, V, L
(V = βF, L = F-V)

€
slope : tanP
€

Numerical example: 100kmol/h mixture of benzene-toluene is separated by flashing

at atmospheric pressure. The feed contains 50 mol% benzene.
a) Determine the composition of the distillate, molar flow rate and temperature of the
products, if the liquid contains 40 mol%benzene
b) What would be the max. purity of distillate?
c) Determine the minimum loss of benzene in the residual liquid

50
Solution:
Benzene (A) - Toluene (B)
(MVC) (LVC)
more volatile comp. less volatile comp.

a) F = 100 kmol/h
xF = 50 mol% = 0.5 (P = 1 atm)
x = 0.4
y = 0.62 (from the graph)

CMB: vIw xE + yI
TMB: x v−y

100 · 0.5 (100 − y) · 0.62 + y · 0.4

Lever Rule:

G 6.7T 6.# 6. T
w 6.7T 6." 6.TT
6. T
y 100 ·
6.TT

L = 54.55 kmol/h
V = 100-L = 100-54.55 = 45.45 kmol/h

The mole fraction of Benzene in the liquid phase:

x = 0.4 → T = 95⁰C (from T-x,y diagram)

(The mole fraction of Toluene in the liquid phase: 1-x = 0.6)

The mole fraction of Benzene in the vapour: y = 0.62
(The mole fraction of Toluene in the vapour: 1-y = 1- 0.62 = 0.38)

51
 b) ymax = ?
G
y = ymax if tanP − ∞ (V≈0)
H

y = f(xF) = 0.72

c) x = xmin if tanα = 0 (L≈0)

xmin = 0.29 xF = f(xmin)

Flashing is a continuous distillation separation on a single theoretical stage.

Theoretical Stage (Plate):

Stage where the outlet streams (the vapour and liquid leaving the stage) are in equilibrium.

The flashing doesn’t provide sharp separation. It is applied for only in the cases where the
relative volatility (α) is very high or sharp separation is not needed (for preliminary
separations followed by rectification).

52
2. Rectification
Continuous separation on several theoretical stages by the application of reflux

3 main parts:
- Column with plates
- Total Condenser
- Partial Reboiler

Column: It contains plates/stages/trays (or packing).

Counter current system: liquid flows down, vapour rises.

53
 Total Condenser: The top vapour is totally condensed, the condensate is divided into
distillate (product withdrawn) and reflux sent back to the top of the column. The
condenser is usually cooled with cooling water.
Partial Reboiler: The liquid arriving from the bottom of the column is partially
vaporized in the reboiler, the vapour is sent back to the column, the liquid is
withdrawn as product (bottoms). The reboiler is heated usually with (water) steam.
Additional parts: Accumulator (for storing the condensate, optional), reflux pump
(optional), product coolers (for cooling the top (overhead) and bottoms products with
cooling water and the cold feed), trap (for retaining that part of the water steam which
has not been condensed and ensuring the overpressure of the steam), two product tanks
(not shown).

If the condenser is placed above the column, the reflux returns by gravity and
accumulator and reflux pump are omitted. A reflux splitter (not shown) may be used to
control the rate of the reflux and the remainder of the condensate forms the top product
(distillate).

Simplifying assumptions:
• constant molar overflow (CMO):
The liquid and vapour molar flow rates do not vary within the given section
RS: L1 = L2 = …. = Lf-1 = L = const.
V1 = V2 = …. = Vf = V = const.
SS: Lf = …. = LN-1 = L’ = const.
Vf+1 = …. = VN = V’ = const.

where N: number of theoretical stages

• P = const.
• The reflux is liquid at its boiling point: L = L0

The most important operational parameter is the reflux ratio:

ƒ ƒ
‚
„ „

54
 Determination of the number of theoretical stages (N) (McCabe-Thiele)

• known: F, xF, q - heat condition of feed (q=1 feed is liquid at its boiling point),
P, R, xD, xB,
optimal feed plate location is assumed
• unknown: N, f

Operating line equations:

I. Rectifying section (RS):

Balance around the condenser and plate n:

Total Material Balance (TMB):
V=L+D
Component Material Balance (CMB):
Vy‡0 Lx‡ + Dx‹
L D
y‡0 x‡ + x‹
V V
Since
y
Œ
•
Υ y

55
 x y+• Œ• + • (Œ + 1)•
Hence
‚ F„
>Ž0 FŽ +
‚+ ‚+
this is the operating line equation for the RS
straight line in the y – x diagram
•
• tanP (slope)
•0
M‘
• intercept: •
•0

It passes through the point (xD, xD).

e.g.

• The operating lines gives the relation between the composition of the
vapour and liquid streams meeting between two neighbour stages.
• yn is in equilibrium with xn (the streams leaving the same stages are in
equilibrium)

56
II. Stripping section (SS):

Balances around plate (m+1) and the reboiler:

Total Material Balance (TMB):
L’ = V’ + B
Component Material Balance (CMB):
L′x“ V′y“0 + Bx•
—′ š
–(0 ™( − ™š
˜′ ˜′
this is the operating line equation for the SS
straight line in the y – x diag.
• it passes through (xB, xB)
G›
• tanP
H›

If q = 1 it intersects RS operating line on

the line x = xF

Graphical construction:
P : point of intersection of the 2 operating lines on x = xF

57
 You start at xD, xD and you decrease step by step (black) by using blue curve
and after passed xF, you use red curve, and you stop after xB

N = 8 (7 plates in the column + partial reboiler) + total condenser

f = 4th from the top.

Summary of steps
1. Draw in points (xD, xD), (xB, xB) and the line x = xF
2. Draw the operating lines
M
RS : points (xD, xD) and (0, •0‘ )

SS : points (xB, xB) and P (intersection of the RS op. line and x = xF)
3. Plate to plate construction in the RS:
y1 = xD ¢££££¤ x1 ¢£££££¤ y2 ¢££££¤ x2 ¢£££¤ …
œ•.žŸ ¡œ •¥ ¦N.§B¨œ œ•.žŸ ¡œ
total cond.

Continue the construction until xf ≤ xF

4. Plate to plate construction in the SS:

58
 xf ¢£££££¤ yf+1 ¢££££¤ xf+1 ¢£££££¤ yf+2 ¢£££¤ …
¥¥ ¦N.§B¨œ œ•.žŸ ¡œ ¥¥ ¦N.§B¨œ

Continue the construction until xN ≤ xB is fulfilled

Number of steps: N

Heat condition of feed

Feed stage

Assumptions:
• hf-1 ≈ hf = h
• Hf ≈ Hf+1 = H
Balances around stage f:
TMB: v + x› + y x + y›
x› − x y› − y − v
Heat balance: vℎw + x › k + yℎ xk + y′ℎ
vℎw + (x › − x)k (y› − y)ℎ

Heat condition of feed:

G« G ¬ -® ¬ -®
ª ° k−ℎ
w ¬ - ¯
H – h = molar heat of vaporization of the feed
H – hF = heat necessary for transforming one mole of feed to saturated vapour

59
Cases:
Feed is
a) subcooled liquid
hF < h(xF) q>1
L’ = L + qF and from TMB of plate f
V = V’ – (q – 1)F
V < V’ One part of the vapour arriving at the plate f is condensed in
order to warm up the feed onto its boiling point.
b) liquid at its boiling point
hF= h (xF) = h q=1 L’ = L + F V = V’
c) two phases
h < hF < H (xF) = H 0<q<1

d) saturated vapour
hF = H q=0 L’ = L V = V’ + F

e) superheated vapour
hF > H q<0 L’ < L
One part of the liquid flowing down onto plate f is vaporized and so it cools down
the feed into saturated vapour state.

60
 Intersection of the operating lines (q-line)

In the point of intersection both operating line equations are satisfied.

• RS: xE yI + •I± (1)
• SS: x ›E y› I − I. (2)
(2) – (1) (x › − x)E (y› − y)I − (•I± + I. )
• CMB for the column:
vIw •I± + I.

• (3) x › − x y› − y − v y› y + ªv

Finally: (ª − 1)vE ªvI − vIw

² F|
> F−
² ²
q-line equation

•
straight line: tan P
•

it passes through the point (xF, xF) (located on the diagonal)

61
 •
Case Slope ( )
•

a >0
b ∞
c <0
d 0
e >0

Optimal feed plate location (fopt)

The feed plate location is optimal if the prescribed separation is provided with the
minimum number of stages if only the feed plate location is varied (all other
parameters are fixed).
Fixed parameters: xF, q, xD, xB, R, (F, P)
Unknown: fopt, (N (number of stages))

62
Possibilities:
1. We change the operating line before reaching P
small stages → high N (not optimal)
2. After reaching P we remain on the RS operating line
some small stages → high N (not optimal)
3. Just after reaching P we change the operating line,
the stages are the biggest possible → N = min. f = fopt

The optimal selection of the feed stage (for a two phase feed, fopt=7)

63
 Heat balance of the column

“in = out”
vℎw + µ. •ℎ± + ℎ. + µ±

QB heat duty of reboiler (Watt)

QD heat duty of condenser (Watt)
Assuming constant molar overflow µ± x° µ. x′°

Relation between QD and QB

x› x + (ª − 1)v
¶ ·¸ + (² − )|¹º ¶„ + (² − )|º
if q = 1 QB = QD
q=0 µ. µ± − v° (The feed need not be vapourized.)

Quantity of cooling water

µ± j»1¼ ½N [ 1¼,¦Ÿ¾ − 1¼,B¨ \ j»1¼ ½N ¿
specific heat of water: cp = 4190 J/kgK
¶„
À» Á (kg/s)
 Ã

64
 Quantity of water steam
µ. j»Ä¾œÅÆ Ç r : specific heat of condensation of the steam (J/kg)
¶
À»ÈÉÊËÀ
Ì

Numerical example:
100 kmol/h mixture of benzene(1)-toluene(2) is separated by rectification. The feed contains
50% benzene. The reflux ratio is 3. The product composition is prescribed: distillate: 95
mol%, bottoms: 5 mol%. The feed is liquid at its boiling point. The average latent heat of
vaporisation of the mixture is 30310 kJ/kmol.
a. Determine the mass flow rates of distillate and bottoms.
b. Determinate the number of plates and feed plate location.
c. Calculate the consumption of heating steam and cooling water
consumption if ΔTCW,max = 20 ⁰C. The specific heat of condensation
of the steam is 2169 kJ/kg

Molecular weights, kg/kmol:

M1 = 78 M2 = 92

Solution:
known: F = 100 kmol/h
xF = 0.5
R=3
q=1
xD = 0.95
xB = 0.05
a. j»± ? j». ?
•. Í ? q ?
ÎÏ
c. j»Ä¾œÅÆ ? ÇľœÅÆ 2169 ÎÐ ¿ 1¼,ÆÅM 20⁰

65
a. Molar flow rates:

TMB of the column: v •+

CMB of the column: vIw •I± + I.

vIw (v − )I± + I.
I± − I. vI± − vIw
(M‘ M® )
v
(M‘ MÑ )
(6.a# 6.#)
100
(6.a# 6.6#)

B = 50 kmol/h and D=F-B= 50 kmol/h

(The product flow rates can be determined by using the lever rule, as well

± M® MÑ
w M‘ MÑ
6.# 6.6#
• 100
6.a# 6.6#
D = 50 kmol/h)

66
 Mass flow rates:
j»± Ó±
•Ò •(I± Ò + (1 I± iÒT i
j»± 50h0.95 g 78 h1 0.95i92i
À»„ 3935 kg/h
j». Ó.
Ò hI. Ò h1 I. iÒT i
j». 50h0.05 g 78 h1 0.05i92i
À» 4565 kg/h

1. Result of the graphical construction (see graph):

N=9
f=4

2. Mass flow rates of steam and cooling water:

x Œ• •
x hŒ 1i• 4 g 50 200 kmol/h
µ. µ± hª 1iv°
µ± µ. (q = 1)
µ± µ. x° 200 g 30310 6062 kJ/h

ÚÑ 767T666
À»ÈÉÊËÀ ¼ÛÜÝÞß
$&9: à*/á=2.8 t/h
T 7a

µ± 6062000 à*
À» Á &$%â &$. % ã/á
½1¼ h 1¼¦Ÿ¾ 1¼B¨ i 4.190 g 20 á

67
 Total Reflux (R = ∞)

R=L/D
if D = 0 R=∞

The batch rectifier is started under R = ∞.

D=0 F=B = 0
The slope of the operation line:
•
lim ç•0 è 1
•→æ

The operation line coincides with the diagonal (y = x).

The steps are the biggest possible.
N = Nmin

68
 Plate to plate construction for total reflux

Determination of Nmin

Methods:
1. Graphical: see above
2. Analytical (by an equation):
Assumption: α (relative volatility) = const.

A rectifying column operating at total reflux

Balances around the condenser and plate n:

TMB: x¨0 y¨

69
 CMB: x¨0 E¨0 y¨ I¨
E¨0 I¨
Both the flow rates and compositions of the liquid and vapour streams meeting
between two neighbour plates are equal.

Plate to plate calculation starting from the reboiler:

a) Reboiler

K] M]
Equilibrium relation: P
K] M]
ê

éP í
Vëê
ì
Vëì

Operation line equation: EC IC

b) Plate (N – 1)

EC IC I.
P PT
1 − EC 1 − IC 1 − I.

EC IC T

.
.
.
c) Plate 1
E I.
P¨
1−E 1 − I.
Since xD=y1 (total condenser)

F„ F
nî
− F„ −F

F„ F
ïðñ F„
·
F ïðñò
Í îÀ=Ž
ïðñn ïðñn
Equation of Fenske, S: separation factor

70
 Minimal Reflux Ratio (Rmin)

if R = Rmin N=∞!

• M‘
E I
•0 •0
RS operating line:

M‘
R↘ tanα ↘ and ↗
•0
if then

R = Rmin if the operating line passes through the point of intersection of the equilibrium
curve and of the q – line (P)

By approaching to P, the steps get smaller and smaller → N=∞

71
 Optimal Reflux Ratio (Ropt)

Costs of a rectifying column:

- Fixed (capital) cost:
õBM qhÍ, •ž¦§ i (•ž¦§ : diameter of column)
At the neighbourhood of Rmin on the increase of R N drastically decreases.

If R increases, Dcol must be increased.

- Operating (energy) costs (steam, cooling water, electricity):

We suppose that q = 1 then V’ = V
¦N ögx öhŒ 1)•
Cop is a linear function of R.

- Total costs:
¾¦¾ õBM + ¦N

Œ Œ¦N¾ if Ctot = min.

72
 Empirical correlations:
Plate columns: Œ¦N¾ h1.1 ÷ 1.5)ŒÆB¨
Packed columns: Œ¦N¾ (1.5 ÷ 4.0)ŒÆB¨

Batch Distillation
Batch distillation is applied when
- the quantity and composition of the mixture to be separated changes frequently,
- the quantity of the mixture to be separated is low (small capacity), or
- a multicomponent mixture must be separated and there is only one column.

Types of batch distillation: differential (simple batch) distillation and batch

rectification.

73
3. Differential Distillation
Batch separation on a single theoretical plate.

Scheme of a simple batch distillation column

The feed (charge) is filled in the still pot (reboiler) and it is progressively
vaporized. The composition of the vapour is in equilibrium with that of the liquid.
The vapour is condensed and the condensate is collected in the receiver.
Notations:
L : amount of liquid in the still pot (mol)
x : composition of liquid in the still pot (mole fraction of MVC)
y : instantaneous composition of vapour
Eø : average composition of vapour (distillate product)
V (= D): amount of distillate

y is in equilibrium with x: y = f(x)

74
 Both x and y decrease with time (t2 > t1)
Since y > x → x2 < x1 → y2 < y1 → yøT < yø

Types of balances
1. Differential balances for a given time
2. Balances for the whole process (“integral” balances)

At a given time the value of the parameters are

L, x, y
By distilling out an infinitesimal quantity dV the variation of parameters are
dL, dx (y is supposed unchanged, that is, dy = 0)

Diff. TMB: dL + dV = 0
Diff.CMB: L·x = (L + dL)·(x + dx) + y·dV where dV = − dL
L·x = L·x + x·dL + L·dx + dL·dx - y·dL
≈0
Separating the variables:
x·dL + L·dx − y·dL = 0
L·dx = (y – x)·dL
dL dx
L y x

75
 Integrating from the start (1) to the end (2) of the process:
ûW üW
dL dx
ú ú
L y x
ûV üV

By exchanging the limits and integrating the left hand side analytically:
û üV þü
ln çûV è ýü ü
Rayleigh equation
W W

The right hand can be integrated analytically if α = const.

L 1 x (1 − xT ) 1 − xT
ln ln + ln
LT α−1 xT (1 − x ) 1−x
Otherwise the RHS must be integrated graphically or numerically.
Graphical integration:

The quantity of the residue

LT L e (mol)
The quantity of vapour V L − LT (mol)
The average composition of the distillate
L x − LT x T
yø
V
The heat to be furnished in the reboiler: Q VΛ (J)

76
Example:
10 kmol of mixture of Benzene – Toluene is separated by differential distillation. The
charge contains 50 mol% of Benzene, the average relative volatility is 2.43. The residue
contains 5 mol% Benzene.
a) Calculate the number of moles to be vaporized.
b) Determine the quantity of the residue.
c) Calculate the average composition of the distillate.
d) Calculate the mass of Benzene in the residue.

Solution:
Benzene (A) – Toluene (B)
MA = 78 kg/kmol
MB = 92 kg/kmol
L1 = 10 kmol
α = 2.43
x1 = 0.5 x2 = 0.05
a) V = ? b) L2 = ? c) yø ?

a)-b)
L 1 0.5(1 − 0.05) 1 − 0.05
ln ln + ln I
LT 2.43 − 1 0.05(1 − 0.5) 1 − 0.5
L 1 0.95 0.95
ln ln + ln 2.7
LT 1.43 0.05 0.5
LT L e 10e T.!
0.67 mol
V = L1 – L2 = 10 – 0.67 = 9.33 mol

c)
L x LT x T 10 · 0.5 − 0.67 · 0.05
yø 0.53
V 9.33
d)
mA,L2 = L2x2MA = 0.67 · 0.05 · 78 2.61 kg
Conclusion:
Differential distillation doesn’t provide sharp separation! If sharp separation is
needed rectification must be applied.

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 2. Batch Rectification
Separation in a column by applying reflux.
The column operates as a rectifying section.

D» − flow rate of distillate (mol/s),

x‹ − the instantaneous composition of the distillate,
xø‹ − the average composition of the distillate,
L» − flow rate of liquid (mol/s),
V» − flow rate of vapour (mol/s),
D − quantity of distillate (mol),
W − quantity of liquid in the reboiler (mol),
x − composition of liquid in the reboiler.

The reflux ratio:

L»
R
D»

The op. line equation:

R x‹
y‡0 x‡ +
R 1 R+1

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 Operational Policies
1. Constant reflux ratio:
R = const. xD is decreasing with time

t2 > t1
R
tanα const.
R 1
The operation lines are parallel.
The design equation is similar to Rayleigh Equation,
but it can never be integrated analitically.
ü V
W dx
ln ú
WT x‹ x
ü W

xD = f(xW, N, R) (Differential distillation: y = f(x), only)

2. Constant distillate composition:
xD = const. R must be progressively increased

tanP is increasing, the end point of the operation lines remains the same.

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 Plate Efficiences

1. Column efficiency
;-œ¦
0.5 − 0.8 (50% − 80%)
Í œÅ§

2. Murphree (individual plate efficiency

xn is the composition of liquid leaving plate n (not the average composition of

liquid on the plate!)
E¨ E¨0 actual change of concn. on plate
,¨
E¨∗ E¨0 theoretical change of concn. on plate

E¨∗ = q(I¨ ) is the vapour composition in equilibrium with xn

ηM can be greater than 1!

3. Local (point) efficiency: ηM for a point of the plate

ηM,p is always less than 1.0

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 Types of plates
Plate: Device by which a liquid layer over the column cross section is so
supported that the vapour can pass through it to enable mass transfer to occur.

Basic types of plates:

1. Bubble Cap
This is the oldest type of plate

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The way of the arriving vapour is closed by the cap.
The liquid flows down through the down-comer over the weir
Characteristics:
- Expensive
- High pressure drop (Δp)
- Wide range of operation (flexible)

2. Sieve tray

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 Comparing with the bubble cap:
- Simpler construction
- Lower Δp
- Less flexible, at low vapour rates weeping occurs:

Weeping: one part of the liquid flows down through the holes
(instead of the downcomer) by-passing the contact with the vapour.

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Vapour load (F-factor) v= Ð Ð

where

82
 Ð : linear velocity of vapour [m/s]

Ð : density of vapour [kg/m3]

Flooding: it is a result of liquid entrainment:
on the increase of vg Δp suddenly increases and it becomes so high that the
liquid cannot flow down.
Flexibility of operation of a plate can be characterized by the turndown ratio
¡ ,ßÞì wßÞì
=
¡ ,ßL wßL

3. Valve Plates
(e.g. Ballast, Glitsch etc.)
Modification of the sieve tray in order to increase its flexibility

At high vapour flow rates the valves are open.

At low vapour flow rates the valves are closed.
The free cross section area for the vapour varies depending on the vapour
flow rate

Ring Valve Tray:

Characteristics:
- More flexible than the sieve tray
- Cheaper than the bubble cap
-

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4. Turbogrid Tray

There is no down-comer.
The liquid rains down the spaces between the bars where the vapour
flows up providing the liquid/vapour contact..
Characteristics:
- Very cheap
- High vapour throughput (absence of down-comers → all the column
area is available for contacting)
- Low efficiency
- Low flexibility

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 Some other types of plate

1. Bubble cap
2. Sieve plate
3. Ballast (valve) tray
4. Uniflux (tunnel cap) tray
- The vapour drives the liquid toward the down-comer
5. Jet tray
- Similar to the UNIFLUX
6. Turbogrid
7. Ripple tray
- The waves are turned away with 90° between two neighbour plates.
- The vapour can escape through the holes on the top of the waves without
meeting the liquid if the liquid level is too low
8. Float valve tray
- Similar to the jet tray but instead of fixed tongues there are valves
(combination of jet and valve trays).

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