Mass transfer

operations
Batch Distillation:
• It is also called as Differential distillation or Rayleigh Distillation.
• Vapour is in equilibrium with liquid during entire operation
• Continuous removal of product thus decrease in more volatile concentration in
distillate over the time.
• Hence condensate is taken out intermittently in the form of cuts.
• Number of moles of liquid ‘L’ with mole fraction of x.
• Moles of distillate ‘D’
• At the end of operation moles remaining ‘W’ with mole fraction xW
• Consider for small time a differential amount dD is distilled.
Problem:
Continuous distillation:
Reflux ratio R=L/D
McCabe-Thiele method
Assumptions:
• Molar rate of overflow of liquid from one plate to other
over any section is constant.
• Molar flow rate of vapour from one plate is constant
over any section of column.
• Latent heat of evaporation is assumed to be constant
over entire concentration range.
• Number of moles evaporated = number of moles
condensed.
• Graphical solution:
• Draw equilibrium line from given data.
• Find equations of operating line and draw them.
• Draw steps between equilibrium line and operating line,
calculated number of stages.
Determination of number of
stages:
• Rectifying section:

• Stripping Section:

• Boil up ratio:
Equation for operating line of rectifying section:
𝑅 𝐷 𝑥
𝑦𝑛+1 = 𝑅+1 𝑥𝑛 + 𝑅+1
Here R = 2, xD = 0.95, putting in above equation:
𝑅 𝐷𝑥 2 0.95
𝑦𝑛 = 𝑅+1 𝑥𝑛 + 𝑅+1 = 2+1 𝑥𝑛 + 2+1
𝑦𝑛+1 = 0.667𝑥𝑛 + 0.317
This is equation of operating line of rectifying section:
Equation for operating line of stripping section:
𝐿 𝑊
𝑦𝑚+1 = 𝐿−𝑊 𝑥𝑚 − 𝐿−𝑊 𝑥𝑊
 𝑘𝑚𝑜𝑙
𝑊𝑒 ℎ𝑎𝑣𝑒 𝐹 = 200 , 𝑥𝐹 = 0.4, 𝑥𝐷 = 0.95, 𝑥𝑊 = 0.04
ℎ
𝑡𝑎𝑘𝑖𝑛𝑔 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 𝑜𝑣𝑒𝑟 𝑏𝑒𝑛𝑧𝑒𝑛𝑒
𝐹 × 0.4 = 𝐷 × 0.95 + 𝑊 × 0.04 → 80 = 0.95𝐷 + 0.04𝑊
𝑡𝑎𝑘𝑖𝑛𝑔 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑏𝑎𝑙𝑎𝑛𝑐𝑒
𝐹 = 𝐷 + 𝑊 → 200 = 𝐷 + 𝑊 → 𝐷 = 200 − 𝑊
𝑆𝑜𝑙𝑣𝑖𝑛𝑔 𝑡ℎ𝑒𝑠𝑒 𝑡𝑤𝑜 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛𝑠
80 = 0.95 200 − 𝑊 + 0.04𝑊 → 190 − 0.95𝑊 + 0.04𝑊 → 110 = 0.91𝑊
110
𝑊 = 0.91 = 120.9 → 𝐷 = 79.1
𝐿 = 𝑅. 𝐷 = 2 × 79.1 = 158.2
𝐿 = 𝐿 + 𝐹 = 158.2 + 200 = 358.2
So we have equation for stripping section as:
358.2 120.9
𝑦𝑚+1 = 358.2−120.9 𝑥𝑚 − 358.2−120.9 × 0.04
𝑦𝑚+1 = 1.51𝑥𝑚 − 0.02
Feed line:

𝑉−𝑉+𝐹 =𝐿−𝐿

q= fraction of feed in the form of liquid

Point of intersection of stripping section and rectifying section satisfy following eqn
Quality of feed:
𝐻𝑣 −𝐻𝐹
• 𝑞 = 𝐿𝑖𝑞𝑢𝑖𝑑 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑒𝑒𝑑 =
𝐻𝑣 −𝐻𝐿

• If feed is saturated liquid, q =1 so slope is infinite.

• If feed is saturated vapour, q=0 so slope is zero.
• If feed is mixture of vapour and liquid, q is between 0 and 1.
• Feed is superheated steam?
• Feed is subcooled liquid?
 𝑅 𝐷 𝑥
𝑦𝑛+1 = 𝑅+1 𝑥𝑛 + 𝑅+1
Here R = 1.5, xD = 0.96, putting in above
equation:
𝑅 𝐷𝑥 1.5 0.96
𝑦𝑛 = 𝑅+1 𝑥𝑛 + 𝑅+1 = 1.5+1 𝑥𝑛 + 1.5+1
𝑦𝑛+1 = 0.6𝑥𝑛 + 0.384
• Total reflux: If no distillate is taken out i.e D=0, the
condition is called as total reflux.
𝐿
𝑅= =∞
𝐷
Number of plates are minimum at this condition.
Fenske’s equation: Analytical solution for minimum
number of plates if relative volatility is assumed to
be constant over operating range.
For reboiler, xw and yw are in equilibrium
𝑦𝐴 𝑦 𝑦𝑊
1−𝑦 𝐴 1−𝑦 1−𝑦 𝑊 𝑦𝑊 𝑥𝑊
𝛼𝐴𝐵 = 𝑥𝐴 → 𝛼= 𝑥 → 𝛼𝑊 = 𝑥𝑊 → = 𝛼𝑊
1−𝑥 𝐴 1−𝑥 1−𝑥 𝑊 1−𝑦 𝑊 1−𝑥 𝑊

For nth plate we have;

𝑦𝑁 𝑥𝑁
= 𝛼𝑁
1−𝑦 𝑁 1−𝑥 𝑁

For total reflux, 𝑥𝑁 = 𝑦𝑊

𝑦𝑁 𝑥
1−𝑦 𝑁
= 𝛼𝑁 𝛼𝑊 1−𝑥𝑊
𝑊

Similarly for n-1th plate we have

𝑦 𝑁 −1 𝑥
1−𝑦 𝑁 −1
= 𝛼𝑁−1 . 𝛼𝑁 . 𝛼𝑊 1−𝑥𝑊
𝑊

For top plate we have:

𝑦1 𝑥𝑊
= 𝛼1 . 𝛼2 . … . . 𝛼𝑁−1 . 𝛼𝑁 . 𝛼𝑊
1−𝑦1 1−𝑥 𝑊

For top plate; 𝑦1 = 𝑥𝐷

𝑥𝐷 𝑥
1−𝑥 𝐷
= 𝛼1 . 𝛼2 . … . . 𝛼𝑁−1 . 𝛼𝑁 . 𝛼𝑊 1−𝑥𝑊
𝑊

If 𝛼 is taken as average
𝑥𝐷 𝑥
1−𝑥 𝐷
= 𝛼𝑎𝑣𝑔 𝑁+1 1−𝑥𝑊
𝑊
 𝛼𝑥
𝑦=
1+ 𝛼−1 𝑥
x 0.000 0.050 0.100 0.150 0.200 0.250 0.300 0.350 0.400 0.450 0.500
y 0.000 0.116 0.217 0.306 0.385 0.455 0.517 0.574 0.625 0.672 0.714
x 0.550 0.600 0.650 0.700 0.750 0.800 0.850 0.900 0.950 1.000
y 0.753 0.789 0.823 0.854 0.882 0.909 0.934 0.957 0.979 1.000
 For the previous problem calculate number of plates required if reflux ratio is kept at 3 and
feed is saturated liquid. The VLE data can be used based on Antoine’s equation constant. Also
plot the temperature profile along the column. Using this data calculate average relative
volatility.
Compound Antoine’s Constants
A B C
Benzene 15.9037 2789.01 220.79
Toluene 16.0053 3090.78 219.14

Psat Psat P P
Temperature Benzene Toluene x benzene toluene y P total x y α
110.65 1788.01 760.00 0.00 0.00 760.00 0.00 760.00 0.00 0.00
106.15 1592.32 667.52 0.10 159.23 600.77 0.21 760.00 0.10 0.21 2.39
102.10 1430.96 592.26 0.20 286.19 473.81 0.38 760.00 0.20 0.38 2.42
98.45 1296.23 530.19 0.30 388.87 371.13 0.51 760.00 0.30 0.51 2.44
95.13 1182.46 478.36 0.40 472.98 287.02 0.62 760.00 0.40 0.62 2.47
92.09 1085.40 434.60 0.50 542.70 217.30 0.71 760.00 0.50 0.71 2.50
89.30 1001.80 397.29 0.60 601.08 158.92 0.79 760.00 0.60 0.79 2.52
86.73 929.21 365.19 0.70 650.44 109.56 0.86 760.00 0.70 0.86 2.54
84.35 865.67 337.33 0.80 692.53 67.47 0.91 760.00 0.80 0.91 2.57
82.13 809.67 312.98 0.90 728.70 31.30 0.96 760.00 0.90 0.96 2.59
80.06 760.00 291.55 1.00 760.00 0.00 1.00 760.00 1.00 1.00
Avg α 2.49
Minimum reflux ratio:

For feed as saturated liquid:

 Underwood equation:
• For mole fractions of A and B over plate

𝑉𝑛 𝑦𝑛+1,𝐴 = 𝐿𝑛 𝑥𝑛,𝐴 + 𝐷𝑥𝑑,𝐴

𝑉𝑛 𝑦𝑛+1,𝐵 = 𝐿𝑛 𝑥𝑛,𝐵 + 𝐷𝑥𝑑,𝐵
Dividing 1 by 2;
𝑦𝑛+1,𝐴 𝐿 𝑥 +𝐷𝑥
= 𝐿𝑛𝑥𝑛,𝐴 +𝐷𝑥𝑑,𝐴
𝑦𝑛+1,𝐵 𝑛 𝑛,𝐵 𝑑,𝐵

But
𝑦𝑛+1,𝐴 𝑥
= 𝛼 𝑥𝑛+1,𝐴
𝑦𝑛+1,𝐵 𝑛+1,𝐵

And for minimum reflux, 𝑥𝑛+1,𝐴 = 𝑥𝑛,𝐴 and 𝑥𝑛+1,𝐵 = 𝑥𝑛,𝐵

𝐿𝑛 𝑥𝑛,𝐴 +𝐷𝑥𝑑,𝐴 𝐿𝑛
𝑥𝑛,𝐴 𝐿𝑛 𝑥𝑛,𝐴 +𝐷𝑥𝑑,𝐴 𝐷
𝑥 +𝑥𝑑,𝐴
𝐷 𝑛,𝐴
𝛼𝑥 =𝐿 = 𝐿𝑛 𝑥𝑛,𝐵 +𝐷𝑥𝑑,𝐵 = 𝐿𝑛
𝑛,𝐵 𝑛 𝑥𝑛,𝐵 +𝐷𝑥𝑑,𝐵 𝑥 +𝑥𝑑,𝐵
𝐷 𝐷 𝑛,𝐵

𝐿𝑛
Putting = 𝑅𝑚
𝐷
𝑥 𝑅 𝑥 +𝑥
𝛼 𝑥𝑛,𝐴 = 𝑅𝑚𝑥𝑛,𝐴 +𝑥𝑑,𝐴
𝑛,𝐵 𝑚 𝑛,𝐵 𝑑,𝐵
𝛼𝑥𝑛,𝐴 (𝑅𝑚 𝑥𝑛,𝐵 + 𝑥𝑑,𝐵 ) = 𝑥𝑛,𝐵 (𝑅𝑚 𝑥𝑛,𝐴 + 𝑥𝑑,𝐴 )
𝑅𝑚 𝛼𝑥𝑛,𝐴 𝑥𝑛,𝐵 − 𝑥𝑛,𝐵 𝑥𝑛,𝐴 = 𝑥𝑛,𝐵 𝑥𝑑,𝐴 − 𝛼𝑥𝑛,𝐴 𝑥𝑑,𝐵

Replacing nth plate with feed plate, we will get equation for 𝑅𝑚

𝑅𝑚 𝛼𝑥𝑓,𝐴 𝑥𝑓,𝐵 − 𝑥𝑓,𝐵 𝑥𝑓,𝐴 = 𝑥𝑓,𝐵 𝑥𝑑,𝐴 − 𝛼𝑥𝑓,𝐴 𝑥𝑑,𝐵

𝑅𝑚 𝛼𝑥𝑓,𝐴 (1 − 𝑥𝑓,𝐴 ) − (1 − 𝑥𝑓,𝐴 )𝑥𝑓,𝐴 = (1 − 𝑥𝑓,𝐴 )𝑥𝑑,𝐴 − 𝛼𝑥𝑓,𝐴 (1 − 𝑥𝑑,𝐴 )
1−𝑥𝑓,𝐴 𝑥𝑑,𝐴 − 𝛼𝑥𝑓,𝐴 1−𝑥𝑑,𝐴 1−𝑥𝑓,𝐴 𝑥𝑑,𝐴 − 𝛼𝑥𝑓,𝐴 1−𝑥𝑑,𝐴
𝑅𝑚 = =
𝛼𝑥𝑓,𝐴 1−𝑥𝑓,𝐴 − 1−𝑥𝑓,𝐴 𝑥𝑓,𝐴 𝑥𝑓,𝐴 𝛼−1 1−𝑥𝑓,𝐴
𝑥 𝑥𝑑,𝐴 𝛼(1−𝑥𝑑,𝐴 )
(1−𝑥𝑓,𝐴 )𝑥𝑑,𝐴 − 𝛼(1−𝑥𝑑,𝐴 ) − (1−𝑥 )
𝑓,𝐴 𝑥𝑓,𝐴 𝑓,𝐴
𝑅𝑚 = =
𝛼−1 (1−𝑥𝑓,𝐴 ) 𝛼−1

1 𝑥𝑑𝐴 (1−𝑥 )
𝑅𝑚 = 𝛼−1 − 𝛼 (1−𝑥𝑑𝐴)
𝑥𝑓𝐴 𝑓𝐴
Selection of economic reflux ratio

• The operating costs rise with increasing reflux ratio and are approximately
proportional to (R + 1).
• The capital cost initially falls since the number of plates falls off rapidly at this stage.
• The capital cost rises at high values of R, since there is then only a very small
reduction in the number of plates, although the diameter, and hence the area,
continually increases because the vapour load becomes greater. The associated
condenser and reboiler will also be larger and hence more expensive.
Reflux below bubble point:
• Vapour from top tray is condensed below its bubble point.
• Reflux in such case is called subcooled reflux.
• Liquid from reflux attains temperature by condensation of vapours on
top tray.
• Vapour flow rate from top tray less than that in bottom trays and liquid
flow rate (L) is higher than that from condenser (L0).
• Apparent reflux ratio R’ larger than overall reflux ratio.
Tray Efficiency
Relationship between efficiencies

Overall efficiency is related to Murphree efficiency by:

For constant slope of equilibrium line and V/L line

How to draw Pseudo equilibrium line?
• Draw equilibrium line and x=y line.
• Derive equations for operating lines for rectifying section and stripping section.
• Draw both operating lines.
• Take any point M on operating line and identify corresponding equilibrium concentration N on
equilibrium curve.
• Draw line MN.
• If Murphree efficiency is given as EM , identify point E on line MN such that ME= EM ×MN.
• For eg, for efficiency of 0.6:
• Identify several E points and draw curve from these points.
• This is pseudo equilibrium curve.
 Multiple feed and side stream:

(a)Typical column with multiple feed and side stream, (b) Column with one side stream and (c) operating line for one side stream
Ponchon and Savarit method:
• Considers heat balance.