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1.
2.
3.
A (solute)
Liquid Out
(C +1 A)
DIFFERENCES BETWEEN
DISTILLATION
GAS ABSORPTION
Depends on difference in
solubility of gases in selective
solvent.
We always have two phases
Starts with single phase and
(liquid is well below its boiling
second phase is generated by
point).
application of energy.
No heat energy is required (pure
Heat energy is required
(Simultaneous heat and mass
mass transfer process).
transfer process).
Gas molecules are diffusing into
There is a diffusion of molecules
the liquid, and the movement in
in both directions, so that for an
the reverse direction is
ideal system equimolecular
negligible.
counter diffusion exists.
Depends on difference in
volatilities.
Note: The ratio of liquid to gas flow rate is considerably greater in absorption
than in distillation with the result that layout of trays are different for the two
operations. Furthermore with higher liquid rates in gas absorption packed type
columns are commonly used.
2
Gas film
Partial Pressure P A
of Solute Gas A
Liquid film
and concentration differences are regarded as negligible except in the vicinity of the
interface between two phases.
On either side of interface the
currents will die out and a thin
Bulk of
film exists. Through the thin
A
PAG
film the transfer is effected
Liquid
solely by molecular diffusion.
PAi
B
The direction of transfer of
D
CAi
material across the interface
is not dependent solely on the
CAL
concentration difference but
Bulk
E
also on the equilibrium
of Gas
relationship. The controlling
factor will be the rate of
diffusion through the two
films where all the resistance
Interface
is considered to be present.
Penetration Theory: In this theory it is assumed that the eddies in the fluid
bring an element of fluid to the interface where it is exposed to the second phase for
a definite interval of time after which the surface element is mixed with the bulk
again. It is assumed that equilibrium is immediately attained by the surface layers,
that a process of unsteady state molecular diffusion than occurs and that the element
3
is remixed after a fixed interval of time.
OPERATING LINE
Liquid is solvent and x1 and x2 are the mol fraction of soluble component in liquid.
Feed is gas mixture in which y1 and y2 are the
Vapor
Liqui
mol fractions of soluble component in liquid.
s y2
d x2
Let Gm1 and Gm2 are the molar flow rates of
gas at points 1 and 2 and Lm1 and Lm2 are the
2
molar flow rates of liquid at points 1 and 2.
Now by soluble component balance:
Gm2y2 - Gm1y1 = Lm2x2 - Lm1x1
If we calculate the molar ratios:
X1,2 = Moles of Solute/ Moles of Solvent
Y1,2 = Moles of Solute/ Moles of inert gas
1
Vapor
Gm = Molar flow rate of Inert gas
Liqui
Lm = Molar flow rate of Solvent
s y1
d x1
Then by solute balance:
(X1,Y
Gm(Y2 Y1) = Lm(X2 X1)
Slope of line = (Y2 Y1)/(X2 X1) = Lm/Gm
1)
For most of the cases, solvent is pure e.g., X 2 = 0
Y
(Y1 Y2) = (Lm/Gm) X1
Mol fr. y = Moles of Solute (A)/{Moles of Solute (A) + Inert (B)}
(X2,Y
Dividing Numerator & Denominator by moles of inert (B)
y = {moles of A/moles of B}/{(moles of A/moles of B) + 1}
2)X
y = Y/(Y+1)
4
For dilute solutions; Y<<1 or Y+1~1
y = Y/1 = Y, For dilute solutions molar fractions can be used.
GAS ABSORPTION
Molar Concentration C A of A
Gas film
Partial
Pressure P A of
Solute Gas A
Liquid film
Diffusion through a stagnant gas: According to the two film theory, solute first has to
diffuse through a stagnant gas film and then through liquid film before entering bulkof
liquid. Let A is soluble in liquid absorbent C and B is insoluble.
Then according to the Stefans Law:
N/A = -Dv(CT/CB)(dCA/dz) where
N/A =Overall molar flux, Dv =Gas phase diffusivity, Z=Distance in the direction of MT
CA, CB & CT are the molar concentration of A, B & total gas.
Integrating over the whole thickness z G of the film.
N/A = (DvCT/zG)ln(CB2/CB1)=(DvP/RTzG)ln(PB2/PB1)
since CT = P/RT (for ideal gas)
Bulk of
P
A
R is gas constant, T is absolute
AG
Liquid
temperature & P is total pressure.
PAi
B
If PBM = logmean difference of
partial pressure.
D
CAi
PBM = (PB2-PB1)/{ln(PB2/PB1)}
N/A = (DvP/RTzG){(PB2-PB1)/PBM}
CAL
Hence the rate of absorption of A
Bulk
E
per unit time over unit area.
of Gas
N/A = k/GP{(PA1-PA2)/PBM}
N/A = kG(PA1-PA2) = kG(PAG PAi)
Interfac
z
where kG = DvP/{RTzGPBM}
1 G 2e
kG = k/G(P/PBM)
Gas film transfer coefficient for absorption. It is a direct measure of rate of absorption per
unit area of interface with a driving force of unit partial pressure.
Diffusion in the liquid phase: The rate of diffusion in liquids is much slower than in
gases, and mixtures of liquids may take a long time to reach equilibrium unless agitated.
This is due to much closer spacing of molecules as a result of which the molecular
attractions are more important. For dilute solutions, N/A = -DLdCA/dz
On integration N/A = -DL{(CA2 CA1)/zL} where CA, CB are the molar concentrations of A
& B, ZL is the thickness of liquid film & D L is the liquid phase diffusivity. Since film
5
thickness is rarely known, N /A = kL(CA1- CA2) = kL(CAi-CAL)
where kL = DL/ZL (m/s) is the liquid film transfer coefficient.
Rate of Absorption
P AGP Ai
Partial
Pressure (P A)
Rate of Absorption
Relationship between Film and Overall Coefficients: The net rate of transfer of A is
N/A = kG(PAG PAi) = kL(CAi CAL) = KG(PAG PAe) = KL(CAe CAL)
1/KG = (1/kG)[(PAG PAe)/(PAG PAi)]
1/KG = (1/kG)[(PAG PAi)/(PAG PAi)] + (1/kG)[(PAi PAe)/(PAG PAi)]
1/KG = (1/kG) + (1/kG)[(PAi PAe)/(PAG PAi)]
But we know that: (1/kG) = 1/(kL)[(PAG PAi)/(CAi CAL)]
1/KG = (1/kG) + (1/kL)[(PAG PAi)/(CAi CAL)]X[(PAi PAe)/(PAG PAi)]
1/KG = (1/kG) + (1/kL)[(PAi PAe)/(CAi CAL)]
[(PAi PAe)/(CAi CAL)] = Average slope of equilibrium curve.
When the solution obeys Henrys Law: H = dPA/dCA = [(PAi PAe)/(CAi CAL)]
A
Therefore: 1/KG = (1/kG) + (H /kL)
B
Similarly: 1/KL = (1/kL) + (1/H kG)
C
From equations A and B: 1/KG = (H /KL)
The validity of using equations A and B in order to obtain an overall transfer
coefficient has been examined and the equilibrium constant H must not vary over the
equipment, there must be no significant interfacial resistance and there must be no
independence over the values of the two film coefficients.
Rates of Absorption in terms of mol fractions:
The mass transfer equations can be written in terms of mol fractions as:
N/A = k//G(yA yAi) = k//L(xAi xA) = K//G(yA yAe) = K//L(xAe xA)
where xA& yA
are the mol fractions of soluble component A in the liquid and gas phases.
k//G, k//L, K//G and K//L are transfer coefficients defined in terms of mol fractions.
7 be
If m is the slope of equilibrium curve [approximately (y Ai yAe)/(xAi xA)], it can
shown that
1/ K//G = (1/k//G) + (m/k//L)
Rate of Absorption
P AGP Ai
Partial
Pressure (P A)
Factors influencing the transfer coefficient: The general influence of the solubility of
the gas on the shape of equilibrium curve and the resulting influence on the film and
overall coefficients, will be seen by considering very soluble, almost insoluble and
D
PAG
moderately soluble gases.
A
a)Very soluble gas: Here the equilibrium curve
lies close to the concentration axis and
E
the point E (in figure) approaches very close to
PAi
B
point F. The driving force over the gas film (DE)
CAiis then approximately equal to the overall driving P
CAL
Ae
F
force (DF), so that kG is approximately equal to KG.
CA
C
CA
Concentration in liquid
b)Almost insoluble gas: Here the equilibrium curve
L forces Ai
Driving
phase
(CA) in gas eand
rises very steeply so that the driving force (EB) in
liquid phases
the liquid film becomes approximately equal to the Overall driving force (AD). In this
case kL will be approximately equal to KL.
c)Moderately soluble gas: Here both films offer an appreciable resistance, and the point
B at the interface must be located by drawing a line through D of slope
(kL/kG) = -(PAG PAi)/(CAi CAL)
In most experimental work, the concentration at the interface cannot be measured
directly, and only overall coefficients will therefore be found. To obtain values for
8 the
film coefficients, the relations between kG, kL and KG are utilized.
Eq
cu ui
rv lib
e riu
O
n g pe
Li rat
ne i
Moles solute/mole
inert gas
e1
e1
e2
e 1
e1
e1
e2
e 1
e 2
e lm
e 1
e 1
e 2
e 2
O
n g pe
Li rat
ne i
Moles solute/mole
inert gas
Y]
1
C Y
Y
ln
mGm
Gm
1
Y Y C Y
m X
F
Lm
Lm
m
Y Y
1
Yi=Ye
u
ln
i
Y Y X X
Y Y
X X
br
Y Y
1
i
Y Y
Y
l
2 B
Y Y
i
Y Y
X X
X X
u
Y Y
q ve
Y Y
ln
E
r
Y Y Y Y Y Y
u
c
X2=
Y Y Y Y
X X1 Xi =
Now logmean value of Y-Y defined as Y-Y
ln{ Y Y / Y Y }
0
Moles
solute/moles
X
12 e
solvent
Therefore the height of column, Z = {Gm/(KGaP)}{(Y1 Y2)/(Y Ye)lm}
PROBLEM 12.1
Some experiments are made on the absorption of Carbon dioxide from carbon dioxideair mixture in 2.5 normal caustic soda, using a 250 mm diameter tower packed to a
height of 3m with 19 mm Raschig rings. In one experiment at atmosphere pressure, the
results obtained were:
Gas rate G/ = 0.34 kg/m2s; Liquid rate L/= 3.94 kg/m2s.
The carbon dioxide in the inlet gas is 315 parts per million and in the exit gas 31 parts
per million. What is the value of the overall gas transfer coefficient K Ga?
y2=31x1
x2=0
Solution: At the top of the tower: y2=31x10-6, x2=0,
L/ = 3.94 kg/m2s;
0-6
D=250 mm
2.5 N NaOH contains = 2.5x40g/l = 100g/l = 100kg/m3 NaOH
Mean molecular weight of liquid = (100x40 + 900x18)/1000 G/=0. H=3m L/=3.9
19 mm
MW = 20.2 kg/kgmol
34kg/
4
Lm = L//MW = 3.94/20.2 = 0.195 kmol/m2s.
Raschig
2
m2s
At the bottom of the tower: y1=315x10-6
Rings kg/m
sx
G/=0.34 kg/m2s, Gm = G//MW = 0.34/29 = 0.0117 kmol/m2s y1=315x1
1
Now from operating line relation:
0-6
x1=x2+(Gm/Lm)(y1-y2)=0+(0.0117/0.195)(315-31)x10-6= 0(approximately)
It may be assumed that as the solution of NaOH is fairly concentrated, there will be
negligible vapor pressure over the solution, therefore all resistance to transfer lies in the
gas phase. Also it is a dilute mixture, height of the tower will be
Z = (Gm/KGaP){(y1-y2)/(y-ye)lm
KGa = (Gm/ZP){(y1-y2)/(y-ye)lm
Driving force at the top of column, (y-ye)2 = 31x10-6 0 = 31x10-6
Driving force at the bottom of column, (y-ye)1 = 315x10-6 0 = 315x10-6
Log-mean driving force difference, (y-ye)lm = {(y-ye)1-(y-ye)2}/ln{(y-ye)1/(y-y3)2}
= (315-31)x10-6/ln(315/31) = 122.5x10-6
13
-6) = 8.93x10-5
Thus, KGa = (0.0117/3x101.3)(315-31)x10-6/(122.5x10
-5
KGa = 8.93x10
The Importance of Liquid and Gas Flowrates and Slope of Equilibrium Curve
For a packed tower operating with dilute concentrations, since x X1 and y Y1, then:
Gm(y1 y2) = Lm(x1 x2)
where, as before, x and y are the mole fractions of solute in the
liquid and gas phases, and Gm and Lm are the gas and liquid
molar flowrates per unit area on a solute free basis.
A material balance between the top and some plane where the
mole fractions are x, y gives:
Gm(y y2) = Lm(x x2)
If the entering solvent is free from solute, then x 2 = 0 and:
x = (Gm/Lm)(y y2)
But the number of overall transfer units is given by:
NOG = y1y2 {dy/(ye - y)}
For dilute concentrations, Henrys law holds and y e = mx.
Thus: NOG = y1y2 [dy/{m(Gm/Lm)(y y2)- y}]
=y1y2 [dy/{m(Gm/Lm-1) y m(Gm/Lm) y2}]
and: NOG = 1/ {1-m(Gm/Lm)} x ln [{1-m(Gm/Lm)} (y1/ y2)+m(Gm/Lm)]
COLBURN has shown that this equation may usefully be plotted as shown in figure above which is taken
from his paper. In this plot the number of transfer units NOG is shown for values of y 1/y2 using mGm/Lm as a
parameter and it may be seen that the greater mG m/Lm, the greater is the value of NOG for a given ratio of
y1/y2. From the above equation:
Lm/Gm = (y1 y2)/x1 = (y1 y2)/(ye1/m)
Thus: mGm/Lm = ye1/(y1 y2) where ye1 is the value of y in equilibrium with x 1.
On this basis, the lower the value of mG m/Lm, the lower will be ye1, and hence the weaker the exit liquid.
Colburn has suggested that the economic range for mG m/Lm is 0.7-0.8. If the value of HOG is known,
15 the
quickest way of obtaining a good indication of the required height of the column is by using figure above.
PROBLEM 12.2
An acetone-air mixture containing 0.015 mol fraction of acetone has the mol fraction
reduced to 1 percent of this value by countercurrent absorption with water in a packed
tower. The gas flow rate G/ is 1 kg/m2s of air and the water entering is 1.6 kg/m2s. For
this system, Henrys Law holds and ye=1.75x, where ye is the mol fraction of acetone in
the vapor in equilibrium with a mol fraction x in the liquid. How many overall transfer
units are required?
y2=0.00
x2=0
Solution:
015
At the top of the tower: y2=0.00015, x2=0,
/
L/ = 1.6 kg/m2s, Lm = L//MW = 1.6/18 = 0.0889 kmol/m2s.
G/=1 2 L =1.6
kg/m2
At the bottom of the tower: y1=0.015,
kg/m2
G/= 1.0 kg/m2s, Gm = G//MW = 1.0/29 = 0.0345 kmol/m2s
s
s
Now from operating line relation:
1
x1=x2+(Gm/Lm)(y1-y2)=0+(0.0345/0.0889)(0.015-0.00015=0.00576
y1=0.0
For dilute system, height of column:
x1
15
Z = (Gm/KGaP){(y1-y2)/(y-ye)lm
HOG = Gm/KGaP
NOG = Z/HOG= (y1-y2)/(y-ye)lm
Driving force at the top of column, (y-ye)2 = y2 mx2 = 0.00015 - 1.75x0 = 0.00015
Driving force at the bottom of column, (y-ye)1 = y1mx1 = 0.0151.75x0.00576= 0.0049
Log-mean driving force difference, (y-ye)lm = {(y-ye)1-(y-ye)2}/ln{(y-ye)1/(y-ye)2}
= (0.0049-0.00015)/ln(0.0049/0.00015)
= 0.00136
Therefore NOG = (0.015-0.00015)/0.00136 = 10.92 = 11(approximately)
Also, NOL = NOG(mGm/Lm) = 10.92(1.75x0.0345/0.0889) = 7.42 = 7 (approximately)
16
O
lin pe
e ra
ti n
g
When the load is more than can be handle in a packed column of about 1 m diameter and when
there is any likelihood of deposition of solids which would quickly choke a packing, plate
columns are preferred.
Gas
Liqui
B
Plate columns are particularly useful when the liquid rate is sufficient
Ys
d
to flood a packed tower. Since the ratio of liquid rate to gas rate is
Xss+1
greater than with distillation, the slot area will be rather less and the
YsX
downcomers rather larger.
On the whole, plate efficiencies have been found to be less than with
s
1
n+1
the distillation equipment, and to range from 20 to 80 percent.;
Yn Xn+
The plate column is a common type of equipment for large installations,
n
but when the diameter of the column is less than 2m, packed columns are
Y
X
1
nn
more often used. For the handling of very corrosive fluids, packed
n-1
columns are frequently preferred for larger units.
1
The essential arrangement of the unit is indicated in figure: Let
Y1
X2
Lm = molar flux of solute free liquid
1
Gm = molar flux of inert gas.
n = refers to the plate numbered from the bottom upwards.
Gas
Liqui
X = molar ratio of absorbed component in liquid.
Y0
d X1
A
Y = molar ratio of absorbed component in gas.
s = total number of plates in the column.
Assumption: Each plate will be taken as an ideal unit.
Material balance for the absorbed component from the bottom plate to a plane above plate n:
A
Gm Yn + LmX1 = GmY0 + LmXn+1
Y0
yn = (Lm/Gm)Xn+1 + {Y0 (Lm/Gm)X1}
3
This equation is a straight line of slope (Lm/Gm), relating the
Y
2
compositions of passing streams, known as the equation of operating line.
Point A represents the conditions at the bottom of the column. The gas
B
m
rising from the bottom plate is in equilibrium with a liquid of
Y
iu
4
r
concentration X1 and is shown as point B on operating line. The point 4
lib
i
indicates the concentration of the liquid on the second plate from bottom. s
u ve
Xs+Equr17
X1
In this way the steps may be drawn to point B, giving the gas Ys rising
c
from the top plate and the liquid Xs+1 entering the top of absorber.
X
PROBLEM 12.3
An oil containing 2.55 mol percent of a hydrocarbon is stripped by running the oil
down a column up which live steam is passed, so that 4 kmol of steam are used per 100
kmol of oil stripped. Determine the number of theoretical plates required to reduce the
hydrocarbon content to 0.05 mol percent, assuming that the oil is non-volatile. The
vapor-liquid relation of the hydrocarbon in the oil is given by y e=33x, where ye is the
mol-fraction in the vapor and x the mol-fraction in the liquid. The temperature is
maintained constant by internal heating, so that the steam does not condense in tower.
Solution: Data: Steam to oil ratio = 4kmol/100kmol
xs+1
ys=
Vapor-liquid equilibrium relationship for hydrocarbon, ye = 33x
=
0
Steam does not condense due to internal heating system
0.02
From steam to oil ratio, Lm/Gm = 100/4 = 25 kmol/kmol
Stripper 55
Since, xs+1 = 0.0255, therefore Xs+1 = xs+1/(1-xs+1)
Stea
x 1=
Xs+1 = 0.0255/(1 - 0.0255) = 0.0262
0.00
And x1 = 0.0005, then X1 = x1/(1x1) =0.0005/(10.0005)= 0.0005 m
05
Operating line equation is: Yn = (Lm/Gm)Xn+1 + {Y0 - (Lm/Gm)X1} y0=
0
Yn = 25Xn+1 + 0 (25)0.0005 = 25Xn+1 0.0125
1
From operating line equation,
Equilibri
Ys = 25Xs+1 0.0125 = 25(0.0262) - 0.0125 = 0.6423
um
Plot the operating line on X-Y diagram by points A and B.
curve
Y
From the equilibrium equation, ye = 33x
Ye/(1+Ye) = 33{X/(1+X)}
Operating
Ye = 33X/(1-32X)
line
8
From
the
above
equation,
make
the
table
and
draw
the
curve.
X 0.0 0.002 0.004 0.006 0.008 0.010 0.012 0.014
Y
18