IN
THIS PART we
CHAPTERS 4. Models in Masstransfer Operations 5 . Models in Heattransfer Operations 6. Models in Fluidflow Operations 7 . Models in Reaction Engineering
CHAPTER 4
MODELS IN MASSTRANSFER OPERATIONS
In this chapter, various models for systems in masstransfer operations (steadystate singlestage solvent extraction, steadystate twostage countercurrent solvent extraction, steadystate twostage crosscurrent solvent extraction, unsteadystate singlestage solvent extraction, unsteadystate mass transfer in a stirred tank, unsteadystate mass transfer in a mixing tank, unsteadystate mass transfer, steadystate multistage countercurrent solvent extraction, multistage gas absorption, multistage distillation) are discussed. A generalized approach is developed for formulating the models. The models are chosen in such a way that various mathematical techniques for solutions of the proposed models are covered. Some models are simple algebraic equations, a few of them are ordinary differential equations, some are finite difference equations, and in some models Laplace transformations are applied for solution.
62
Toluene
Water Mixer
aToluene + BA (organic layer) Settler (B) Idealized singlestage solvent extraction system (Raffhate) R m3/s of toluene x kg/m of BA
Step 2 The second step is to see if there is a possibility of simplifying the schematic representation of the system under consideration. The above system can be idealized and simplified as follows by combining two stages into a single stage (Fig. 4.2), as we know that Input  output + generation  depletion = accumulation
c kg/m BA
s m/s water
y kg/m3 BA
s m3/swater
0 kg/m3of BA
(extract)
Fig. 4.2 idealized system
The various streams have been labelled and two material balances have already been used: (a) Conservation of toluene and (b) conservation of water. These flow rates have been expressed on a solutefree basis to simplify the analysis. The concentration of BA in each stream has also been stated and this completes the mathematical model.
Step 3 The third step is to make reasonable assumptions, and also justifying the assumptions made with reference to retaining accuracy. So far, it has been assumed that (1) all flow rates are steady and (2) toluene and water are immiscible (basic criterion for choosing a solvent). Further, it is assumed that (3) the feed concentration c remains constant. Now, have a look at the number of unknowns and the number of equations we can formulate with the known information so far. In fact, we have two unknowns
63
( x and y ) and one equation to be formulated based on the mass balance on benzoic acid [Eq. (4.2)]. That means we still need another equation to get the solution. Obviously, in the present problem, we are looking for another equation relating the two unknowns x and y . This being a model based on mass transfer, an equilibrium relation may do the job for us.
Step 4 Look for additional assumptions to be made in order to balance the number of unknowns and the number of equations required. For the present problem, we need to make another assumption that (4) the mixer is so efficient that the two streams leaving a stage are always in equilibrium with one another. This last fact can be expressed mathematically by the following expression: y=mX (4.1) where, m is distribution coefficient. The model equation is now derived by writing a mass balance for BA (component balance):
Input of BA = Rc (kg/s) Output of BA = Rx + Sy (kg/s) As the system is in steady state, i.e., BA must leave at the same rate as it enters,
Rc=Rx+Sy (4.2) Equations (4.1) and (4.2) contain four known quantities (R, S, c, m ) and two unknown quantities (x, y ) and can be solved for the unknowns as follows: Rc = Rx + mSx (4.3)
+ Rc = ( R + mS)x
Rc : x = R+mS .
~
(4.4) (4.5)
y =  mRc R + mS
Step 5 Always express all the quantities (both known and unknown, or a combination of both) in terms of dimensionless groups which explain the physics of the system. Therefore, the fraction of BA extracted is
j=
S Y
($)+1
(4.7)
64
At this stage it can be seen that even in this simple problem, two dimensionless groups which are characteristic of the problem have arisen quite naturally as a result of the investigation: the ratio of the feed to the solvent flow rate at equilibrium,
E= 1 a+l and multiplying both numerator and denominator by (a l), we get E= a  1
a21
Step 6 The final result should be expressed in a generalized form as far as possible, so that the method of induction principles can be applied for a cascade of stages. This means the fraction extracted is governed solely by the value of the dimensionless group a (the ratio of rates of feed to the solvent at equilibrium).
Example 4.1 Compute the fraction of solute that could be extracted in a singlestage solvent extraction using the numerical values of S = 12R, m = 118, and c = 0.1 kg/m3. Solution IfS =12R, m = 1/8, and c = 0.1,
x=
Rc
0.1R R( 1 +
mS
1 8
f)
= 0.04
.*.
y = m~ =  x 0.04 = 0.005
and
E =  Sy = Rc
or
65
Stage
Stage
t
Solution In accordance with chemical engineering practices, the suffix denotes the stage from which the stream is leaving. The following assumptions are made again: (i) The feed concentration c remains constant. (ii) The mixer is so efficient that the two streams leaving a stage are always in equilibrium with each other. The equation y = w: is still valid for each stage separately, giving
Y 1 = w:,
Y2 = m 2
(4.8)
(4.9)
where m is the distribution coefficient. It is constant for the given system. A BA mass balance is now taken for each stage:
66
Stage 2
RXl
k,+ SY,
Since the operation is carried out in steady state, the BA must enter and leave a stage at the same rate, i.e., Stage 1: Re + Sy, = Rx,
+ Sy,
(4.10)
(4.11) Stage 2: Rx, = Rx, + Sy, To get an expression for y , in terms of known quantities, substitute x1 and y , from Eqs (4.8) and (4.9) in Eqs (4.10) and (4.11). Equation (4.10) becomes
(4.12) (4.13)
 ( R + mS) Y1
(4.14)
(4.15) R Since x2 is unknown, it is to be expressed in terms of known quantities. Substituting y1 from Eq. (4.15) in Eq. (4.13), we get
Rc + mSx, =
+ mRS + m 2 S 2 )
(4.16)
R2c ,+ m R S + m 2 S 2 R
1 
(4.17)
SYl  
Re
(4.18)
67
Multiplying and dividing the righthand side (rhs) of Eq. (4.18) by m2S2, we get
SYl 
Rc
(4.19)
a + l a2+a+1
(4.20)
Multiplying and dividing the rhs of the above equation by (a 1) , we get
E=
a2 1 a3 1
aN1
(4.2 1)
Example 4.2 Compute the fraction of solute that can be extracted in a twostage countercurrent solvent extraction using the same numerical values of S = 12R, m = 1/8, and c = 0.1 kg/m3, which were used for singlestage extraction, and compare the results. Solution
x2= R2c 2 R +mRS+m2S2
R2 (0.1) R2 + 'R(12R) 8
+ '(144R2) 64
'(
= 0.02105
and
mRc(R + mS) y1 = R2 + mRS + m2S2
68
R a=
=
0.66667
(i)12R
' E = a
Therefore, E = fraction extracted = 0.789= 78.9%. A greater degree of extraction has thus been obtained with two stages (78.9%) than with one stage (60%), everything else being the same.
Example 4 3 160 cm3/s of a solvent S is used to treat 400 cm3/s of a 10% by . weight solution ofA in B, where A is being extracted from B in a twostage countercurrent liquidliquid extractioncolumn. What is the compositionof the final &mate and the fraction extracted if m (distribution coefficient) = 3 and the densities of A , B, and S are 1200,1000,and 800 kg/m3, respectively? Solution S = 160 cm3/s = 1 6 x lo4 m3/s . Mass flow of S = 1.6 x 1 " x 800 = 0.128kg/s 0 Considering the solution, 400 cm3/s = 4 x 104 m 3/s. Considering a m3/s of A and (4x lo4  U) m3/s of B, Mass flow of A = 1200a kg/s 0 Mass flow of B = (4x 1 "  a ) x 1000 kg/s = (0.4 1000a)kg/s Total mass flow = (0.4 + 200a) kg/s
Concentration of the solution = 01 = .
1200a 0 4 + 200a .
a = 3.39 x 10~ m3/s Mass flow of A = 0.041 kg/s Mass flow of B = 0.366 kg/s
.: .:
Now,
R (volumetric flow rate of B) = 4 x 10"  3.39 x 10~ = 3.661 x 1 4 m3/s 0 c (kg of A/m3 of B ) = (kg/s of A)/(m3/sof B )
c = 0.04V3.661 x
lo4
= 112.02kg/m3
69
+ m2S2)
:.
and
x2 = 27.795 kg/m3
.*.E
= 0.7538
Stage 1
Stage 2
s, 0
s, 0
Solution The following assumptions are made: 1. Toluene and water are immiscible. 2. We are considering a pure solvent. 3. The mixer is so efficient that the leaving streams are always in equilibrium. 4. The concentration of BA in the feed is constant. 5. The solvent flow rate is the same in both stages. 6. All the quantities are expressed on a solutefree basis. 7. The composition of a stream leaving a stage is the same as that in the stage.
70
RX,+O SY, + 4
+ Rx,
+ Rx,
(4.22) (4.23)
Since there are four unknowns ( x l ,yl, x2, y2) and only two equations, therefore two more equations are required and these are the equilibrium relations given by Y 1 = m, (4.24) (4.25) The objective in this problem is to find the total fraction of BA that can be extracted by the crosscurrent mode of extraction operation under steadystate conditions. The fraction of BA extracted,
Y2
=m
Hence, we have to obtain the expressions for y1and y, in terms of known quantities by eliminating x1 and x2. So, from Eq. (4.24), we have
(4.26)
(4.27)
Therefore,
x1 = 
Re R+mS
(4.28)
(4.29)
71
Substituting x1 and x2 from Eqs (4.26) and (4.29) in Eq. (4.23), we get
R + s y , = [)Y2 + m S
mR2c y2 = ( R + mSI2
*E=
Rc
On multiplying and dividing both the terms in the parentheses by mS, we get
We know that
=a
R mS
*E =
*E=
[
1 1+ a+l a+l
+1 (a+ I)*
2a
Example 4.4 Compute the fraction of solute that can be extracted in a twostage crosscurrent solvent extraction using the same numerical values of S = 6R, m = 1/8, and c = 0.1 kg/m3, which were used for singlestage extraction, and compare the results. Solution If S = 6R (since 2s here = S in countercurrent), m = 1/8, c = 0.1 kg/m3,
R R
=  = 1.3333
8 6
mRc
mR2c ( R + m+!7)2] Re
( =)(
mRc
=)
72
*E=
E =  = 0.789 = 78.9%
Note As expected and as can be seen from the above comparison, with the same
conditions the fraction of solute extracted in the countercurrent operation is higher than that in the crosscurrent operation. This is attributed to the fact that the driving force available at any stage is higher in the case of the countercurrent mode of operation, as no extract is taken out from any intermediate stage. However, in the crosscurrent operation, the extract is taken out from each of the stages and so the driving force is comparatively less in any given stage.
[: I
Exercise 4.1 How do you compare the cocurrent operation with countercurrent and crosscurrent operations? Example 4.5 160 cm3/s of a solvent S is used to treat 400 cm3/s of a 10%by weight solution of A in B, where A is being extracted from B in a twostage countercurrent liquidliquid extraction column. The distribution coefficient m = 3 and the densities ofA, B, and S are 1200,1000,and 800 kg/m3,respectively.All the quantities are expressed on a solutefree basis. (a) What is the composition of the raffinate leaving from stage 1 and stage 2? (b) What is the final fraction extracted? Solution S = 160 cm3/s = 1.6 x 104 m3/s Mass flow of S = 1.6 x 1W x 800 = 0.128 kg/s Considering the solution, 400 cm3/s= 4 x lo4 m3/s.Considering a m3/s of A and (4 x lo4  a) m3/sof B, Mass flow of A = 1200a kg/s Mass flow of B = (4 x lo4  a ) x lo00 kg/s = (0.4  1 O a kg/s O O) Total mass flow = (0.4 + 200a) kg/s
Concentration of the solution = 0.1 =
: . : .
73
Now,
RC
(R+ mS)
R2C
( R + mSl2
= 20.9,692 kg/m3
and
E= 2 a + l
(a+ 1)2
where a = WmS = 0.762 .*.E = 0.806 Therefore the fractional recovery is 80.6%.
Note Compare Examples 4.4 and 4.5 on twostage steadystate countercurrent and crosscurrent extraction. For the same numerical data, the fractional recovery obtained in countercurrent and crosscurrent operations is 78.9% and 80.6% respectively. We expect the fractional recovery to be more in the countercurrent operation than in the crosscurrent operation. Can you find out what is the reason of this contradictory result? The clue is, have a close look at the data given for S.
74
Illustration 4.4 The singlestage steadystate example is reconsidered as follows: 1. Assume that the singlestage contains Vl m3 of toluene, V, m3 of water, and no benzoic acid (solutefree basis). 2. Assume, as before, that the mixer is so efficient that the compositions of the two liquid streams are in equilibrium at all times. 3. Assume that a stream leaving the stage is of the same composition at that phase in the stage. 4. c is constant in feed. This is illustrated in Fig. 4.5, which shows the state of the system at a general time 8 , where x and y are now functions of time.
R m3/s
c kg/m
Sm3/s
Y kg/m3
I
v,, x
vz,x
1
R m3/s xkg/m3
s m3/s 0 kg/m3
Since the flow rates of water and toluene are constant (solutefree basis), V , and V , will remain constant (solutefree basis). The system being in unsteady state, the conditions are always changing, and so the material balance must be applied during a small time increment 68. Using Taylors theorem, a function of 8 can be expanded, and this allows the state of the system at a time 0 + 68 to be expressed in terms of its state at time 0 . In this case it is helpful to draw up a table (see Table 4.1). Mass balance for BA during a time interval 68: Input of BA = Rc&? kg, output of BA = average of Rr + Sy at 8 and 6 + 68. (The difference is not taken because the amount is varying with time. So the average has to be taken.) Therefore,
and
dx Accumulation = V, 88 dB
Since,
dY + V, 68 d6
75
(y 2+
 Rx
v d0 9 0 2
y+60
+RcR~+60
[ :de ]  S[
d0 d0
dx =V,+V2 dY d0 d0
dx dY  Sy = V,  + V2
(4.30)
Table 4.1 The system condition before and after a time increment
Property of the system 1. 2. 3. Flow rate of toluene phase Flow rate of water phase Volume of toluene phase in stage Volume of water phase in stage Concentration of BA in entrance toluene Concentration of BA in exit toluene Concentration of BA in water (extract) Amount of BA in the toluene layer
X
e+&
4.
5.
6.
7.
x + dxe de
8.
V,X
v,x
dx + v,  6e de
9.
v*y
V2Y
+ v 2
dY  66
de
In stating the output, the arithmetic mean of the concentrations was taken, but the later calculations show that this is not necessary; the same Eq. (4.30) would have been obtained by using the concentrations at time 0 instead. Only the first two terms of Taylors series were taken for x and y , and these are all that are necessary since further terms which contain a factor (60)*will disappear when the limit 68 + 0 is taken, i.e., d0 2 do2 Equation (4.30)must now be solved in conjunction with the equilibrium relationship y=mX (4.31) x dx 1 d2x +  60 + (60)2
*.
76
Eliminating y from Eq. (4.30) using Eq. (4.31), we get dx dx Rc  R x  S~.X= VI + m v 2 d8 d8 Rearranging,
(4.32)
dx
Rc  (R + mS)x On integrating,
V,
do
+ mV2
(4.33)
+ mV,
+A
(4.34)
The constant of integrationA can be evaluated by using the given initial state of the system that the stage contains no BA initially, i.e., (4.35) Initial condition (IC): when 8 = 0, x = 0 . From Eqs (4.34) and (4.33, ln(Rc) =A R + mS Therefore, ln(Rc)  ln[Rc  (R + mS)x] = (R + mS)8 (V, + my,)
(4.36)
(4.37)
or in exponential form,
*1
+ mS x = exp[RC
( R + mS)8 V, mV2
77
R R
+ mS
+ mS
(4.38)
1. This equation satisfies the boundary condition (BC), i.e., x = 0 at 8 = 0 (since e" = l/eo = 1). 2. It satisfies the differential equation [model Eq. (4.30)] for any positive value of 8 , (find &/do ). 3. And when 8 j ,
Rc (4.39) R+mS When 8 + 00, the system reaches steady state, and hence this should be converted back to the steadystate model equation, which has already been obtained, as shown by Eq. (4.39). Therefore, for steady state,
*X=
x=
Rc R +mS R + mS V, +mV,
+ mS
(4.40)
*E=
a+ll
Here, 8 is the independent variable, x and y are the dependent variables (static variables), and m, R , S, c, V,, and V, are parameters.
Example 4.6 160 cm3/s of a solvent S is used to treat 400 cm3/s of a 10% by weight solution of A in B, where A is being extracted from B under unsteadystate conditions in a single stage using the countercurrent mode of operation in a liquidliquid extraction column. The volume of B(V,) is 100 dm3 and the volume of solvent (V,) is 75 dm3. The distribution coefficient m = 3 and the densities of A, B, and S are 1200, 1000, and 800 kg/m3, respectively. All the quantities are expressed on a
78
solutefree basis. (a) What is the composition of the final raffinate and fraction extracted after 1 min? (b) If 50% of A is to be extracted then what is the time required if V , and V, are same. Solution S = 160 cm3/s = 1.6 x 10 4m3 /s Mass flow of S = 1.6 x lo4 x 800 = 0.128 kg/s Considering the solution, 400 cm3/s= 4 x lo4 m3/s. Considering a m3/s of A and (4 x lo4  a) m3/sof B, Mass flow of A = 1200a kg/s Mass flow of B = (4 x lo4  a) x 1000 kg/s = (0.4  1000a) kg/s Total mass flow = (0.4 + 200a) kg/s Concentration of the solution is = 0.1 = a = 3.39 x 10 m3/s Mass flow of A = 0.041 kg/s Mass flow of B = 0.366 kg/s Now,
R (volumetric flow rate of B ) = 4 x lo4  3.39 x lo = 3.661 x 1W m3/s c (kg of A/m3 of B ) = (kg/s of A)/(m3/sof B ) c = 0.041/3.661 x lo4 = 112.02 kg/m3
.: : .
: .
and
x = 40.904 kg/m3
)j
a = = 0.76271
(b) If 50% of A is to be extracted, E = 0.5. Substitutingthe values of E, a , V,, V,, m, and S in Eq. (l),we get 8 = time required for 50% extraction = 819 s = 13.65 min
79
I1
II
5.55 x lo4 m3/s
The system properties at time 8 and at incremental time B + 88 are tabulated and shown in Table 4.2.
Table 4.2 The system condition before and after a time increment
Property 1. 2.
3.
At
At
e + se
Rate of brine input (m3/s) Rate of brine output (m3/s) Input salt concentration (kg/m3) Volume of brine in tank (m3) Salt concentration in output stream (kg/m3)
4. 5.
V
X
dV v + dm e
x
dx + 6e de
x
6.
vx
(v +$ss)(
+ $Je)
In a small interval 68, accumulation of brine in the tank = dV/d8 88 Volume balance: Input  output = accumulation
80
(4.41)
= 2.78 X lo4 (4.42) de On integrating, we get V = 2.78 x lo4 + C,, where C, is a constant. By applying we the boundary condition that at 8 = 0, V = 20 m3, get C, = 20. Therefore, (4.43) v = 2.78 x lo4 e + 20 Mass balance for salt in time interval of 68 : Input  output = accumulation (i.e., the difference of amount at 8 + 68 and 0 )
= ( v + %6e)( x
+ $m)  v x
 5.55 x 104x
= V
+ dV X de de
dx
(4.44)
Substituting V and dV/de from Eqs (4.42) and (4.43), respectively, in Eq. (4.44), we get 16.66 x lo4  5.55 x 104x
d0 The variables are separable, hence dx
= (2.78 x lo4
(4.45)
16.66 x lo4
io4e + 20
(4.46)
(4.47) Boundary condition 1: At 8 = 0, x = 0 (pure water) We have to find out the value of x when the volume of brine in the tank = 30 m3, i.e., 8 = ? when V = 30 m3. From Eq. (4.43), v = 2.78 x 104 e + 20
j
+e=
81
Boundary condition 2: At 8 = 35,972s, x = x kg/m3 (4.48) Integrating Eq. (4.46) using the suitable limits from Eqs (4.47) and (4.48), we get
[
8.33 x lo4
ln(16.66 x lo4
 8.33 x lo4
x)
= 2.78 x lo4
* 8.33 x1 lo4

2.78 x lo4
1 *   ln(1  0 . 5 ~= In ) 3
(1  O . ~ X )  ~= 1.5
* 1 0 . 5 ~ =
3x
(A)
3
= 0.2963
= 1.4074 kg/m3
Therefore the concentration of salt when the tank contains 30 m3 of water (after 35,972 s) = 1.4074 kg/m3.For 40 m3 of brine,
e=
20
2.78 x lo4
= 7 1,944s
40 * (1  O . ~ X )  ~ = 2 20
* X =
Therefore,
x = 1.75 kg/m3
82
Q m/s Y (t) k d d
Since the holdup volume is fixed, and the solution density is constant, the inflow rate must be equal to the outflow rate (i.e., Qin= Q,,,). Mass Balance: Inflow rate of salt  outflow rate of salt = rate of accumulation of salt in tank
(4.49)
Qx,  QY, = 0 Subtracting Eq.(4.50) from Eq. (4.49), get we
(4.50)
(4.5 1)
Introducing the deviation variables X = x  x s , Y = y  y s , and dyldt = dY/dt, we have
dY QX  QY = V dt XY=(E)$
(4.52) (4.53)
83
Putting
z = V/Q
(4.54) It is clear from the above transfer function that the mixing process is also a firstorder process. For sinusoidal input change [i.e., X ( r ) = x  x, = Asinwt],
A@ X(s)= s2
+ w2
(4.55)
whereA is the amplitude of variation, w is the radian frequency in rads. Eliminating X ( s ) from Eq. (4.54) using Eq. (4.55), we get
Y (s) =
(4.56)
This equation can be solved for Y(t)by means of partial fraction expansion, which gives
A Awz e  t / r sinwt (4.57) coswt + (z2w2+ 1) (z2w2+ 1) (z202 1) + Equation (4.57) can be written in another form by using the trigonometric identity, (4.58) pcosA + qsinA = rsin(A + 6)
Y (r) =
where r = d p 2 + q2 and tan8 = p/q. Applying the identity to Eq. (4.57), we get (4.59) As where @ = tan' (ox). t + 00, the first term on the rhs of Eq. (4.59) vanishes and leaves only the ultimate periodic solution, which is sometimes called the steadystate solution. (4.60) We know that the input X ( t ) = A sin wr (4.61) Comparing Eq. (4.61) for the input forcing function with Eq. (4.60) for the ultimate periodic response, we see that
1. The output is a sine wave with frequency 0 equal to that of the input
signal.
84
This is always smaller than 1. We often state this by saying that the signal is attenuated. 3. The output lags behind the input by an angle @ . It is clear that lag occurs, for the sign of 4 , the phase angle, is always negative.
I I
If the input peak occurs before the output peak, then @ < 0, i.e., phase lag. If the output peak occurs before the input peak, then @ > 0, i.e., phase lead.
Example 4.8 Consider an unsteadystate mass transfer in a mixing tank. The inlet stream is subjected to a sinusoidal input with an amplitude of 0.015 m3/min about a mean flow rate of 0.3 m3/min. The time constant for the flow process is taken to be 0.2 min. The frequency of the input sine wave is 4 cycles/min. Describe the output response, giving its frequency, amplitude, and by how many minutes it lags or leads the input response? Solution Input:f = cycle frequency of the input = 4 cycles/min, w = radian frequency = 2nf = 25.1 radmin, and x( t ) = A sin(wt) = 0.015 sin(25.lt). Here w = 25.1 radmin, z = 0.2 min, and A = 0.015. output:
Y ( t )=
A [sin(wt + cp)] (1 + w2z2)0,5
1. The frequency of the output signal is same as that of the input signal. 2. Output amplitude = A/(1 + w222)0.5 0.003 and input amplitude = 0.015. =
Therefore the ratio of the output amplitude to the input amplitude is 0.2. This ratio is less than 1. Hence the signal is attenuated. 3. The output lags the input by a phase of 78.7'. Input frequency = 4 cycle/ min. Therefore the period per cycle = period of 360' = 1/4 min. Hence time for 78.7' = 0.055 min. Hence the output has an amplitude of 0.003, a frequency of 25.1 radmin, and lags behind the input by 0.055 min.
Exercise 4.2 Consider an unsteadystate mass transfer in a mixing tank. The inlet stream is subjected to a sinusoidal input with an amplitude of 0.015 m3/min about a mean flow rate of 0.3 m3/min. The time constant for the flow process is taken to be 0.5 min. Find the frequency of the input sine in cycles/min. The output lags behind the input by 80'. Determine the number of minutes by which it lags or leads the input response.
85
(4.63) N + N, = N A The movement of A is made up of two parts, namely, (1) that resulting from the bulk motion N and the fraction xAof N, which is A, and (2) that resulting from diffusion JA: (4.64) N = NxA + J A A since, by definition,
i.e., the flux of A relative to the average molar velocity of all constituents. Here, W, = moles of A , W, + WE= total number of moles of A and B. Consider the volume element of a fluid shown in Fig. 4.8,where a fluid is flowing through the element. We shall need a material balance for a component of the fluid applicable to a differential fluid volume of this type.
86
Y
Fig. 4.8 Fluid volume element
The massflow rate of componentA into the three faces with a common comer at E is (4.65) M ( ( N A , x )x A Y h + ( N A , y ) y Ax& + ( N A , z )z hxAY) A where N,, signifies xdirected flux and (N,, ,>, signifies its value at location x. Similarly, the massflow rate out of the three faces with a common comer at G is M A ( ( N ~ , x ) x + b + ( N A , ~ ) ~ + A + ( N A , ~ ) ~ + ~ (4.66) AYAz AX& ~ Ax&') The total component A in the element = (Ax Ay Az) p A and its rate of accumulation = (k &) ,+,/a. If, in addition, A is generated by a chemical reaction at the AY z rate RA mol/(volume)(time), its production rate is MARAAx Ay A massltime. Since, in general, Rate in  rate out = rate of accumulation  rate of generation 3 Rate out  rate in + rate of accumulation = rate of generation Then,
M A { [ ( N A , ~ ) x N A , ~ ) ~ I A Y A Z [ ( N A , ~ ) ~ +N A ~y ) y l b k (+& ( A,
dP*
(4.67)
Dividing by Ax Ay Az , and taking the limit as the three distances become zero gives
87
From Eq. (4.64), the counterpart of Eq. (4.64) in terms of masses and in the xdirection is MANA,x = M A N X A+ M A J A , ~
* M A N A ,= Yx P A + M A ~
PUX
(4.69)
* ux
PB
(4.70)
d2CA
dX2
++I+d2cA
dy2
d2CA
dz2
'PA =MARA dt
(4.72)
which is the equation of continuity for substance A. For a solution of constant density, u d u x Y d uZ = dO + + ax ay dz Dividing Eq. (4.72) by MA and substituting p A / M A = cA, we get (4.73)
(4.74) In the special case where the velocity equals zero and there is no chemical reaction, Eq. (4.74) reduces to Fick's second law of difision: i.e., u x = uY = u Z = O and R,=O
00
Illustration 4.6 The diffusion equation derived in the previous section can be extended for cylindrical coordinates. The diffusion equation for cylindrical coordinates can be obtained by doing an energy balance over a differential element, a procedure similar to that derived in the previous section.
x=rcos$
y = r sin$
z=z
$ = tan(y/x)
Using the chain rule we can carry out the partial differentiation of c with respect to rand $ as
or
d c ~ cos $ = cos2+% dr dX
+ sin4 cos4d C A
dY
(3)
Similarly,
89
d2 C A cos$dX
dr
cos$
dcA
sin$dcA  sin$dcA
sin $ d cA or
dcA dr
dX2
dr
sin2 ++ 0 d c A r
dr
sin2 $ d 2 cA r2
+[
C O S sin$ ~
r2
1
dcA d$
(9)
Similarly,
C O S ~ sin4
r2
r2
dcA d$
or
We know that for Cartesian coordinates, Ficks second law of diffusion is given by
If there is no chemical reaction and diffusivity is constant, then by substituting Eq. (12) in Eq. (13)
90
(14)
This is the final expression for Fick's second law of diffusion in cy coordinates.
rical
+ Syp
91
Yp+I
A A"
YN 1
N1
(4.76) (4.77)
The equilibrium equation 0,= mx) is still valid for any value of p .
*Yp
=mxp
Rx,,+ mSx,,,
( R + mS)x,
(4.78)
92
xp1 mS
+ Xp+l
(2
+ + ax,,,
+ l)x,
(4.79)
* ax,, +
XP+,
XP+,
= (a 1)x, =0
(4.80)
Writing Eq. (4.80) in standard form, (4.81) This is a secondorder linear finite difference equation. Putting Eq. (4.81) in the operational form and factorizing gives
[ E 2  (1 + a ) E + a ] x , = ( E + 1)(E  a ) x , = 0
 (a+ l ) x ,
+K2aP
+ K 2 a 0 = K , + K2
(4.82)
where K , and K , are arbitrary constants. Now, where xo is the concentration of BA at the zeroth stage, which is the concentration of BA before entering the first stage = c
+c=K,+K, + K ~ = c  K ~ Similarly,
(4.83)
(4.84)
Here, xN is the concentration of the solute (BA) in the raffinate at the ( N + 1)th stage = 0 (because N + 1 is very large).
+ 0 = K , + K2 aN+l
Substituting K , from Eq. (4.83) into Eq. (4.85), get we
(4.85)
K1
CaN+l aN+l
1
93
xp =
rnc(aN+' aP) (aN+l 1) Therefore, the proportion of BA extracted is (put p = 1 in the above equation)
Y p
For N = 2,
E = a '  1 a3  1
which was derived earlier.
Example 4.9 Compute the fraction of solute that can be extracted in countercurrent solvent extraction with N stages (for values of N from 1 to 30) using the same numerical values of S = 12R, rn = 1/8, and c = 0.1 kg/m3, which were used for singlestage extraction, and compare the results. Solution If S = 12R and m = 1/8,
By putting various values of N in the above equation, the proportion extracted in N stages is given in Table 4.3. This table shows that more than 10 stages are wasteful, whereas one stage gives a poor degree of extraction. The most economical number of stages can be determined by optimization (tradeoff between operating and capital costs).
94
1 2 3 5 10 20 30
Illustration 4.8
G N + kg moVs of a wet gas containing YN+ kg mol of solutekg mol of wet gas is fed into the base of a plate absorption column where the solute is to be stripped from the gas by absorption in Lokg moVs of lean oil, which is fed at the top of the column. The solute in the entering oil is Xo kg mol/kg mol of lean oil and the solute in the exit gas is Y , kg mol/kg mol of wet gas. The equilibrium constant K, is given as K, = y,/x,, where y , and x, are the mole fractions of the solute in the gas and liquid phases, respectively. Show that the performance of the absorber can be I expressed in terms of the absorption factorA = (L,/KGN+) and the number of ideal stages (N) by the KremserBrown equation (which relates the fractional solute recovery to the absorption factor):
95
m1
m+l
y=
(1 + y > (1  Y> Considering Fig. 4.10 and taking material balance over plate m gives
(4.86) Lo ( X m  X m  1 ) = GN+1( Y m t l  Y m ) (The gas and liquid ratios on a solutefree basis are same on every plate, though the actual L and G may be different on each plate.) We have to eliminate X,,, and X, from Eq. (4.86). But
*Y=
(4.87)
96
= Kmxm
(4.88) Similarly, (4.89) Substituting the values of Xm andXm,and from Eqs (4.88) and (4.89),respectively, in Eq. (4.86) gives
(4.90)
Lm
KmGm Lm1
K m  1 m 1 G
(4.91) (4.92) (4.93) Taking the mean value of the absorption factor between the top and the bottom of the column as A, and rearranging Eq. (4.93) in the form of a finite difference equation, Ym+l (1 + A)Ym + AYm, = 0 (4.94)
97
m = 0, Yo = C,+ C ,
and
m = 1, Y, = C,+ C,A Similarly,
m =N
+ 1, YN+l= C, + C2AN+'
 Yo = C2 (AN+'  1)
: Y,+' .
and
(4.101)
(4.102)
Equation (4.102) is the wellknown KremserBrown equation. The physical significanceof this equation is: The normalized fractional recovery of the solute in a multicomponentabsorber operated in a countercurrentmode of operation depends on the absorption factor.
Example 4.10 Some experiments are done on the absorption of air mixture in 2.5N caustic soda. In one experiment at atmospheric pressure, the results obtained are as follows (Fig. 4.1 1): Gas rate at the bottom of the tower = 0.34 kg/m2s Liquid rate at the top of the tower = 3.94 kg/m2s The CO, in the inlet gas is 315 ppm (parts per million) and in the exit gas it is 31
ppm. Find the mole fraction of CO, absorbed by NaOH. Solution At the bottom of the tower:
y N + = 315 x lo4
G,,
= 0.34 kg/m2s
98
Lo = 3.94 kg/m2 s
x,= ?
G,
, = 0.34 kg/m s
xo = 0
Lo = 3.94 kg/m2s
Now, 2.5N NaOH contains 2.5 x 40 ( g L ) = 100 kg/m3 NaOH Mean molecular weight of the liquid

=  =0.195
kmol/m's
99
Solution
Let x be the mole fraction of the more volatile component in liquid leaving plate n, , xD be the mole fraction of the more volatile component in product D withdrawn from the condenser, y,* be the mole fraction of the more volatile component in the vapour in equilibrium with the liquid of composition xn, y, be the mole fraction of the more volatile component in the vapour leaving plate n (y, = y,* if the plate efficiency is loo%), 0 be the constant molar flow rate of liquid down the column, V be the (constant molar flow rate of vapour up the column, and D be the molar flow rate of the product from the condenser.
...........................................
I
I I
I I
n+l
F, xF
C (condenser) R (reboiler)
4
3
I
Fig. 4.12 Multistage distillation
Considering Fig. 4.12 and writing the material balance for the more volatile component around the section which includes the nth plate and the condenser,
VY,1  OX,  Dx, = 0 
(4.103)
100
This is known as the operating line for the enriching section. The definition of relative volatility is (4.104) This is the equation of the equilibrium line. Combining Eqs (4.103) and (4.104), we get
x,x,l Let
a=X + 2+ a1
Dx, (a 1)  aV O ( a  1)
Xn1 
DxD = 0 O(a  1)
(4.105)
+ c =0
+ 6:
(4.106)
(4.107)
jX,X,~
6
we have
X,X,~
a+6 *1++Xfl1
=O
x,
Put
101
1
(b + 6)
+ (a + 6)
(4.116)
Let the intersection of the equilibrium and operating lines occur at the point ( x i ,yJ:
Vyi  Oxi  Dx, = 0
(4.120) (4.121)
+ (a + b)x; + c = 0
(4.122)
6 = xi (4.123) Therefore, the translation of axis required to linearize the Riccati equation corresponds to the new origin of coordinates at the intersection of the equilibrium and operating lines.
Example 4.11 A benzenetoluene feed containing 60 mol% of benzene is fed continuously to a distillation column. If there are nine plates between the reboiler and the feed plate, and the top product contains 98 mol% benzene whilst the liquid leaving the base of the column contains 2 mol % benzene, estimate the overall plate
102
efficiency of the column. The feed enters the column at its boiling point and the relative volatility of benzene to toluene can be considered to be constant at 2.3. The reflux ratio is 3. Solution Basis Consider 100 lbmol feed (F), moles of the distillate, and W moles of the D residue. Therefore the material balances are 1 0 0 = D +W and
(1)
(2) Solving Eqs (1) and (2), D = 60.4 lbmol and W = 39.6 lbmol. A mass balance between the bottom of the column and some plate n in the stripping section is
(3) where L is the molar reflux down the column and G is the molar vapour rate up the column. The equation for the relative volatility is
Yn
(4)
+ wx,
or
x, Now L = F
x,
+ ax,
bx,
c
=0
(7)
a= 1
= aG
(a  1)
1 = 0.769 1.3
+ (a  l)Wxw
L ( a  1)
103
a2  (a  b)6  c = 0
62  0.5746 = 0.0022
The roots of this equation are 6 = 0.757 or 0.003 Selecting the root 6 =  0.003 and inserting the boundary condition that when n = 0, x = 0.02 gives K = 42.2. The value of n corresponding to x = 0.6 is given , , by 1.66 = 42.2
[y:i;i]n+

1.32
As n = 7.0 ideal stages, subtracting the reboiler from this number gives the overall plate efficiency as 6.0/9 I 67%.
EXERCISES
4.1 A solute is continuously extracted from a diluent using a twostage cocurrent mode of operation using a solvent. Each stage consists of (1) a mixer where vigorous stirring of the contents takes place and (2) a settler where the mixture pumped from the mixer is allowed to settle into two layers. The upper raffinate layer and the lower extract layer are removed separately. (a) Develop a mathematical model to find the total fraction of solute extracted under unsteadystate conditions by clearly mentioning the assumptions involved in the analysis. (b) Identify the dimensionless groups in the final expression and explain their physical significance. (c) Compare the performance of the cocurrent and countercurrent modes of operation if m = 1/8, c = 0.1 kg/m3, S = 12 R, and 8 = 1 h. 4.2 Acetic acid is continuously extracted from benzene using a multistage cocurrent mode of operation using water as a solvent. Each stage consists of (1) a mixer where vigorous stirring of the contents takes place and (2) a settler where the mixture pumped from the mixer is allowed to settle into two layers. The upper raffinate layer and the lower extract layer are removed separately and sent to the subsequent stage.
104
(a) Develop a mathematical model to find the total fraction of solute extracted under unsteadystate conditions by clearly mentioning the assumptions involved in the analysis. (b) Identify the dimensionless groups in the final expression and explain their physical significance. (c) Compare the performance of the cocurrent and countercurrent modes of operation for ten stages if m = 1/8, c = 0.1 kg/m3, S = 12R, and 8 = 1 h. 4.3 A falling film on a wetted wall column is brought into contact with a gas A for absorption of solute in the gas. The gas is consumed in the liquid phase by a firstorder reaction in terms of the gas concentration c. Develop a mathematical model for the concentration of A in the liquid phase in the form of a differential equation. 4.4 Benzoic acid is continuously extracted from toluene using water as the solvent in a countercurrent mode using two stages. Each stage consists of (1) a mixer where vigorous stirring of the contents takes place and (2) a settler where the mixture pumped from the mixer is allowed to settle into two layers. The upper toluene layer from the second stage and the lower water layer from the first stage, which vary with time, are removed separately. Develop a mathematical model to find the final fraction of benzoic acid extracted by clearly mentioning the assumptions involved in the analysis. 4.5 A tank contains 20 m3 of water. A stream of brine containing 2 kg/m3 of salt is fed into the tank at a rate of 8.33 x 10 4m3 /s. Liquid flows from the tank at a rate of 5.55 x 104 m3/s. If the tank is well agitated, what is the concentration of salt in the tank when the tank contains 30 m3 of brine? 4.6 A continuous extraction of benzoic acid from toluene is carried out in a twostage crosscurrent mode of operation under steadystate conditions using water as the solvent. Each stage consists of (1) a mixer where vigorous stirring of the contents takes place and (2) a settler where the mixture pumped from the mixer is allowed to settle into two layers. The upper toluene layer and the lower water layer are removed separately. (a) Develop a mathematical model to find the total fraction of benzoic acid extracted by clearly mentioning the assumptions involved in the analysis. (b) Identify the dimensionless groups in the final expression and explain their physical significance. (c) Compare the performance of the crosscurrent and countercurrent modes of operation if m = 1/8 and c = 0.1 kg/m3, and S = 12R for countercurrent operation. 4.7 Acetic acid is continuously extracted from benzene using water as the solvent in a countercurrent mode using four stages. Each stage consists of (1) a mixer where vigorous stirring of the contents takes place and (2) a settler where the mixture pumped from the mixer is allowed to settle into two layers. The upper Benzene layer and the lower water layer from each stage are removed separately
105
under steadystateconditions.Develop a mathematical model to find the final fraction of acetic acid extracted by clearly mentioning the assumptions made in the analysis. 4.8 A wetted wall column is to be used for the absorption of a gas A. The gas is consumed in the liquid phase by a firstorder reaction in terms of the gas concentration c. Develop a mathematical model for the concentration of A in the liquid phase in the form of a differential equation. 4.9 Benzoic acid is continuously extracted from toluene using a twostage cocurrent mode of operation under steadystate conditions using water as the solvent. Each stage consists of (1) a mixer where vigorous stirring of the contents takes place and (2) a settler where the mixture pumped from the mixer is allowed to settle into two layers. The upper toluene layer and the lower water layer are removed separately. (a) Develop a mathematicalmodel to find the total fraction of benzoic acid extracted by clearly mentioning the assumptions involved in the analysis. (b) Identify the dimensionless groups in the final expression and explain their physical significance. (c) Compare the performance of the crosscurrent and countercurrent modes of operation, if m = 1/8, and c = 0.1 kg/m3, and for countercurrent operation S = 12R. 4.10 GN+ kmol/s of a wet gas containing Y N + kmol of s o l u t e h o l of wet gas are fed into the base of a plate absorption column where the solute is to be stripped from the gas by absorption in Lo kmoVs of lean oil which is fed at the top of the column. The solute in the entering oil is X, kmoVkmol of lean oil and the solute in the exit gas is Yl kmoVkm01 of wet gas. The equilibrium constant K,,, is given as where ym and x,,, are the mole fractions of the solute in the gas and equal to y mh,,,, liquid phases, respectively. Show that the performance of the absorber can be expressed in terms of the absorption factor A = Lo /KG,+ and the number of ideal stages N by the KremserBrown equation as follows:
'N+1
'I
YN+1  yo 4.11 A wellagitated tank contains 10 m3 of salt solution of concentration 5 kg/m3. Fresh water enters the tank at the rate of 2 m3/h and the salt solution is withdrawn at the rate of 3 m3/h. What is the concentration of the salt in the tank when it contains 2 m3 of the solution? 4.12 Benzoic acid is continuously extracted from toluene using water as the solvent in a cascade of stages in series. Each stage consists of (1) a mixer where vigorous stirring of the contents takes place and (2) a settler where the mixture pumped from the mixer is allowed to settle into two layers. The upper toluene layer from the second stage and the lower water layer from the first stage are removed separately.
AN+^  A AN+^  1
106
Develop a mathematical model to find the final fraction of benzoic acid extracted by clearly mentioning the assumptions involved in the analysis for the following cases: (a) Steadystate singlestage countercurrent operation (b) Steadystate singlestage cocurrent operation (c) Steadystate singlestage crosscurrent operation (d) Unsteadystate singlestage countercurrent operation (e) Unsteadystate singlestage cocurrent operation (f) Unsteadystate singlestage crosscurrent operation 4.13 Solve Problem 4.12 for the following cases: (a) Steadystate twostage countercurrent operation (b) Steadystate twostage cocurrent operation (c) Steadystate twostage crosscurrent operation (d) Unsteadystate twostage countercurrent operation (e) Unsteadystate twostage cocurrent operation (f) Unsteadystate twostage crosscurrent operation 4.14 Solve Problem 4.12 for the following cases (i) by the method of induction and (ii) by the finite difference equation approach and compare the results: (a) Steadystate Nstage countercurrent operation (b) Steadystate Nstage cocurrent operation (c) Steadystate Nstage crosscurrent operation (d) Unsteadystate Nstage countercurrent operation (e) Unsteadystate Nstage cocurrent operation (f) Unsteadystate Nstage crosscurrent operation 4.15 A benzenetoluene feed containing 60 mol% of benzene is fed continuously to a distillation column. If there are nine plates between the reboiler and the feed plate, and the top product contains 98 mol % benzene whilst the liquid leaving the base of the column contains 2 mol% benzene, estimate the overall plate efficiency of the column. The feed enters the column at its boiling point and the relative volatility of benzene to toluene can be considered to be constant at 2.3. The reflux ratio is 3.0. 4.16 A system consists of Nstirred tanks each of volume v m3 arranged in a cascade. If each tank initially contains pure water, and a salt stream of concentration xo kg/m3is fed to the first tank at a rate R m3/s,calculate what the output concentration from the last tank should be as a function of time if the stirring is 100%efficient. Use the result to compare the transient behaviour of all systems of total volume Nv = V = constant.