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PART II

CHEMICAL SYSTEM MODELLING


will apply the modelling principles and the generalized approach to model various chemical engineering systems. The models for chemical engineering systems are divided into four groups: models in mass-transfer operations, models in heat-transfer operations, models in fluid-flow operations, and models in reaction engineering, This part also focuses on the mathematical techniques that will be used for solving the model equations developed (such as algebraic equations, ordinary differential equations, partial differential equations, finite difference equations, Laplace transformations, solution by series or method of Frobenius, Bessel equations, etc.).

IN

THIS PART we

CHAPTERS 4. Models in Mass-transfer Operations 5 . Models in Heat-transfer Operations 6. Models in Fluid-flow Operations 7 . Models in Reaction Engineering

CHAPTER 4
MODELS IN MASS-TRANSFER OPERATIONS

In this chapter, various models for systems in mass-transfer operations (steadystate single-stage solvent extraction, steady-state two-stage counter-current solvent extraction, steady-state two-stage cross-current solvent extraction, unsteady-state single-stage solvent extraction, unsteady-state mass transfer in a stirred tank, unsteady-state mass transfer in a mixing tank, unsteady-state mass transfer, steadystate multistage counter-current 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.

4.1 Steady-state Single-stage Solvent Extraction


Illustration 4.1 Consider that benzoic acid (BA) is continuously extracted from toluene using water as the solvent. The two streams are fed into tank A (mixer) where they are stirred vigorously and the mixture is then pumped into tank B (settler) where it is allowed to settle into two layers (extract and raffinate). The upper toluene layer (raffinate) and the lower water layer (extract) are removed separately. Model the system to find out what fraction of BA has passed into the solvent phase. Solution Step 1 The first step in modelling of any system is to schematically represent the given system by understanding the actual process occumng in the system (Fig. 4.1).

62

Process Plant Simulation

Toluene

Water Mixer

Water + BA (aqueous layer)

aToluene + BA (organic layer) Settler (B) Idealized single-stage solvent extraction system (Raffhate) R m3/s of toluene x kg/m of BA

Fig. 4.1 Single-stage mixer settler

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 solute-free 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

Models in Mass-transfer Operations

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

Plvcess Plant Simulation

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,

and the fraction of BA extracted,

Substituting these two dimensionless groups in Eq. (4.7), we get

E=- 1 a+l and multiplying both numerator and denominator by (a- l), we get E=- a - 1

a2-1
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

12R x 0.005 = 0.6 = 60% 0.1 x R

Models in Mass-transfer Operations

65

1 - 12 .I. E = - - - - 0.6 = 60% 8 1 20 -+


12

4.2 Steady-state Two-stage Solvent Extraction


Illustration 4.2
Develop a model and obtain an expression for the extraction of BA in a steadystate operation with two stages. The input data are same as in the previous problem. Each stage still consists of two tanks, a mixer and a settler, with counter-current flow through the stages. The idealized flow system is shown in Fig. 4.3, where the symbols have the same meaning as in the previous example, and the different concentrations in a particular phase are distinguished by suffixes.

Stage

Stage

t-

Fig. 4.3 Two-stage settler mixer

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

Pmcess Plant Simulation

Stage 1 Input of BA (kgh): Output of BA (kgh):


Re + Sy, RXl + SY,

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

RYl Re + mSx, = -+ Sy, m m and Eq. (4.11) becomes

(4.12) (4.13)

- ( R + mS) Y1

- - - Rx2 + mSx, Ryl


m m + y1 = -(Rx2 + mSx,)

(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, =

( R + mS) m -(Rx, + mSx, ) m R

* R2e + mRSx, = R2x, + mRSx, + mRSx, + m2S2x,


R2e = x,(R2 *x2=

+ mRS + m 2 S 2 )
(4.16)

R2c ,+ m R S + m 2 S 2 R

Substituting x2 from Eq. (4.16) in Eq. (4.15), we get


mRc(R + mS) R +mRS+m2S2 Again, the proportion of BA extracted is

1 -

(4.17)

SYl -- -

Re

mS(R + mS) R2 + mRS + m2S2

(4.18)

Models in Mass-transfer Operations

67

Multiplying and dividing the right-hand side (rhs) of Eq. (4.18) by m2S2, we get
S-Yl -

Rc

(WmS) + 1 (R2/m2S2)+ (WmS) + 1

(4.19)

Now introducing the dimensionless groups E = Sy,/Rc and a = WmS , we get


E=

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
aN-1

(4.2 1)

By the method of induction, for N stages,


= aN+l - 1

Example 4.2 Compute the fraction of solute that can be extracted in a two-stage counter-current solvent extraction using the same numerical values of S = 12R, m = 1/8, and c = 0.1 kg/m3, which were used for single-stage extraction, and compare the results. Solution
x2= R2c 2 R +mRS+m2S2
R2 (0.1) R2 + 'R(12R) 8

+ '(144R2) 64

'(

12 144 1+-+8 64)

= 0.02105

and
mRc(R + mS) y1 = R2 + mRS + m2S2

- vs(R)(O.l)[R + v8(12R)] R2 (1 + 1U8 + 144/64)


-

68

Process Plant Simulation

- R2(0.V8)1+ 12/8) ( = 0.00658 Therefore,

R2(1+ 12/8 + 144/64)

R a=--

--=

0.66667

(i)12R

' E = -a

- 1 - (0,66667)' - 1 - -0.55555 a3- 1 (0.66667)3- 1 -0.703699

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 two-stage countercurrent liquid-liquid 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

Models in Mass-transfer Operations

69

The composition of final raffinate ( x 2 ) = R 2 d ( R 2+ mRS

+ m2S2)

:.
and

x2 = 27.795 kg/m3

where a = WmS = 0.762

.*.E

= 0.7538

Therefore the conversion is 75.38%.

4.3 Steady-state Two-stage Cross-current Solvent Extractlon


Illustration 4.3
Consider the idealized flow system shown in Fig. 4.4where the symbols have the same meaning as in the previous model.

Stage 1

Stage 2

s, 0

s, 0

Fig. 4.4 Idealized flow system

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 solute-free basis. 7. The composition of a stream leaving a stage is the same as that in the stage.

70

Process Plant Simulation

BA balance (mass component balance for each stage): Stage 1 Stage 2


Input of BA (kgh): Output of BA (kgh): In steady state: Stage 1: Rc = Sy, Stage 2: Rx, = Sy,
Rc + 0 SY, + RX,

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 cross-current mode of extraction operation under steady-state 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

Y 1 x1 = m From Eqs (4.22) and (4.26),


m mRc
Y l = G

(4.26)

(4.27)

Therefore,
x1 = -

Re R+mS

(4.28)

From Eq. (4.25), we have


Y2 x, = m

(4.29)

Models in Mass-transfer Operations

71

Substituting x1 and x2 from Eqs (4.26) and (4.29) in Eq. (4.23), we get

R--- Rc - Ry2 R+mS m

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 two-stage cross-current solvent extraction using the same numerical values of S = 6R, m = 1/8, and c = 0.1 kg/m3, which were used for single-stage extraction, and compare the results. Solution If S = 6R (since 2s here = S in counter-current), m = 1/8, c = 0.1 kg/m3,
R R
= - = 1.3333

8 6

mRc

mR2c ( R + m+!7)2] Re

( =)(

mRc

=)

72

Pmcess Plant Simulation

*E=

2(1.3333)+ 1 = 0.6735 = 67.35% (1.3333 + 1)2

Comparison For counter-current steady-state two-stage extraction, a = 0.66667 (since S = 12R)

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 counter-current operation is higher than that in the cross-current operation. This is attributed to the fact that the driving force available at any stage is higher in the case of the counter-current mode of operation, as no extract is taken out from any intermediate stage. However, in the cross-current 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 co-current operation with counter-current and cross-current 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 two-stage countercurrent liquid-liquid 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 solute-free 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 =

1200a (0.4 + 200a)

: . : .

a = 3.39 x 10 m3/s Mass flow of A = 0.041 kg/s

Models in Mass-transfer Operations

73

Mass flow of B = 0.366 kg/s


R (volumetric flow rate of B ) = 4 x 10-4 - 3.39 x 10 = 3.661 x lo4 m3/s c (kg of A/m3of B ) = (kg/s of A)/(m3/sof B) c = 0.04U3.661 x lo4 = 112.02 kg/m3 The composition of the extract from stage 1
XI

Now,

RC

(R+ mS)

= 48.456 kg/m3 The composition of the extract from stage 2


x2

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 two-stage steady-state counter-current and cross-current extraction. For the same numerical data, the fractional recovery obtained in counter-current and cross-current operations is 78.9% and 80.6% respectively. We expect the fractional recovery to be more in the counter-current operation than in the cross-current 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.

4.4 Unsteady-state Single-stage Solvent Extraction


In the models considered so far, the system has been in a steady state, allowing the material entering the system to be equated to the material leaving the system, which has always given an algebraic equation. In unsteady-state problems, however, time enters as a variable and some properties of the system become functions of time. In the application of conservation laws, it is no longer true that the rate of input will equal the rate of output, since an allowance must be made for the material accumulating within the system. The general conservation law now becomes Input - output = accumulation

74

Pmcess Plant Simulation

Illustration 4.4 The single-stage steady-state example is reconsidered as follows: 1. Assume that the single-stage contains Vl m3 of toluene, V, m3 of water, and no benzoic acid (solute-free 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

Fig. 4.5 Time-dependent single-stage extraction (unsteady state)

Since the flow rates of water and toluene are constant (solute-free basis), V , and V , will remain constant (solute-free 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

Input - output = accumulation

Models in Mass-transfer Operations

75

(y- 2+
- Rx

v d0 9 0 2
y+--60

+Rc-R~+--60

[ :de ] - S[
d0 d0

Taking the limit as 60 + 0 , Model: Rc

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.

Amount of BA in the water layer

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

Process Plant Simulation

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)

-ln[Rc - (R + mS)x] R+mS V,

+ 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

Models in Mass-transfer Operations

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 steady-state 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,

For the unsteady state,

+ mS

(4.40)

Therefore, the fraction of BA extracted = Sy/Rc

*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 unsteady-state conditions in a single stage using the counter-current 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

Process Plant Simulation

solute-free 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

1200a (0.4 + 200a)

.: : .

(a) The composition of the final raffinate

: .
and

x = 40.904 kg/m3

E = J [- exp( -(a + l)8 -1 a+l (v, + rnV2)/mS


where
R mS : E = 0.082 . Therefore the fractional conversion is 8.2%.

)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

Models in Mass-transfer Operations

79

4.5 Unsteady-state Mass Balance in a Stirred Tank


Example 4.7 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 lo4 m3/s. Liquid flows from the tank at a rate of 5.56 x lo4 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? Solution The system is schematically represented as shown in Fig. 4.6.
8.88 x lo4 m3/s 2 kg/m3 2 kg/m3

I1

II
5.55 x lo4 m3/s

Fig. 4.6 Stirred tank

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)

8.88 x lo4 5.55 x 10-4 2

8.88 x 10-4 5.55 x 1oJ 2

4. 5.

V
X

dV v + -dm e
x

dx + --6e de
x

6.

The amount of salt in tank (kg)

vx

(v +$ss)(

+ $Je)

In a small interval 68, accumulation of brine in the tank = dV/d8 88 Volume balance: Input - output = accumulation

80

Process Plant Simulation

dV (8.33 x m4)68- (5.55 x io4)6e = -68 de


3

(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 )

dV - = (8.33 - 5.55) x lo4

(8.33 x 1 0 3 2 6 8 - (5.55 x lo4).&

= ( v + %6e)( x

+ $m) - v x

dx dV dV dx = vx + v-6e + --6e + ---(se)* - vx de de de de Simplifying and taking the limit as 68 + 0 , we get


16.66 x lo4

- 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

dx e + 20) - + 2.78 x lo4 x


dx

(4.45)

8.33 x lo4 2.78 x

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

30 = 2.78 x 10-~ + 20 e 10 = 35,971.22 = 35,972s (2.78 x lo4)

+e=

Models in Mass-transfer Operations

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

ln(2.78 x 104 e + 20)

* -8.33 x1 lo4
-

16.66 x lo4 - 833 x lo4 x 16.66 x lo4 In( In(;)

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 =

1 - 0.125 = 1.75 0.5

Therefore,
x = 1.75 kg/m3

82

Process Plant Simulation

4.6 Unsteady-state Mass Balance in a Mixing Tank


Illustration 4.5 A stream of solution containing dissolved salt flows at a constant volumetric flow rate Q m3/s into a tank of constant holdup volume V. The concentration of the salt in the entering stream, x kg/m3, varies with time. Develop a model for the outlet concentration, y kg/m3, when there is a sinusoidal input change in the inlet concentration. Assume the density of the solution to be constant. Solution The above system is schematically represented in Fig. 4.7.
Q m/s
x ( t ) kg/m

-@$Fig. 4.7 Mixing tank

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 X-Y=(E)$

(4.52) (4.53)

Models in Mass-transfer Operations

83

Putting

z = V/Q

= time constant, and taking the Laplace transform, we get

(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) =

vz (s2 + w 2 )(s + Vz)


A@

(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

Process Plant Simulation

2. The ratio of the output amplitude to the input amplitude is VJz2w2+ 1

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 unsteady-state 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

@ = tan-' (-wz) tan-' (-5.02) = -78.7' =

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 unsteady-state 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.

Models in Mass-transfer Operations

85

4.7 Unsteady-state Mass Transfer (Fick's Second Law of Diffusion)


Consider two-component diffusion: A w B The rates will be most conveniently described in terms of a molar flux or moll (area)(time). The area is measured in the direction normal to the diffusion. In a nonuniform solution containing only two constituents, however, both constituents must diffuse if uniformity is the ultimate result. This leads to the use of two fluxes to describe the motion of one constituent: N is the flux relative to a fixed location in space. It is important in the application to design the equipment. For example, a fisherman is most interested in the rate at which a fish swims upstream against the flowing current to reach his baited hook (analogous to N).J i s the flux of a constituent relative to the average mass velocity of all the constituents. It is characteristic of the nature of the constituent. of The diffusivity, or diffusion coefficient, DAB a constituent A in a solution in B, which is a measure of its diffusive mobility, is defined as the ratio of its flux JA to its concentration gradient: (4.62) which is Fick's first law written for the z-direction. The negative sign emphasizes that diffusion occurs in the direction of the drop in concentration. The flux NAof A relative to a fixed position P is positive and the NB of B is negative. For a condition of steady state, the net flux is

(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

Pmcess Plant Simulation


Z
A x

Y
Fig. 4.8 Fluid volume element

The mass-flow 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 x-directed flux and (N,, ,>, signifies its value at location x. Similarly, the mass-flow 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,

+ [ ( N A , z ) z + & - (NA,z)zlhxAy~+ hxAyAz- at


= MARAAxAyAz

dP*

(4.67)

Dividing by Ax Ay Az , and taking the limit as the three distances become zero gives

Models in Mass-transfer Operations

87

From Eq. (4.64), the counterpart of Eq. (4.64) in terms of masses and in the x-direction is MANA,x = M A N X A+ M A J A , ~

* M A N A ,= Yx P A + M A ~
PUX

(4.69)

where ux is the mass average velocity in d s .


= uA,x P A + U B , PB = M A N A , + M B N B , ~ ~ ~ = uA,x PA +

* ux

PB

(4.70)

From Eq. (4.69)

(4.71) Equation (4.68) becomes

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

Process Plant Simulation

Ficks second law, therefore, is


(4.75)

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 cos4-d C A
dY

(3)

From Eqs (1)-(4) we get

Similarly,

Models in Mass-transfer Operations

89

If we multiply Eq. ( 5 ) with d c A / d x ,

Substituting the value of ( d c , / d x ) in Eq. (7)

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,

r dr Now, adding Eqs (9) and (10)

COS +--COS* $ dcA +---( Q d 2 C A

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

Process Plant Simulation

(14)

This is the final expression for Fick's second law of diffusion in cy coordinates.

rical

4.8 Steady-state N-stage Counter-current Solvent Extraction


Illustration 4.7 Benzoic acid is continuously extracted from toluene using water as the solvent in a counter-current mode using N stages under steady-state conditions. 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. Develop a mathematical model to find the final fraction of benzoic acid extracted by clearly mentioning the assumptions involved in the analysis. Solution The improved extraction leads to the consideration of more than two stages in the extraction system. In the single stage, the algebraic treatment was quite simple. There were two equations in two unknowns for finding the solution. In two stages, there were four equations in four unknowns for finding the solution. Following the same procedure for N stages, it would be necessary to solve 2N equations in 2N unknowns. This is too laborious and would require an individual solution for every integer value of N . Therefore, more advanced mathematical techniques are obviously needed to reduce the work. Among these; one method uses matrix algebra and another method uses finite differences. The general arrangement is as shown in Fig. 4.9. The flow rates of the two streams (feed and solvent) are R and S (on a solutefree basis). The benzoic acid concentrations in the extract and raffinate are y and x , respectively. The suffix notation is again used to distinguish between the different stages of each stream, the suffix denoting the stage which the stream has just left. The assumptions remain the same as those made in the single- and two-stage extraction problems. Now, a benzoic acid material balance is applied to the general stagep of the system:
Input of acid (kg/s) = f i p - l+ SY,+~ Output of acid (kg/s) = Rx,

+ Syp

Models in Mass-transfer Operations


S

91

Yp+I

A A"
YN- 1

N-1

Fig. 4.9 Idealized N-stage extraction

At steady state, entry rate = exit rate


hp-l

+ SYP+l = Rx, + SYP

(4.76) (4.77)

The equilibrium equation 0,= mx) is still valid for any value of p .
*Yp

=mxp

Then, Eq. (4.76) becomes [from Eq. (4.77)]

Rx,-,+ mSx,,,

( R + mS)x,

(4.78)

92

Process Plant Simulation

Dividing by mS on both sides, we get

-xp-1 mS

+ Xp+l

(2
+ + ax,,,

+ l)x,

(4.79)

We know that RImS = a,which is a dimensionless group.

* ax,-, +
XP+,

XP+,

= (a 1)x, =0

(4.80)

Writing Eq. (4.80) in standard form, (4.81) This is a second-order 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 ,

which has the solution


xp = K,
xo = K ,

+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)

+ K2aN xN+1= K1 + K2aN+l


xN = K ,

(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

Models in Mass-transfer Operations

93

Substituting K,and K2 in Eq. (4.82), the solution is

xp =

c(aN+l aP) (aN+l 1) -

rnc(aN+' aP) (aN+l 1) Therefore, the proportion of BA extracted is (put p = 1 in the above equation)
Y p

E = - SYl - s rnc(aN+'a ) -Rc Rc (aN+l 1) -

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 single-stage 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 (trade-off between operating and capital costs).

94

Process Plant Simulation

Table 4.3 Percentage extraction as a function of number of stages

1 2 3 5 10 20 30

60 78.9 87.7 95.2 99.4 99.98 99.99

4.9 Multistage Gas Absorption (Kremser-Brown Equation)


Chemical processes involving separation, purification, and chemical reactions are frequently carried out in a series of stages, and these processes are often analysed by stage-to-stage calculations or in simple examples by graphical methods. Thus distillation, gas absorption, and the extraction operation performed in plate columns involve stepwise changes in the concentration of each phase as it passes from plate to plate. In particular, in a distillation column, the vapours leaving any plate differ in composition from the vapours entering the same plate by a finite amount; thus an abrupt change in the vapour composition occurs on the plate. Therefore, in contrast with a packed distillation column where the vapour composition changes continuously throughout the packed height and where the height of the packing is estimated from the solution of a differential equation, a plate column should be analysed in such a way that these abrupt finite changes enter into the analysis. This is possible with the solution of finite difference equations.

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 Kremser-Brown equation (which relates the fractional solute recovery to the absorption factor):

Models in Mass-transfer Operations

95

m-1

m+l

Fig. 4.10 Multistage absorption

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 solute-free 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=-

Y m G m = YmGNt, xmLm= XmL,

(4.87)

96

Process Plant Simulation

We know that the equilibrium relation is


Ym

= 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 Lm-1

- A (absorption factor for plate rn) m


-

- Am-l (absorption factor for plate m - 1)

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)

Models in Mass-transfer Operations

97

Putting Eq. (4.94) into the operational form and factorizing,

[ E 2 - E ( 1 + A ) + A]Ym = [ ( E- 1)(E - A)]Y, = 0 which has the solution


Y,,, = C, + C2Am-' Put

(4.95) (4.96) (4.97) (4.98) (4.99) (4.100)

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

YN+' - Yl = C2 (AN+' - A ) Dividing Eq. (4.101) by Eq. (4.100), we get

(4.101)

(4.102)
Equation (4.102) is the well-known Kremser-Brown equation. The physical significanceof this equation is: The normalized fractional recovery of the solute in a multicomponentabsorber operated in a counter-currentmode 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

G N + = 0.34/29 = 0.0117 kmol/m2s

98

Process Plant Simulation


y , = 31 x 10"
xo= 0

Lo = 3.94 kg/m2 s

y,,, =315 x 10"

x,= ?

G,

, = 0.34 kg/m- s

Fig. 4.1 1 Absorption of CO, from air using NaOH solution

At the top of the tower:


y, = 31 x

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
-

40) + (900 x 18) 1000 = 20.2 kgkmol


(100
x

3.94 20.2 By overall material balance


Lo
%+I
bN+I

= - =0.195

kmol/m's

-Y,)=Lo(xN-xo) 1 0 . 0 1 1 7 ( 3 1 5 ~ 0 - 6 - 3 5 ~10-6)=0.195(xN-O) xN= 0.00001704 = 17.04 x loe6 ppm

4.1 0 Multistage Distillation


Illustration 4.9 A continuous flow distribution column is fed with a binary mixture of A and B. The relative volatility a of the mixture is constant. By considering the plate above the feed plate, derive the difference equation that relates the liquid composition to the plate number n if the overall plate efficiency is 100%.Reduce the equation to a linear one with constant coefficients. Show that the axis translation required involves the points where the equilibrium and operating lines intersect.

Models in Mass-transfer Operations

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

Process Plant Simulation

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+ a-1

Dx, (a- 1) - aV O ( a - 1)

Xn-1 -

DxD = 0 O(a - 1)

(4.105)

Dx, (a- 1) - a V 1 , b= , c = DXD a-1 O(a - 1) O ( a - 1)

Equation (4.105) becomes


x , x , - ~+ ax, + bx,-,

+ c =0
+ 6:

(4.106)

This is known as Riccati equation. Put x , = x ,


(x,

+ 6)(x,-, + 6 )+ a(x, + 6 ) + b(x,-, + 6) + c = 0 + x,(a + 6 ) + x , - ~( b + 6 )+ 6 + (a + b)6 + c = 0

(4.107)

jX,X,-~

If the value of 6 is such that

6
we have

+ (a + b)6 +c = 0 + x,(a + 6 ) + xn-l(b+ 6 ) = 0


b+6

(4.108) (4.109) (4.110)

X,X,-~

a+6 *1+-+Xfl-1

=O

x,

Put

v, = VX,, : V,(b+ 6 ) + V,-l(a + 6 ) + 1 = 0 . V,(b + 6 ) + V,-~(U 6) = -1 +


[E(b+ 6 ) + (a + S ]V,-I = - 1 )

(4.111) (4.1 12) (4.113) (4.114)

Putting this in the operational form,

Models in Mass-transfer Operations

101

The complementary solution is (4.115) The particular solution is


V,-I

-1
(b + 6)

+ (a + 6)

(4.116)

Hence the complete solution is (4.117)

(4.118) Since V, = V(x, - l), K = constant, (4.119)

Let the intersection of the equilibrium and operating lines occur at the point ( x i ,yJ:
Vyi - Oxi - Dx, = 0

(4.120) (4.121)

On eliminating yi, we have from the above two equations,


x ;

+ (a + b)x; + c = 0

(4.122)

With the usual notation for a, b, and c,

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 benzene-toluene 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

Process Plant Simulation

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

60 = 0.98 D + 0.02 (100 - D)

(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

Lx,+ 1 = GY, + wxnI

ax, 1 + (a - 1)x, aGx, 1 + (a - l)x,

(4)

Substituting Eq. (4) in Eq. (3) gives


k + l

+ wx,

or

This is the Riccati equation of the form

x, Now L = F

x,

+ ax,

bx,

-c

=0

(7)

+ RD = (100 + 3 x 60.4) = 281.21 lb molh

a=--- 1

= aG

(a - 1)

1 = 0.769 1.3

+ (a - l)Wxw
L ( a - 1)

- (2.3 x 4 x 60.4) + (1.3 x 39.6 x 0.02) = 1.523 281.2 x 1.3

Models in Mass-transfer Operations

103

The complete solution of Eq. (7) is

where 6 is obtained from the equation

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 two-stage co-current 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 unsteady-state 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 co-current and counter-current 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

Process Plant Simulation

(a) Develop a mathematical model to find the total fraction of solute extracted under unsteady-state 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 co-current and counter-current 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 counter-current 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 cross-current mode of operation under steady-state 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 cross-current and counter-current modes of operation if m = 1/8 and c = 0.1 kg/m3, and S = 12R for counter-current operation. 4.7 Acetic acid is continuously extracted from benzene using water as the solvent in a counter-current 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

Models in Mass-transfer Operations

105

under steady-stateconditions.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 first-order 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 two-stage cocurrent mode of operation under steady-state 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 cross-current and counter-current modes of operation, if m = 1/8, and c = 0.1 kg/m3, and for counter-current 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 Kremser-Brown equation as follows:
'N+1

-'I

YN+1 - yo 4.11 A well-agitated 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

Process Plant Simulation

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) Steady-state single-stage counter-current operation (b) Steady-state single-stage co-current operation (c) Steady-state single-stage cross-current operation (d) Unsteady-state single-stage counter-current operation (e) Unsteady-state single-stage co-current operation (f) Unsteady-state single-stage cross-current operation 4.13 Solve Problem 4.12 for the following cases: (a) Steady-state two-stage counter-current operation (b) Steady-state two-stage co-current operation (c) Steady-state two-stage cross-current operation (d) Unsteady-state two-stage counter-current operation (e) Unsteady-state two-stage co-current operation (f) Unsteady-state two-stage cross-current 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) Steady-state N-stage counter-current operation (b) Steady-state N-stage co-current operation (c) Steady-state N-stage cross-current operation (d) Unsteady-state N-stage counter-current operation (e) Unsteady-state N-stage co-current operation (f) Unsteady-state N-stage cross-current operation 4.15 A benzene-toluene 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 N-stirred 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.