Equilibrium Stage Operations

BGHiggins/UCDavis//Feb1, 2008

Introduction
Consider a gas phase containing a solute of concentration y0 that is mixed with an immiscible liquid phase at constant T and P. If the solute is miscible in both the liquid and gas phases, it will partition between the two phases as the system attempts to attain equilibrium, thereby reducing the concentration of the solute in the gas phase. At equilibrium, the concentration of solute in the liquid phase is related to the concentration in the gas phase by an equilibrium relation that may be taken to be linear at sufficiently low concentrations: y=Kx (1)

where K is the equilibrium constant. Since the concentration y in the gas phase at equilibrium is less than y0 , this suggests a way for removing an unwanted solute from a gas stream; the process is called gas absorption. A schematic of such a process is shown below in Figure 1

L, x0 V , y0 V, y

Single Stage

L, x
Figure 1 The contacting unit is called an equilibrium stage if the streams leaving the unit are in equilibrium; that is, the solvent in the gas stream leaving the unit is given by y = K x. If the concentration of solute in any given stream is sufficiently low then it is permissible to assume that the molar (or mass) flow rate of any given phase is constant from stream to stream. With this assumption, a solute balance over the equilibrium stage gives ( see Figure 1) L x0 + V y0 = L x + V y We can represent this equation on a y-x plot by writing (2) as Hx0 - xL (3) V Thus the solute balance can be represented by a straight line that passes through the point Hx0 , y0 Land has slope y = y0 + L -L/V. According to the mass balance any {x,y} pair of values that satisfies Eq. (3) is possible. However, if the exit streams are in equilibrium, then this line must intersect the equilibrium line y = K x. which determines the minimum value of y that can be reached in an equilibrium stage when L/V is fixed, see Figure 2 (2)

EquilStageNotes.nb

Thus the solute balance can be represented by a straight line that passes through the point Hx0 , y0 Land has slope -L/V. According to the mass balance any {x,y} pair of values that satisfies Eq. (3) is possible. However, if the exit streams are in equilibrium, then this line must intersect the equilibrium line y = K x. which determines the minimum value of y that can be reached in an equilibrium stage when L/V is fixed, see Figure 2

y0 y
* y0

-LV

x0
y H1 + AL = y0 + y y0 = H1 + AL 1

x
Figure 2

Substituting x=y/K into (3) and defining A = L V K and then solving for y gives, x0 V where A is called the absorption factor. A further rearrangement of (4) gives 1+ L x0 V y0 L

(4)

The ratio y y0 represents the fraction of solute not extracted or absorbed from the gas phase. Hence, the defining a hypothetical value y* , which is the concentration of solute that would be in equilibrium with the inlet 0 liquid stream (see Figure 2). This strategem gives y y0 = = H1 + AL 1 1 1+ L VK y* 0 y0

(5)

fraction of solute absorbed into the liquid phase H1 - y y0 L increases with increasing absorption factor A. To appreciate the limiting behavior when A becomes small or large, it is convenient to eliminate x0 from Eq. (5) by K x0 y0 (6)

where we have used the relationship

of interest. The first limit of interest is when A 0. The RHS of Eq. (6) is then 1, which means that y y0 and there is then no absorption of solute. The second limit is when A . The RHS of (6) approaches y* y0 , 0 which implies that y y* . This limit represents the minimum solute concentration that can be achieved in an 0 equilibrium stage.

H1 + AL

1+A y* 0

= K x0 to define the hypothetical value y* . There are two limits that are 0

Example

EquilStageNotes.nb

Example
A gas stream containing acetone and air is to be passed through an equilibrium stage so that the acetone can be absorbed in a water stream. The inlet gas contains 1.0 mol % acetone, and has a molar flow rate of 30 kg mol/h. The pure water stream has a molar flow rate of 90 kg mol/h. The process is to operate isothermally and at constant pressure. The equilibrium relationship for the acetone in the gas liquid system is y = 2.53 x. You may assume that the water and air are immiscible and the molar flow rates entering and leaving the equilibrium stage are constant. (i) Determine the absorption factor for any equilibrium stage (ii) Determine the concentration of acetone in the exit streams

Solution
Solution (i) Since the air and water can be taken as inert streams, we can determine the absorption factor by noting that A= L VK = H30L H2.53L 90 1+ = 1.18577 (7)

(ii) The mole fraction leaving the equilibrium stage is given by (5) y y0 where L = = H1 + AL 1 L x0 V y0 (8)

90

V 30 VK 2.53 Substituting these values into (8) gives y= H1 + AL y0 y K = = 0.01 2.18577

= 3, A =

= 1.18577, x0 = 0

(9)

= 0.00457505

(10)

Recall that the acetone in the water stream is in equilibrium with acetone in the leaving gas stream. Thus x= 0.00457505 2.53 = 0.00180832 (11)

Efficiency of Multiple Countercurrent Stages

In the previous section we saw that the fraction of solute absorbed or extracted from the V-phase depended on the absorption factor A. Suppose now we added an additional equilibrium stage in series with the previous stage, as shown in Fig 3. We would like to know is how the additional stage affects the absorption of the solute.

EquilStageNotes.nb

L, x0

V , y1

Stage 1 L, x1 V , y2

Stage 2 L, x2
Figure 3 Intuitively we expect the absorption of the solute to depend on the absorption factor A. To show this mathematically, we consider control volumes for each stage. In the previous section we showed that the solute species balance (in terms of mole fraction ratios) around Stage 1 gives y1 H1 + AL = y2 + y2 = H1 + AL y1 y3 = L x2 + y2 L V x0 (12)

V , y3

which we rewrite as

L V

x0

(13)

Similarly, solute balance over stage 2 gives

x1 (14) V V The terms involving x2 , x1 in (14) can be expressed in terms of y2 , y1 using the equilibrium relation yj = K xj to give y3 = H1 + AL y2 - A y1 (15)

Using (13) to eliminate y2 gives

y3 = H1 + AL H1 + AL y1 - A y1 - H1 + AL The above expression can be expressed more compactly as = I1 + A + A2 M y1 - H1 + AL L V x0

L V

x0 (16)

EquilStageNotes.nb

yN+1 = bN y1 - bN-1 where

x0 , with N = 2

(17)

If we have more than two stages we can show that Eq. (17) holds when N>2. Thus we can use the above expression to determine the fraction of solute not absorbed in the L-phase using N multiple stages. Consider the case when N=2; then from Eq. (16) we have 1 = I1 + A + A2 M y1 y3 = 1 b2 + It follows from the definition of bN that y1 y3 b1 b2 - H1 + AL x0 y3 L V x0 y3 (19)

bN = Ai , with N = 2
N i=0

(18)

which means we can express bN as

H1 - AL bN = H1 - AL I1 + A + A2 + + AN M = I1 - AN+1 M bN = I1 - AN+1 M

(20)

(21) 1-A We can use this result to determine the limiting value of the solute fraction as N . There are two cases to consider. Case I: When A < 1, the limiting values for the functions depending on b are Limit
N->

1 bN bN-1 bN

1 - A, (22)

Limit
N->

so that y1 yN+1 1-A+ L V x0 yN+1 as N (23)

Hence if there is no solute in the entering L-phase (x0 = 0), then limiting value of the solute fraction not absorbed in the L-phase is y1 yN+1

1-A

as

N , with A < 1

(24)

Case II: When A > 1, the limiting values for the corresponding b functions are

(25)

EquilStageNotes.nb

Limit
N->

1 bN bN-1 bN

0,

Limit
N->

1 A

so that y1 yN+1 1 A L V x0 yN+1

as

N , with A > 1

(26)

The last result shows that if x0 = 0, and A > 1, we can absorbed all of the solute in the V-phase as N . One can show further that counter current operations are more efficient than co-current operations, and for this reason they are widely used in the chemical process industry. Keep in mind that the above result assumes K is a constant (i.e. independent of the stage), which is a good approximation if the solute concentration is sufficiently dilute at each stage.

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