Exercise 4.

24

Subject: Cooling of a reactor effluent with recycle liquid from a partial condensation.

Given: Reactor effluent temperature of 1000oF and composition in lbmol/h of 2000 H2, 2000
CH4, 500 benzene, and 100 toluene. Partial condensation conditions or 100oF and 500 psia, and
component K-values at these conditions. Two heat exchangers in a recycle loop.

Find: (a) Composition and flow rate of vapor leaving flash drum in Fig. 4.24.
(b) Proof that vapor flow rate is independent of quench rate.

Analysis: : The calculations made here were not made with a process simulator using the SRK
EOS, but the results should be similar. (a) Assume that vapor rate is independent of quench rate.
Therefore, conduct the flash calculation on just the reactor effluent at the flash drum conditions
of temperature and pressure. Use the Rachford-Rice equations.

f {}  
C
b
zi 1  Ki g0
b
i 1 1   Ki  1 g (1)

zK
y 
1  b K  1g
i i
i (2)
i

Nonlinear Eq. (1) is solved for  = V/F , followed by calculation of V = F, and then
calculations of vapor mole fractions from Eq. (2). The given input for Eq. (1) is:

Component f, lbmol/h zi Ki
Hydrogen 2,000 0.4348 80
Methane 2,000 0.4348 10
Benzene 500 0.1087 0.010
Toluene 100 0.0217 0.004

One method for solving Eq. (1) is to use a spreadsheet to make a plot of f{} vs. in
increments of 0.1 from 0.0 to 1.0. Then, use smaller increments in  in the vicinity of f{}= 0
to obtain the solution. The results are shown in the two figures on the next page. The converged
solution is
= 0.8697.Therefore, V = 0.8697(4,600) = 4,000.6 lbmol/h. The composition of the
equilibrium vapor from Eq. (2) is as follows:
Component zi yi xi
Hydrogen 0.4348 0.4990 0.0062
Methane 0.4348 0.4925 0.0493
Benzene 0.1087 0.0078 0.7820
Toluene 0.0217 0.0007 0.1625
 Exercise 4.24 (continued)

Analysis: (a) (continued)

 Exercise 4.24 (continued)

Analysis:

(b) When the flash conditions of temperature and pressure are fixed, the compositions of the
equilibrium vapor and liquid are independent of any recycle of equilibrium liquid or vapor. To
prove this, draw a material balance envelope around the system in Fig. 4.24 as shown below.
Now, the flash equations are the same, except for the energy balance. But, that equation is only
solved after all of the other equations are solved. Thus, the results for the compositions of the
net vapor and liquid products are the same as when there is no recycle.
 Exercise 4.32

Subject: Bubble and dew point pressures of binary mixture at constant temperature.

Given: Mixture of 50 mol% benzene (A) and 50 mol% toluene (B) at 90 oC (194oF). Vapor
pressures from Fig. 2.4 (19.5 psia for A and 7.9 psia for B).

Assumptions: Raoult's law for K-values.

Find: Bubble and dew point pressures.

Analysis: Substitution of Raoult's law into (4-30) and (4-31) for the bubble and dew points,
respectively, gives,

C C
Pi s zi C
Bubble point: 
i 1
Ki zi  
i 1 P
 10
. or P z
i=1
i
s
i P (1)

C C C
zi zP zi 1
Dew point: 
i 1 Ki
  i s  10
i 1 Pi
. or P i=1
s

P
(2)
i

Eq. (1) gives 13.70 psia for the bubble point. Eq. (2) gives 15.8 psia for the dew point.
 Exercise 4.33

Subject: Bubble point, dew point, and flash of a water (W) - acetic acid (A) mixture.

Given: Equimolar mixture of W and A at 1 atm. Correlations of liquid-phase activity

coefficients for W and A as a function of liquid-phase mole fractions and temperature:

Assumptions: Modified Raoult's law applies.

Find: Dew point, bubble point, and equilibrium vapor and liquid at a temperature halfway
between the bubble and dew points.

Analysis: The Rachford-Rice flash equations can be used.

f {}  
C
b
zi 1  Ki
0
g
b
i 1 1   Ki  1 g (1)

zK
y 
1  b K  1g
i i
i (2)
i

z
x 
1  b K  1g
i
i (3)
i

where, zW = 0.5 and zA = 0.5 and the modified Raoult's law is:

 iL Pi s
Ki  (4)
P

Antoine vapor pressure equations are given in Perry's Handbook for water and acetic acid:

1730.63
log PWs  8.07131  (5)
T ( C)  233.426
o

1936.01
log PAs  8.02100  o (6)
T ( C)  258.451

The equations for the liquid-phase activity coefficients, given in the Chemical Engineering
Science article of 1967 by Sebastiani and Lacquaniti, are incorrect. They are of the Redlich-
Kister form (see Walas, S. M., "Phase Equilibria in Chemical Engineering", Butterworth, 1985,
page 184) and should be:

b g b
log  W  xA2 B  C 4 xW  1  C xW  xA 6 xW  1 gb g (7)
log  A  xW2 B  Cb4 x  3g  Cb x
W W  x gb6 x  5g
A W (8)
 Exercise 4.33 (continued)

Analysis: (continued)

64.24
where, A  01182
.  (9)
T ( K)
43.27
B  01735
.  (10)
T ( K)
C  01081
. (11)

Since P = 1 atm and the normal boiling points of water and acetic acid are 100 oC and 118.1oC,
respectively, it might be expected that the dew and bubble point of the mixture would be in the
vicinity of 100oC, unless the liquid-phase activity coefficients are much different from 1. To
check this, activity coefficients are computed from Eqs. (7) and (8) with a spread sheet at 100 oC,
with the following result as a plot. It is seen that in the vicinity of mole fractions equal to 0.5,
the coefficients are not large, but are about 1.2.
 Exercise 4.33 (continued)

Analysis: (continued)

At the bubble point,  = V/F = 0, and Eq. (1), combined with (4), becomes:

FG
f {T}  zW 1 
 W PWs {T}IJ FG  P s {T}
 zA 1  A A 0
IJ
H P K H P K (12)

Also, at the bubble point, xi = zi = 0.5. Then, the only unknown in Eq. (12) is T.
Solving nonlinear Eq. (12), with Eqs. (5) to (11), by trial and error with a spreadsheet, starting
from a guess of T = 100oC, quickly leads to a bubble-point temperature of 101.6oC. The
composition of the vapor bubble is obtained from Eq. (2), which at the bubble point reduces to yi
= xiKi = ziKi.. The K-values at the bubble point are computed to be KW = 1.364 and KA = 0.636,
giving yW = 0.682 and yA = 0.318.

At the dew point,  = V/F =1, and Eq. (1), combined with (4), becomes:

FG P IJ FG
 1  zA
P IJ
1  0
f{xW, xW, T} = zW
H s
W {xW , xA , T} PW {T} K H  A {xW , xA , T} PAs {T} K
where because yi = zi = 0.5, T , xW , and xA = (1 - xW) are left as unknowns. The liquid phase
mole fractions are from Eq. (3), xi = zi /Ki . Solving these equations by trial and error with a
spread sheet, starting from T = 105oC, xW = 0.4 and xA = 0.6, quickly leads to a dew-point
temperature of 105.8oC. The K-values at the dew point are computed to be KW = 1.578 and KA =
0.732, with xW = 0.3169 and xA = 0.6832.

The equilibrium flash calculation is carried out at T = (101.6 + 105.8)/2 = 103.7oC. In

this case, the values of  xW, and xA are computed from Eqs. (1) and (3), where the vapor
pressures are computed from Eqs. (5) and (6) to be 867 torr for W and 473 for A. Values of yW
and yA are obtained from Eq. (2). Using, again, a spreadsheet with a trial and error procedure,
the following result is quickly obtained:

V/F = 0.49 xW = 0.4100 xA = 0.5900 yW = 0.5937 yA = 0.4063

 Exercise 4.47

Subject: Comparison of solvents for single-equilibrium-stage liquid-liquid extraction.

Given: Feed, F = 13,500 kg/h of 8 wt% acetic acid (B) in water (A) at 25oC. Four solvents
(C), each with a different distribution coefficient, KC, in mass fractions, xB, for acetic acid, as
given in the table below, where (1) is the extract of flow rate E and (2) is the raffinate of flow
rate R, where for a single equilibrium stage, the raffinate is to contain only 1 wt% B

KDB  xB( E ) / xB( R ) (1)

Assumptions: Water is insoluble in the solvent and the solvent is insoluble in water.

Find: The kg/h, S, of each solvent required.

Analysis: In Eq. (1), xB(R ) = 0.01. Therefore, xB(E ) = 0.01 K DB (2)

A total material balance gives: F = 13,500 = E + R - S (3)

An acetic acid material balance gives:

xB( F ) F  (0.08)(13,500)  1,080  xB( E ) E  xB( R ) R  xB( E ) E  0.01R (4)

92 wt% of the feed is water, or (0.92)(13,500) = 12,420 kg/h. Since all of the water appears in
the raffinate, which is 99 wt% water, R = 12,420/0.99 = 12,546 kg/h. Eq. (3) becomes:
S = E - 954 (5)

and Eq. (4) becomes: xB(E ) E  954.5 (6)

Eqs. (2), (5), (6) are three equations in three unknowns: S, E, and xB(E ) . For each solvent, solve
Eq. (2) for xB(E ) . Solve (6) for E. Solve (5) for S. The results are:

Solvent KD xB(E ) E, kg/h S, kg/h

Methyl acetate 1.273 0.01273 74.984 74,030
Isopropyl ether 0.429 0.00429 222,500 221,500
Heptadecanol 0.312 0.00312 305,940 305,000
Chloroform 0.178 0.00178 536,260 535,300

Although methyl acetate is the best solvent, the solvent rates required are very large. To reduce
the solvent rate, use a countercurrent, multiple-stage system.
 Exercise 4.50

Subject: Liquid-liquid extraction of acetic acid from chloroform by water at 18oC and 1 atm.

Given: Equilibrium data for the ternary mixture

Assumptions: Equilibrium stages.

Find: (a) Compositions and weights of raffinate and extract when 45 kg of a 35 wt%
chloroform (C) and 65 wt% acetic acid (A) feed mixture (F) is extracted with 22.75 kg of water
(S) in a single-stage extraction.
(b) Compositions and weights of raffinate and extract if the raffinate from part (a) is
extracted again with half its weight of water.
(c) Composition of the raffinate from part (b) if all the water is removed from it.

Analysis: Use a right-triangle diagram of the equilibrium data, which is easily produced
with a spreadsheet.
(a) In the diagram on the next page, the feed and solvent are represented by points F and
S, respectively. The mixing point is M1, which is the sum of the feed and solvent (67.75 kg)
with an overall composition of 33.58 wt% S, 23.25 wt% C, and 43.17 wt% A. A tie line passing
through point M1 locates, on the equilibrium curve, the extract E 1 and the raffinate R1. If the
inverse lever arm rule is used to obtain E1 and R1, and their compositions are read from the
diagram, the following results are obtained:
Feed Solvent Extract Raffinate
F S E1 R1
Amount, kg 45 22.75 55 12.75
Composition, wt%:
Chloroform 35 0 11.5 74.5
Acetic acid 65 0 48.0 22.0
Water 0 100 40.5 3.5

(b) If R1 is mixed with half its weight of solvent (6.375 kg), the mixing point is M 2,
shown in the diagram on the next page, with an overall composition of 14.6 wt% A, 49.7 wt%
C, and 35.7 wt% S. . A tie line passing through point M2 locates, on the equilibrium curve, the
extract E2 and the raffinate R2. If the inverse lever arm rule is used to obtain E2 and R2, and their
compositions are read from the diagram, the following results are obtained:
Feed Solvent Extract Raffinate Water-free
(R1) S E2 R2 Raffinate
Amount, kg 12.75 6.375 8.895 10.23 10.10
Composition, wt%:
Chloroform 74.5 0 1.0 91.0 93.2
Acetic acid 22.0 0 24.0 6.7 6.8
Water 3.5 100 74.9 1.3 0.0
(c) The water-free raffinate is included in the above table.
Exercise 4.50 (continued)