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Module 11 Practice Problem Solutions

Note: Practice Problems are marked either R: Recommended or FE: Further Enrichment
1. (R) Consider a process for converting lignocellulosic materials into ethanol. The ethanol
made via fermentation is separated from the solid residue to produce a process
stream that we will assume to be ca. 20% (w/w) ethanol, the rest being water. A
multi-stage distillation operation is used to produce 95.6% (w/w) ethanol fuel. If
the product stream has 20% of the mass flow rate of the feed stream, calculate the
composition of the waste stream and the fractional mass of the ethanol lost to waste.
Answer:
First, draw PFD:
2

F = 1000 kg/h
x1E=0.2
1
x1W =0.8
feed

Distillation
tower

Heat exchanger

reflux

product

3
waste

Assumptions:
-Steady-state
-Basis:

Given:
-x1E = 0.20 kgE/kg1
-x6E = 0.956 kgE/kg6

-E: ethanol; W: water


-No generation
-No consumption
-Streams 1, 3, and 6 containethanol and water
-Control volume defined overentire process, as shown
Goal: Find x3E, x3W,
Mass Balance:

ACCN = IN OUT + CONS GEN


ACCN, GEN, CONS = 0
IN = OUT
IN = ; OUT =

x6E=0.956
x6W =0.044

Mass Balance for Ethanol:

ACCN = IN OUT + GEN CONS


IN = OUT
IN =
; OUT =
In general:

m3E
m3E
kg
kg1
hr
kg

8.8 E

0.011 E
m3 0.80m1
hr 0.80kg3 1000kg1
kg3
kg
x 3E 0.011 E
kg1
x 3E

Now,(xij) = 1

x 3E x 3W 1
x 3W 1 x 3E (1 0.011)
x 3W 0.989

kgW
kg
0.989 W
kg1
kg1

kgW
kg1

2. (R) Like distillation, which relies on establishing equilibrium between a vapor and a
liquid phase,
liquid-liquid extraction is another equilibrium separation process.
Here, a solute of interest is preferentially extracted from a complex solution by an
immiscible solvent. (Think back to your separatory funnel experiment in Intro Chem
lab.) The key challenge is to find an appropriate immiscible solvent that has a high
affinity for the solute of interest, but is also non-toxic and environmentally safe.
Supercritical CO2 is one such solvent. At high pressure and ambient temperature, it
behaves as an interesting hybrid between a liquid and a gas. On one hand, it can fill
a container like a gas; on the other, its density is comparable to that of a liquid. It
therefore has solvent-like extraction properties. After equilibrium has been

achieved between the feed stream and the inlet supercritical fluid, the two
(immiscible) fluids are separated and CO2 is depressurized. At that point CO2 gas is
purged, leaving the solute of interest behind. Decaffeination of coffee beans and dry
cleaning of clothes are two examples of large-scale industrial processes that use
supercritical CO2 as an extraction solvent.
You wish to use supercritical CO2 to make a new brand of non-alcoholic beer. Your
fermentation-derived beer contains 10% w/w ethanol. To obtain a non-alcoholic
label, the marketed product must have less than 0.1% w/w ethanol. At equilibrium,
the mass fraction of ethanol in beer (x) and supercritical CO2 (y) are related by the
relationship y = K(T,P)x. Under typical operating conditions, K=1.25.
a) First evaluate a single-stage, continuous, steady state unit operation. Both the
beer and supercritical CO2 are pumped into a stirred tank at high pressure.
The effluent is allowed to separate into two phases, also at high pressure, and
the CO2 and beer are drained into separate tanks. If supercritical CO2 costs 10
cents per kilogram, how much does this process add to the cost of a liter of
non-alcoholic beer?
b) Your marketing consultant has advised you to keep the incremental of
making the beer non-alcoholic to less than $1/pint. Design a continuous
process that achieves this target with no more than two stages.
Hints:
(i) Assume that the mass of ethanol exchanged between the beer and the
supercritical CO2 phases is negligible relative to the beer stream and the CO2
stream. That is, the mass flow rates of the beer streams in and out of the
process are the same, and the mass flow rates of the CO2 streams in and out
of the process are also the same.
(ii) In part b, assume that the equilibrium constant K is the same for both stages
of the process.
Answer:
a) First, draw PFD:

Beer

CO2

B, x0

B, x1

S, y0

S, y1

Assumptions:
-Steady-state

Beer

CO2

-Equilibrium
-Beer = 1 g/cm3 1 kg/hr 1 L/hr
-B = Beer; S = Supercritical CO2
- x = mole fraction of ethanol in beer; y = mole fraction of ethanol in CO2
-Bin = Bout = B; Sin = Sout = S
-No generation, no consumption
Basis: 1 kg Beer/hr
Control volume as shown
Given:
-x0 = 0.1 (kg EtOH/kg Beer); x1 = .001
-y0 = 0
-K = 1.25
-At equilibrium, y1 = Kx1
Goal: Calculate S/B
Mass Balance for Ethanol:ACCN = IN OUT + GEN CONS
ACCN, GEN, CONS = 0 0 = IN OUT
0 = (Bx0 + Sy0) (Bx1+ Sy1)
Sy0 = 0
Sy1 = B(x0 x1)
From equilibrium y1 =Kx1
S = B(x0 x1)/Kx1
S = (1 kg/h) (.1 - .001)/((1.25)(.001))
S = 79.2 kg CO2/h
Now, we find the incremental cost per L
kg
hr
kg
$
79.2 CO2 1
1 Beer .10
hr
kgBeer
LBeer
kgCO2
Incremental cost = $7.92/ L Beer

b) There are two ways to configure such a multi-stage unit operation. Lets look at both.
Cross-Current configuration: Here, the beer is sequentially passed through both stages, and
one-half of the supercritical CO2 is used in each stage. First, draw a PFD:

CO2

CO2

S,
y0

Beer

B, x0

S,
y0

B,
x1

S,
y1
CO2

B,x2

S,
y2
CO2

Assumptions:
-Steady-state
-Equilibrium
-Beer = 1 g/cm3 1 kg/hr 1 L/hr
-B = Beer; S = Supercritical CO2
- x = mole fraction of ethanol in beer; y = mole fraction of ethanol in CO2
-B0 = B1 = B2 = B; Sin = Sout = S (for both streams)
-No generation, no consumption
-Basis: 1 kg Beer/hr
Given:
-x0 = .1 (kg EtOH/kg Beer); x2 = .001
-y0 = 0
-K = 1.25
-At equilibrium, y1 = Kx1, y2= Kx2
-Note: we will have 4 equations and 4 unknowns!
Goal: Calculate S/B
Mass Balance for Ethanol on Control Volume #1:
Steady-state separation ACCN = IN OUT + GEN CONS
ACCN, GEN, CONS = 0 0 = IN OUT
0 = (Bx0 + Sy0) (Bx1+ Sy1) Sy0 = 0
Bx0 = Bx1 + Sy1

Beer

Mass Balance for Ethanol on Control Volume #2:


Steady-state separation ACCN = IN OUT + GEN CONS
ACCN, GEN, CONS = 0 0 = IN OUT
0 = (Bx1 + Sy0) (Bx2 + Sy2) Sy0 = 0
Bx1 = Sy2 + Bx2
Now, remember that because we are at equilibrium y1 = Kx1 and y2 = Kx2
From the mass balance on #2:
Bx1 = Sy2 + Bx2 and y2 = Kx2 x1 = x2(SK + B)/B
From the mass balance on #1:

Bx 0 Bx1 Sy1 y1 Kx1


(SK B)
B
SK(SK B)
Bx 0 (SK B)x 2 x 2
B
2
2
B x 0 (BSK B )x 2 (SK) 2 x 2 (BSK )x 2
Bx 0 Bx1 SKx1 x1 x 2

(K 2 x 2 )S 2 2(BKx 2 )S B 2 (x 2 x 0 ) 0
Now, we plug in our given numerical values

(1.252 .001)S 2 2((1)(1.25)(.001)S (1)2 (.001 .1) 0


S = 7.2 kg CO2/hr (or 2S = 14.4 kg CO2/hr used by both streams together)

Now, solving for the new cost per pint of Beer


14.4

kgCO2 /hr kgBeer 1 LBeer


$

.10
kgBeer /hr LBeer 2 pint Beer
kgCO2

New cost = $0.72/pint Beer, which is less than the goal of $1/pint Beer
Counter-Current Method: Here, the beer and CO2 are introduced into different stages, and
their direction of flow is cross-current.

Beer

CO2

B, x0

S,y0

B, x1

S, y1

Assumptions:
-Steady-state
-Equilibrium
-Beer = 1 g/cm3 1 kg/hr 1 L/hr
-B = Beer; S = Supercritical CO2
- x = mole fraction of ethanol in beer; y = mole fraction of ethanol in CO2
-B0 = B1 = B2 = B; S0 = S1= S2 = S (for both streams)
-No generation, no consumption
-Basis: 1 kg Beer/hr
Given:
-x0 = .1 (kg EtOH/kg Beer); x2 = .001
-y2 = 0
-K = 1.25
-At equilibrium, y1 = Kx2, y0= Kx1
-Note: we will have 4 equations and 4 unknowns!
Goal: Calculate S/B
Mass Balance for Ethanol on Control Volume #1:
Steady-state separation ACCN = IN OUT + GEN CONS
ACCN, GEN, CONS = 0 0 = IN OUT
0 = (Bx0 + Sy1) (Bx1 + Sy0)
Mass Balance for Ethanol on Control Volume #2:
Steady-state separation ACCN = IN OUT + GEN CONS
ACCN, GEN, CONS = 0 0 = IN OUT
0 = (Bx1 + Sy2) (Bx2 + Sy1) Sy2 = 0
Bx1 = Sy1 + Bx2

B, x2
S, y2

Beer

CO2

Now, remember that because we are at equilibrium y1 = Kx2 and y0 = Kx1


From the mass balance on #2:
Bx1 = Bx2 + Sy1 y1 = Kx2
Bx1 = Bx2 + SKx2
x1 = x2(B+SK)/B
From the mass balance on #1:
B(x0-x1) = S(y0-y1)) remember that y0 = Kx1 and y1 = Kx2

(B SK)
B
(B SK)
Bx 0 (B SK)x 2 SKx 2 (
1)
B
B 2 x 0 (B 2 SKB)x 2 (SK) 2 x 2
Bx 0 Bx1 SK(x1 x 2 ) x1 x 2

(K 2 x 2 )S 2 (BKx 2 )S B 2 (x 2 x 0 ) 0
Now we plug in our given numerical values

(1.252 .001)S 2 (1)(1.25)(.001)S (1)2 (.001 .1) 0


S = 7.6 kg CO2/hr

Now, solving for the new cost per pint of Beer


7.6

kgCO2 /hr kgBeer 1 L


$

.10
kgBeer /hr LBeer 2 pint
kgCO2

New cost per pint of beer = $0.38/pint of Beer

Again, this value beats our goal of $1/pint of Beer, but the counter-current methods
efficiency is nearly twice that of the cross-current.
3. (R) Mixtures of benzene and toluene are commonly produced in the production of
gasoline. These chemicals are often separated by distillation for use as solvents and
precursors in the production of other chemicals.
a. A 50. mol% benzene-toluene mixture is fed to a flash drum at 95C. The
equilibrium relationship at this temperature is yB=1.54xB. Assuming the

vapor and liquid products from the flash drum have the same flow rate,
calculate the molar composition of these streams.
b. You are now going to create your own Txy diagram, which shows the liquidvapor equilibrium of benzene-toluene mixtures as a function of temperature.
To do this, follow the steps below:
i. Create an Excel spreadsheet that contains the following columns: P
(system pressure-given), xB (mol fraction benzene in the liquid), xT
(mol fraction toluene in the liquid), T (system temperature), pB*
(vapor pressure of benzene), pT* (vapor pressure of toluene), P(sytem
pressure-calculated),yB (mol fraction benzene in the vapor), and yT
(mol fraction toluene in the vapor).
ii. Fill the xB column with 0, 0.05, 0.10, 0.15etc. Use these numbers to
fill in the xT column. Place 760 (mmHg) in all cells in the system
pressure column. The system pressure will remain the same for all
data points and is a characteristic that must be reported for all Txy
diagrams. Leave the T column blank for now.
iii. You can solve for the vapor pressures at a specific temperature using
the Antoine equation:
where A, B, and C are constants that depend on the material.
For benzene: A=6.89; B=1203.53; C=219.89.
For toluene: A=6.96; B=1346.77; C=219.69.
Use this equation to fill the cells in your vapor pressure columns.
Reference the adjacent temperature cell but do not fill in a
temperature value yet.
iv. Fill in the calculated system pressure column by referencing the vapor
pressure and liquid mol fraction columns (recall Raoults law and
Daltons law).
v. You can now solve for T by using the constraint that the given system
pressure and the calculated system pressure must be equal. You can
do this by guess and check or using the solver or goalseek functions in
Excel.
vi. Finally, use Raoults law to solve for yB and yT.
vii. Plot T vs. xB and yB on the same plot. Txy diagrams are often
constructed for the more volatile component, which is in this case
benzene.
c. Use your Txy diagram to plot the feed stream to the flash drum in part a. Also
use the Txy diagram to determine the vapor and liquid compositions
emerging from this flash drum. Are these molar compositions consistent with
those you calculated in part a?

Answer:
a. Draw a PFD:
Benzene, yB
Toluene, yT 2
V (mol/hr)
Benzene, zB
Toluene, zT
F (mol/hr)

Flash Drum
T=95C

1
Benzene, xB
Toluene, xT 3
L (mol/hr)
Our control volume will be around the flash drum. We arent given a flow rate, so
lets take a basis of F=100 mol/hr. We were told that V=L, so we know that V=L=50
mol/hr. We were also given that zB=zT=0.50.
Lets write our mass balances:
Overall: F=L+V
Benzene: FzB=LxB+VyB
And we have our equilibrium relationship: yB=1.54xB
We can solve this system of equations for xB and yB:
100(0.50)=50(xB)+50(yB)
50=50(xB)+50(1.54xB)
50=127xB
xB=0.39, xT=0.61
50=50(0.39)+50(yB)
50=19.5+50(yB)
yB=0.61, yT=0.39

b. The excel spreadsheet should look something like this:

P
(given)
760
760
760
760
760
760
760
760
760
760
760
760
760
760
760
760
760
760
760
760
760

xB
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1

xT
1
0.95
0.9
0.85
0.8
0.75
0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0

T
110.467
108.204
106.059
104.024
102.09
100.249
98.4949
96.8205
95.2203
93.6893
92.2227
90.8161
89.4656
88.1676
86.9187
85.7159
84.5564
83.4377
82.3573
81.3131
80.3031

pB*
1765.53
1666.29
1576.22
1494.24
1419.39
1350.85
1287.92
1230
1176.54
1127.09
1081.25
1038.65
998.982
961.978
927.39
895
864.619
836.073
809.211
783.895
760

pT*
760
712.301
669.309
630.428
595.153
563.05
533.747
506.924
482.305
459.651
438.754
419.432
401.527
384.899
369.427
355
341.526
328.917
317.099
306.004
295.572

The calculated pressure=xBpB*+xTpT* and yB=xBpB/P.

Pcalculated
760.00018
760
760.00022
760
760
760.00002
760.00008
760.00023
760
760
760.00002
760.00005
760.00014
760.00033
760.00069
760
760
760
760
760
760.00001

yB
0
0.10962
0.2074
0.29492
0.37352
0.44436
0.50839
0.56645
0.61923
0.66736
0.71135
0.75165
0.78867
0.82274
0.85417
0.88322
0.91012
0.93508
0.95828
0.97987
1

yT
1
0.89038
0.7926
0.70508
0.62648
0.55564
0.49161
0.43355
0.38077
0.33264
0.28865
0.24835
0.21133
0.17726
0.14583
0.11678
0.08988
0.06492
0.04172
0.02013
-1E-08

The Txy
diagram:

c. The feed is shown as a black triangle at 50% benzene and 95C. The liquid and vapor
streams have compositions on the blue and red curves respectively (blue: bubble point
curve, red: dewpoint curve) at 95C. These streams are shown with yellow triangles
below. We see that the liquid stream is ~40% benzene and the vapor stream is ~61%
benzene. These numbers are consistent with those calculated in part a.

4. (R) Recall Practice Problem 11 from Module 5. Polystyrene is currently produced at a


rate of 1010kg/year. Styrene, the precursor of polystyrene, is produced industrially
through the following set of chemical reactions:

a. Consider only the distillation column. The feed stream enters at a rate of
F=1.0*102mol/h and is composed of styrene and ethyl benzene, with a styrene
mole fraction of =0.65. The styrene-rich liquid outlet stream is removed at a
rate of 75mol/h. Calculate the molar compositions of the two product streams
obtained from the distillation column if the column has (i) one stage and (ii)
three stages with a reflux ratio of 10. The Raoults law constants for styrene for
stages 1, 2, and 3 are K1=0.45, K2=0.35, K3=0.25, respectively.
b. What fraction of the styrene in the feed is recovered in the liquid product stream
for parts a) (i) and (ii)?
c. The following alternative method for producing styrene is being considered:
+ CH3OH

+ H2O + H2

This process generally works under excess toluene conditions with a recycle
stream of toluene. Why might this process be attractive, notwithstanding the
poorer atom economy of this process compared to that in problem 4ab? Give at
least two reasons.
Answer:
a.
(i) For a one-stage distillation, we will consider the control volume shown below.

Ethyl benzene and styrene are the two species to be separated. Following the nomenclature
in the modules, F,V, and L are molar flow rates and z, x, and y are mole fractions. First,
write the overall mole balance:

Next, write a mole balance on styrene


Finally, we will use

in Raoults law

We are given F, zS, and L, which leaves us with V, xs, and ys as unknowns. We have three
equations, so we can solve for the unknowns.

(ii)
We can visualize three distillation stages as follows:

First, do a mole balance on the entire system:


Styrene mole balance on the entire system:
Mole balance on just the first stage:
Styrene mole balance on just the first stage:
Mole balance on the third stage:
Styrene mole balance on the third stage:
Raoults law

The reflux ratio R

Our unknowns are


and we have eleven equations, so we can solve the system. You can solve this system with
software or by hand using algebra. The solutions (to two sig figs) turn out to be

(Additional sig figs were carried through the calculation despite the fact only two are
reported here. Answers may vary slightly depending on the point at which sig figs were
truncated).So the compositions of the aromatic-rich product streams are

b.

For part (i)

For part (ii)

c.
1) Single reactor

2) The difference between the boiling points of toluene and styrene is greater than the
difference between the boiling point of ethyl benzene and styrene, which will allow
for a more effective distillation.
3) Toluene is cheaper than benzene.
5. (R) Recall Practice Problem 9 from Module 3, Practice Problem 10 of Module 4 and
Practice Problem 5 of Module 9. 4-methylthiazole (4-MT) is an important intermediate in
the production of pharmaceuticals. Two processes for making 4-MT are shown below:
(i)

(ii)

a. The product stream from the CSTR is to be purified using distillation. Assume
that the actual volume of the CSTR is 100L and that the concentration of all
components other than acetone, water, and 4-MT in the feed stream of the
distillation column can be ignored. The vapor is removed at a rate of 50mol/h.
The acetone-rich stream from the distillation column can be recycled, so long as
it has a water composition below 10mol%. Will a single-stage distillation column
suffice? If not, will a 2-stage distillation column with a reflux ratio of 10 suffice?
The Raoults law constants (yi=Kixi, where xi and yi are the mole fractions of

species i in the liquid and vapor phases, respectively) for the first stage are 0.55,
0.30, and 0.15 for acetone, water, and 4-MT, respectively. For the second stage,
the constants are 0.45, 0.25, and 0.10, respectively.
b. Draw an overall PFD for process (ii).
Answer:
a.
The requirement is that

.The feed flow rate is

The acetone does not react in the second reaction. From Practice Problem 10 of Module 4 and
Practice Problem 5 of Module 9 we see that

The molar composition of the feed stream is

Overall mole balance


Water mole balance
Raoults
Solving by substitution,

No, this mole fraction is too high with one stage. We need more stages. For two stages,
Overall mole balance
Overall water mole balance
Mole balance on first stage
Water mole balance on first stage
Raoults:

Reflux

Solving by substitution,
Overall mole balance

Overall water mole balance

Mole balance on first stage

Water mole balance on first stage

Raoults:

Reflux

Yes, two stages with R=10 works.