ChE 430 Exam 3 Solutions Thursday, April 25, 2002

Part I.

Problem 1. PFR Energy Balance. 25 pts.

The first-order reaction

A B

is carried out in a tubular reactor. Costs dictate that we must reach 90% conversion
for this process to be feasible. We would like to operate the reactor adiabatically, but
product B degrades if the reactor temperature exceeds 500 K.

(a) Is it possible to operate the reactor adiabatically with this constraint (i.e. what
is the outlet temperature)? The inlet flow is pure A, inlet temperature is 300 K,
inlet pressure is 10 atm, NA0 = 2 kmol/hr, MA = 50 kg/kmol, Cp = 3.09 kJ/kgK,
HR = 41, 900 kJ/kmol, Ea = 37, 700 kJ/kmol, and k0 = 3.27 106 1/hr. Val-
ues of the gas constant include R = 8.314 J/molK and R = 82.06 atm cm3 /molK.
The energy balacne for an ideal gas in a PFR is
dT X
QCP = HRi ri + q
dV
i

For the single reaction in an adiabiatic reactor, we have

dT
QCP = HR r
dV
The material balance for component A is
dNA
= r
dV
If we substitute the material balances value of r into the energy balance we have
dT dNA
QCP = HR
dV dV
Notice Q is the total mass flow, which is a constant. Assuming constant thermal
properties and integrating both sides gives
HR
T Tf = (NA NAf ) (1)
QCP

1
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

At 90% conversion, NA = 0.1NAf , and

HR
T = Tf (0.1)NAf
QCP
Substituting in the values of the parameters gives

T = 544 K

So, no, the reactor cannot be operated adiabatically without exceeding the tem-
perature limit of 500 K.

(b) If adiabatic operation is not possible, assume we have a heating/cooling system

available to help us reach the desired conversion. We now will use two reactors
in series, operating the first adiabatically to 500 K, and the second isothermally
in order to obtain the desired conversion. What is the outlet conversion from the
adiabatic reactor, and what are the reactor volumes required for each reactor?
(Note: If finding the reactor volume requires a numerical solution, set up but do
not solve the equations that are needed to obtain the reactor volume.) How much
heat must be added or removed from the isothermal reactor?
We now rearrange Equation 1 to solve for NA

QCP
NA = NAf + (T Tf )
HR
Substituting T = 500 K and the parameter values produces

NA = 0.525 kmol/hr xA = 0.737

To find the volume of the reactor, we must integrate the material balance
dNA
= k(T )cA
dV
The concentration can be found in terms of the molar flow NA and the ideal-gas
equation of state
cA = (NA /NAf )(P/RT )

To find the volume of the second, isothermal, reactor, we must solve the material
balance and find the volume to achieve 90% conversion
dNA
= r = k(NA /NAf )(P/RT ) NA (0) = NAf 2
dV

2
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

Notice we have calculated the feed to the second tube is NAf 2 = 0.263NAf . Inte-
grating this equation and solving for the volume of the second reactor yields

VR2 = NAf (RT /P )(1/k) ln(0.263/0.2) = 21.03 L

We must solve numerically the adiabatic, non-isothermal mass balance for the
volume of the first reactor. The result is plotted in Figure 1 and the result is

VR1 = 591 L

The heat removed to keep the second reactor at constant temperature is calculated
from
Q = (NAf 2 (1 xA )NAf ) HR = 1.36 104 kJ/hr

3
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

500

450
T (K)

400

350

300
0 100 200 300 400 500 600
VR (L)

1.8

1.6
NA (kmol/hr)

1.4

1.2

0.8

0.6

0.4
0 100 200 300 400 500 600
VR (L)
Figure 1: First PFRs temperature and molar flow versus length.

4
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

Problem 2. CSTR Energy Balance. 25 pts.

The liquid-phase reactions

A B
A C

are each first order in the concentration of A. The feed to a nonisothermal CSTR
contains pure A at 45 C and 5 mol/lit. Table 1 lists additional information for the
reactions and the reactor. We want to operate this reactor such that the selectivity to
B is greater than the selectivity to C, i.e., the rate at which B forms is greater than the
rate at which C forms.
Item value units
VR 1000 lit
Qf 100 lit/min
f 932 g/lit
k1 3.16 1014 exp(12, 500/T ) min1 ; T in K
k2 2.52 109 exp(8, 500/T ) min1 ; T in K
HR1 12, 000 cal/mol
HR2 15, 000 cal/mol
CP 0.22 cal/(g K)

Table 1: Kinetic and reactor parameters.

(a) Defining the selectivity as S = RB /RC , determine the rate at which heat is
transferred to the surroundings to achieve a selectivity of 5.

RB = r1 = k1 cA
RC = r2 = k2 cA

S = RB /RC = (k1 cA )/(k2 cA ) = k1 /k2

S = k10 /k20 exp ((E1 E2 )/T )

(E1 E2 )
T =
ln (Sk20 /k10 )

5
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

(12500 8500)
T = = 395 K
ln ((5)(2.52 109 )/(3.16 1014 ))
A reasonable energy balance for this situation is
X
HRi ri VR + Qf f CP (Tf T ) + Q = 0
i

Solving for Q gives

X
Q = HRi ri VR Qf f CP (Tf T )
i

The rate constants at this temperature are given by

k1 = 5.65 k2 = 1.13
We use the mass balance for the CSTR to calculate the A concentration
cA = cAf /((k1 + k2 ))
The mean residence time of the reactor is = VR /Qf = 10 min. Substituting the
other values gives
cA = 0.0738 mol/lit Q = 4.88 106 cal/min (2)

(b) Determine the rate at which heat is transferred to the surroundings to achieve a
selectivity of 4.

(12500 8500)
T = = 386 K
ln ((4)(2.52 109 )/(3.16 1014 ))
At this temperature the values are
k1 = 2.81 k2 = 0.703
cA = 0.143 mol/lit Q = 5.10 106 cal/min (3)

(c) Explain why the answer to part (a) or part (b) is greater.
The activation energy of the first reaction is larger. Therefore to lower selectivity,
i.e. lower the rate of the reaction with the larger activation energy, one lowers the
temperature. In this case, we lower the reaction temperature by 9 K. To lower the
temperature, one must remove more heat. Notice that the conversion decreases to
achieve this increase in yield.

6
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

Part II.

Problem 3. Steady-state multiplicity in a CSTR. 50 pts.

Consider the liquid phase, elementary reaction
k
A B

The rate constant is temperature dependent:

  
1 1
k(T ) = km exp E
T Tm

Since the chemical B is currently in great demand, Badger Chemicals has decided to
start producing B. They have hired you as a consultant to address operational issues for
their constant-volume, nonisothermal, nonadiabatic CSTRs. Heat is removed from the
reactor by use of a cooling coil. You may assume that the cooling medium maintains a
constant temperature of Ta . Also, define: = VR /Qf .
Table 2 contains the data for the reaction system.

Parameter Value Units

Tf 298 K
Tm 298 K
Ta 300 K
CP 4.0 kJ/kg K
cAf 2.0 kmol/m3
km 0.001 min1
E 8.0 103 K
103 kg/m3
HR 3.0 105 kJ/kmol

Table 2: Parameter values.

(a) Write down the material and energy balance equations for this system. State all
assumptions.
Assume constant volume and constant properties (densities and HR independent
of temperature, Cp independent of composition and temperature). The mass and

7
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

energy balances are then:

dcA cAf cA
= r (4)
dt
dT HR Tf T U oA
= r+ + (Ta T ) (5)
dt Cp Cp VR
r = kcA (6)

(b) The available cooling coils can provide heat exchange in the range:

kJ
U o A/VR = 0 100
min K m3
Generate two plots:

1. the steady-state conversion of A as a function of , and

2. the steady-state temperature as a function of

comparing the steady-state solutions for U o A/VR values of 0, 20, 40, 60, 80,
and 100 minkJ
K m3
. For which of these U o A/VR values are multiple steady states
possible?

8
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

1
0
0.9 20
0.8 40
60
0.7 80
100
Conversion

0.6
0.5
0.4
0.3
0.2
0.1
0
1 10 100 1000 10000 100000
(min)
460
0
440 20
40
420 60
80
Temperature K

400 100
380
360
340
320
300
280
1 10 100 1000 10000 100000
(min)
Figure 2: CSTR steady states for varying values of U o A/VR

kJ
There is steady-state multiplicity for U o A/VR values of 0-60 min K m3
.

(c) For safety reasons, the reactor temperature must not exceed 350 K. Accordingly,
Badger Chemicals decides to operate at the following reactor conditions:

9
ChE 430 Exam 3 Solutions Thursday, April 25, 2002

Parameter Value Units

kJ
U o A/VR 40 min K m3
44 min
cA 1.76 kmol/m3
T 311 K

Table 3: CSTR conditions.

You are asked to monitor the test run of the reactor. Unfortunately, you fall asleep
on the job! When you wake up, you discover that the flow rate has changed, so
for the past five hours = 46 minutes. You quickly adjust the flow rate so that
= 44 minutes again. Now you are faced with the decision: should you shut down
the reactor?
Plot the dynamic response of the reactor temperature for twenty-four hours, start-
ing when the feed flow rate first changed (i.e., = 46 minutes). Assume that the
reactor was initially at the steady state corresponding to the values given in Ta-
ble 3.

440

420

400
Temperature (K)

380

360

340

320

300
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 3: Dynamic reactor temperature

Figure 3 indicates that the reactor temperature exceeds 350 K. Therefore you
should shut down the reactor.

10