Nama : Ibnu Mubarok

NPM : 3335180063

Example 12–1 Butane Isomerization Continued—OOPS!

When plant engineer Maxwell Anthony looked up the vapor pressure at the exit to the adiabatic
reactor in Example 11-3, where the temperature is 360 K, he learned the vapor pressure was about
1.5 MPa for isobutene, which is greater than the rup- ture pressure of the glass vessel the company
had hoped to use. Fortunately, when Max looked in the storage shed, he found there was a bank of
10 tubular reactors, each of which was 5 m3. The bank reactors were double-pipe heat exchangers
with the reactants flowing in the inner pipe and with Ua = 5,000 kJ/m3·h·K. Max also bought
some thermodynamic data from one of the companies he found on the nternet that did Colorimeter
experiments to find HRx for various reactions. One of the companies had the value of HRx for
his reaction on sale this week for the low, low price of $25,000.00. For this value of HRx the
company said it is best to use an initial concentration of A of 1.86 mol/dm 3. The entering
temperature of the reac- tants is 305 K and the entering coolant temperature is 315 K. The mass
flow rate of the coolant, m ̇ C , is 500 kg/h and the heat capacity of the coolant, , is 28 kJ/kg·K.
The temperature in any one of the reactors cannot rise above 325 K. Carry out the following
analyses with the newly purchased values from the Internet:

(a) Co-current heat exchange: Plot X, Xe, T, Ta, and –rA, down the length of the reactor.
(b) Countercurrent heat exchange: Plot X, Xe, T, Ta, and –rA down the length of the reactor.
(c) Constant ambient temperature, Ta: Plot X, Xe, T, and –rA down the length of the reactor.
(d) Adiabatic operation: Plot X, Xe, T, Ta, and –rA, down the length of the reactor.
(e) Compare parts (a) through (d) above and write a paragraph describing what you find.

Additional information
Recall from Example 11-3 that CPA = 141 kJ kmol ⋅ K, CP0 = CPi = 159 kJ/kmol • K, and
data from the company Maxwell got off the Internet are HRx = -34,500 kJ/kmol with CPA = 0
and CA0 = 1.86 kmol/m3
Solution
We shall first solve part (a), the co-current heat exchange case and then make small changes in the
Polymath program for parts (b) through (d).
For each of the ten reactors in parallel
𝑘𝑚𝑜𝑙 1 𝐴
𝐹𝐴0 = (0.9)(163 × = 14.7 𝑘𝑚𝑜𝑙
ℎ0 10 ℎ
The mole balance, rate law, and stoichiometry are the same as in the adiabatic case previously
discussed in Example 11-3; that is,
The Algorithm
𝑑𝑋 −𝑟𝐴
Mole Balance : =
𝑑𝑉 𝐹𝐴0
1
Rate Law and Stoichiometry : 𝑟𝐴 = −𝑘𝐶𝐴0 ⌊1 − (1 + 𝐾 ) 𝑋⌋
𝑐
𝑇−360
With 𝑘 = 31.1 exp [7906 ( ) ℎ−1 ]
360𝑇
𝑇 − 333
𝑘𝑐 = 3.03 exp [−830.3 ( )]
333𝑇
The equilibrium conversion is
𝐾𝑐
𝑋𝑒 = 1+𝐾
𝑐
Energy Balance
The energy balance on the reactor is
𝑑𝑇 𝑟𝐴 ∆𝐻𝑟𝑥 − 𝑈𝑎 (𝑇 − 𝑇𝑎 ) 𝑟𝐴 ∆𝐻𝑟𝑥 − 𝑈𝑎 (𝑇 − 𝑇𝑎 )
= =
𝑑𝑉 𝐹𝐴0 ΣΘ𝑖 𝐶𝑝𝑖 𝐹𝐴0 𝐶𝑝0

Part (a) Co-current Heat Exchanger

We are now going to solve the coupled, ordinary differential and explicit equations (E11-3.1),
(E11-3.7), (E11-3.10), (E11-3.11), (E11-3.12), and (E12-1.1), and the appropriate heat-exchange
balance using Polymath. After entering these equations we will enter the parameter values. By
using co-current heat exchange as our Poly- math base case, we only need to change one line in
the program for each of the other three cases and solve for the profiles of X, Xe, T, Ta, and –rA,
and not have to re-enter the program.
For co-current flow, the balance on the heat transfer fluid is (E12-1.2)
𝑑𝑇𝑎 𝑈𝑎 (𝑇 − 𝑇𝑎 )
=
𝑑𝑉 𝑚𝑐 𝐶𝑝𝑐)
with Ta = 310 K at V = 0.
Analysis: Part (a) Co-current Exchange: We note that reactor temperature goes through a
maximum. Near the reactor entrance, the reactant concentrations are high and therefore the
reaction rate is high [c.f. Figure E12-1.1(a)] and Qg > Qr. Conse- quently, the temperature and
conversion increase with increasing reactor volume while Xe decreases because of the increasing
temperature. Eventually, X and Xe come close together (V = 0.95 m3) and the rate becomes very
small as the reaction approaches equilibrium. At this point, the reactant conversion X cannot
increase unless Xe increases. We also note that when the ambient heat-exchanger tempera- ture,
Ta, and the reactor temperature, T, are essentially equal, there is no longer a temperature driving
force to cool the reactor. Consequently, the temperature does not change farther down the reactor,
nor does the equilibrium conversion, which is only a function of temperature.

Part (b) Countercurrent Heat Exchange:

For countercurrent flow, we only need to make two changes in the program. First, multiply the
right-hand side of Equation (E12-1.2) by minus one to obtain
𝑑𝑇𝑎 𝑈𝑎 (𝑇 − 𝑇𝑎 )
= −
𝑑𝑉 𝑚𝑐 𝑐𝑝𝑐
Next, we guess Ta at V = 0 and see if it matches Ta0 at V = 5 m3. If it doesn’t, we guess again. In
this example, we will guess Ta (V = 0) = 340.3 K and see if Ta = Ta0 = 315 K at V = 5 m3.
Analysis: Part (b) Countercurrent Exchange: We note that near the entrance to the reactor, the
coolant temperature is above the reactant entrance temperature. However, as we move down the
reactor, the reaction generates “heat” and the reactor tempera- ture rises above the coolant
temperature. We note that Xe reaches a minimum (corre- sponding to the reactor temperature
maximum) near the entrance to the reactor. At this point (V = 0.5 m3), X cannot increase above
Xe. As we move down the reactor, the reactants are cooled and the reactor temperature decreases
allowing X and Xe to increase. A higher exit conversion, X, and equilibrium conversion, Xe, are
achieved in the countercurrent heat-exchange system than for the co-current system.

Part (c) Constant Ta

For constant Ta, use the Polymath program in part (a), but multiply the right side of Equation
(E12-1.2) by zero in the program, i.e.,
𝑑𝑇𝑎 𝑈𝑎 (𝑇 − 𝑇𝑎 )
= ∗0
𝑑𝑉 𝑚𝑐 𝑐𝑝𝑐
Analysis: Part (c) Constant Ta: When the coolant flow rate is sufficiently large, the coolant
temperature, Ta, will be essentially constant. If the reactor volume is suffi- ciently large, the reactor
temperature will eventually reach the coolant temperature, as is the case here. At this exit
temperature, which is the lowest achieved in this example, the equilibrium conversion, Xe, is the
largest of the four cases studied in this example.
Part (d) Adiabatic Operation
In Example 11-3, we solved for the temperature as a function of conversion and then used that
relationship to calculate k and KC. An easier way is to solve the gen- eral or base case of a heat
exchanger for co-current flow and write the correspond- ing Polymath program. Next, use
Polymath [part (a)], but multiply the parameter Ua by zero, i.e.,
𝑈𝑎 = 5,000 ∗ 0
Analysis: Part (d) Adiabatic Operation. Because there is no cooling, the tempera- ture of this
exothermic reaction will continue to increase down the reactor until equilibrium is reached, X =
Xe = 0.365 at T = 384 K, which is the adiabatic equilib- rium temperature. The profiles for X and
Xe are shown in Figure E12-1.4(b) where one observes that Xe decreases down the reactor because
of the increasing tempera- ture until it becomes equal to the reactor conversion (i.e., X ≡ Xe), which
occurs circa 0.9 m3. There is no change in temperature, X or Xe, after this point because the
reaction rate is virtually zero and thus the remaining reactor volume serves no purpose.
Finally, Figure E12-1.4(c) shows –rA increases as we move down the reactor as the temperature
increases, reaching a maximum and then decreasing until X and Xe approach each other and the
rate becomes virtually zero.

Overall Analysis: This is an extremely important example, as we applied our CRE PFR algorithm
with heat exchange to a reversible exothermic reaction. We analyzed four types of heat-exchanger
operations. We see the countercurrent exchanger gives the highest conversion and adiabatic
operation gives the lowest conversion.