Teknik Reaksi Kimia 2

Oleh:

Anggota Kelompok

Muhammad Fauzi Putra ( )

Muhammad Febryan Caesar (1706038481)
Muhammad Rafi Hayudo (1706985792)
Naufal Azrizal Prasetyo (1706985804)
Sholeh Nur Udin (1706038456)

UNIVERSITAS INDONESIA

DEPOK

2020
PR1-Problem 1:
Biodiesel@MIT is working to convert the waste cooking oils from local dining halls and
restaurants into diesel fuel to run the MIT shuttle buses.

Waste cooking oils can be converted to biodiesel in several ways. One way is by gas phase
pyrolysis:
(RC(O)OCH2)3  (RCH2)3 + 3 CO2

This can be modeled as first-order irreversible reaction with a measured k=5x10-3 min-1 at 150 oC
and a measured Ea =85 kJ/mole.
Pure cooking oil is injected into a hot (T=227 C) reactor at a rate of 2.5 mole/min. At this
temperature all the species are in the vapor phase. The steady-state pressure in the reactor is 10
atm.
a) If the reactor is a CSTR, what reactor volume is required to achieve 90% conversion?
b) If the reactor is a PFR and the pressure drop is negligible, what reactor volume is
required to achieve 90% conversion?
c) If you had a PFR half the volume you computed in part (b), and then fed its output into a
CSTR half the volume you computed in part (a), what would the conversion be? What if
you hooked them up the other way round : the half-size CSTR first and the half-size PFR
afterwards?

Suppose the reaction is carried out in a batch reactor, by filling it with enough cooking oil and
heating rapidly to 227 C, so that when the oil all vaporizes, but before any significant reaction
has occurred, the initial pressure in the reactor will be 2.7 atm.

d) What will the pressure be in the isothermal batch reactor when the reaction has run to
90% conversion?
e) What would the batch reactor volume have to be if we were to process 3600 moles/day (=
2.5 moles/minute) of cooking oil this way? Assume that the batch reactor can be emptied
and refilled very rapidly, and that it is not necessary to clean the reactor between batches.
f) Which reactor (CSTR, PFR, batch) would you recommend be used for this process?
Explain briefly.

Solution:

(RC(O)OCH2)3  (RCH2)3 + 3 CO2

A  B + C

Given :
T0 = 150 oC
FA0 = 2.5 mole/min
X = 0.9
k(T0) = k0 = 5x10-3 min-1
YA0 =1
P =10 atm
Ea = 85 kJ/mole
T0 = 150 oC = 423 K
T = 227 oC = 500 K

First, find k at the reaction temperature using Eq 3-21 from Fogler:

85 kJ /mol 1 1
5 x 10−3 8.314 x10 −3
( −
kJ /(mol . K ) 423 k 500 k
)
¿ xe
min

= 0.206/min

Next, make a stoichiometric table for the flow system (see Table 3-4 in Fogler). This table
applies to both a PFR and CSTR reactor.

Since this is a gas-phase reaction, with a change in the total number of moles, the volumetric
flow rate (v) will not be constant. Simplify Eq 3-41 in Fogler for the steady state (constant P and
T) ideal gas case to:

a) CSTR
The design equation for CSTR volume in terms of conversion is :
 = 1655.36 L

b) PFR
Neglect pressure drop, so v equation is the same as above. The design equation for a PFR
in terms of conversion is

From integration by parts

When x1 = 0, this simplifies to:

Integrating and plugging in numbers gives:

= 323.63 L
c) Now find X in a CSTR/PFR combination for a given V

First: PFR then CSTR, where the volume of each is ½ the volume calculated in parts a
and b.

PFR equation will be the same as derived in part b, but with V = ½ VPFR,b and X = X1:

using goalseek in excel to find X1 , and we get X1= 0.75

A mole balance on the CSTR gives:

Again, solve the above equation using goalseek in excel and we get X2= 0.95

Now: CSTR followed by PFR, where the volume of each is ½ the volume calculated in
parts a and b.
 FA0

FA1, FB1, FC1 FA2, FB2, FC2

X1 X2

CSTR equation will be the same as derived in part a, but with V = ½ VCSTR,a and X = X1:

using goalseek in excel to find X1 , and we get X1= 0.83

A mole balance on the PFR gives

Rearrange, divide by ∆V and take the limit as ∆V approaches zero to get:

Integrate with the limits V = 0 when X = XA1 and V = ½ VPFR,b when X = X2 to get:

From integration by parts

`
 solve the above equation using goalseek in excel and we get X2= 0.93

Now, consider an isothermal batch reactor system with P0 = 2.7 atm. Make a
stoichiometric table for the batch system (see table 3-3 in Fogler)

d) The volume of the batch reactor is fixed, so the change in moles as the reaction proceeds
will cause an increase in P. For an isothermal, constant volume batch reactor (Eq 3-38 in
Fogler, rearranged):

P = P 0(1 + 3X )= 2.7atm(1 + 3( 0.9)) = 9.99atm

e) Want to process 2.5 mol/min of cooking oil in the batch reactor (assume that the down
time between batches is negligible).

Assuming ideal gas

Find treact from design equation for a constant volume batch reactor

Rearrange and integrate:

Plug in numbers to get:

 = 423.94 L

f) Since the characteristic reaction time is on the order of minutes, a flow reactor is
recommended for this process. If minimizing volume is the most important design
criteria, a single PFR is the best choice. If maximizing conversion is the most important
design criteria, the half-size PFR followed by a half-size CSTR is the best choice.

PR2-Problem 3:
Two configurations of CSTRs are contemplated for performing reversible hydrolysis of
compound A to produce compounds B and C. The forward reaction is pseudo-first-order with
respect to A, with rate constant k1= 1.82 x 10-4 s-1. The reverse reaction is second-order with rate
constant k-1 = 4.49 x 10-4 M-1s-1 .
(1) A → B + C; r1 = k1[A]
(2) B + C → A; r2 = k−1[B][C]

The feed is a dilute aqueous solution of A (concentration 0.25 mol/L) at a rate of 0.25 liters per
hour.

Consider the following two configurations:

a) a single 15 liter CSTR.

b) three 5-liter CSTRs in series, with 75% of product species B & C selectively removed
between stages 1 and 2 and between stages 2 and 3, with appropriate adjustment in flow rate;
the volumetric flow rates in the two streams leaving a separator are proportional to the total
number of moles of A, B, and C in each stream. See the separator diagram below.
If q is the volumetric flow rate and F is the molar flow rate, then the separator follows the
relationships:

A full flow diagram is shown below.

Determine the steady-state production of compound B in mol/h for options a) and b).

Solution:

First, consider the 1-reactor case. Draw a diagram of the situation (the control volume).

q0 [A]0 [B]0=[C]0=0 V=15 L

[A] [B] [C]

Define extents of reaction:

ξ&1 = r1V = k1[A]V
&
ξ 2 = r2V = k−1[B][C]V
Steady state A, B, and C material balances give the following equations:

0 = FA0 − FA −ξ&1 +ξ&2

0 = FB0 − FB +ξ&1 −ξ&2

0 = FC0 − FC +ξ&1 −ξ&2

These three equations can be written in terms of only threevariables: [A], [B], and [C]. The
system is fullyspecified. We must solve these equations simultaneously.The algebra is easier if
we combine equations creatively tomake them simpler. When you combine two equations,
youkeep the new equation and only one of the old ones, just as is done in linear algebra.

Notice that :

FB0 = FC0 = 0
Hence, subtracting the B balance equation from the C balance equation gives the result:

FB = FC q0[B]=q0[C]
[B] = [C]

Let this new equation replace the C mole balance.

The equality of concentrations of C and B is true whenever [C]0 and [B]0 are equal. [B]0 has
been intentionally left as a variable so that the same equations derived here will also apply to
the reactors in part b, where [B]0 will not necessarily equal zero.

Adding together the B and A balance gives the following equation:

0 = FA0 − FA + FB0 − FB = q([A]0 − [A] + [B]0 − [B])

Dividing by q0 and solving for [A] we get:

[A] = ([A]0 + [B]0 − [B])

Let this new equation replace the B mole balance.

Now we can write the A balance as a single equation with a single variable, [B] using our two
new equations:
 0 = FA0 − FA −ξ&1 +ξ&2

0 = q0 ([A]0 − [A])− k1V[A] + k−1V[B][C]

0 = q0 ([A]0 −([A]0 + [B]0 − [B]))− k1V ([A]0 + [B]0 − [B])+ k−1V[B][B]

0 = q0[B] − q0[B]0 − k1V[A]0 − k1V[B]0 + k1V[B] + k−1V[B]2

0 = (k−1V )[B] 2 +(q0 + k1V )[B] + (− q0[B]0 − k1V[A]0 − k1V[B]0 )

0 = a[B]2 + b[B] + c

a = (k−1V )

b = (q0 + k1V ) c = (− q0[B]0 − k1V[A]0 − k1V[B]0 )

This quadratic equation in [B] can be solved with the quadratic formula:

Since the coefficient b will always be positive, we know that we have to take the (+) root. The (-)
root will always be negative. Also notice that a is always positive and c is always negative, so
that the descriminant,

(b 2 − 4ac)> 0

is always positive, and both roots are real. Hence, we may write:

Converting all time to hours, we find that for part a

Plugging the values of the coefficients into the quadratic equation, we find:

[B] = 0.172 M

Hence, the desired production rate of B is:

In order to do part b, it is helpful to notice that everything flows from left to right, with no
recycle loops. Hence we can solve each reactor and separator in sequence, and add up the total
B recovery at the end of the process. Also, we could get it from an overall balance (a box
around the entire system) once we knew the final outlet concentration of A.

For simplicity of notation, let the zero subscript refers to the current reactor feed; no subscript
refers to the current reactor output.

Reactor 1
q0=0.25L/h
V=5 L
[A]0=0.25M [A] [B] [C]
[B]0=[C]0=0M

Reactor 1 follows the same relationships as the single reactor system, but with different volume.
Hence the same material balances apply, and the final equation in terms of [B] is once again:
Plugging in the numbers, we find the quadratic coefficients to be:

Plugging the quadratic coefficients into the formula for [B] we find:
[B] = 0.168M

Using our formula for [A] in terms of [B], we find:

[A] = ([A]0 + [B]0 − [B])

[A] = 0.25M + 0 M − 0.168M = 0.082M

Next, we proceed to separator 1, carry forward our inputs, and rename our subscripted variables,
so that they refer to the current separator.
 q1
q0=0.25 L/h
Separator [A]1
[A]0 = 0.082 M
1 [B]1
[B]0=[C]0=0.168 M

q2
[A]2
[B ]2

First, we need to find the flow rate partitioning, then we can calculate the new concentrations
from an A and B balance. (Since the separator treats B and C the same, these concentrations
will continue to be equal in all streams exiting the separator.) The separator equations are:

Hence using the definition of molar flow rate, the knowledge that [B]0 = [C]0, and the above
separator relationships, we find that:

Assuming a constant density liquid phase, we have a volume balance:

Thus, we have recovery of product B at this stage of:

The last things to calculate at this step are the concentrations that are fed to the next reactor.
Using the mole balance on A:

Using the separator relationships for B and C:

Next, we proceed to reactor 2 using the results from separator 1 and rename our variables so they
refer to the current reactor.

Reactor 2
q0=0.100L/h
V=5 L
[A]0=0.205 M [A] [B] [C]
[B]0=[C]0=0.105 M

All the same equations apply with different initial concentrations and flow rates.

The quadratic solution gives:

[B] = 0.204 M
Solving for [A] from the [A]/[B] relationship we find:

[A] = ([A]0 + [B]0 − [B])

[A] = 0.262 M + 0.126 M − 0.243M = 0.145M

These concentrations will be fed to separator 2.

Next, we proceed to separator 2 and rename our subscripted variables.

The flow rate partitioning is given by:

Hence, from the constant density volume balance:

The amount of [B] recovered is:

The concentrations of [A], [B], and [C] into the next reactor are:
Lastly, we rename our concentrations and proceed to reactor 3. We proceed to reactor 3 using the
results from separator 2.

Reactor 3
q0=0.0405L/h
V=5 L
[A]0=0.262 M [A] [B] [C]
[B]0=[C]0=0.126 M

All the same equations apply with different initial concentrations and flow rates.

The quadratic solution gives:

[B] = 0.243M

Solving for [A] from the A/B relationship equation we find:

[A] = ([A]0 + [B]0 − [B])
[A] = 0.262 M + 0.126 M − 0.243M = 0.145M

Since there is no separator, the amount of B recovered on this step is just the amount leaving the
reactor:
Thus the total amount of B recovered by this path is:

Another way to calculate it, and check our consistency, isto calculate the amount of B recovered
from the overall A and B balances around the whole reaction system (any A thatdisappears must
be present as B):

From the agreement of the numbers, it appears that mass wasconserved overall.

Notice that incorporating the selective separation processto remove product along the way, the
amount of B recoveredwas improved with the same total volume of reactor.

Due to the truncation error and numerical rounding, acceptany answers within 2% of these
values.