CENG 3230 Assignment 3

Prob 1 (Individual)

GIVEN

CAo= 0.2 lbmol/ ft3

FBo= 5FAo
kA= 1.2 ft3/ lbmol-hr (at 100oF)
V= 1000 gal
t= 30 days

FIND

a) Exit conversion to produce 4M lb/ yr of DBP

b) How to increase the conversion for the same FAo; conversion after a second 1000-gal
CSTR was connected in series or parallel with the first CSTR
c) CSTR volume to achieve 85% conversion if FAo= 1 lbmol/min
d) PFR volume to achieve 85% conversion
e) Number of 1000-gal reactors operated in batch mode to meet the required production
of 4 M pounds in a 30-day period and the cost of the reactors in the system.

ASSUMPTIONS

1) Well-mixed condition
2) Isothermal
3) Isochoric
4) Steady-state condition for CSTR and PFR
5) The reactants are liquid [v=vo]

EQUATIONS
1) For batch reactor,
𝑑𝑥 −𝑟𝐴 𝑉
=
𝑑𝑡 𝑁𝐴𝑜

2) For CSTR,
𝐹𝐴𝑜 𝑥
𝑉=
−𝑟𝐴

3) For PFR,
 𝑑𝑥 −𝑟𝐴
=
𝑑𝑉 𝐹𝐴𝑜

SOLUTION
a) First, stoichiometric table was made
Let A- MBP, B- n-butanol, C- DBP, D- H2O
A + B → C + D
Initial FAo 5 FAo
Change - FAox - FAox FAox FAox
Final FAo(1-x) FAo(5-x) FAox FAox

The rate equation for the given reaction is

-rA= kCACB
𝐹𝐴 𝐹𝐵
−𝑟𝐴 = 𝑘 [ ] [ ]
𝑣 𝑣
−𝑟𝐴 = 𝑘𝐶𝐴𝑜 (1 − 𝑥)𝐶𝐴𝑜 (5 − 𝑥)
−𝑟𝐴 = 𝑘𝐶𝐴𝑜 2 (1 − 𝑥)(5 − 𝑥)
For a CSTR:
𝐹𝐴𝑜 𝑥 𝐹𝐶
𝑉𝐶𝑆𝑇𝑅 = = 2
−𝑟𝐴 𝑘𝐶𝐴𝑜 (1 − 𝑥)(5 − 𝑥)

𝑙𝑏 1 𝑙𝑏𝑚𝑜𝑙 1 𝑦𝑟 1 𝑑𝑎𝑦 𝑙𝑏 𝑚𝑜𝑙

𝐹𝑐 = 4𝑥 106 𝑥 𝑥 𝑥 = 19.984
𝑦𝑟 278 𝑙𝑏 30 𝑑𝑎𝑦𝑠 24 ℎ𝑟𝑠 ℎ𝑟
3
1 𝑓𝑡
𝑉𝐶𝑆𝑇𝑅 = 1000 𝑔𝑎𝑙 𝑥 = 133. 6898 𝑓𝑡 3
7.48 𝑔𝑎𝑙
𝑙𝑏 𝑚𝑜𝑙
19.984
133.6898 𝑓𝑡 3 = ℎ𝑟
1.2 𝑓𝑡 3 0.2 𝑙𝑏𝑚𝑜𝑙 2
[ ] (1 − 𝑥)(5 − 𝑥)
𝑙𝑏𝑚𝑜𝑙 − ℎ𝑟 𝑓𝑡 3

(1 − 𝑥)(5 − 𝑥) = 3.114175326
x= 0.3328

b) The following can be done to increase the conversion (x):

1) Use higher temperature
2) Use PFR
3) Use greater concentration of B to increase B
4) Use better catalyst

i) If we add another CSTR in parallel, it will neither increase nor decrease the
conversion.
ii) If we add another CSTR in series with the first CSTR,
𝐹𝑐
𝐹𝐴𝑜 = = 60.048 𝑙𝑏𝑚𝑜𝑙/ℎ𝑟
𝑥
𝐹𝐴𝑜 (𝑥2 − 𝑥1 )
𝑉2 =
−𝑟𝐴2
 60.048 𝑙𝑏𝑚𝑜𝑙/ℎ𝑟 (𝑥2 − 0.3328)
133.6898 𝑓𝑡 3 =
1.2 𝑓𝑡 3 0.2 𝑙𝑏𝑚𝑜𝑙 2
[ ] (1 − 𝑥)(5 − 𝑥)
𝑙𝑏𝑚𝑜𝑙 − ℎ𝑟 𝑓𝑡 3

𝒙𝟐 = 𝟎.5479

c) Recall for CSTR,

𝐹𝐴𝑜 𝑥
𝑉𝐶𝑆𝑇𝑅 =
−𝑟𝐴
1 𝑙𝑏𝑚𝑜𝑙 60 𝑚𝑖𝑛 𝑙𝑏𝑚𝑜𝑙
𝐹𝐴𝑜 = 𝑥 = 60
𝑚𝑖𝑛 1 ℎ𝑟 ℎ𝑟

𝑙𝑏𝑚𝑜𝑙
60 (0.85)
𝑉𝐶𝑆𝑇𝑅 = ℎ𝑟 = 𝟏𝟕𝟎𝟔. 𝟖𝟑 𝒇𝒕𝟑
3 2
1.2 𝑓𝑡 0.2 𝑙𝑏𝑚𝑜𝑙
[ ] (1 − 0.85)(5 − 0.85)
𝑙𝑏𝑚𝑜𝑙 − ℎ𝑟 𝑓𝑡 3

d) For PFR,
𝑑𝑥 −𝑟𝐴
=
𝑑𝑉 𝐹𝐴𝑜
𝐹𝐴𝑜 𝑑𝑥
∫ = ∫ 𝑑𝑉
−𝑟𝐴
0.85
𝑙𝑏𝑚𝑜𝑙 𝑑𝑥
𝑉𝑃𝐹𝑅 = 60 𝑥 ∫ 2 = 𝟓𝟑𝟒. 𝟔𝟐𝟐 𝒇𝒕𝟑
ℎ𝑟 0 1.2 𝑓𝑡 3 0.2 𝑙𝑏𝑚𝑜𝑙
[ ] (1 − 𝑥)(5 − 𝑥)
𝑙𝑏𝑚𝑜𝑙 − ℎ𝑟 𝑓𝑡 3

e) For batch reactor,

𝑑𝑥 −𝑟𝐴 𝑉
=
𝑑𝑡 𝑁𝐴𝑜
𝑥 𝑥
𝑑𝑥 𝑁𝐴𝑜 𝑑𝑥
𝑡 = 𝑁𝐴𝑜 𝑥 ∫ = 𝑥 ∫ 2
0 −𝑟𝐴 𝑉 𝑉 0 𝑘𝐶𝐴𝑜 (1 − 𝑥)(5 − 𝑥)

1 1 5−𝑥
𝑡= ln ( )
𝑘𝐶𝐴𝑜 5 − 1 5 − 5𝑥
The expression of product per day of each reactor can be written as:

𝑙𝑏𝑚𝑜𝑙
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑁𝐴𝑜 (𝑥)(24 ℎ𝑟𝑠) 133.7 𝑓𝑡 3 (0.2 )(𝑥)(24 ℎ𝑟𝑠)
𝑓𝑡 3
= =
𝑟𝑒𝑎𝑐𝑡𝑜𝑟 − 𝑑𝑎𝑦 𝑡𝑟𝑥𝑛 + 3 1 1 5−𝑥
ln ( )+3
𝑘𝐶𝐴𝑜 4 5 − 5𝑥

The amount of mole product per day is expressed as

4 𝑥 106 𝑙𝑏𝑠 1 𝑙𝑏𝑚𝑜𝑙 𝑚𝑜𝑙
𝑥 = 479.6163
30 𝑑𝑎𝑦𝑠 278 𝑙𝑏𝑠 𝑑𝑎𝑦
The number of reactors can be determined by dividing the amount of mole product per day
and the product per day of each reactor.
𝑚𝑜𝑙
479.6163
𝑑𝑎𝑦
𝑛=
641.76(𝑥)
5−𝑥
1.0416667 (ln ( )) + 3
5 − 5𝑥

Plotting n vs. x,

Number of reactors vs. conversion

250
Number of reactors vs. conversion
200 6
No. of reactors

4
No. of reactors

150
2
0
100 0.6 0.7 0.8 0.9 1
conversion (x)
50

0
0 0.2 0.4 0.6 0.8 1
conversion (x)

The minimum appears in x=0.82, and the number of reactors is at 4.12. Thus, five (5) reactors
will be needed to meet the production of 4M pounds in 30-day period.
Prob 2 (Group/Pair)

GIVEN
REACTOR
L [mm] 20
d [micrometer] 500
T [K] 393.15
kA [m6 / (mol-s-kg catalyst)] 0.004
W_catalyst (kg) 0.0000035
FAO [mol / s] 0.00002
FBO [mol / s] 0.00002
Vo [m3 / s] 0.000000283
PA,O [Pa] 231000

CATALYST PROPERTIES
Dp_catalyst [micrometer] 35
alpha [per kg catalyst] 355000
porosity or void fraction 0.4
density [kg / m3] 7
viscosity [kg / m-s] 0.0000194
Ac [m2] 0.000000196
G [kg / m2-s] 10.1

Chemical Reaction:
𝐶𝑂 + 𝐶𝑙2 → 𝐶𝑂𝐶𝑙2
𝐴+𝐵 →𝐶
−𝑟𝐴 ′ = 𝑘𝐴 𝐶𝐴 𝐶𝐵

FIND
a) Plot of FA, FB, FC, conversion (X), and pressure ratio(p) along the reactor length.
b) Number of microreactors needed in parallel to produce 10,000 kg phosphene/year.
c) The effect on molar flow rates, conversion, and pressure ratio when particle diameter
is halved.
d) The effect on molar flow rates, conversion, and pressure ratio if the reaction is
reversible (Kc=0.4 m3/mol).
e) Advantages and disadvantages of using microreactor instead of conventional packed
bed reactor.
ASSUMPTIONS
1) Steady-state operation
2) Isochoric
3) Isothermal
4) Step size (dW)= 0.000000035 kg (equal to 1/100 of the total catalyst weight)

EQUATION
For a Packed Bed Reactor (mole balance),
𝑑𝐹𝐴
= 𝑟𝐴 ′
𝑑𝑊
 𝑑𝐹𝐵
= 𝑟𝐵 ′
𝑑𝑊
𝑑𝐹𝐶
= 𝑟𝐶 ′
𝑑𝑊
𝑑𝑋
𝐹𝐴𝑂 = −𝑟𝐴 ′
𝑑𝑊
The pressure drop along the length of the PBR for isothermal operation can be determined
using Equation (5-27) in Fogler’s Elements of Chemical Reaction Engineering (5th edition):
𝑑𝑃 −𝛼𝑃𝑜 𝐹𝑇
= [ ]
𝑑𝑊 2𝑝 𝐹𝑇𝑜
where p is the pressure ratio (P/P0).
Looking at the rate law of the reaction with respect to each reactant and product,
−𝑟𝐴 ′ −𝑟𝐵 ′ 𝑟𝐶 ′
= = 𝑤ℎ𝑒𝑟𝑒 𝑎 = 𝑏 = 𝑐 = 1 𝑖𝑛 𝑡ℎ𝑖𝑠 𝑐𝑎𝑠𝑒
𝑎 𝑏 𝑐
𝑟𝐵 ′ = 𝑟𝐴 ′ 𝑎𝑛𝑑 𝑟𝐶 ′ = −𝑟𝐴 ′
The change in molar flow rates for B and C may then be expressed in terms of r A’.
𝑑𝐹𝐵
= 𝑟𝐵 ′ = 𝑟𝐴 ′
𝑑𝑊
𝑑𝐹𝐶
= 𝑟𝐶 ′ = −𝑟𝐴 ′
𝑑𝑊

SOLUTION
a) The change in conversion, molar flow rates, and pressure along the length of the
microreactor can be determined using the equations above. The concentrations of A
and B can be expressed as
𝐹𝐴 𝑃 𝐹𝐴
𝐶𝐴 = 𝐶𝑇𝑜 = 𝐶𝑇𝑜 𝑝
𝐹𝑇 𝑃𝑜 𝐹𝑇
𝐹𝐵 𝑃 𝐹𝐵
𝐶𝐵 = 𝐶𝑇𝑜 = 𝐶𝑇𝑜 𝑝
𝐹𝑇 𝑃𝑜 𝐹𝑇

Substituting these to the mole balance equation,

𝑑𝑋 𝐹𝐴 𝐹𝐵
𝐹𝐴𝑂 = −𝑟𝐴 ′ = 𝑘𝐴 𝐶𝐴 𝐶𝐵 = 𝑘𝐴 𝐶𝑇𝑜 2 2 𝑝2
𝑑𝑊 𝐹𝑇
2
𝑑𝑋 𝑘𝐴 𝐶𝑇𝑜 𝐹𝐴 𝐹𝐵 2
= 𝑝
𝑑𝑊 𝐹𝐴𝑂 𝐹𝑇 2
For the molar flow rate,
𝑑𝐹𝐴 𝐹𝐴 𝐹𝐵
= −𝑘𝐴 𝐶𝑇𝑜 2 2 𝑝2
𝑑𝑊 𝐹𝑇

𝑑𝐹𝐵 𝐹𝐴 𝐹𝐵
= −𝑘𝐴 𝐶𝑇𝑜 2 2 𝑝2
𝑑𝑊 𝐹𝑇

𝑑𝐹𝐶 𝐹𝐴 𝐹𝐵 2
= 𝑘𝐴 𝐶𝑇𝑜 2 𝑝
𝑑𝑊 𝐹𝑇 2

And lastly for the pressure drop,

 𝑑𝑃 −𝛼𝑃𝑜 𝐹𝑇
= [ ]
𝑑𝑊 2𝑝 𝐹𝑇𝑜
These substituted ODEs will be used in calculating for the flow rates, pressure drop, and
conversion along the reactor.
It is important to note that:
• Not all reactants are consumed since conversion at the end of the reactor
length is 0.7896.
• The graph of FA is behind FB since the stoichiometric ratio is just 1:1, and the
reactor feed is equimolar in terms of A and B, hence the same plot profile.

b) To determine how many microreactors is needed, the amount of phosphene that each
microreactor can yield was already calculated from (a). The molar flow rate of
phosphene at the end of reactor length is 1.57916 x 10-5 mol/s.

Converting the required production to mol/s,

𝑘𝑔 1 𝑘𝑚𝑜𝑙 1000 𝑚𝑜𝑙 1 𝑦𝑟 1 𝑑𝑎𝑦 1 ℎ𝑟 𝑚𝑜𝑙
10,000 𝑥 𝑥 𝑥 𝑥 𝑥 = 0.003205924
𝑦𝑟 98.91 𝑘𝑔 1 𝑘𝑚𝑜𝑙 365 𝑑𝑎𝑦𝑠 24 ℎ𝑟 3600 𝑠 𝑠

Therefore,
𝑚𝑜𝑙
0.003205924 𝑠 = 203.0143986 𝑚𝑖𝑐𝑟𝑜𝑟𝑒𝑎𝑐𝑡𝑜𝑟𝑠
𝑚𝑜𝑙
1.57916 𝑥 10−5 𝑠 − 𝑚𝑖𝑐𝑟𝑜𝑟𝑒𝑎𝑐𝑡𝑜𝑟
≈ 204 𝑚𝑖𝑐𝑟𝑜𝑟𝑒𝑎𝑐𝑡𝑜𝑟𝑠

c) The conversion, molar flow rates, and pressure ratio will be affected if the particle
diameter is halved since based on the Ergun equation, it will affect the change in
pressure through the reactor length. If the pressure drop (dP) changes, pressure ratio
will change also and eventually, it will also affect the conversion and molar flow rates
since both have pressure ratio (p) in their respective equations.

Recalling Ergun equation,

The first term inside the closed bracket is dominant if laminar flow, while the second term is
dominant if turbulent flow. The Reynolds number in the reactor was calculated and it was
found that the flow inside is laminar.

𝑘𝑔
𝐷𝐺 (500 × 10−6 𝑚) (10.1 2 )
𝑚 −𝑠
𝑅𝑒 = = = 260.31 < 2100
𝜇 𝑘𝑔
0.0000194 𝑚 − 𝑠

Hence, the 2nd term can be cancelled out and since the reaction is also isothermal, the
equation above can be simplified as

𝑑𝑃 𝐺(1 − 𝜙) 150(1 − 𝜙)𝜇 𝐹𝑇

= − [ ] 𝑝
𝑑𝑧 𝜌𝐷𝑝 𝜙 3 𝐷𝑝 𝐹𝑇0

𝐺(1 − 𝜙) 150(1 − 𝜙)𝜇 150𝐺𝜇(1 − 𝜙)2

𝛽0 = [ ]=
𝜌𝐷𝑝 𝜙 3 𝐷𝑝 𝜌𝐷𝑝 2 𝜙 3

In addition, the change in pressure through the reactor length depends on the value of alpha
expression for alpha (a) is given as
2𝛽0
𝛼=
𝐴𝑐 (1 − 𝜙)𝜌𝑃0

With these, if the particle diameter (Dp) is halved, beta will increase by a factor of 4. This will
also increase the value of alpha by a factor of 4.

If this happens, the value of alpha is large enough, and it will cause a large drop in pressure
to the flow. The given flow does not have enough pressure to overcome such high pressure
drop. Thus, it will not reach the end of the reactor length and the catalyst inside the
microreactor will not be fully utilized. The threshold value of the alpha for this given problem
is around 500,000 / kg catalyst. Beyond this value, the pressure drop would be too large for
the system.

Using the given properties of the catalyst, the alpha value was calculated to be 647,060 / kg
catalyst which is already around twice the given alpha value. Assuming all other catalyst
properties are constant aside from the catalyst diameter, back-solving the original catalyst
diameter for the alpha value of 355,000 / kg catalyst gives a catalyst diameter of 49.8
micrometers. Halving this value still provides a large pressure drop for the system.

Taking the case wherein the catalyst diameter is 95% of the original value which still falls
under the threshold value of alpha, the following plots have been generated.
The general trend of the plots remained the same. Comparing the two cases by
superimposition, the following plots below were obtained.

From the plots, it is seen that decreasing the particle size has a greater effect on the pressure
ratio compared to the conversion. A 5% decrease in catalyst size is enough to give a noticeable
change in pressure ratio.

d) If the reaction is reversible, the reaction rate expression will be

𝐶𝐶
−𝑟𝐴 ′ = 𝑘 [𝐶𝐴 𝐶𝐵 − ]
𝐾𝑐

𝐹𝐶 𝑃 𝐹𝐶
𝐶𝐶 = 𝐶𝑇𝑜 = 𝐶𝑇𝑜 𝑝
𝐹𝑇 𝑃𝑜 𝐹𝑇

Thus, the expression for the change in conversion and molar flow rate will also change. Only
the expression for change in pressure will not change.
𝑑𝑋 𝑘𝐴 𝐶𝑇𝑜 2 𝐹𝐴 𝐹𝐵 2 𝐶𝑇𝑜 𝐹𝐶
= [ 𝑝 − 𝑝]
𝑑𝑊 𝐹𝐴𝑂 𝐹𝑇 2 𝐹𝑇 𝐾𝐶
 𝑑𝐹𝐴 𝐶𝑇𝑜 2 𝐹𝐴 𝐹𝐵 2 𝐶𝑇𝑜 𝐹𝐶
= −𝑘𝐴 [ 𝑝 − 𝑝]
𝑑𝑊 𝐹𝑇 2 𝐹𝑇 𝐾𝐶

𝑑𝐹𝐵 𝐶𝑇𝑜 2 𝐹𝐴 𝐹𝐵 2 𝐶𝑇𝑜 𝐹𝐶

= −𝑘𝐴 [ 𝑝 − 𝑝]
𝑑𝑊 𝐹𝑇 2 𝐹𝑇 𝐾𝐶

𝑑𝐹𝐶 𝐶𝑇𝑜 2 𝐹𝐴 𝐹𝐵 2 𝐶𝑇𝑜 𝐹𝐶

= 𝑘𝐴 [ 𝑝 − 𝑝]
𝑑𝑊 𝐹𝑇 2 𝐹𝑇 𝐾𝐶

𝑑𝑃 −𝛼𝑃𝑜 𝐹𝑇
= [ ]
𝑑𝑊 2𝑝 𝐹𝑇𝑜
The following plots were generated:
The graphs retained the same shape as that of the irreversible reaction in item A. By
superimposing the individual graphs of pressure ratio and conversion of the reversible
reaction with those of the irreversible reaction, the following plots below were obtained.
From these, the pressure ratio difference is almost negligible with the reversible reaction
gaining a slightly larger drop in pressure. Since the reaction became reversible, it is expected
that conversion decreased since some of the products are also consumed to produce the
reactant. From 0.790, the final conversion became 0.746. The rate law has a greater effect on
the conversion rather than the pressure drop.

e) Microreactors can have precise and uniform reaction variables like temperature and
pressure since it is just small and compared to conventional packed bed reactor, it is
more space efficient.

On the other hand, reactor clogging is more likely to occur in microreactors and it has limited
reaction time range.