HOMEWORK 1 ENGINEERING OF CHEMICAL REACTIONS

DIANA SOFIA FRANCO ALVAREZ

JUAN DAVID GALLO ZAPATA
RONALDO ANDRES PASCUALES CENTENO

UNIVERSITY OF ANTIOQUIA
FACULTY OF ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING

MEDELLÍN-ANTIOQUIA
2019
1. (28%) The exothermic reaction

𝐴→𝐵 +𝐶 Reaction 1

was performed adiabatically and the data given in Table 1 were obtained.

Table 1
Data of conversion and reaction rate for Reaction 1

X 0 0.15 0.3 0.4 0.5 0.6 0.75 0.9

-rA (mol/(dm3 min) 2 2.71 4.21 6.67 6.67 6.67 4.14 3

If several types of reactors must be designed with a feed molar flow rate of A of 300 mol/min:

a. (3%) What are the volumes of PFR and CSTR necessary to achieve a 40% conversion?
b. (3%) At what conversion interval would the CSTR and PFR volumes be identical? And
what is that volume?
c. (3%) What is the maximum conversion that can be achieved in a CSTR of 10.5 dm3?
d. (4%) What conversion can be achieved if a PFR of 39 dm3 is followed in series by a CSTR
of 18 dm3?
e. (4%) What conversion can be achieved if there is a 18 dm3 CSTR followed in series by a
39 dm3 PFR?
f. (6%) Plot the conversion and reaction rate as a function of the volume of a 70 dm3 PFR.
g. (5%) Analyze the answers obtained in the solution of this exercise (better arrangement,
variation of the conversion with the type of reactor, how to obtain greater conversion with
the smaller volume).

2. (38%) In a plug flow reactor, the Reaction 2 is carried out in the gas phase at constant
temperature, the reactor is made up of a pipe of nominal diameter 32 in with Sch 40 and 40
ft of length. The reaction rate is shown in Equation 1, where k = 7.43x10-3.

𝐴→𝐵 Reaction 2

𝑟 = 𝑘√𝐶𝐴 Equation 1

a. (2%) Determine the units of k if r is given in lbmol/(ft3.min).

b. (5%) Calculate the volume of the tubular reactor and the maximum conversion reached by
the reactor.
c. (3%) Calculate the maximum conversion in a CSTR with the same volume.
d. (3%) Calculate the dimensions of a CSTR to obtain the same conversion as in the tubular
reactor. Consider an L/D ratio of 1.2.
e. (8%) What happens (with respect to part b) if the experiment cannot be carried out in a
pipeline of nominal diameter 32 in but in a 26 in (Sch 20 XS) or 20 in (Sch 20 STD) in
pipeline with a length of 60 and 80 ft in length, respectively? Conclude from your results.
 f. (5%) Propose the arrangement of CSTR and PFR that occupies the lowest volume, to obtain
a conversion of 90%.
g. (12%) Perform all previous calculations if the reaction order is 1 with k equal to 9.1x10-4
s-1.

Additional data:
At initial conditions A is a fluid that is governed by the power law (Ostwald-de Waele's
model) with the following properties:
μ: viscosity of 81.49 μP
υ: stirring rate of 240 rpm
Re: Reynolds number of 12875
f: friction factor of 0.006451
ρ: density of 157 mol/m3
PM: molecular weight of 58 g/mol
Assume that the process is carried out at constant pressure and temperature and the rheology
of A does not change with the length. Consider n = n’.

3. (17%) The reaction rate law (in mol L-1 h-1) of the Reaction 3 can be represented with
Equation 2:

2𝐴 → 3𝐵 + 𝐶 Reaction 3

𝐾 √𝐶𝐴
1
𝑟 = 1+𝐾 Equation 2
2 𝐶𝐴

a. (4%) If the concentration is expressed in molarity (mol/L) and the reaction rate units are
mol/L.h, what are the units of k1 and k2?
b. (13%) Determine the PFR, CSTR or combination of reactors that give the minimum total
volume to achieve a conversion of 98%.
Additional information:
k1 =13
k2 = 19
FA0 = 2 mol/min
CA0 = 0.4 M

4. (14%) Make a list of different kinds of reactors, include the main uses, characteristics,
advantages and disadvantages, as well as examples of their use in Colombia, if available.

5. (3%) Order, clarity, presentation and writing of the information provided in the
development of the homework.
 BRIEF INTRODUCTION - DEMONSTRATION EQUATIONS TO USE

This balance is expressed as Input - Output + Generation = Accumulation, obtaining equation 3, where
Nj is the number of moles of species j in the system at time t. The generation term can be found as
shown in equation 4, where rj is the reaction rate of species j and 𝑉 is volume.

𝑑𝑁𝑗
𝐹𝑗0 − 𝐹𝑗 + 𝐺𝑗 = Equation 3
𝑑𝑡

𝐺𝑗 = 𝑟𝑗 𝑉 Equation 4

Equation 4 is applicable when all system variables are uniform in the volume of the system. If the
rate of formation of species j varies with position i, equations 5 and 6 are applied.

𝐺𝑗 = ∑𝑀
𝑖=1 𝑟𝑖𝑗 ∆𝑉𝑖 Equation 5
𝑣
𝐺𝑗 = ∫0 𝑟𝑗 𝑑𝑉 Equation 6

In this way, the balance of moles for species j is equation 7.

v dNj
Fj0 − F𝑗 + ∫0 rj dV = Equation 7
dt

Design equation for a batch reactor.

Figure 1 Batch Reactor.

For this type of reactor, the following considerations are taken into account:

- It assumes calculation based of 1 L for the system.

- System closed (𝐹𝑗0 = 𝐹𝑗 = 0).
- Not stationary state.
- Reactions in liquid or gas phase.
- V or P constant.
- It assumes good agitation, homogeneous temperature and concentration in the reactor
v
(∫0 rj dV = rj V).
- Design parameter is time.

The equation of balance of moles is then reduced to equation 8 and expressing it in terms of the limit
reagent (A) equation 9 is obtained.

𝑑𝑁𝑗
𝑟𝑗 𝑉 = Equation 8
𝑑𝑡
𝑑𝑁𝐴
𝑟𝐴 𝑉 = Equation 9
𝑑𝑡

When applying the definition of conversion shown in equation 10, we find equations 11, 12, 13 and
14.

𝑁𝐴0 −𝑁𝐴
𝑋= Equation 10
𝑁𝐴0

𝑑(𝑁𝐴0 −𝑁𝐴0 𝑋)
𝑟𝐴 𝑉 = Equation 11
𝑑𝑡

𝑑𝑋
𝑟𝐴 𝑉 = −𝑁𝐴0 𝑑𝑡 Equation 12

𝑡 𝑋 𝑑𝑋
∫0 𝑑𝑡 = 𝑁𝐴0 ∫0 −𝑟𝐴 𝑉
Equation 13

𝑋 𝑑𝑋
𝑡 = 𝑁𝐴0 ∫0 Equation 14
−𝑟𝐴 𝑉

For a batch reactor of constant volume, equation 9 can be expressed as shown in equation 15 and
therefore equation 14 can be expressed as shown in equation 16. The equation for conversion
𝐶𝐴0 −𝐶𝐴
(equation 10) can also be expressed as 𝑋 = , in the case of having a constant volume.
𝐶𝐴0

𝑑(𝑁𝐴 /𝑉) 𝑑𝐶𝐴

𝑟𝐴 = = Equation 15
𝑑𝑡 𝑑𝑡
𝑋 𝑑𝑋
𝑡 = 𝐶𝐴0 ∫0 Equation 16
−𝑟𝐴
Design equation for a CSTR reactor.

Figure 2 CSTR reactor.

For this type of reactor, the following considerations are taken into account:
- Open system.
- Stationary state.
dN
- There is no accumulation ( dtj=0).
- Good agitation, identical temperature and concentration throughout the interior of the reactor and
v
at the outlet of this (∫0 rj dV = rj V).
- Design parameter is the volume.

The equation of balance of moles is then reduced to equation 17, from which the volume is cleared
(equation 18).
Fj0 − F𝑗 + rj V = 0 Equation 17

Fj0 − F𝑗
𝑉= Equation 18
−rj

Expressing the conversion in terms of the molar flows of j to the input and output equation 19 is
obtained, it is cleared from this Fj0 − Fj and it is replaced in equation 18 obtaining equation 20.
Fj0 − Fj
𝑋= Equation 19
Fj0

Fj0 𝑋
𝑉= Equation 20
−rj

Equation 20 is the design equation of a CSTR reactor in terms of the conversion.

Design equation for a PFR reactor.

Figure 3 PFR reactor.

For this type of reactor, the following considerations are taken into account:
- Open system.
- Stationary state.
- Highly turbulent flow.
- The concentration varies continuously in the axial direction.
dN
- There is no accumulation ( dtj=0).
- The reactor is divided into several subvolumes for analysis. ∆𝑉 = 𝐴(∆𝑦), where A is the cross-
sectional area of the reactor, which is constant.

The equation of balance of moles is then reduced to equation 21. In equations 22, 23 and 24 the
differential analysis that is made to the system is shown.

v
Fj0 − F𝑗 + ∫0 rj dV = 0 Equation 21

𝑉
Fj |𝑦 − Fj |𝑦+∆𝑦 + ∫0 𝑟𝑗 𝑑𝑉 = 0 Equation 22

Fj |𝑦 − Fj |𝑦+∆𝑦 𝑟𝑗 𝐴∆𝑦
lim + =0 Equation 23
∆𝑦→0 ∆𝑦 ∆𝑦

𝑑𝐹𝑗
= 𝑟𝑗 Equation 24
𝑑𝑉

Separating variables and integrating with respect to volume, we obtain equation 25, which is the
design equation for this reactor.

𝑑𝐹𝑗
𝑉=∫ Equation 25
𝑟𝑗
This design equation can be expressed in terms of the conversion using equation 24 and clearing Fj
from the definition of conversion. The equation obtained is 26, and separating variables and
integrating, equation 27 is obtained.

𝑑𝑋
𝐹𝑗0 𝑑𝑉 = −𝑟𝑗 Equation 26

𝑋 𝑑𝑋
𝑉 = 𝐹𝑗0 ∫0 Equation 27
−𝑟𝑗

Equations for space time.

Space time 𝜏, average residence time or retention time is defined by equation 28.

𝑉
𝜏=𝑣 Equation 28
0

For a CSTR reactor: it is divided by 𝑣0 both sides of equation 20 and equations 29 and 30 are
obtained.
𝑉 𝐹𝐴0 𝑋
= ∗ −𝑟 Equation 29
𝑣0 𝑣0 𝐴

𝐶𝐴0 𝑋
𝜏= Equation 30
−𝑟𝐴

For a PFR reactor: equation 26 multiplies by 𝑣0 on both sides, obtaining equations 31 and 32.
𝑑𝑋 𝑟
𝑣0 𝑑𝑉 = − 𝐹 𝐴 𝑣0 Equation 31
𝐴0

𝑑𝑋 −𝑟𝐴
= Equation 32
𝑑𝜏 𝐶𝐴0
 SOLUTION

1. From the data reported in Table 1, the parameters 𝑟𝐴 , 1⁄−𝑟𝐴 data are obtained, as well as the
volume for a CSTR and PFR (see Table 2), using equation 20 and 27 respectively; which will be
necessary for the resolution of each of the proposed items.

Table 2
Reaction rate and volume for a CSTR and PFR.

rA 1/-rA CSTR PFR

3
X (mol/(dm3 min) 1/ (mol/(dm min)) (L) (L)
0 2 0,50 0,00 0,00
0,15 2,71 0,37 16,61 19,55
0,3 4,21 0,24 21,38 33,19
0,4 6,67 0,15 17,99 39,00
0,5 6,67 0,15 22,49 48,74
0,6 6,67 0,15 26,99 58,49
0,75 4,14 0,24 54,35 83,42
0,9 3 0,33 90,00 112,50

a. CSTR

The design equation for a CSTR in terms of the conversion is reduced to equation 20, expressing it
in terms of the limit reagent (A), equation 1.1 is obtained.

𝐹𝐴𝑜 𝑋
𝑉= 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1.1
−𝑟𝐴

The problem indicates that the feed flow rate of component A is 300 mol /min, in addition to this it
is desired to find the volume necessary for a conversion of 40%. With this conversion value, Table
2 is entered and the factor of −𝑟𝐴 is read. Each of these values is replaced in equation 1.1 and
obtained,

𝑚𝑜𝑙
300 𝑚𝑖𝑛𝑢𝑡𝑜 × 0,4
𝑉=
𝑚𝑜𝑙
6,67 𝐿𝑚𝑖𝑛𝑢𝑡𝑜

𝑉 = 17,99𝐿

- PFR

The design equation for a PFR in terms of the conversion is reduced to equation 27, expressing it in
terms of the limit reagent (A), equation 1.2 is obtained.
𝑥
1
𝑉 = 𝐹𝐴𝑜 ∫ 𝑑𝑥 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1.2
0 −𝑟𝐴

1
Since the term −𝑟 𝑑𝑥 varies point to point, it is necessary to use an alternative mathematical model
𝐴
to solve the integral, for this case it was determined to use the numerical method of the trapeze,
represented by equation 1.3.

𝑏
(𝑏 − 𝑎)
∫ 𝑓(𝑥)𝑑𝑥 = [𝑓(𝑎) + 𝑓(𝑏)] 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 1.3
𝑎 2

1
From Table 2 the values of 0,5 and 0,15 are read, represented by the parameter −𝑟 for a conversion
𝐴
of 0 and 0,4 respectively; each of these values is replaced in equation 1.3, with the aim of obtaining
the volume that a PFR can reach with a conversion of 40%.

𝑚𝑜𝑙 0,4 − 0 𝐿𝑚𝑖𝑛𝑢𝑡𝑜

𝑉 = 300 [( ) (0,5 + 0,15) ]
𝑚𝑖𝑛𝑢𝑡𝑜 2 𝑚𝑜𝑙

𝑉 = 39𝐿

b. To determine the conversion intervals at which the CSTR and PFR volumes would be
1
identical, initially the conversion parameter (X) vs. −𝑟 is plotted from Table 2, the
𝐴
representation obtained is approximated to one line of trend of degree 2 (see graph 1)

X vs 1/-rA
0.6
0.5 y = 1.3106x2 - 1.3786x + 0.5173
R² = 0.9759
0.4
1/-rA

0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
X

Graph 1 X vs 1/-rA.
From graph 1, it can be seen that in the conversion range of 0.4 to 0.6, the volumes of the CSTR and
PFR are identical, this is because the reaction rate is constant in this conversion interval.

To obtain the volume of the conversion interval analytically, the design equation of a PFR is used
(equation 27)

𝐹𝐴𝑜 (𝑋2 − 𝑋1 )
𝑉= 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 27.1
−𝑟𝐴

𝑚𝑜𝑙
300 𝑚𝑖𝑛 × (0,6 − 0,4)
𝑉=
𝑚𝑜𝑙
6,67
𝐿𝑚𝑖𝑛

𝑉 = 8,99𝐿

c. From Table 2, the values reported in Table 3 are extracted, with which an interpolation is
performed with a volume of 10.5 L for a CSTR, in order to determine the maximum
conversion with respect to this volume.

Table 3
Conversion and volume of a CSTR.

X CSTR (L)
0 0
0,15 16,6

The maximum conversion value obtained is 𝑋 = 0,095

d. Error! Reference source not found. shows the arrangement of a PFR and a CSTR in series
with the corresponding nomenclature.
V1 = 39 L
FA1, CA1, VO, X1
FAO
CAO
VO
V2 = 18 L

FA, CA, VO, X2

Figure 4 PFR and CSTR in series.

From literal (a) it is known that for a PFR volume of 39 𝐿 the conversion is 𝑋 = 0,4.

𝐹𝐴𝑂 ((𝑋2 − 𝑋1 )
𝑉𝐶𝑆𝑇𝑅 =
−𝑟𝐴 ⃒𝑋2

𝑋2 − 0,4 𝑉𝐶𝑆𝑇𝑅
= = 0,06
𝐹𝐴𝑂
−𝑟𝐴 ⃒𝑋2

Assuming 𝑋2 = 0,6 → −𝑟𝐴 ⃒𝑋2 = 6,67

𝑉𝐶𝑆𝑇𝑅 0,6 − 0,4

= = 0,029
𝐹𝐴𝑂 6,67

Assuming 𝑋2 = 0,8 → −𝑟𝐴 ⃒𝑋2 = 3,76

𝑉𝐶𝑆𝑇𝑅 0,8 − 0,4

= = 0,106
𝐹𝐴𝑂 3,76

Assuming 𝑋2 = 0,71 → −𝑟𝐴 ⃒𝑋2 = 4,81

𝑉𝐶𝑆𝑇𝑅 0,71 − 0,4

= = 0,06
𝐹𝐴𝑂 4,81

After performing the mathematical procedure, the result is

𝑋2 ≅ 0,71

e. Error! Reference source not found. shows the arrangement of a CSTR and a PFR in
series with the corresponding nomenclature.
FA1
FAO CA1
CAO VO
VO X1

FA, CA, VO, X2

Figure 5 CSTR and PFR in series.

From literal (a) it is known that for a CSTR of volume18 𝐿, the conversion 𝑋1 = 0,4
From the design equation of a PFR (equation 27), we obtain:
𝑋2
1
𝑉𝑃𝐹𝑅 = 𝐹𝐴𝑂 ∫ 𝑑𝑥
𝑋1 −𝑟𝐴

𝑋2 − 𝑋1 1 1
𝑉𝑃𝐹𝑅 = 𝐹𝐴𝑂 [( )[ │𝑋1 + │𝑋 ]]
2 −𝑟𝐴 −𝑟𝐴 2

𝑉𝑃𝐹𝑅 𝑋2 − 𝑋1 1 1
= [( )[ │𝑋1 + │𝑋 ]]
𝐹𝐴𝑂 2 −𝑟𝐴 −𝑟𝐴 2

Now, each of the data is replaced

39 𝑋2 − 0,4 1
= [( ) [0,1499 + │𝑋 ]]
300 2 −𝑟𝐴 2

𝑋2 − 0,4 1
0,13 = [( ) [0,1499 + │𝑋 ]]
2 −𝑟𝐴 2
1
Assuming 𝑋2 = 0,75 → −𝑟 │𝑋2 = 0,2415
𝐴

𝑉𝑃𝐹𝑅 0,75 − 0,4

= [( ) [0,1499 + 0,2415]] = 0,068
𝐹𝐴𝑂 2
1
Assuming 𝑋2 = 0,9 → −𝑟 │𝑋2 = 0,3333
𝐴

𝑉𝑃𝐹𝑅 0,9 − 0,4

= [( ) [0,1499 + 0,2415]] = 0,1208
𝐹𝐴𝑂 2

1
Assuming 𝑋2 = 0,98 → −𝑟 │𝑋2 = 0,3818
𝐴

𝑉𝑃𝐹𝑅 0,98 − 0,4

= [( ) [0,1499 + 0,3818]] = 0,15
𝐹𝐴𝑂 2

1
Assuming 𝑋2 = 0,93 → −𝑟 │𝑋2 = 0,3516
𝐴
 𝑉𝑃𝐹𝑅 0,93 − 0,4
= [( ) [0,1499 + 0,3516]] = 0,13
𝐹𝐴𝑂 2

The conversion achieved is, 𝑋2 ≅ 0,93

f. From Table 2, the values reported in Table 4 for a PFR are extracted, in order to
determine the conversion obtained with a volume of 70 L.

Table 4
Conversion and volume of a PFR.

X PFR (L)
0,6 58,49
0,75 83,42

The conversion is obtained is 𝑋 = 0,67

Subsequently, an interpolation is performed to determine the reaction rate (see Table 5)
Table 5
rA and volume of a PFR.

rA PFR (L)
6,67 58,49
4,14 83,42

With the conversion value and reaction rate obtained above, the limits for a volume of 70 L
are determined, in
Table 6 they report this data as well as those obtained in Table 2.

Table 6
Conversion, volume and rA for a PFR

X PFR (L) rA
0 0,00 2
0,15 19,55 2,71
0,3 33,19 4,21
0,4 39,00 6,67
0,5 48,74 6,67
0,6 58,49 6,67
 0,67 70,00 5,5

From Table 6, two graphs are generated, the first representing the conversion and the second
the reaction rate, both in terms of a fixed volume of 70 L.

Conversión (X) vs Volume (L)

0.8
0.7
0.6
Conversión (X)

0.5
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50 60 70 80
Volumen (L)

Graph 2 X vs Volume (L) for a PFR.

-rA vs Volume (L)

8
7
6
5
-rA

4
3
2
1
0
0 10 20 30 40 50 60 70 80
Volume (L)

Graph 3 -rA vs Volume (L).

g. FALTA ANALIZAR