1 Reactor Sizing and Design

In this section, the procedure to estimate the required catalyst weight to reach the desired
conversion was introduced. In the beginning, mass and heat balance equation were derived, then
an algorithm of 10 steps was followed to estimate the required mass of catalyst, which are:

1) Obtain heat capacities and heat of formation for all reactant entering the reactor.
2) write heat of reaction as a function of temperature.
3) write reaction rate and equilibrium constant as function of temperature.
4) Express partial pressure of all species in the inlet and effluent in term of molar flowrate.
5) Express the rate of reaction in term of molar flowrate.
6) write the net reaction rate for each component in the reaction.
7) Write mole balance equation for each component in the reaction.
8) Write the energy balance equation.
9) Write the Ergun’s equation to account for the pressure drop.
10) Solve the system of equation using ODE solver.

1.1 Mole Balance Equation Derivation

Figure 1: schematic representation of packed bed reactor.

For PBR, overall mole balance equation is:

( Accumulationrate of species i ) =¿
If the system is operating at steady-state condition, there is no accumulation of species i; Hence:
0=Fi ¿w −F i ¿w+ ∆ w +r i ∆ W

By rearranging the equation and taking the limit, the mole balance equation can be written in the
following form:
Fi ¿w +∆ w −F i ¿ w
lim =r i
∆W →0 ∆W

In mathematics, the definition of derivative is:

df f ¿ x+∆ x −f ¿ x
= lim
dx ∆ x → 0 ∆x

Hence:
Fi ¿w +∆ w −F i ¿ w dF net
lim = =r i =∑ (υ ij r j )
∆W →0 ∆W dW

where r j is the generalized reaction rate, and υ ij is the stoichiometric coefficient of species i in
reaction j.

1.2 Energy Balance Equation Derivation

For PBR, overall energy balance equation is:

Rate of energy = Rate of energy − Rate of energy + Rate of heat the system − Rate of work
{ accumulated }{
entering the system }{
leaving the system added
¿
}{ ¿
}{
done by the system }
If adiabatic reactor operating at steady state condition was used, there will be no accumulation of
energy; Thus:

0=∑ Fi ^
Ei ¿W −∑ Fi ^
Ei ¿W + ∆ W + ∑ F i P V
^i ¿ W −∑ F i P V
^i ¿W + ∆ W −W shaft
 E 1
E = , and E=U + m v 2+ mgh. Since kinetic energy, potential energy, and the shaft
Where ^
Fi 2
work are small compared to the other terms in the equation, the equation can be simplified to the
following form:

0=∑ Fi u^ ¿W −∑ Fi u^i ¿W + ∆ W + ∑ F i P V
^i ¿ W −∑ F i P V
^i ¿W + ∆ W

From thermodynamics, it is known that H=U + PV ; Hence:

0=∑ Fi h^i ¿W −∑ Fi h^i ¿W +∆ W

After rearranging the equation, dividing by ∆ W , and taking the limit, the equation can be written
in following:

lim
∑ Fi h^i ¿W +∆ W −∑ Fi h^i ¿W =0
∆W →0 ∆W
Therefore:
d ( Fi h^i )
=0
dW

By performing product rule, we get the following equation:

dF d h^
∑ dWi h^i+∑ Fi dWi =0

d Fi n
From mass balance, =∑ υ r . In addition, from thermodynamics, we know that d h^i=C pi dT
dW j=1 ij j
, Therefore:

n
dT
∑ ∑ (υij r j) h^i +∑ F i C pi dW =0
j=1
 n

∑ ¿¿
j=1

where −Δ H R ( T ) =∑ (υ ij h^i). Hence:

n
dT
=∑ ¿ ¿ ¿
dW j=1

1.3 Reactor Design Algorithm

1) Obtain heat capacities and heat of formation for all reactant entering the reactor.

Heat capacities and heat of formation where obtained from Elementary Principles of Chemical
Engineering by Felder. The values are as following:

kJ
C p ,CO 2=36.11 ×10−3 + 4.233 ×10−5 T −2.887 ×10−8 T 2+ 7.464 ×10−12 T 3
mol ℃
kJ
C p , H 2 =28.84 ×10−3+ 0.00765× 10−5 T −0.3288× 10−8 T 2 +0.8698 ×10−12 T 3
mol ℃
kJ
C p , MeOH =42.93 ×10−3 +8.301× 10−5 T −1.87 ×10−8 T 2+ 8.03× 10−12 T 3
mol ℃
kJ
C p ,CO =28.95 ×10−3+ 0.411× 10−5 T + 0.3548× 10−8 T 2−2.22×10−12 T 3
mol ℃
kJ
C p , H 2 O =33.46 ×10−3 +0.688 × 10−5 T +0.7604 × 10−8 T 2−3.593× 10−12 T 3
mol ℃

kJ
H f ,CO 2=−393.5
mol
kJ
H f , H 2 =0
mol
kJ
H f , MeOH =−201.2
mol
kJ
H f ,CO =−110.52
mol
 kJ
H f , H 2 O =−241.83
mol

2) write heat of reaction as a function of temperature.

T
∆ H R ,1 =∆ H oR ,1 ( T R ) + ∑ υ i∫ C pi dT
25

Where,

∆ H oR ,1 ( T R ) =(−1 × H f ,CO 2−3 × H f , H 2+ 1× H f , MeOH +1× H f ,H 2 O )

∑ υ i∫ C pi dT =−4.1194 ×10−12 T 4 +2.63664 ×10−9 T 3 +2.366525× 10−5 T 2 −0.04624 T +1.14117

25

T
∆ H R ,2 =∆ H oR ,2 ( T R ) + ∑ υ i∫ C pi dT
25

Where

∆ H oR ,2 ( T R ) =(−1× H f ,CO 2−1 × H f , H 2+1 × H f ,CO +1× H f , H 2 O )

∑ υi∫ C pi dT =−3.1018 ×10−12 T 4 +12.2446 × 10−9 T 3 −1.570825× 10−5 T 2−0.00254 T +0.07313

25

3) write reaction rate and equilibrium constant as function of temperature.

k 1=1.07 exp
( 8.314∗40000
( T +273.15 ) )
k 2=3453.38exp ( 0 )

k 3=0.499 exp
( 8.314∗17197
( T + 273.15 ) )
k 4=6.62× 10−11 exp
( 8.314∗124119
( T +273.15 ) )
−98084
k 5=1.22e 10 exp
( 8.314∗( T +273.15 ) )
3066
−10.592
T
K 1=10
2073
−2.029
T
K 2=10

4) Express partial pressure of all species in the inlet and effluent in term of molar flowrate.

F CO2
PCO 2= P
FT
FH 2
PH2= P
FT
F MeOH
P MeOH = P
FT
F CO
PCO = P
FT
FH 2O
PH2O= P
FT

where F T =F CO2 + F H 2 + F MeOH + F CO + F H 2 O

5) Express the rate of reaction in term of molar flowrate.

P MeOH
( )
(( )
k 1 PCO 2 P H 2 1−PH 2 O
K 1 P CO2 P H 23
r 1=
PH 2 O 3
× ( 3600 ) mol
1 kg h
1+ k 2
PH 2
+ k 3 P H 20.5 +k 4 P H 2 O )
 P CO
( )
( )
k 5 P CO2 1−K 2 PH 2 O
PCO 2 P H 2
r 2=
1+ k 2
PH 2 O 0.5
+ k 3 P H 2 +k 4 P H 2 O
× ( 3600 mol
1 ) kg h
PH 2

6) write the net reaction rate for each component in the reaction.
r CO 2=−r 1−r 2
r H 2=−3 r 1−r 2
r MeOH =r 1
r CO =r 2
r H 2O =r 1+ r
7) Write mole balance equation for each component in the reaction.

d F CO2
=r CO 2
dW

d FH 2
=r H 2
dW

d F MeOH
=r MeOH
dW

d F CO
=r CO
dW

d FH 2O
=r H 2O
dW

8) Write the energy balance equation.

dT
=¿ ¿
dW

9) Write the Ergun’s equation to account for the pressure drop

dP
Since the reactor is assumed to be isobaric, no pressure-drop occur; Hence, =0 .
dW

10) Solve the system of equation using ODE solver.

In this work, Polymath was used to solve the system of equations. The results are discussed in
the next section.

2 Results and discussion

Since the reaction rates are complex and the reactor is not isothermal, Hand-calculation of final
flowrates is not practical; Hence, Polymath was used to solve the complex set of differential
equations. The initial values of flowrates and temperature were specified, and the necessary
equations were written explicitly.

2.1 Polymath Results

Figure 80 illustrate the codes used in Polymath to obtain the required weight of catalyst. In
addition, the program provides a summary of the result, as illustrated in Table 61.
 Figure 2: Code used in polymath.

From the results, it is clear that the weight of catalyst required to reach 19.9% conversion of CO2
is 1708 kg. Table 60 comprises between the results obtained from HYSYS and polymath.

Table 1: comparison between results obtained from Polymath and HYSYS.

Polymath Hysys %Error

FCO2 (kmol/h) 1470.108 1470.09 0.001224
FH2 (kmol/h) 8483.513 8487.98 0.052627
FMeOH (kmol/h) 401.05 398.81 0.561671
FCO (kmol/h) 625.81 628.08 0.361419
FH2O (kmol/h) 381.35 381.38 0.007866
X (%) 19.9 19.9 0
T (oC) 279.714 280 0.102143
Table 2: Summary of the results obtained from Polymath.
In addition, the following graphs, which relate molar flowrate and temperature with catalyst
weight, were obtained from the software.

12000

10000
Molar Flowrate (kmol/h)

8000

6000
FCO2
FH2
4000

2000

0
0 200 400 600 800 1000 1200 1400 1600 1800
W (Kg)

Figure 3: graph of reactants molar flowrate vs. catalyst weight.

The graph in Figure 81 shows that molar flowrates of reactants decrease as the weight of the
catalyst increases, which is obvious since the reactants are consumed in the reaction. In addition,
we can see that the reduction of H2 is three times larger than the reduction of CO, which is a
result from the assumption that the second reaction is totally suppressed, and the only contributor
in CO2 conversion is the first reaction.
 700

600

500
Molar Flowrate (kmol/h)

400

FMeOH
300 FCO
FH2O
200

100

0
0 200 400 600 800 1000 1200 1400 1600 1800
W (Kg)

Figure 4: graph of products molar flowrate vs. catalyst weight.

The graph in Figure 82 demonstrates the relationship between molar flowrates of the products
and catalysts weight. Several observations can be noticed. Firstly, CO molar flowrates is
constant. Secondly, both MeOH and H2O have similar kinetics even though H2O produced
through two reaction. Thirdly, the ratio of MeOH to H2O production flowrate is close to 1.
Again, these observations can be attributed to the fact that second chemical reaction was
assumed to be suppressed, which means that no CO is assumed to be produced, and both MeOH
and H2O are produced from the same reaction.
 290

280

270

260
Temperature (oC)

250

240

230

220

210

200
0 20 40 60 80 100 120
W (kg)

Figure 5: Temperature profile of the reactor.

The above graph in Figure 83 demonstrates the temperature profile of the reactor. It can be seen
that temperature increases as the catalysts weight increases. This behavior can be attributed to
the fact that methanol synthesis reaction is exothermic, and the reactor is operating adiabatically,
which means that loss of heat to the ambient is limited, and no cooler is used.

2.2 Reactor Dimensions

The volume of the reactor VB is one of the most important parameters to be considered during
reactor design, it can be calculated by the following equation:

W
V B=
ρC (1−ϕ)

kg
Where ρC is catalyst particle density, and ϕ is bed void fraction. By knowing that ρC =1300 ,
m3
and ϕ=0.5,
bed volume can be calculated:

1708
V B= =2.63 m3
1300(1−0.5)

In addition, reactor length can be calculated by the following relation:

V B =L × A
π 2
where A= D
4
By assuming D=1, reactor length can be calculated by the following expression:

VB V 2.63
L= = B = =3.34
A π 2 π 2
D (1)
4 4

2.3 Space Time

Space time is “the time necessary to process one volume of reactor fluid at the entrance

conditions”. In other words, it is the time required for a fluid with a volume equal to the reactor
volume to either completely entering or existing from the reactor (Fogler, 2006). Space time can
be expressed by the following equation:

V
τ=
vο

m3
where v ο=398.9 , Therefore:
h
2.63
τ= =0.00659 h−1
398.9

Another useful notion is space velocity. Space velocity indicates how many reactor volumes can
be processed in unit time. It can be expressed by the following equation:

vο 1
SV = =
V τ
Hence:
1
SV = =151.67 h−1
0.00659

Table 62 summarize the results.

Table 3: summary of reactor specification and design parameters.

Parameter Value
Weight of the catalyst (W ) 1708 kg
Bed volume (V ¿¿ B)¿ 2.63 m3
Reactor diameter ( D) 1m
Reactor length ( L) 3.34 m
Space time ( τ) 0.00659 h-1
Space velocity ( SV ) 151.67 h-1

3 Material of construction

Before selecting the proper material of construction, chemicals present in the inlet and outlet
streams as well as reactor condition should be taken into consideration. Some chemical may
cause severe corrosion for specific metals. In addition, conditions involve high temperature and
pressure may require the use of special material of construction to withstand these extreme
conditions. For example, in elevated temperature, a significant drop in tensile strength may occur
for some material, while in high pressure, thicker walled, more expensive equipment is
necessary. In this work, two candidates were considered as materials of construction for the
reactor, which are stainless steel and carbon steel.
 Figure 6: Maximum allowable stress vs temperature for different alloys.

Stainless steel are high-alloy steels which contain no less than 12 wt% of chromium. It can be
used in processes involve the use of corrosive chemicals due to its high corrosion resistivity
(Turton et al., 2012). On the other hand, Carbon steel is an alloy consist of iron and contains a
maximum of 1wt% carbon and 1wt% manganese (Ahmad, 2006). In contrast to stainless steel, It
cannot withstand contact with corrosive materials. Hence, it is not recommended to use it if
corrosive chemicals are present. Both these alloys can withstand high temperature and pressure.
Figure 84 shows the maximum allowable stress for different alloys of carbon steel and stainless
steel at different temperature degrees.

In our reactor, the maximum temperature is 280 C, while the maximum pressure is 50 bar. Both
stainless steel and carbon steel can withstand these conditions. In addition, the materials present
in the reactor are CO2, CO, methanol, Hydrogen, and Methanol. All of these materials do not
cause severe corrosion for both candidates. However, since carbon steel has a lower price
compared to stainless steel, it is more economically preferable to use carbon steel in constructing
the reactor.

In our reactor, the maximum temperature is 280 C, while the maximum pressure is 50 bar. Both
stainless steel and carbon steel can withstand these conditions. In addition, the materials present
in the reactor are CO2, CO, methanol, Hydrogen, and Methanol. All of these materials do not
cause severe corrosion for both candidates. However, since the system contains water and CO2,
there is a risk for carbonic acid formation, which is highly corrosive to carbon steel; Hence,
stainless steel must be used.

4 Conclusion
At the end, the reactor was designed by following an algorithm of 10 steps to construct the
system of ODEs, then the system was solved by polymath. The reactor is operating at pressure of
50 bar, and the inlet and outlet temperature are 223 and 280 oC, respectively. The results showed
that 1708 kg of catalyst is sufficient to achieve 19.9% conversion of CO 2. In addition, the
required reactor volume is 2.63 m3, while its length and diameter are 3.34 and 1 m. Furthermore,
the space time and space velocity are 0.00659 h-1 and 151.67 h-1, respectively. Finally, since the
system operates at high pressure and involve water and carbon dioxide, there is a risk for
carbonic acid formation; Thus, stainless steel must be used due to its high resistivity against
corrosion.