SESSION: 2019/2020 SEMESTER 1

BKF2453– CHEMICAL REACTION ENGINEERING I

MINI PROJECT
Reactor Design and Thermodynamics
Lecturer: MD. MAKSUDUR RAHMAN KHAN

Section: 03

Member: Matric ID:

KELVIN TING HONG MING KA17097

PREETHPAL SINGH SANDHU KA17200

SHERLYN HAU YEAN YING KA17048

AHMAD FAIZ BIN ABDUL MALEK KA18205

MUHAMMAD ARIFF AZWAN BIN AZMI KA17191

Task 1
The multiple reaction is a complex type. Thus, the selectivity is employed here and defined
r CH OH
S CH 3 OH = 3

C H2 O +C O2+ H 2 O
r C H O +r C O +r H
2 2 2 O

k1
k 1 C CO C 2H − C −k C
2
K 1 CH OH 3 CH OH 3 3

¿
k 3 CCH OH 3

k 1 C CO C 2H k
¿ − 1 −1
2

k 3 C CH OH K 1 k 3
3

From the selectivity, concentration of methanol will increase and decrease the selectivity,
respectively. Excess hydrogen can be set to the feed and separating reactor can be applied
using membrane or else to remove simultaneously and continuously removed from the
reactor by using gas separation membrane. This solution however takes into account the first
action as the second one is not covered in the syllabus.
The selectivity is having concentration of product as the nominator, which is similar to series
reaction. Thus, the optimization cannot be suggested. A complete mole-balance calculation,
using the algorithm, is necessary to determine the optimum design variable i.e. mass of the
catalyst to find the ratio between CH3OH and the design variable.
Algorithm
Mole balance of species in PFR, although it is catalytic, the rate is expressed in mol/L/min:
dFi
 ri
dV where i is for all reacting species. The initial molar flow rate of methanol is
backward calculation from 40,000 tonnes per annum of methanol at 8000 hr/yr for initial
guess.
Net rate laws:
rA1=-ka1*((Ca*Cb^2)-Cc/K1)
rA2=-ka2*((Ca*Cd)-Ce*Cb/K2)
rC3=-kc3*Cc
rA=rA1+rA2
rB=2*rA1-rA2-rC3
rC=-rA1+rC3
rD=rA2
rE=-rA2
rF=-rC3
K1 = 131667*(0.00198*T)^2*exp(-30620/R*(1/298-1/T)) #L2mol-2
K2 = 103943*exp(-9834/R*(1/298-1/T))
ka1 = 0.933*exp(78500/R*(1/330-1/T)) #L2mol-2 s-1
ka2 = 0.636*exp(18000/R*(1/300-1/T)) #Lmol-1 s-1
kc3 = 0.244*exp(43434/R*(1/325-1/T)) #s-1
Stoichiometry

 F  T  P0
Ci  CT 0  i  y  0  CT 0  F T =F CO + F H + F CH OH + F H O + F CH O
 FT   T 
2 3 2 2

where RT , and
P
y
P0

Analysis
r CH OH
Instantaneous selectivity, S=
3

rC H O + rC O
2 2

F CH OH
Overall selectivity, Ś=
3

F C H O + FC O
2 2

r CH OH
Instantaneous yield based on carbon monoxide, Y = 3

−r CO

r CH OH
Instantaneous yield based on hydrogen, Y =
3

−r H 2

FCH OH
Overall yield based on carbon monoxide, Ý = 3

F CO0−F CO

F CH OH
Overall yield based on hydrogen, Ý =
3

F H 0−F H
2 2
 Figure 1. Result of Graph
The Polymath file is attached and the graphical result is shown in Figure 1 above. Selectivity
and yield do not show maximum trend. Nevertheless, like series reaction, the optimum
volume of reactor can be determined from the differentiation (Analysis tab in Table result) of
CH3OH versus V. At 900 L, the maximum FCH3OH is obtained at 9.272 mol/s. This value is
lower than the desired rate of production. Scale up by increasing the feed flow rate of
reactants at the same ratio can be done so that the rate is 43.35 mol/s CH 3OH. This will be in
Task 3.

Coding in Polymath
#A-carbon monoxide
#B-hydrogen
#C-methanol
#D-steam
#E-carbon dioxide
#F-formaldehyde

#mol balance
d(Fa)/d(V)=rA #A
Fa(0)=43.35 #mol/s
d(Fb)/d(V)=rB #B
Fb(0)=101.15 #mol/s
d(Fc)/d(V)=rC #C
Fc(0)=0 #mol/s
d(Fd)/d(V)=rD #D
Fd(0)=28.9 #mol/s
d(Fe)/d(V)=rE #E
Fe(0)=43.35 #mol/s
d(Ff)/d(V)=rF #F
Ff(0)=0 #mol/s
#Net rate law
rA1=-ka1*((Ca*Cb^2)-Cc/K1)
rA2=-ka2*((Ca*Cd)-Ce*Cb/K2)
rC3=-kc3*Cc

rA=rA1+rA2
rB=2*rA1-rA2-rC3
rC=-rA1+rC3
rD=rA2
rE=-rA2
rF=-rC3
K1 = 131667*(0.00198*T)^2*exp(-30620/R*(1/298-1/T)) #L2mol-2
K2 = 103943*exp(-9834/R*(1/298-1/T))
ka1 = 0.933*exp(78500/R*(1/330-1/T)) #L2mol-2 s-1
ka2 = 0.636*exp(18000/R*(1/300-1/T)) #Lmol-1 s-1
kc3 = 0.244*exp(43434/R*(1/325-1/T)) #s-1
T=330 #Kelvin
P0=50 #atm
R=1.987 #calmol-1

#Stoichiometry #Ci = Ct0*(Fi/Ft)*y*(T0/T)

Ca=Ct0*(Fa/Ft)*y*(T0/T)
Cb=Ct0*(Fb/Ft)*y*(T0/T)
Cc=Ct0*(Fc/Ft)*y*(T0/T)
Cd=Ct0*(Fd/Ft)*y*(T0/T)
Ce=Ct0*(Fe/Ft)*y*(T0/T)
Cf=Ct0*(Ff/Ft)*y*(T0/T)
T0=T
Ct0=(P0)/(82.057e-3*T)
Ft=Fa+Fb+Fc+Fd+Fe+Ff
y=1
V(0) = 0
V(f) = 900

#analysis
Xa=(Fa0-Fa)/Fa0 #Conversion of methanol
Fa0=43.35 #mol/s
S=rC/(rE+rF+1e-11) #S = desired/rundesired
Sbar=Fc/(Fe+Ff+1e-11) #Overall selectivity = Fdesired/Fundesired
Y=rC/(-rA) #Yield of methanol
Ybar=Fc/(Fa0-Fa+1e-11) #Overall yield of methanol
Task 2
Heat effect of the reactor is decided from calculation of energy balance of the PFR. The heat
capacity of species in the reaction is calculated using hyperbolic equation as shown in Table
1.
Table 1: Heat capacity from Perry Handbook
C1 x 10-5 C2 x 10-5 C3 x 10-3 C4 x 10-5 C5 Cp at
Tmin x 10-
5
Hydrogen 0.2762 0.0956 2.4660 0.0376 567.6 0.2843
(250K)
Carbon 0.2937 0.3454 1.4280 0.2640 588 0.2937
Dioxide (50K)
Carbon 0.2911 0.0877 3.0851 0.0846 1538.2 0.2911
Monoxide (60K)
Steam 0.3336 0.2679 2.6105 0.089 1169 0.3336
(100K)
Formaldehyd 0.3327 0.4954 1.8666 0.2808 934.9 0.3327
e (50K)
Methanol 0.3925 0.8790 1.9165 0.5365 596.7 0.3980
(200K)

t t
C3 C5
Cp °=C 1+C 2
[ T
sinh sinh ( CT3 ) ] [ +C 4
T
cosh cosh ( CT5 ) ] ,
J
kmol . K

Enthalpy of reaction is calculated using the following equation: -

T
∆ H Rx =∆ H ° Rx + ∫ ∆ Cp° dT where∆ H ° Rx =∑ υ i H i0 dT ∧∆ Cp°=∑ υi C°pi .υ i
Tref

Denotes stoichiometric coefficient. Since enthalpy of reactions is determined by using

integral equations and the equation of heat capacities is complex, we have to equate
separately the enthalpy using ODE Solver in Polymath for each reaction, the coding is as
follows: -
Heat capacity on differential equations
d ∆ H Rxj
=∆C pi whereat T 0 , ∆ H Rxj =∆ H ° Rxj and ∆ H ° Rxj =∑ υ ij H ° fi
dT
(Equilibrium Profile Graph is needed here)

Table 2: Ideal Gas Enthalpy of formation from Perry Handbook

Species Heat of formation, Hf°
(J/mol)
Hydrogen 0
Carbon Dioxide -393510
Carbon Monoxide -110530
Steam -241814
Formaldehyde -108600
Methanol -200940

Using ODE solver in Polymath, we can get the constant from Regression in Table Result
deltaHrx1 = -1.165e5+43.55121*T-0.0084519*T^2+0.0002279*T^3
deltaHrx2 = -3.889e4-22.01159*T+0.0600082*T^2-0.0241538*T^3
deltaHrx3 = -7928.423+51.84787*T-0.1127704*T^2+9.412e-5*T^3

From Polymath using ODE solver, the graph in Figure 2 below is obtained, the reactor is
highly exothermic. If inlet temperature is 250 K 2.5 L reactor is required to achieve
0.01459% conversion! Thus, the heat effect of PFR can be decided to be isothermal or has
optimum temperature (not too high but not too low) for an adiabatic reactor.
Figure 2 X-T plot for the adiabatic PFR using inlet temperature of 250 K.
Coding in Polymath
#mol balance
d(Fa)/d(V)=rA #A
Fa(0)=43.35 #mol/s
d(Fb)/d(V)=rB #B
Fb(0)=101.15 #mol/s
d(Fc)/d(V)=rC #C
Fc(0)=0 #mol/s
d(Fd)/d(V)=rD #D
Fd(0)=28.9 #mol/s
d(Fe)/d(V)=rE #E
Fe(0)=43.35 #mol/s
d(Ff)/d(V)=rF #F
Ff(0)=0 #mol/s

#Net rate law

rA1=-ka1*((Ca*Cb^2)-Cc/K1)
rA2=-ka2*((Ca*Cd)-(Ce*Cb/K2))
rC3=-kc3*Cc

rA=rA1+rA2
rB=2*rA1-rA2-rC3
rC=-rA1+rC3
rD=rA2
rE=-rA2
rF=-rC3
K1 = 131667*(0.00198*T)^2*exp(-30620/1.987*(1/298-1/T)) #L2mol-2
K2 = 103943*exp(-9834/1.987*(1/298-1/T))
ka1 = 0.933*exp(78500/1.987*(1/330-1/T)) #L2mol-2 s-1
ka2 = 0.636*exp(18000/1.987*(1/300-1/T)) #Lmol-1 s-1
kc3 = 0.244*exp(43434/1.987*(1/325-1/T)) #s-1
P0=160#atm
T(0)=250
#R=1.987 calmol-1

#Stoichiometry #Ci = Ct0*(Fi/Ft)*y*(T0/T)

Ca=Ct0*(Fa/Ft)*(300/T)
Cb=Ct0*(Fb/Ft)*(300/T)
Cc=Ct0*(Fc/Ft)*(300/T)
Cd=Ct0*(Fd/Ft)*(300/T)
Ce=Ct0*(Fe/Ft)*(300/T)
Cf=Ct0*(Ff/Ft)*(300/T)
Ct0=(P0)/(0.082*300)
Ft=Fa+Fb+Fc+Fd+Fe+Ff
V(0) = 0
V(f) = 2.5

#analysis
Xa=(Fa0-Fa)/Fa0 #Conversion of methanol
Fa0=43.35 #mol/s
S=rC/(rE+rF+1e-11) #S = desired/rundesired
Sbar=Fc/(Fe+Ff+1e-11) #Overall selectivity = Fdesired/Fundesired
Y=rC/(-rA) #Yield of methanol
Ybar=Fc/(Fa0-Fa+1e-11) #Overall yield of methanol
#Energy Balance
d(T)/d(V) = (rA1*deltaHrx1 + rA2*deltaHrx2 + rC3*deltaHrx3)/(Fa* CpA + Fb*CpB + Fc*CpC +
Fd*CpD + Fe*CpE + Ff*CpF) #Energy balance for multiple reaction
CpA = (0.2911e5 +0.0877e5 * (3.0851e3/T/sinh(3.0851e3/T))^2 +
0.0846e5*(1538.2/T/cosh(1538.2/T))^2)/1000
CpB = (0.2762e5 +0.0956e5 * (2.466e3/T/sinh(2.466e3/T))^2
+0.0376e5*(567.6/T/cosh(567.6/T))^2)/1000
CpC = (0.3925e5 +0.879e5 * (1.9165e3/T/sinh(1.9165e3/T))^2 +
0.5365e5*(596.7/T/cosh(596.7/T))^2)/1000
CpD = (0.3336e5 +0.2679e5 * (2.6105e3/T/sinh(2.6105e3/T))^2 +
0.089e5*(1169/T/cosh(1169/T))^2)/1000
CpE = (0.2937e5 +0.3454e5 * (1.428e3/T/sinh(1.428e3/T))^2 + 0.264e5*(588/T/cosh(588/T))^2)/1000
CpF = (0.3327e5 +0.4954e5 * (1.8666e3/T/sinh(1.8666e3/T))^2 +
0.2808e5*(934.9/T/cosh(934.9/T))^2)/1000

# from ODE solver for deltaHrxn

deltaHrx1 = -1.165e5+43.55121*T-0.0084519*T^2+0.0002279*T^3
deltaHrx2 = -3.889e4-22.01159*T+0.0600082*T^2-0.0241538*T^3
deltaHrx3 = -7928.423+51.84787*T-0.1127704*T^2+9.412e-5*T^3
Task 3
Optimum temperature of the feed can only be meaningful if the costs of heating system,
catalyst and reactor are included. In Task 1, high temperature is suggested to get high
selectivity but in heat-effect analysis of the PFR, high temperature of feed will result in
extremely low temperature of reaction and conversion. Thus, moderate temperature of
325 K is preferred. The temperature of reaction is in the range of 450 K  T  1003 K
For 43.35 mol/s methanol production (equivalent to 40,000 tonnes per annum methanol),
75.0982 mol/s carbon monoxide (7:3:3 ratio of H2:CO2:CO) (larger flow rate) is required
and volume of the reactor is 65.7843 L if the PFR is isothermal at 325K.
If the PBR is isothermal at 400 K, 2855.9 mol/min ethylene oxide of the same feed ratio is
required and the volume of the reactor is 1134.1 L (bigger reactor) (CHANGE THE BOLD
WORDS)
Students can show more variety in optimization from various perspectives.
Coding Task 3
#A-carbon monoxide
#B-hydrogen
#C-methanol
#D-steam
#E-carbon dioxide
#F-formaldehyde

#mol balance
d(Fa)/d(V)=rA #A
Fa(0)=75.0982 #mol/s
d(Fb)/d(V)=rB #B
Fb(0)=175.2291#mol/s
d(Fc)/d(V)=rC #C
Fc(0)=0 #mol/s
d(Fd)/d(V)=rD #D
Fd(0)=0 #mol/s
d(Fe)/d(V)=rE #E
Fe(0)=75.0982#mol/s
d(Ff)/d(V)=rF #F
Ff(0)=0 #mol/s

Fa0 =75.0982

#Net rate law

rA1=-ka1*((Ca*Cb^2)-Cc/K1)
rA2=-ka2*((Ca*Cd)-Ce*Cb/K2)
rC3=-kc3*Cc

rA=rA1+rA2
rB=2*rA1-rA2-rC3
rC=-rA1+rC3
rD=rA2
rE=-rA2
rF=-rC3
K1 = 131667*(0.00198*T)^2*exp(-30620/R*(1/298-1/T)) #L2mol-2
K2 = 103943*exp(-9834/R*(1/298-1/T))
ka1 = 0.933*exp(78500/R*(1/330-1/T)) #L2mol-2 s-1
ka2 = 0.636*exp(18000/R*(1/300-1/T)) #Lmol-1 s-1
kc3 = 0.244*exp(43434/R*(1/325-1/T)) #s-1
T=325 #Kelvin
P0=160 #atm
R=1.987 #calmol-1

#Stoichiometry #Ci = Ct0*(Fi/Ft)*y*(T0/T)

Ca=Ct0*(Fa/Ft)*y*(T0/T)
Cb=Ct0*(Fb/Ft)*y*(T0/T)
Cc=Ct0*(Fc/Ft)*y*(T0/T)
Cd=Ct0*(Fd/Ft)*y*(T0/T)
Ce=Ct0*(Fe/Ft)*y*(T0/T)
Cf=Ct0*(Ff/Ft)*y*(T0/T)
T0=T
Ct0=(P0)/(82.057e-3*T)
Ft=Fa+Fb+Fc+Fd+Fe+Ff
y=1
V(0) = 0
V(f) = 65.7843 #L

#analysis
Xa=(Fa0-Fa)/Fa0 #Conversion of methanol
S=rC/(rE+rF+1e-11) #S = desired/rundesired
Sbar=Fc/(Fe+Ff+1e-11) #Overall selectivity = Fdesired/Fundesired
Y=rC/(-rA) #Yield of methanol
Ybar=Fc/(Fa0-Fa+1e-11) #Overall yield of methanol