Methanol synthesis reactor

The main objective of the design is to calculate the weight of the catalyst used in
the methanol synthesis reactor. The methanol synthesis reactor has three
reactions tacking place in itll three reactions area equilibrium reactions. The
process undertaken to design the reactor are outlined by giving the assumptions
used and the method used to design the reactor.

Assumptions

Plug flow is assumed.

The concentration and temperature changes only in the longitudinal
direction and not in the radial direction.
Temperature in the rector is assumed to be constant because of the jacked
round it.
The reactor is assumed to be one dimensional.
Pseudo homogeneous.
=1868.85
Density of the catalyst and porosity are assumed to be ),

( =0.0393) reaspectively

Alpha for pressure drop is assumed to be 0.0001

Method

Perform a mole balance of all species reacting in the rector e.g.

d F methanol
=Rmethanol which is the mole balance for methanol to obtain
dW
ordinary differential equations.
Compute the net rates of each species in the three reaction which is given
by equation 9 to equation 13, this is to be used with the mole balance
F methanol
Cmethanol =CT 0 ( )
FT
Consider the stoichiometry and compute the concentration and convert
the concentration into partial pressures using the ideal gas law (
Pi=C i RT )
The resulting differential equation are solved simultaneously using
polymath which has ode45 ode solver built in. The inlet flowrates are
given as initial conditions and the ode solves for flowrates for different
weights of the catalyst. The weight and flowrates are plotted together and
the plot is examined to find the weight of the catalyst that must be used
for the reactor. The weight that is taken is the point where the flowrate
 stops changing since this is an equilibrium limited reaction. From the
weight of the catalyst bed the volume and other dimensions of the rector
are calculated.

Results and Discussion

Sammary of parameters of methanol synthesis reactor

Reactor
parame
ters
1868.8
catalyst 5
0.0393
Wcatalyst 14420
Vpacked 8.0316
bed 1764
VPBR 24.094
reactor 8529
1.9720
Dreactor 8124
7.8883
Lreactor 2497
1795.4
bulk 042
2.6294
Beddepth 4166
Figure 1: Flowrate vs Catalyst weight.

Figure 2: Summary of flowrates of reacting species in the methanol reactor

vs the weight of the catalyst.
 Figure 3: Ratio of inlet pressure and outlet pressure y vs catalyst weight.

9.00E+06

8.00E+06

7.00E+06

6.00E+06

5.00E+06 Ccarbon moxide

Chydrogen
(*10^-4)concentrations(mol/m^3) 4.00E+06
Cmethanol
3.00E+06 Ccarbon dioxide
2.00E+06 Cwater
Chydrogen
1.00E+06

0.00E+00
20000
0 40000

Catalyst weight(kg)

Figure 4: concentration vs catalyst weight.

Methanol synthesis is governed by reactions which are equilibrium limited so the

production of methanol is affected greatly by the temperature so the assumption
that the reactor temperature remains constant in the reactor may not be valid
because in general the rate at which heat is removed or added to a reactor is not
enough to allow for isothermal operation. Due to this the temperature and
concentration will vary not only in the longitudinal direction but also on the radial
direction as well. The ratio of inlet pressure ( P0 ) and outlet pressure ( P ) , y
starts with a values of unity (1) and 0.8758527 which is close to 1 which
means the effect of pressure drop is minimal and can be ignore.

Appendix C

The volume of a packed bed of a packed bed reactor can be calculated from
the mass of the catalyst weight ( M catalyst ) using equation 1 and can be
related to the volume of the reactor using equation 2, which assumes that the
catalyst occupy one third of the reactor volume, Obereti (June 2013),. The
dimensions of the reactor can then be evaluated using the volume of the
reactor. Equation 3 shows the relationship between volume and diameter of
the reactor. The length of the reactor can then be evaluated assuming a
diameter to length ( D reactor : Lreactor ) ratio of one is to 4 ( 1: 4 ) , this
relationship is given by equation 4, Obereti (June 2013). The bed depth of the
reactor is then calculated using bulk density given by equation (5) and the
diameter of the reactor, the equation for bed depth is given by equation (6)

M catalyst 1
V packed bed= ( )
catalyst 1
, Sofiane et al .(2014) (1)

1
V = V reactor (2)
3

D reactor =

3 V reactor
(3)

Lreactor=4 Dreactor (4)

bulk =c ( 1 ) (5)

4 M catalyst
Bed lengh =
Dreator bulk (6)
2
The rate laws for the reactions that govern methanol synthesis are given by
equations 6 to equation 9 which were developed by Graaf,
Sofiane et al .(2014) where the fugacity term. The Soave-Redlick-Kwong
equation of state is used to estimate the compressibility factor(Z) for a gas
mixture at high temperature and it is found to be close to unity which means
the use of the ideal gas law provides a good approximation and pressures can
be used in equation 5 to equation 8 instead of fugacity, Sofiane et al .(2014) .

f methanol
(
r methanol ,1 =k 1 K CO 1 f co f 3H/2 2 2
( f 1H/2 K 1 )
2
) =R1 ,
(6)

H 2 0,2
f H 0 f co
2
(
r =k 1 K co 1 f co f H
2 2
K2
2
=R 2
) (6)

f methanol f H 0
r methanol ,3 =k 3 K co 1 f co f 3/H 2 2
=R3
3/ 2 (8)
2 2 2
(f H2 K3)

=( 1+ K co f co + K co f co f co ) f 1H/2 +
2 2 2
[ ( ) ]
2
KH
K
2

1 /2
H2
O
fH 2 0 (9)

Table 1-Equilibrium constants and heats of reaction (Graaf et al., 1986;

Gallucci et al., 2004)

Reaction log 10 ( k i ) r 298 K ( kj mol1 )

1) 2 90.70

5139
12.621
T
2) +41.19
2073
2.029
T
3) 2 49.51

3066
10.592
T
 Table 2-Kinetic parameters used to simulate methanol reactor (Graaf et al.,
1990)

Parameters Expression units

k1
mol s1 kg1
4.89 107 exp ( 113,000
RT ) catalyst

k2 /2 kg1
1
exp ( )
152,900
9.64 10 11 catalyst
RT 1
mol s
k3 1 kg1
1.09 105 exp ( 857,500
RT ) catalyst
mol s1
K CO 46,800 1
2.16 105 exp ( ) RT

KCO
exp (
61,700 1
RT )
2
6.37 107

K H O / K H 84,000 /2
1
exp (
RT )
2 2
7.05 109

Defining rate of reaction of all components reacting in the methanol synthesis

reactor

RCO =R 1+ R 3 (10)

R H =2 R1R 23 R 3 (11)
2

Rmethanol=R 2+ R 3( 12)

RC O =R2R 3 (13)
2

R H 0 =R1 + R3 (14 )
2
Ordinary differential equation from mole balace which are solved sulteneously
using polymath.
Let carbon monoxide=A,hydrogen=B,methanol=C,Carbon dioxide=D and
water=C

d FA
=RCO (15)
dW

d FB
=R H (16)
dW 2

d FC
=R methanol (17)
dW

d FD
=R C O (18)
dW 2

d FE
=R H 0 (19)
dW 2

d( y) alpha FT
d (W )
= (
(2 y)
)( )
FT 0

P0
y= (20)
P

The flowrates are related to the concentration as follows

FT=FA+FB+FC+FE+FD
CA=CT0*(FA/FT)
CB=CT0*(FB/FT)
CC=CT0*(FC/FT)
CD=CT0*(FD/FT)
CE=CT0*(FE/FT)
Similar ordinary differential for concentrations are given by equations 20 to
equation are
dCA
=RCO (21)
dW

d CB
=R H (22)
dW 2
 d CC
=R methanol (23)
dW

d CD
=R C O (24)
dW 2

d CE
=R H 0 (25)
dW 2

Obereti, 2012.Kinetic Modelling and Reactor Design, Methanol Synthesis, Aston

University
Sofiane,A,Jean-Marc,c,Jean-Francois,P,Laurent,F 2014,Methanol synthesis for
C O2 and H 2 in multi-tube fixed-bed reactor and multi-tube reactor filled
with monoliths, Chemical Engineering Research and Design,vol. CHERD-1530,no.
pp.5