You are on page 1of 27

1.

INTRODUCTION
Methanol synthesis is a widely studied process but still there is no mutual agreement
about the reactions occurring within the process. Nowadays, the interest is in the production of
methanol from CO2-rich feed gas, instead of the traditional CO-rich feed. The economic
operation of methanol synthesis from CO2 requires an efficient catalyst allowing high enough
methanol yields. The kinetics of methanol synthesis has also been studied widely. Many different
kinds of kinetic equations have been derived based on different assumptions about the limiting
phenomena. Maybe the most profound model is de-rived by Vanden Bussche and Froment
(1996). Vanden Bussche and Froment (1996) and Setinc and Levec (2001) have reviewed some
of the proposed kinetic equations in their articles [1, 2].
Methanol is very commonly used as a feedstock in the chemical industries. It is also used
as a fuel and as a solvent. It is produced commercially from synthesis gas (CO/CO 2/H2) under
high pressure and temperature. The used catalyst is mainly the copper/zinc based oxide catalyst.
Used oxide additives include, for example, Al2O3, Cr2O3 and ZrO2 [4,5] . Methanol is used when
producing for example formaldehyde, acetic acid, and methyl tertiary butyl ether (MTBE) [1].
The use of CO2 as a feedstock in methanol synthesis has gained a lot of attention and nowadays
is widely studied. The research has focused mainly on the search for the most suitable catalyst, as
the performance of the process is highly dependent on used catalyst. In methanol synthesis,
either CO or CO2 or both hydrogenate to methanol.
Recently, methanol synthesis with CO2-rich feed has drawn a lot of attention and
research is currently aimed at finding a suitable catalyst for such a task. A pseudo-homogeneous
model was developed for fixed bed catalytic methanol reactor based on the reaction mechanisms
and mass and energy balance equations.

2. LITERATURE REVIEW
Methanol synthesis occurs via three reactions namely: hydrogenation of carbon monoxide,
hydrogenation of carbon dioxide, and water gas shift reactions. There have been a number of
studies on methanol synthesis kinetics involving Cu-based catalysts for decades now but
controversies still remain regarding the reaction mechanism. One of the major concerns has been
the role of CO2 in methanol production.
Initial kinetic studies on methanol synthesis by Natta et al. and Leonov et al. considered
only CO and H2 as the main reactants and neglected any contribution from CO2 [13]. Later, Klier
et al. in 1982 showed that methanol was mainly formed from CO and H 2 that adsorbed on the
catalyst and CO2 acted only as a promoter and not as a main reactant. They also suggested that
methanol production rate was maximum at a CO 2/CO ratio of 2:28 which was governed by a
balance between the promoting effect of CO2 and retarding effect due to strong adsorption of CO2
[14].
Liu et al. conducted initial rate experiments in a batch reactor to determine the effect of
feed composition on methanol production rate and obtained conflicting results. They showed that
methanol formation rate increased with increasing CO2 pressure. A year later, they presented a
more detailed study and proposed that hydrogenation of CO 2 was the primary reaction in
producing methanol at low temperature, low conversion, and in the absence of water but at high
temperature, high conversion, and in the presence of water, methanol was primarily produced via
CO hydrogenation [15].
Chinchen et al. reported in their study that CO 2 was the primary reactant in methanol
production using

14C-labeled

reactants [16]. Takagawa and Ohsugi, in 1987, determined the

empirical rate equations for all the three methanol synthesis reactions and showed that methanol
production rate increased with increase in CO 2/CO ratio in the beginning of the reaction but
decreased as the ratio increased and water started to form.They claimed their results to be in
accordance with both Klier et al. and Liu et al. [17].

McNeil et al. in their experimental study found that 2 mole % CO 2 in the feed yielded
optimum methanol production rate. They also found the contribution of CO 2 to methanol
formation to be more at lower temperatures. Unlike other studies, they developed a rate
expression based on mechanistic information which included the effects of CO2, both as a
methanol producer as well as a rate inhibitor [18].
Rozovskii et al. showed that there was no direct path for hydrogenation of CO to
methanol. They reported in their earlier study, using C-14 labeling techniques and in a more
recent study using Temperature Programmed Desorption technique that methanol formation
takes place through CO2 hydrogenation [19]. In a methanol synthesis study conducted by Fujita
et al. at atmospheric pressure in a flow reactor, it was found that CO 2 produced methanol via
hydrogenation of formate species formed on Cu and CO produced methanol via hydrogenation
of formate species formed on ZnO. CO2 hydrogenation rates were found to be more rapid than
CO hydrogenation rates. They reported that the presence or absence of water and the difference
in the reactivity of the former and latter formate species mainly caused a difference in the
methanol production rates from CO and CO2 [20].
In 1998, Sun and coworkers studied methanol synthesis and water gas shift reaction
using IR technique and found that CO2 hydrogenation was the principle pathway in methanol
production for both CO2 and CO2/CO hydrogenation reactions. The rate determining step was
found to be the hydrogenation of formate species. They suggested that CO addition lowers the
activation energy of the production process, in addition to affecting the reaction path [4].
Sahibzada et al. showed that the intrinsic rate of CO2 hydrogenation was twenty times
faster than CO hydrogenation and at CO2 > 1%, it was the main source of methanol production.
They reported that methanol formation rate increased linearly with increase in CO 2 concentration
in the absence of products [21]. Further establishing the role of CO 2 in methanol production,
Ostrovskii, studied methanol synthesis mechanism on Cu/Zn containing catalyst under a wide
range of experimental conditions and showed that CO 2 was the principal source of methanol
production [22].

Lim et al. conducted a comprehensive study assuming CO and CO 2 to adsorb on different


Cu sites and water to adsorb on a ZnO site. They found that CO 2 hydrogenation rate was slower
than CO hydrogenation rate which decreased methanol formation rate but since CO 2 decreases
WGS reaction rate, it, therefore decreases the production of DME, a byproduct from methanol. It
was therefore, concluded that methanol production rate can be indirectly enhanced by finding an
optimum CO2 concentration. They claim to be the first study among the various ones reporting
the role of CO2 in methanol synthesis, suggesting a kinetic mechanism relating CO and CO 2
hydrogenation reactions [2]. In a more recent study by the same authors, they have used the
developed kinetic model to evaluate the effect of carbon dioxide fraction on the methanol yield,
and have also devised an optimization strategy to maximize methanol production rate taking CO 2
fraction and temperature profile into account [30].

3.

OBJECTIVES

To formulate a one dimensional mathematical model for methanol production from


syngas in a shell and tube fixed bed reactor.
To solve the mathematical model using equation solver tool in MATLAB with RungeKutta-Verner fourth and fifth order method with automatic step size to ensure accuracy
To validate the model by comparing the predicted results with those available in the
literature.
To perform the simulation of shell and tube fixed bed reactor for methanol synthesis from
syngas and to study the effects of following reaction parameters on molar flow rates of
hydrogen, carbon monoxide, carbon dioxide, methanol, steam, yield of methanol,
conversion of hydrogen and conversion of carbon dioxide
Temperature
Pressure
H2:CO2 molar feed ratio

4.

REACTION RATE AND KINETICS

4.1 Reaction Kinetics


Synthesis of methanol from syngas is an exothermic equilibrium reaction. The
used catalyst is mainly the copper/zinc based oxide catalyst. Used oxide additives include, for
example, Al2O3, Cr2O3 and ZrO2 [4,5]
The main reactions involved in the production of methanol are
Hydrogenation of carbon monoxide
(H298= - 90.55 kJ.mol-1; G = -25.34 kJ.mol-1)

CO +2H2 CH3OH

(1)

Hydrogenation of carbon dioxide


CO2 + 3H2 CH3OH + H2O

(H298= - 49.43 kJ.mol-1; G = 3.30 kJ.mol-1)

(2)

(H298= 41.12 kJ.mol-1; G = -28.60 kJ.mol-1)

(3)

Water-gas shift reaction


CO + H2O CO2 + H2

The model utilizes the kinetic equation proposed by Vanden Bussche and Froment in 1996.

k 1 p CO p H 1
2

CH 3 OH

RWGS

OH

eq
2

PH

K pCO p
2

3
H2

)
)

k3 PH O
1+
+ k 4 PH +k 5 P H O
PH
2

[ (

PH O PCO
PCO P H
2

)]

k3 PH O
1+
+ k 4 PH +k 5 P H O
PH
2

k 2 p CO 1K 3eq
2

PCH

All the constants (kj) in the above equation follow the general Arrhenius equation and
equilibrium constants were obtained from analyses that are listed in Table 1 [8].
Bj
RT

( )

k j= A j exp

Table 1. Frequency Factors of Kinetic Equation [8]


k1
k1
k1
k1
k1
K eq
2
K eq
2

A
B
A
B
A
B
A
B
A
B

1.07
36696
3453.38
0.499
17197
6.62*10-11
124119
1.22*1010
-94765
10

3066
10.592
T

2073
+2.029
T

10

4.2 Development of Modeling Equations


The mathematical model for the simulation of the pipe shell fixed bed reactor has been
developed based on the following assumptions:
a) A plug flow reactor model is assumed.
b) Heat and mass transfer as well as diffusion in the catalyst pellet were lumped in rate
constants.
c) The gas mixture is considered as an ideal gas.
d) The reactor is simulated in the steady state condition and one dimensional mathematical
model is considered.
e) The radial diffusion in the catalyst particles is neglected in the shell and tube fixed bed
reactor.
f) The reactor is considered single phase.

For modeling of methanol reactor, a plug flow reactor model was assumed. Steady state
conditions is considered. In this model, reactor is considered single phase. Since in multi-phase
reactor, molar flows of components are used, mass balance equations are written based on molar
flow of components. Balance equations of components are expressed as follows:
dFi
= c ( r i ) A
dl

where i is the molar flow of component i,

density of catalyst,

ri

the rate of reaction i and

A is cross-sectional area of reactor.


Energy balance equation is given by
2

( H i ) c ( r i ) A
dFi
i
=
dl
F iC p
i

Where Hi is heat of reaction,


the rate of reaction i,

Fi

density of catalyst, A cross-sectional area of reactor,

the molar flow rate of component i and

Cp

ri

is molar heat capacity

of i.
Relationship of partial pressure and molar flow of components the assuming ideal gas is given by
Pi=P

Fi F
= F i
Ft t
i

Where Pi is partial pressure of component i, P total pressure, Fi the molar flow rate of component
i and Ft is total molar flow rate.
Molar heat capacity of the components in the reactor is found from the following equation and
the information of Table 2

Cp
= Ai + Bi T +C i T 2+ D i T 2
R
Where Cp is molar heat capacity, R gas constant and Ai, Bi, Ci and Di are constants
Enthalpy change of reactions is calculated and used in modeling of the reactor.
T

H oT = H o298 + C p dT
298

Also C p= C p ( products ) C p ( reactants )


Table 2. Frequency Factors of Enthalpy Equation
Chemical
Species
CH3OH
H2O
H2
CO2
CO

103B

106C

10-5D

2.211
3.47
3.249
5.457
3.376

12.216
1.45
0.472
1.045
0.557

-3.450
-

0.121
0.081
-1.157
-0.031

5. SOLUTION TECHNIQUE
The set of ordinary differential equations (FIVE components participating in the reaction; H 2,
CO2, CO, H2O, CH3OH and Temperature) are solved using MATLAB 2013a professional
software. This set of SIX differential equations are solved at each step interval of the tube of the
pipe-shell fixed bed reactor. The step size is given as 0.02, i.e. the tube length is divided into 500
separate sections for the tube length of 10 m. The related set of ordinary differential equations
are solved simultaneously using the ode solver tool ode45 in MATLAB.
Based on the initial values and boundary conditions, solver computes all the parameters and
create the molar flow rate profile at each step interval. The reactor operating conditions are listed
in Table 3 that have been used in this simulation. With the inbuilt subroutines, the solver (ode45)

checks for required tolerance, relative error and absolute error in the calculations. Thus, it keeps
on solving for every step interval, until it reaches the final length of the reactor.
Finally, the whole of reactor data is saved in Microsoft Excel file for further analysis. The reactor
data is compared and analysed for best reactor configuration.
Table 3, Industrial Reactor Specification, Catalyst Properties and Feed Conditions
Parameter
Feed composition (mole fraction)
H2
CO
CO2

Value

Unit

80
4.76
2.95

CH3OH

0.3

H2O

0.06

N2

0.01

CH4
Inlet temperature
Inlet pressure
Number of tubes
Diameter of tube
Flow rate of feed gas
Length of reactor

11.92
498
50
5947
0.04
47400
10

K
Bar
m
Kmol hr -1
m

Typical properties of catalyst


Density of catalyst bed

1063

kg m-3

6. RESULTS & DISCUSSIONS


The results of modelling and simulation done with the help of MATLAB code is showed here.
The effects of various parameters like the inlet temperature of the reactor, reactor pressure are
studied. Molar flow rate profile of the components hydrogen, carbon monoxide, carbon dioxide,
methanol and steam against the tube length has been tabulated and graphed. In addition to the
molar flow rate profiles of the components, graphs showing the yield of methanol, conversion of
hydrogen and conversion of carbon dioxide along the tube length are also provided.

Four definitions are introduced to examine the conversion of carbon monoxide, conversion of
hydrogen and yield of DME through the reactor length:
X CO

XH

F CO

FH

F H

out

YieldCH OH (H )=
2

F CO

FH

FCO out

FCH OH
* 100
FH
3

YieldCH OH (C )=
3

F CH

OH

( FCO + F CO ) * 100
2

where

FCO

FH

flow rates at the reactor outlet,


YieldCH OH (H )
3

FCO out

are molar flow rates at the reactor inlet,


X CO

methanol yield against

conversion of
H2

CO2

XH

and

F H out
2

are molar

conversion of

existent in synthesis gas and

YieldCH

H2,

OH (C )

is

methanol yield against carbon existent in synthesis gas.


The reactor conditions have been tried to be optimized for the maximum conversion of carbon
dioxide.

6.1 Validation of model


Industrial results for synthesis of methanol ether are obtained from the work of Panahi et. al. The
simulated results for the shell and tube fixed bed reactor model has been validated against the
results of Panahi et. al. indicating that the model used in this study can be utilized for simulation

to find the optimum operating conditions and maximum conversion of carbon dioxide and yield
of methanol.
Table 4, Comparison of results with simulated results given by Panahi et. al.
CO2 Conversion
Temperature

Panahi et. al.


49.15
528.2

Matlab Model
47.855
515.25

Percentage Error
2.634
2.452

(a)

(a)

(e)

(b)

(b)

(f)

Fig. 1. Model Results of various parameters at T=498 K & P=50 bar (a) production of methanol (b) yield of
methanol wrt C (c) yield of methanol wrt H2 (d) conversion of carbon monoxide (e) conversion of hydrogen,
and (f) temperature along the length of the reactor

6.2 Effect of Pressure


The effect of temperature on the production of methanol, conversion of hydrogen, conversion of carbon dioxide
and yield of methanol at the outlet of the reactor is shown in the following figures. In these figures, H 2:CO2
molar feed ratio is 3 at different constant temperatures
As it can be concluded from the graph of methanol flowrate that molar flowrate of methanol increases with
increasing pressure. This happens because, high pressure favours the production of methanol. High pressure
also favours the conversion of carbon dioxide, conversion of hydrogen and the yield of methanol.

(a)

(b)

(c)

(d)

Fig. 2. Effect of Pressure on the molar flow rates of methanol


(a) T=478 K (b) T=488 K (c) T=498K (d) T=508K

(a)

(b)

(c)

(d)

(e)

Fig. 3. Effect of Pressure on the conversion of carbon


dioxide (a) T=478 K (b) T=488 K (c) T=498K (d)
T=508K (e) T=518 K

(a)

(b)

(c)

(d)

(e)

Fig. 4. Effect of Pressure on the conversion of hydrogen


(a)T=478 K (b) T=488 K (c) T=498K (d) T=508K (e) T=518
K

(e)
.
K

(a)

(b)

(c)

(d)

Fig. 5. Effect of Pressure on the yield of methanol w.r.t. H2


(a)T=478 K (b) T=488 K (c) T=498K (d) T=508K (e) T=518

(a)

(b)

(c)

(d)

(e)

Fig. 6. Effect of Pressure on the conversion of carbon dioxide


(a) T=478 K (b) T=488 K (c) T=498K (d) T=508K (e) T=518 K

6.3 Effect of Temperature


The effect of temperature on the production of methanol, conversion of hydrogen, conversion of carbon dioxide
and yield of methanol at the outlet of the reactor is shown in the following figures. In these figures, H 2:CO2
molar feed ratio is 3:1 at different constant pressures.
As it can be concluded from the graph of methanol flowrate that molar flowrate of methanol, conversion of
carbon dioxide, conversion of hydrogen and the yield of methanol increases with increasing temperature but
there are not considerable changes i.e. these changes are very less as compares to that of changing pressures. So
it can be concluded that the methanol synthesis process is greatly affected by changes in pressures as compared
to that of change in the temperatures.

(a)

(b)
Fig. 7. Effect of Temperature on the molar flow rates of methanol (a) P=38 bar (b) P=50 bar

(a)

(b)
Fig. 8. Effect of Temperature on the yield of methanol w.r.t. C (a) P=38 bar (b) P=50 bar

(a)

(b)

Fig. 9. Effect of Temperature on the yield of methanol w.r.t. H2 (a) P=38 bar (b) P=50 bar

(a)

(b)

Fig. 10. Effect of Temperature on the conversion of carbon dioxide (a) P=38 bar (b) P=50 bar

7. REFERENCES

[1] Shahrokhi, M., Baghmisheh, G R. (2005)

Modeling, simulation and control of a methanol synthesis fixed bed reactor,

Chemical Engineering Science 60 42754286.

[2] Lvik, I. (2007)

Modelling estimation and optimization of the methanol synthesis with catalyst deactivation.

Doctoral thesis, Norwegian University of Science and Technology 127.

[3] Vanden Bussche1. K. M., Froment. G. F. (1996)

A Steady -State Kinetic Model for Methanol Synthesis and the Water Gas Shift Reaction on

a Commercial Cu/ZnO/Al2O3 Catalyst.

Journal of Catalysis 161 1 10.

[4] Raudaskoski R., Niemel M. and Keiski R.L. (2007)

The effect of ageing time on co -precipitated Cu/ZnO/ZrO2 catalysts used in methanol

synthesis from CO2 and H2.

Topics in Catalysis 45(2007) 57-60.


[5] Yang R., Yu X., Zhang Y., Li W. and Tsubaki N., A new method of low-temperature methanol
synthesis on Cu/ZnO/ Al2O3 catalysts from CO/CO2/H2, Fuel 87 (2008) 443-450.
[6] Bussche K.M. V. and Froment G.F., A steady-state kinetic model for methanol synthesis and
the water gas shift reaction on a commercial Cu/ZnO/Al 2O3 catalyst Journal of Catalysis
161(1996) 1-10.
[7] Klier K., Chatikavanij V., Herman R.G. and Simmons G.W., Catalytic synthesis of methanol
from CO/H2: 1V. Effects of carbon dioxide, Journal of Catalysis 74(1982) 343-360.
[8] Liu G., Willcox D., Garland M. and Kung H.H., The role of CO 2 in methanol synthesis on
Cu-Zn Oxide: An isotope labeling study, Journal of Catalysis 96(1985) 251-260.
[9]. G.C. Chinchen, P.J. Denny, D.G. Parker, M.S. Spencer and D.A. Whan, Mechanism of
methanol synthesis from CO/CO2/H2 mixture over copper/zinc oxide/alumina catalysts: Use of
14C-labelled reactants, Applied Catalysis 30(1987) 333-338.

[10] Takagawa M. and Ohsugi M., Study on reaction rates for methanol synthesis from carbon
monoxide, carbon dioxide and hydrogen, Journal of Catalysis 107(1987) 161-172.
[11] McNeil M. A., Schack C.J. and Rinker R.G., Methanol synthesis from hydrogen, carbon
monoxide, and carbon dioxide over a Cu/ZnO/Al 2O3 catalyst: II. Development of a
phenomenological rate expression," Applied Catalysis, 50(1989) 265-285.

[12] Rozovskii A.Y. and Lin G.I., Fundamentals of methanol synthesis and decomposition, Top
Catal., 22 (3-4) (2003), 137-150.
[13] Fujita S., Usui M., Ito H. and Takezawa N., Mechanisms of methanol synthesis from carbon
dioxide and from carbon monoxide at atmospheric pressure over Cu/ZnO, Journal of Catalysis
157(1995), 403-413.
[14] Sahibzada M., Metcalfe I.S. and Chadwick D., Methanol synthesis from CO/CO 2/H2 over
Cu/ZnO/Al2O3 at differential and finite conversions, Journal of Catalysis 174(1998), 111-118.
[15] Ostrovskii V.E., Mechanisms of methanol synthesis from hydrogen and carbon oxides at
Cu-Zn containing catalysts in the context of some fundamental problems of heterogeneous
catalysis, Catal. Today 77(2002), 141-160.
[16] Lim H.W., Jun H., Park M., Kim H., Ha K., Chae H., Bae J.W. and Jun K., Optimization of
methanol synthesis reaction on Cu/ZnO/Al2O3 /ZrO2 catalyst using genetic algorithm:
Maximization of the synergetic effect by the optimal CO 2 fraction,Korean J. Chem Eng. 27(6)
(2010) 1760-1767.
[17]. Lim H.W., Jun H., Park M., Kim H., Ha K., Chae H., Bae J.W. and Jun K.,Modeling of the
kinetics for methanol synthesis using Cu/ZnO/Al2O3 /ZrO2 catalyst: Influence of carbon dioxide
during hydrogenation," Ind. Eng. Chem. Res., 48(23) (2009) 10448-10455.
[4] Raudaskoski R., Niemel M. and Keiski R.L. The effect of ageing
time on co -precipitated Cu/ZnO/ZrO2 catalysts used in methanol
synthesis from CO2 and H2. Topics in Catalysis ,vol. 45, pp. 57-60,2007.
[5] Yang R., Yu X., Zhang Y., Li W. and Tsubaki N. A new method of
low-temperature methanol synthesis on Cu/ZnO/Al2O3 catalysts
from CO/CO2/H2. Fuel, Vol. 87, pp. 443-450, 2008.
[8] Sinadinovic -fiser S.V, Jankovic M. R and Radicevic R. Z. simulation of the fixed - bed
reactor for methanol synthesis.

Petroleum and coal,vol. 43, pp. 31 -34, 2001.