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Methanol Synthesis Model and Reactor Design

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 Scientific Research
Methanol Synthesis Model and Reactor Design

Md. Firoz Kalam

Scientific Research Assistant

Institute of Thermal Process Engineering
Bremerhaven University of Applied Sciences
Bremerhaven, Germany
CRG Lab Table of Contents

Table of Contents
1 Introduction 4

2 Prediction of Gaseous Equilibrium 4

2.1 Literature Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2 Thermodynamic Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3 Calculation of Equilibrium Composition . . . . . . . . . . . . . . . . . . . 7
2.3.1 Simultaneous Known Chemical Reactions . . . . . . . . . . . . . . 7
2.3.2 Simultaneous Unspecified Chemical Reactions . . . . . . . . . . . 9
2.4 Excel Spreadsheet Calculation . . . . . . . . . . . . . . . . . . . . . . . . 9
2.5 Other Calculation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.5.1 Stanjan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.5.2 Aspen HYSYS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.5.3 HSC Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.6 Comparison of Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

3 Modelling of Chemical Reactor 15

3.1 Literature Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2 Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.3 Excel Spreadsheet Calculation . . . . . . . . . . . . . . . . . . . . . . . . 19
3.4 Comparison of Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.5 Axial Dispersion Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.5.1 Tubular Reactor (PFR) . . . . . . . . . . . . . . . . . . . . . . . . 21
3.5.2 Internal Recycle Reactor (CSTR) . . . . . . . . . . . . . . . . . . . 21
3.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

References 24

Research is what I’m doing when I don’t know what I’m doing.
Wernher von Braun (1912–1977)

Methanol Synthesis Model 2

CRG Lab List of Figures

List of Figures
1 Excel Property Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2 Excel Equilibrium Solver Sheet . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3 PFD of the Gibbs reactor in Aspen HYSYS for equilibrium calculation purpose 12
4 Plot of Excel spreadsheet calculations . . . . . . . . . . . . . . . . . . . . . . 13
5 Excel Plot of Calculations done via the Stanjan routine . . . . . . . . . . . . . 13
6 Excel Plot of Calculations done in Aspen HYSYS . . . . . . . . . . . . . . . . 13
7 Bigger plot of Excel spreadsheet calculations . . . . . . . . . . . . . . . . . . 14
8 Plot of Calculations done in HSC environment . . . . . . . . . . . . . . . . . . 14
9 Kinetic rate expressions for the methanol synthesis . . . . . . . . . . . . . . . 16
10 Construction details of the tubular reactor . . . . . . . . . . . . . . . . . . . . 17
11 Measurement data from [2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
12 Calculated conversions vs. experimental data . . . . . . . . . . . . . . . . . . 20
13 Axial Dispersion Correlation for Fixed-Bed Reactors from [3] . . . . . . . . . 20
14 Errors compared with the experimental data for different calculation methods . 21
15 Probability graph . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
16 F–curve for a closed vessel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
17 F(t)–Curve for an Residence Time Distribution (RTD) experiment of [4] . . . . 23
18 Fitted exponential function for the F–Curve of fig. 17 . . . . . . . . . . . . . . 23

List of Tables
1 Equilibrium Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2 Comparison of Entropies and heat capacities for . . . . . . . . . . . . . . . . . 6
3 Enthalpies of formation from different literature . . . . . . . . . . . . . . . . . 6
4 Equilibrium mole fraction expressions . . . . . . . . . . . . . . . . . . . . . . 8
5 Atom matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Methanol Synthesis Model 3

CRG Lab 1 Introduction

1 Introduction
Methanol is used widely in many industrial products. In 2007, 39% of all methanol was used
for the synthesis of formaldehyde; other important products are MTBE and acetic acid with a
share of 15% and 11%, respectively [5]. The usual synthesis involves the reaction of syngas
(carbon monoxide and hydrogen) over a highly selective catalyst which is in most cases made
of copper, zinc oxide and alumina oxide. The exothermic, reversible, catalytic reaction usually
takes place at 50–100 bar [6]. The equilibrium normally favours low temperatures, however,
to achieve the highest conversion rates at present pressures a temperature of 250 ◦C has been
established.
The production of syngas from methane produces three moles of hydrogen for every mole of
carbon monoxide, whereas the reaction for the methanol synthesis

CO + 2H2 → CH3 OH

only needs two moles of hydrogen. A common solution is to introduce carbon dioxide into
the reactor, which would then react by the equation

CO2 + 3H2 → CH3 OH + H2 O.

Here, the methanol synthesis is investigated two-fold: first by looking at the gaseous equilib-
rium of the synthesis at ambient pressure (section 2), second by reviewing data of experimental
reactor set-ups (section 3). Calculations in both parts are done in Microsoft Excel 2010 and
then compared with results of commercial software.

2 Prediction of Gaseous Equilibrium

2.1 Literature Review
For a long time, there has been the need to define thermodynamic equilibria of complex
chemical systems. NASA developed a software for equilibrium calculations as early as 1967
[7]. This software, as most of the other considered programs, takes the approach of the Gibbs
free energy minimization method. The advantage is here that no conversion rates have to be
defined, as would be the case with calculations involving equilibrium conversions.
The Gibbs Energy Minimization method has already been widely discussed for use in Mi-
crosoft Excel; for example, Lwin proposed a spreadsheet for use in engineering courses
[8]. However, in using this calculation routine, often the fugacities of the components have
to be calculated by equations of state (e.g. SRK or Peng-Robinson). Still, this approach

Methanol Synthesis Model 4

CRG Lab 2 Prediction of Gaseous Equilibrium

bypasses the tedious calculations of multiple chemical reactions, as would be present in coal
gasification processes [9].
Methanol Synthesis Reaction coefficients can be found in literature: Chang et al. included
temperature-dependent functions for the equilibrium constants for the methanol synthesis of
carbon monoxide and carbon dioxide, proposed by Bissett and Cherednichenko, respectively,
as follows:
" #
9143.6
KCO = 9.740 · 10 · exp 21.225 +
−5
− 7.492 · ln T + 4.076 · 10 T − 7.161 · 10 T ,
−3 −6 2
T
" #
5639.5 49170
KCO2 = exp 13.148 − − 1.077 · ln T − 5.44 · 10 T + 1.125 · 10 T +
−4 −7 2
.
T T2

Properties for the compound methanol can be found in an article of Goodwin [10]. These
are important for further investigation of the reactions, since methanol is the only compound
that would not have been widely researched, i.e., in this article discrete equations of state for
methanol are proposed.

2.2 Thermodynamic Data

For the calculations in Microsoft Excel, thermodynamic data from Fitzer & Fritz [11] was
used. Since this data is only given for 298 K and further values have to be calculated from
thereon, it seemed useful to compare the calculations with data taken from other literature
and to eventually switch to more appropriate sources.
Table 1 compares the resulting equilibrium concentrations, whereas table 2 compares entropies
and heat capacities from two sources. The equation of Bisset is used as cited in Chang et
al. [12], where the equilibrium constant is directly calculated with a given temperature. In table
3 enthalpies calculated from Fitzer/Fritz are compared to data taken from a Thermodynamic
data handbook [13] for different temperatures and data calculated by regression equations by
Baron et al. [14]. Baron’s methanol cells are empty, as the team didn’t provide an equation.

Table 1: Equilibrium Constants.

T in K Fitzer-Fr. Barin Bisset

298 1.01 × 10−5 0.98 × 10−5 1.00 × 10−5
400 0.000688 0.000663 0.000678352
600 0.039987 0.036154 0.037254722
800 0.294836 0.241955 0.249805240

The data from the tables compares well, though the equilibrium constants of Fitzer/Frirtz
Methanol Synthesis Model 5
CRG Lab 2 Prediction of Gaseous Equilibrium

Table 2: Comparison of Entropies and heat capacities for methanol at different tempera-
tures from [13, 10].

Barin Goodwin
S0 kJ/mol*K 0.253804 0.253189
400 K
C 0p kJ/mol*K 0.051801 0.05422
S0 kJ/mol*K 0.277692 0.277501
600 K
C 0p kJ/mol*K 0.066815 0.067410
S0 kJ/mol*K 0.298756 0.298663
800 K
C 0p kJ/mol*K 0.079794 0.079830

Table 3: Enthalpies of formation (and calculated) for different temperatures taken from
different literature sources [11, 13, 14].

H 0f, 298 K kJ/mol CO2 CO CH3OH H2 H2O

Fitzer-Fritz -393.770 -110.620 -201.300 0.000 -242.000
Barin -393.505 -110.541 -201.167 0.000 -241.826
Baron -393.814 -110.582 — -0.013 -241.981

H 0f, 400 K kJ/mol CO2 CO CH3OH H2 H2O

Fitzer-Fritz -389.982 -107.648 -196.705 2.943 -238.575
Barin -389.501 -107.564 -196.297 2.959 -238.375
Baron -389.757 -107.642 — 2.971 -238.541

H 0f, 600 K kJ/mol CO2 CO CH3OH H2 H2O

Fitzer-Fritz -382.554 -101.820 -187.695 8.713 -231.859
Barin -380.596 -101.599 -184.413 8.811 -231.326
Baron -380.855 -101.659 — 8.818 -231.487

H 0f, 800 K kJ/mol CO2 CO CH3OH H2 H2O

Fitzer-Fritz -375.126 -95.992 -178.685 14.483 -225.143
Barin -370.696 -95.364 -169.707 14.702 -223.825
Baron -370.968 -95.401 — 14.709 -223.978

Methanol Synthesis Model 6

CRG Lab 2 Prediction of Gaseous Equilibrium

diverge pretty quickly compared to those of Barin and Bisset. This is the result of slowly
diverging values that go into the calculation of the equilibrium constant via an exponential
function. Table 1 is as such a direct result of the values in table 3. Although the data from
other sources seemed more reliable, the Fitzer/Fritz values were deemed sufficient for two
reasons:
• unlike the Baron source [14], this data includes all the components and
• unlike the Barin source [13], Fitzer/Fritz can be used for variable temperatures.

2.3 Calculation of Equilibrium Composition

This section first describes the mathematical system for known chemical reactions (2.3.1),
i.e., using equations for the equilibrium constants, and then discusses the Gibbs free energy
minimization method (2.3.2). Most of these equations are based on the Handbook of Chemical
Engineering Calculations [15]. Here, only the methanol synthesis system is studied rather
than a general approach of the subject.

2.3.1 Simultaneous Known Chemical Reactions

Methanol is mainly produced via the hydrogenation of carbon monoxide:

CO + 2H2 → CH3 OH ∆H(298 K) = −91 kJ mol−1 . (1)

Another pathway is the hydrogenation of carbon dioxide, as CO2 sometimes is substituted for
the lack of CO in syngas (cf. 1). The following equation therefore should also be considered:

CO2 + 3H2 → CH3 OH + H2 O ∆H(298 K) = −50 kJ mol−1 . (2)

Another important reaction is the water–gas–shift over the catalyst [16]:

CO + H2 O → CO2 + H2 ∆H(298 K) = −47 kJ mol−1 . (3)

Those equations are not independent: equation 2 can easily be reproduced by algebraic
manipulation of equations 1 and 3 and so forth. Therefore one of the equations can be
dropped1 . The complete system for the methanol synthesis therefore only consists of two
independent reactions.
From those equations the equilibrium constants can be calculated via the Gibbs free energy of

1
To make sure that this statement holds true for the system, both cases with two and three equations were
studied. Both arrived at the same calculations for equilibrium compositions.

Methanol Synthesis Model 7

CRG Lab 2 Prediction of Gaseous Equilibrium

the reactions. The Gibbs energy is calculated as follows:

X X
∆G0f (T ) = ∆H 0f (T ) − S 0 (T ) · T.

The enthalpies and entropies of formation for a specific temperature are calculated as

∆H 0f (T ) = ∆H 0f,298 + C 0p · (T − 298 K) and S 0 (T ) = S 298

0
+ C 0p · ln(T/298 K).
 
Finally, the equilibrium constant is equal to exp −∆G0f /RT .
For each of these equilibrium constants another equation can be developed, consisting of the
product of the activities of the components with their stoichiometric numbers for exponents,
i.e. K = aνi i . Because the methanol synthesis equilibrium is only considered at ambient
Q

pressure and relatively high temperatures, the activities can be reduced to the corresponding
equilibrium mole fractions.
The equilibrium mole fractions have to be expressed in terms of reaction–progress variables.
This way, more than two simultaneous reactions can be easily calculated. Reaction–progress
variables measure the extent to which a reaction has taken place. If — as in this case — only
the hydrogenation of carbon monoxide and the water–gas–shift reaction are considered, the
two needed variables are labelled as xCO (eq. 1) and xWGS (eq. 3). By doing this, the mole
fractions can be expressed as shown in table 4.

Table 4: Expressions for the equilibrium mole fractions for the five components in the
methanol synthesis system.

Number of moles
Component Initially At equilibrium Equilibrium mole fraction y
CO2 0.03 0.03 + xWGS (0.03 + xWGS )/(1 − 2 · xCO )
CO 0.29 0.29 − xCO − xWGS (0.29 − xCO − xWGS )/(1 − 2 · xCO )
CH3 OH 0.00 xCO xCO /(1 − 2 · xCO )
H2 0.67 0.67 − 2 · xCO + xWGS (0.67 − 2 · xCO + xWGS )/(1 − 2 · xCO )
H2 O 0.01 0.01 − xWGS (0.01 − xWGS )/(1 − 2 · xCO )

Finally, the equilibrium mole fractions can be introduced into the equations for the equilibrium
constants, so that there is a system of (in this particular case) two equations for which the two
variables, i.e. the reaction–progress variables, can be solved.

Methanol Synthesis Model 8

CRG Lab 2 Prediction of Gaseous Equilibrium

2.3.2 Simultaneous Unspecified Chemical Reactions

If the reaction mechanism for a system of chemical components is unknown or the system is
too complex, often the Gibbs free energy minimization method is used to determine gaseous
equilibria. To do this, first the number of atoms of each element in a chemical compound has
to be determined, as has been done in table 5. The initial number of "moles" of atoms has
also to be defined, for example AH = 2 · y0H2 + 2 · y0H2 O + 4 · yCH
0
3 OH
, and so on.

Table 5: Matrix of atom numbers of each element present in the compounds involved in
methanol synthesis.

i ai,C ai,O ai,H

CO 1 1 0
CO2 1 2 0
CH3 OH 1 1 4
H2 0 0 2
H2 O 0 1 2

The Gibbs energy equations for each component have then to be determined. This involves
the method of Lagrange undetermined multipliers and yields the following equations:
X
∆G0f + RT · ln(yi · φi · p/ fi0 ) + (λk · ai,k ) = 0.
k

These equations simplify if ideal gases are assumed (φi = 1) and f 0 = 1 atm.
The material–balance equations for each element and the mole–fraction sum equation com-
bined with the Gibbs energy equations compose a set of equations for which first the Lagrange
multipliers, then the equilibrium mole fractions of the components can be computed. As this
involves many equations to be solved simultaneously, this is best done by a robust software
routine2 . In fact, all of the software looked at in section 2.5 is calculating equilibria by this
method, as it doesn’t require any equilibrium constant expressions and is more easily defined
by equations of state.

2.4 Excel Spreadsheet Calculation

The first Excel spreadsheet can be seen in figure 1. It calculates the standard enthalpy and
the entropy of formation for each component at the given temperature. Data has been taken
from Technische Chemie (1995) [11, p. 110]. Further, and probably more precise data could
be taken from, e.g., Thermodynamic Data of Pure Substances [17]. For the purpose on hand
2
In the case of methanol synthesis there are nine equations to be solved: three element material balances, one
total mole fraction sum and five Gibbs minimization equations.

Methanol Synthesis Model 9

CRG Lab 2 Prediction of Gaseous Equilibrium

the data from the first book was sufficient, as can be seen in section 2.6. The thermodynamic
properties are calculated via the equations given in section 2.3.1.
Figure 2 shows the Excel sheet for calculation of the equilibrium mole fractions via the
equilibrium constant route described in section 2.3.1. Grey fields can be entered by hand,
such as the stoichiometric coefficients for specific reactions, initial composition and the
progress–rate variables. The solver function can be used to minimise the difference between
the equilibrium constant calculated by the Gibbs free energy of reaction and the one calculated
by the product of the activities. The reaction sets can be changed freely, since the underlying
functions are very general. That way the third reaction set can be neglected, although it is part
of all equations.
The use of the solver to specify the progress–rate variables (called x_1, x_2 and x_3 in the
spreadsheet) by reduction of the sum of all errors of the equilibrium constants turned out to
be problematic. The solver won’t reduce both (or all three) errors, but rather only reduce one
to a minimum. That’s why the resulting calculations involved a repeated use of the solver
routines, by first minimising one error, then the other, and so forth. This way the overall and
each specific error was sufficiently reduced and one arrived at plausible equilibrium mole
fractions.

2.5 Other Calculation Methods

To be able to compare the results of the Excel calculations, the same initial mole compositions
were taken to different calculation environments, Stanjan, Aspen HYSYS and HSC Chemistry.
It should be noted here that all of these programs make use of the Gibbs minimization method
rather than the equilibrium reaction route.

2.5.1 Stanjan
"Stanjan", derived from its roots at Stanford and its connection with the Jannaf thermochemical
data tables, was developed by W.C. Reynolds in the 1980s [18]. There was a computer program
comprising the calculation routines, however, since the author passed away nearly a decade
ago, it is not distributed anymore and probably can’t be run on current systems. The program
is still available through a webinterface from the Colorado State University3 . From this, the
equilibrium mole fractions were calculated and are shown graphically in figure 5.

2.5.2 Aspen HYSYS

The software Aspen HYSYS includes a "Gibbs reactor", which calculates the equilibrium
composition of a given feed stream. The process flowsheet can be seen in figure 3, whereas
3
http://navier.engr.colostate.edu/ dandy/code/code-4/

Methanol Synthesis Model 10

CRG Lab 2 Prediction of Gaseous Equilibrium

Figure 1: Calculation of Component Properties (enthalpy and entropy of formation) in

Excel.

Figure 2: Excel Sheet for Computation of Equilibrium Constants: Matrix of Stoichio-

metric Coefficients (lines 1-4), initial composition (6), calculation of Gibbs free energy
of reaction for each reaction set (8-21), determination of progress-rate variables and error
calculation for solver (23-26), equilibrium mole compositions of all components (28-29).

Methanol Synthesis Model 11

CRG Lab 2 Prediction of Gaseous Equilibrium

the graphical representation of the calculations can be viewed in figure 6. By means of

so-called "case studies", curves from the exiting mole streams can be generated for different
temperatures.

Figure 3: PFD of the Gibbs reactor in Aspen HYSYS for equilibrium calculation
purpose.

2.5.3 HSC Chemistry

The HSC Chemistry software package provides a means for equilibrium calculations, too,
via either the "Gibbs"– or the "SolGasMix"–routine. It can also calculate heat and material
balances or Mollier diagrams, for example. Work with the program in version 5.1 was not
straight forward and took quite a while to get used to. The results are shown in figure 8.

2.6 Comparison of Results

The Excel calculations closely resemble the results obtained in Aspen HYSYS and Stanjan.
HYSYS didn’t obtain results for temperatures < 330 K. Below those temperatures not all the
components are gaseous anymore, so probably the results from the other two calculations in
this region could also be questioned. Figures 4, 5 and 6 clearly show that the reaction rate
route can be just as reliably used as the Gibbs energy minimization technique.
The HSC chemistry package didn’t arrive at good results, as can be shown by comparing
figures 7 and 8. Somehow it calculated completely different equilibria than all the other
software mentioned before. This can easily be an input error of the user, as the software
wasn’t easy to handle. It won’t be used anymore for eqilibrium calculations.

Methanol Synthesis Model 12

CRG Lab 2 Prediction of Gaseous Equilibrium

Figure 4: Plot of Excel spreadsheet calculations.

Figure 5: Excel Plot of Calculations done via the Stanjan routine.

Figure 6: Excel Plot of Calculations done in Aspen HYSYS.

Methanol Synthesis Model 13

CRG Lab 2 Prediction of Gaseous Equilibrium

Figure 7: Bigger plot of Excel spreadsheet calculations.

Figure 8: Plot of Calculations done in HSC environment.

Methanol Synthesis Model 14

CRG Lab 3 Modelling of Chemical Reactor

3 Modelling of Chemical Reactor

3.1 Literature Review
For the methanol synthesis reaction many different expressions were developed over the
decades (figure 9 shows some examples), from first–order reactions to very complex expres-
sions, derived from reaction mechanisms involving the adsorption of different species and the
formation of many intermediates previous to methanol formation.
A common proposed mechanism is the synthesis of methanol via a formyl and methoxy
species that finally evolves to methanol. The mechanism involves metal cations and vacant
zinc and/or oxygen sites for adsorption [19]. However, this mechanism seems to be outdated,
as there has been a new mechanism proposed for nearly two decades which involves carbon
dioxide as a necessary intermediate [20]. Without the presence of CO2 any methanol synthesis
seems highly unlikely. Furthermore, the catalyst plays an important role in the mechanism,
since the adsorption can differ a lot on different metal surfaces. The common catalyst is
copper, with a stabilizing grid of either alumina oxide and/or zinc oxide.
In the following, experimental data of different papers from a Dutch team has been investigated.
They used a pure H2 /CO–stream for methanol synthesis over a copper catalyst. Because of
this set–up they arrived at very different conclusions than most other scientists before and
after. Methanol synthesis still proceeds with much lower conversion as with streams in which
carbon dioxide would be present, but it happens nonetheless.

3.2 Experimental Data

Kuczynski and colleagues investigated the methanol synthesis extensively in different kinds
of reactors: tubular reactor [2], internal recycle reactor [4] and trickle–flow reactor [21, 22].
In all of their experiments they focused on the kinetics of the methanol synthesis when there
is no carbon monoxide in the feed stream.
Their paper on the tubular reactor experiment includes extensive reaction measurement data.
That’s why this setup was mainly chosen for investigation of their findings. Their tubular
reactor setup can be reviewed in figure 10. Their measurements are included in the report (fig.
11). The following two sections deal with this data (sec. 3.3 & 3.4). The axial dispersion
model is then investigated in section 3.5 for both the tubular and the continuously stirred
(internal recycle) reactor.
Their reactor gives highly idealized results, as the temperature differences are very minimal
and the whole bed is only a few millimetres in diameter and length.

Methanol Synthesis Model 15

CRG Lab 3 Modelling of Chemical Reactor

Figure 9: Kinetic rate expressions for the methanol formation and the reverse water–gas
shift reaction on CuO–ZnO containing system from [1].

Methanol Synthesis Model 16

CRG Lab 3 Modelling of Chemical Reactor

Figure 10: (a) Construction details of the reactor from [2]: 1 gas inlet, 2 gas outlet, 3
reactor tube, 4 bronze block, 5 heating oven, 6 insulation, 7 support grid, 8 inert packing,
9 catalyst bed, 10 thermocouple sheaths, 11–13 thermocouples. (b) Typical temperature
profiles measured along the reactor axis: curve a without and curve b with reaction.

Methanol Synthesis Model 17

CRG Lab 3 Modelling of Chemical Reactor

Figure 11: Measurement data from [2].

Methanol Synthesis Model 18

CRG Lab 3 Modelling of Chemical Reactor

3.3 Excel Spreadsheet Calculation

Kuczynski et al. [2] arrived at two possible rate equations that fitted the data satisfactorily.
Those are stated in their paper as follows:

2.68 · 109 · exp(−18 400/T ) · (φCO · φH2 − φM /Keq )

R1 = ,
(1 + 0.069 · φCO + 6.19 · 10−8 · exp(6610/T ) · φH2 )3

18.01 · exp(−9032/T ) · (φCO · φH2 − φM /Keq )

R2 = .
1 + 2.97 · 10−4 · exp(3539/T ) · φCO + 2.59 · 10−4 · φCO · φ2H2
Both of these were taken into account while calculating the theoretical conversions. Here, the
investigation focused on the accuracy of the calculations, when the simple equation
Z τ
ζCO = RCO · τ becomes ζCO = RCO · dτ.
0

For this purpose, the weight time τ was divided into twenty parts and the reaction rate was
calculated for each one of them. The resulting conversions were either added or subtracted
from the molar fractions of the components of the system via their stoichiometric balance.
Only then the terms for the equilibrium inhibition of the system (namely φM /Keq ) are even
considered by the calculation. The ζCO –values were added up from each calculation step to
arrive at a final conversion value.
At some pressures and/or initial mole fractions of carbon monoxide, the reaction rate expres-
sions differed widely from the measurements. Figure 12 shows how the rate expressions
overestimate the measurements at p = 60.5 bar, whereas the integrated expression resembles
the experimental data closely.
For higher pressures the formulas after integration still overestimate the data. For these cases
the axial dispersion model was tried according to Levenspiel [3]:
 D 
[A] 
 2· · R · ln(1 + R)  1
!
= 1 + uL 
, R = k · [A]0 · τ
 ·
[A0 ]  1+R  1 + R

D
As a first approximation, a dispersion coefficient of = 0.5 for flow in fixed beds ( ≈ 0.4)
uL
and Re  10 was chosen (see fig. 13). The so calculated reaction rates deliver a prediction far
below the experimental values, so it can be assumed, that axial dispersion in the experimental
reactor (as assumed) is minimal.

Methanol Synthesis Model 19

CRG Lab 3 Modelling of Chemical Reactor

Figure 12: Calculated conversions compared with the experimental data for different
space/weight times at p ≈ 60.5 bar and for yCO,in = 0.102.

Figure 13: Axial Dispersion Correlation for Fixed-Bed Reactors from [3].

Methanol Synthesis Model 20

CRG Lab 3 Modelling of Chemical Reactor

3.4 Comparison of Results

If one compares the relative errors of the calculated conversions to the experimental values,
the integrated forms altogether show better results than those calculated in one step (see fig.
14). The fact that all errors are either positive or negative for a certain residence (space) time
τ means that the overall error is due to errors of the experimental data.
The Axial Dispersion Model widely underestimates the data. To conclude that axial dispersion
does not play a role in the reactor, the dispersion coefficient is estimated in the next chapter.

Figure 14: Errors compared with the experimental data for different calculation methods.

3.5 Axial Dispersion Model

3.5.1 Tubular Reactor (PFR)

D
For an evaluation of the dispersion coefficient for the tubular reactor in [2], the first 21
uL
experimental data points in fig. 11 were plotted in a probability graph as shown in figure 15.
As described by Levenspiel [3], the line that fits the experimental data gives the coefficient
D 1 2σ
by = , the 2σ–value being the the difference in time between the 16% and the 84%
uL 2 t
conversion rates (vertical lines in the diagram). The so calculated diffusion coefficient has a
value of ≈ 0.178, not far below the estimated value of 0.2 in the previous section.

3.5.2 Internal Recycle Reactor (CSTR)

For a continuously stirred tank reactor (CSTR), as the internal cycle reactor of [4] is supposed
to be, the dispersion should be approaching infinity. As can be seen in figure 16, the resulting

Methanol Synthesis Model 21

CRG Lab 3 Modelling of Chemical Reactor

D
Figure 15: Probability graph for the determination of from the F–curve; conversion
uL
in % over residence time in s.

F–curve should approach an exponential function.

The F–curve presented in the paper of Bos et al. [4] clearly resembles an exponential function.
The values for this function were determined in Excel by overlaying the plot of calculated
values with the F–curve of the paper. The resulting calculations give an exponential function
of F(t) = 1 − exp{−0.0137 · t}. If the volume of the reactor is known, a compartment model
can be developed. For example, in a CSTR with dead volume, the value of the exponential
V̇
function would mean that 0.0137 = .
Vdead
3.6 Conclusion
Although the development of a meaningful rate expression for the conversion rate of a
reaction seems to be the most important step in evaluating a reaction, some properties of
the chemical reactor data presented could be used for finding important properties of those
reactors. Whereas the axial dispersion doesn’t seem to play a role in a experimental tubular
reactor, the dispersion approaches infinity for the external recycle reactor, so that both reactors
very well resemble the ideal PFR and CSTR, respectively.
Integrating over small steps of the residence (or space) time is also important in calculating the
conversion. Only then the negative influence of the products on the equilibrium is noticeable.

Methanol Synthesis Model 22

CRG Lab 3 Modelling of Chemical Reactor

D
Figure 16: F–Curve for a closed vessel with large dispersion, > 0.1 from [3].
uL

Figure 17: F(t)–Curve for an Residence Time Distribution (RTD) experiment of [4].

Figure 18: Fitted exponential function for the F–Curve of fig. 17.

Methanol Synthesis Model 23

CRG Lab References

References
[1] Skrzypek, Jerzy ; Lachowska, Maria ; Grzesik, Miroslav ; Slosczynski, Jerzy ; Nowak, Pawel:
Thermodynamics and kinetics of low pressure methanol synthesis. In: The Chemical Engineering
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[2] Kuczynski, M. ; Browne, W.I. ; Fontein, H.F. ; Westerterp, K.R.: Reaction Kinetics for the
Synthesis of Methanol from CO and H2 on a Copper Catalyst. In: Chemical Engineering and
Processing 21 (1986), S. 179–191
[3] Levenspiel, Octave: The Chemical Reactor Omnibook. Print on Demand by Lulu.com, 2013. –
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[4] Bos, A.N.R. ; Borman, P.C. ; Kuczynski, M. ; Westerterp, K.R.: The Kinetics of the Methanol
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com/ourcompany/documents/3395_Methanex_CorpBrochure_12pp.pdf. – 04.01.2013
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and Kinetics. John Wiley & Sons, Inc., 1999
[7] Gordon, Sanford ; McBride, Bonnie J.: Computer Program for Calculation of Complex Chemical
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[12] Chang, Te ; Rousseau, Ronald W. ; Kilpatrick, Peter K.: Methaniol Synthesis Reactions:
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[17] Barin, Ihsan (Hrsg.): Thermodynamic Data of Pure Substances Part I and II. VCH Verlagsge-
sellschaft mbH, 1989

Methanol Synthesis Model 24

 CRG Lab References

[18] Reynolds, W.C.: The Element Potential Method for Chemical Equilibrium Analysis. Implemen-
tation in the Interactive Program STANJAN. Department of Mechanical Engineering, Stanford
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Methanol Synthesis Model 25

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