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Kinetic Modelling
and Reactor Design
Methanol Synthesis
Kelvin Obareti
CE4005
4/26/2013
Abstract
The primary purpose of this project is to develop kinetic modelling methods and
approaches. A pseudo-homogeneous model was developed for a shell and tube
methanol reactor based on the reaction mechanisms and mass and energy balance
equations. Shell and tube reactor consist of tubes packed with catalyst particles and
operated in a vertical position. The catalyst particles are of spherical shape. Feed is
passed from the top of reactor in to the tubes; due to exothermic reaction the rate will
be relatively large at the entrances to the reactor tube owing to the high concentrations
of reactants existing there. It will become even higher as the reaction mixture moves a
short distance into the tube, because the heat liberated by the high rate of reaction is
greater than that which can be transferred to the cooling fluid as water at high pressure.
Hence the temperature of the reaction mixture will rise, causing an increase in the rate
of reaction. This continues as the mixture moves up the tubes, until the disappearance
of reactant has a larger effect on the rate than the increase in the temperature. Farther
along the tube the rate will decrease. Langmuir-Hinshelwood model was used to derive
[ ]
a kinetic rate equation ( ) With the proposed mathematical
model, a plant scale reactor was simulated for a feed temperature of 475K with a feed
composition of 70mol% H2 and 30mol%CO. Properties of the reactor and the catalyst
bed was determined. The Reynolds number was calculated to be less than 2000 which
means the flow will be laminar and the velocity profile will be parabolic. This
contradicts the assumption of a steady state plug flow where reactor mixture of
different age will not mix.
The dimensions of the reactor were calculated based on information from specification,
literature and reasonable assumptions. The reactor worked out to be an adiabatic
cylindrical vessel, 15.95m long with a diameter of 3.19m with a pressure drop around
0.5 bar, the catalyst (assumed to be Cu/ZnO/Al2O3) weight was calculated to be
37257kg for the specified molar feed rate of 5947.66 mol/s. The sensitivity of the vessel
to allowable pressure drop was also investigated. This suggests that for a given amount
of catalyst, a reduced pressure drop can be obtained by reducing the bed depth at the
expense of increasing the bed diameter. Although reducing the pressure drop will
reduce the operating power cost, it will increase the vessel cost.
CE4005 | Abstract 1
The reactor simulation was repeated with three kinetic models from literature and
compared to the developed kinetic model. The kinetic equation proposed by Agny and
Takoudis (1985) fitted best with the experimental data and was closest to the proposed
kinetic data that was derived from the kinetic experimental data provided. The Agny
and Takoudis mathematical model was used to simulate the reactor for adiabatic and
non-adiabatic setup from the given kinetic data. The equilibrium conversion (highest
conversion possible for reversible reactions) was found to be 23% with a
corresponding equilibrium temperature of 550K, hence a coolant temperature of 550K
was recommended for the shell side of the reactor in order to be able to achieve the
equilibrium conversion. Interstage cooling was suggested in order to be able to achieve
higher conversion.
The modelling process was repeated on ASPEN in order to observe the temperature
profile and the effects of different feed composition as well as feed temperature. The
optimum feed composition was found to be 70mol% H2 and 30mol%CO as this
produced the highest amount of methanol under the same conditions. The ASPEN
simulation results also showed a conversion range between 20%-30% which is similar
to that of the equilibrium conversion obtained earlier. A sensitivity analysis was carried
out on Aspen to check the effect of varying the feed temperature on the rate of
production of methanol. The analysis showed that increasing the feed temperature will
lead to decrease in methanol production and vice versa. The optimum temperature
from the graph was 100 C (373K). This results follows from the strong exothermic
nature of the methanol synthesis. At equilibrium, the rate of backward reaction will
increase more relative to the rate of backward reaction with temperature rise which
means there will be less conversion of the reactants to products.
The high adiabatic temperature rise observed in all the simulation suggested that an
adiabatic reactor running at the specified condition is not suitable for the methanol
synthesis process and therefore an operation with an heat exchange medium should be
considered. An optimisation of the temperature regime was suggested. This can be
achieved by using a type of reactor where the temperature profile can be adjusted such
that the reaction mixture is allowed to be heated by the heat of reaction in the region
free of the effect of chemical equilibrium , to be later cooled by heat exchange in the
region effected strongly by chemical equilibrium.
CE4005 | Abstract 2
Table of Contents
Abstract ..................................................................................................................................... 1
1. Introduction ...................................................................................................................... 7
2. Background ....................................................................................................................... 7
2.1. Available Process Routes .......................................................................................... 8
2.2. Reactor Model Description ..................................................................................... 12
3. Literature Review ........................................................................................................... 15
3.1. Process Description ................................................................................................. 15
3.2. Reaction Mechanisms and Kinetic Models ............................................................ 18
3.2.1. Mechanisms involving CO ................................................................................ 18
3.2.2. Mechanisms Involving CO2 ............................................................................. 19
3.3. Thermodynamic Equilibrium ................................................................................. 20
3.4. Selectivity ................................................................................................................. 22
3.5. Catalysts ................................................................................................................... 23
3.5.1. High-pressure Catalysts ................................................................................... 23
3.5.2. Low-pressure Catalysts ................................................................................... 24
3.6. Kinetic Models.......................................................................................................... 26
3.6.1. Natta et al (1953) ............................................................................................. 27
3.6.2. Rozovskii (1980) and Klier (1982) ................................................................ 27
3.6.3. Agny and Takoudis (1985) .............................................................................. 28
3.6.4. Skrzypek's (1985 and 1991) ........................................................................... 29
3.6.5. Lim (2009) ........................................................................................................ 31
3.6.6. Literature Review Conclusion ......................................................................... 34
4. Work Plan and Methodology ......................................................................................... 35
4.1. To develop a kinetic model for the synthesis of methanol from the synthetic
rate data given in Appendix 1 ........................................................................................... 35
4.1.1. Developing Langmuir-Hinshelwood Kinetic Model from Experimental Data
35
4.1.2. Experimental Data Incorporated into Kinetic Model From Literature ........ 36
4.2. Simulating a Plant-Scale Catalytic Reactor ............................................................ 39
4.2.1. Reactor Volume ................................................................................................ 40
4.2.2. Reactor Length and Diameter ......................................................................... 40
CE4005 | Abstract 3
4.2.3. Reactor Dome Closure ..................................................................................... 41
4.2.4. Catalyst Bed Characteristics ............................................................................ 42
4.3. Sensitivity to pressure drop ................................................................................... 43
4.4. Effect of Coolant Temperature ................................................................................... 43
4.5. Modelling with ASPEN Process Modelling Software. ........................................... 44
4.6. Gantt Chart ............................................................................................................... 44
5. Results and Discussion .................................................................................................. 44
5.1. Developing a kinetic model from experimental data ........................................... 44
5.1.1. Dependence on the product methanol ........................................................... 46
5.1.2. Dependence on Carbon Monoxide .................................................................. 47
5.1.3. Dependence on Hydrogen ............................................................................... 47
5.1.4. Finding k and K Values ..................................................................................... 48
5.2. Plant-Scale Catalytic Reactor Simulation ............................................................... 51
5.2.1. Reactor Dimension ........................................................................................... 59
5.3. Experimental Data Incorporated Into Kinetic Models from Literature .............. 66
5.4. Effect of Coolant Temperatures .............................................................................. 74
5.5. Modelling with ASPEN Process Modelling Software ............................................ 76
5.6. Further Discussion .................................................................................................. 81
6. Conclusion ....................................................................................................................... 82
7. Recommendations .......................................................................................................... 84
8. Nomenclature ................................................................................................................. 86
9. References ....................................................................................................................... 87
10. Appendices
10.7 Appendix 7: USB stick with ASPEN and Microsoft Excel Simulation and
Graphs
CE4005 | Abstract 4
List of Figures
Figure 1 Structural formula of methanol ................................................................................... 7
Figure 2. The ICI-steam-raising reactor for low-pressure methanol synthesis [iv]. ................ 10
Figure 3 Simplified route to methanol production [].............................................................. 11
Figure 4 Production of methanol from atmospheric carbon dioxide or from neutral gas
(methane), and its use as a fuel. DMFC: direct methanol fuel cell [i]. .................................... 11
Figure 5 Schematic diagram of a plug flow reactor ................................................................. 12
Figure 6 Mass balance around a plug flow reactor ................................................................. 12
Figure 7. Essential process steps in Lurgi’s Low Pressure Methanol Process []. ..................... 16
Figure 8. Flow sheet of Lurgi's Methanol Synthesis Loop [xii] ................................................. 17
Figure 9. Thermodynamics of methanol synthesis. Variation of equilibrium constant kp with
temperature and pressure [iv] ................................................................................................. 21
Figure 10. Reaction temperature profile of adiabatic and non-adiabatic set up at conversion
between 0 and 0.9 ................................................................................................................... 59
Figure 11. Reactor hemispherical dome closure dimension ................................................... 61
Figure 12. Preliminary dimension of the plant-scale catalytic reactor.................................... 62
Figure 13. Reactor dimension sensitivity to pressure drop ..................................................... 66
Figure 14. Reaction rate as a function of degree of conversion in the adiabatic reactor. ...... 71
Figure 15. Relationship between temperature and degree of conversion in the adiabatic
reactor. ..................................................................................................................................... 71
Figure 16. Reaction rate as a function of degree of conversion in the non-adiabatic reactor.
.................................................................................................................................................. 73
Figure 17. Relationship between temperature and degree of conversion in the non-adiabatic
reactor. ..................................................................................................................................... 73
Figure 18. Plot of equilibrium conversion as a function of temperature. ............................... 75
Figure 19. Interstage cooling []. ............................................................................................... 76
Figure 20. Reactor model summary......................................................................................... 77
Figure 21. Flow sheet with heat and material balance for ASPEN simulation at a feed inlet
temperature of 473K (200 C) ................................................................................................... 78
Figure 22. Temperature profile of the reactor at a feed composition of 70% H 2 and 30% CO
.................................................................................................................................................. 79
Figure 23. Sensitivity of methanol production to different feed temperatures. ................... 80
CE4005 | Abstract 5
List of Tables
Table 1. Catalysts proposed or used for industrial process [iv]. .............................................. 23
Table 2. Important rate expressions for methanol synthesis []. ............................................. 26
Table 3. Elementary Reactions for Cu/ZnO/Al2O3/ZrO2 catalysed methanol synthesis [] ....... 32
Table 4. Reaction rates for methanol synthesis reaction and DME production [xxvi]. ........... 33
Table 5. Methanol synthesis kinetic models to be compared to developed kinetic model.... 34
Table 6. Data for Kinetic Analysis............................................................................................. 45
Table 7. Experiment 1 compared to experiment 5. ................................................................. 46
Table 8. Experiments to deduce the dependence on carbon monoxide ................................ 47
Table 9. Effect of decreasing the partial pressure of hydrogen on the rate of reaction. ........ 47
Table 10. Constant hydrogen partial pressure for kinetic parameter ..................................... 49
Table 11. Constant methanol partial pressure for kinetic parameter ..................................... 50
Table 12. Experimental data table modified to include values of V O , CA0, FA0 and ṁ ........... 55
Table 13. Experiment 12 reaction conditions 1 ....................................................................... 57
Table 14. Experiment 12 reaction conditions 2...................................................................... 57
Table 15. Reactor volume and temperature profiles for adiabatic and non-adiabatic setup at
conversion between 0 and 0.9................................................................................................. 58
Table 16. Summary of reactor cylindrical section dimension.................................................. 60
Table 17. Summary of overall rector dimension ..................................................................... 62
Table 18. Summary of catalyst bed characteristics. ................................................................ 64
Table 19. Reactor dimension sensitivity to pressure drop ...................................................... 65
Table 20. Methanol synthesis kinetic models and rate equation............................................ 66
Table 21. Comparison of kinetic model simulation results. .................................................... 67
Table 22. Summary of Agny and Takoudis model for an adiabatic reactor using the provided
experimental data .................................................................................................................... 69
Table 23. Summary of Agny and Takoudis model for non-adiabatic reactor setup using the
experimental data provided .................................................................................................... 72
Table 24. Results table for temperature-conversion relationship. ......................................... 74
CE4005 | Abstract 6
1. Introduction
The primary purpose of this project is to develop a kinetic model for the synthesis of
methanol from given set of synthetic rate data. The result of the kinetic model will then
be used to simulate a shell-and-tube reactor at specified conditions, using a simple one-
dimensional, plug-flow, pseudo homogeneous, nonisothermal reactor model. The
kinetic model developed will be compared to other kinetic models suggested by
literature and the best model will be used in the reactor design and to study the
performance of the reactor. This will provide an opportunity to demonstrate and apply
technical knowledge. Also, the ability in critical analysis will be demonstrated.
2. Background
The issue of sustainability is that which concerns many industries and given the option
of moving from the consumption of fossil fuels towards renewable/cleaner energy
makes the synthesis of methanol very important.
Methanol is the simplest alcohol (one carbon backbone). It is a clear, colourless liquid
with a characteristics alcohol odour.
There are various means of producing methanol and these includes the anaerobic
metabolism of many varieties of bacteria (natural), pyrolysis of wood, and most
importantly from fossil fuel based synthesis gas, which is the main method of producing
methanol industrially.
According to the 1994 Nobel Prize in Chemistry winner, George Andrew Olah [i],
Methanol can replace fossil fuels as a means of energy storage, in what is now referred
CE4005 | Introduction 7
to as the methanol economy. Apart from the current use of methanol today as chemical
feedstock for producing useful chemical products like, acetic acid, formaldehyde (used
in construction and wooden boarding) and methyl tert-butyl ether (MBTE), due to its
high octane rating, and biodegradability, methanol can be used directly as a fuel in
hybrid vehicles and as a fuel in fuel cells which are renewable forms of energy
production.
The synthesis gas that was first used for the production of methanol was manufactured
by coke gasification. In recent times, the synthesis gas is now almost invariably
produced by steam reforming or partial oxidation of hydrocarbons, usually natural gas
[iv].
The production of methanol from synthesis gas occurs in two steps. The first step
involves the conversion of the feedstock natural gas (methane) into a synthesis gas
stream that consists of carbon monoxide (CO), carbon dioxide (CO2), water (H2O) and
hydrogen (H2). The first step is usually carried out by the catalytic steam reforming of
hydrocarbon feedstock or by non-catalytic partial oxidation of hydrocarbon or coal [iii].
Methanol produced via the catalytic hydrogenation of carbon monoxide and/or carbon
dioxide occurs via the three reactions given below [iv].
CE4005 | Background 8
3. Water-gas shift reaction:
Synthetic route for methanol production was first commercialised by BASF in Germany.
The process was based on the reaction of synthesis gas which is a mixture of hydrogen
and carbon oxides. The reaction occurred over a zinc chromite catalyst at relatively high
temperatures of 300 to 400°C and high pressures (250 to 350atm). Synthesis gas was
derived from coal via the water gas reaction [v]. By 1965, a state-of-the-art, high
pressure methanol unit typically had the following characteristics: Capacity, 70 to 150
thousand tonnes per year; Operating pressure, 350atm; Consumption, 11-12 million
kcal per tonne of methanol (130-140 ft3 of natural gas per gallon).
In 1966, Imperial Chemical Industries (ICI) developed the low pressure methanol
synthesis which was a significant breakthrough in methanol technology. The synthesis
was carried out over a proprietary based copper catalyst. This high activity catalyst
allowed the methanol synthesis reaction to proceed at commercially acceptable levels at
relatively low temperatures (220 - 280°C) which allowed operation at a notably
reduced pressure of 50 atm. Overall, the ICI low-pressure was more economical than
the high pressure system in terms of capital and operating cost [vi]. Figure 2 below
shows the ICI process which uses multi-bed synthesis reactors with feed gas quench
cooling.
CE4005 | Background 9
Figure 2. The ICI-steam-raising reactor for low-pressure methanol synthesis [iv].
A, catalyst is charged and inspected through these manholes; B, the pressure vessel is of
simple design; C, cooling tubes are welded to a simple header system, F, embedded in
the catalyst bed; D, perforated catalyst support grids allow gas to be distributed along
the length of the catalyst bed; E, an upper header system collects steam from the tube
bundle, which then passes to the steam drum, I; H, boiler feed water enters the base of
the converter; G, gravity discharge of catalyst permits rapid preparation for
maintenance or recharging.
CE4005 | Background 10
Figure 3 below shows some of the possible routes to methanol synthesis, a detailed
figure can be found in appendix 2.
(2.4)
Figure 4 Production of methanol from atmospheric carbon dioxide or from neutral gas (methane), and its use as a fuel.
DMFC: direct methanol fuel cell [i].
CE4005 | Background 11
2.2. Reactor Model Description
The reactor to be simulated is a simple one-dimensional, plug flow, pseudo
homogeneous, nonisothermal reactor model.
Due to the turbulence of gas phase reactions such as the methanol synthesis, they are
usually carried out in a plug flow reactor. The assumption made when choosing this
type of reactor is that there is no dispersion and no radial gradients in temperature,
velocity or concentration. The problem statement for this project states that ideal gas
law can be applied in all calculations, so the design equation can be written using the
ideal plug flow reactor model.
In an ideal plug flow reactor, velocity flow is assumed to be uniform or constant i.e. the
residence time is the same for every molecule throughout the flow. In this type of
reactor, there is no radial variation in velocity, concentration, temperature, or rate of
reaction [viii].
Figure 5 below shows a schematic diagram of a plug flow reactor. In this type of reactor,
there is no radial variation in velocity, concentration temperature, or rate of reaction.
The design Equation of a PFR (plug flow reactor) operating at steady state is given
below.
CE4005 | Background 12
Where:
v (2.8)
v (2.9)
At steady state, there is no accumulation and for a differential element of volume, dV,
∫ (2.16)
Equation 2.16 above is the design equation for a plug flow reactor.
CE4005 | Background 13
V/vo = CAo ∫ =∫ (2.17)
The pseudo homogeneous part of the reactor specification describes the catalyst
system. In a pseudo homogeneous system, the small sized (approximately spherical)
unsupported catalyst particles are uniformly dispersed throughout the feed. As a result
of the particle size, the particles are suspended and exhibit properties similar to
colloidal solutions. Due to the exothermic nature of the methanol synthesis, a non-
isothermal reactor will be used. This means heat will vary along the length of the
reactor [xi].
CE4005 | Background 14
3. Literature Review
This literature review will cover the methanol production process and some of the
previous kinetic models developed for methanol synthesis. The knowledge of the kinetic
mechanism of a chemical process presents a considerable importance in the reactions
which corresponds to the chemical equilibrium because this alone can allow the design
of the devices and sizing of the appliances needed to remove the heat conducted in
different parts of a reactor. Mathematical models of methanol synthesis are often
valuable tools that can be used in the evaluation of those systems. Any successful kinetic
model must include the rate equations of the reaction that accurately predict the effects
of process variable changes on reactor performance. Linear and nonlinear regression is
a method often used by many researchers to analyse data collected in order to produce
a reaction rate expression [ii]. The rate equations will vary depending on the assumed
mechanism and the role of each reactant in the reaction. In a case where a particular
reactant is weakly adsorbed to the surface of the catalyst used to catalyse the reaction,
such weakly adsorbed reactants are usually left out of the rate equation.
Before discussing the kinetic model, factors affecting the rate of the methanol synthesis
reaction will be discussed. Such factors are:
Reaction mechanism
Thermodynamic equilibrium
Process condition (Temperature, pressure)
Catalysts
As discussed earlier, methanol synthesis has improved from using high pressure to low
pressure which is more cost effective. Two low-pressure methanol synthesis processes
dominates the market; the ICI process which uses multi-bed synthesis reactors with
feed gas quench cooling and the Lurgi process [xii] that makes use of multitubular
Figure 7. Essential p ocess steps in Lu gi’s Low P essu e Methanol P ocess [xiii].
Natural gas first undergoes desulphurization and gets saturated with process steam
then undergoes three steps of reforming (using Ni-based catalyst.):
The water gas shift (equation 3) occurs in all the reforming steps.
Due to the quasi-isothermal reaction conditions and high catalyst selectivity, only small
amounts of by-products are produced during methanol synthesis. The methanol
synthesis loop consists of two parallel reactors with a common steam drum,
feed/effluent interchanger, a cooler, a methanol separator and a recycle compressor.
The methanol produced needs to be distilled to remove water, dissolved gases and
ethanol. Ethanol is the most difficult component to remove due to the small difference in
Herman et al., [xiv,xv] believes that carbon monoxide is adsorbed (with a carbon-metal
bond) and then successively hydrogenated to form formyl, hydroxycarbene and
hydroxyl-methyl species leading to methanol. Alternatively, Deluzarche et al., [xvi]
suggested that carbon monoxide is inserted into a surface hydroxyl group to form a
surface formate species (with an oxygen-metal bond), followed by hydrogenation and
dehydration to form a surface methoxide that leads to methanol. This mechanism
requires an oxygen bond to an active site. Although ICI investigators documented the
formation of a stable intermediate formate species, Kung et al., analysed the available
data [xvii] from the mechanisms proposed by Herman et al., and Deluzarche et al.,
sufficient evidence was found, which disprove those mechanisms. Kung found evidence
for carbon monoxide adsorption with the carbon end of the molecule towards the metal.
Agny and Takoudis [xviii] reiterated and refined a third mechanism that was proposed
by Henrici-Olive and Olive [xix]. This third mechanism introduced a new intermediate
between the formyl and methoxide species- surface bonded formaldehyde as shown in
equation 3.4 below.
(3.4)
Bowker et al., [xxv] and Chinchen et al., [xxiv] proposed mechanisms that are similar in
nature. In their mechanisms, carbon dioxide is hydrogenated to form a surface formate
species which is further hydrogenated to form a surface formate species that is further
hydrogenated to produce methanol. Bowker et al speculated that this hydrogenation
proceeds through the methoxide species.
Detailed kinetic mechanism, on the basis of different sites on Cu for the adsorption of
carbon monoxide and carbon dioxide, was applied, and the water-gas shift reaction was
included in order to provide the relationship between the hydrogenations of carbon
monoxide and carbon dioxide. Parameter estimation results show that, among 48
reaction rates that was developed from different combinations of rate determining
steps in each reaction, the surface reaction of a methoxy species, the hydrogenation of a
formate intermediate HCO2, and the formation of a formate intermediate are the rate
However, it was also found that carbon dioxide indirectly accelerates the production of
methanol because it decreases the rate of reaction of the water gas shift. A decrease in
the rate of reaction of the water gas shift prevents the conversion of methanol to
dimethyl ether [xxvi]. The rate of reaction for methanol synthesis and DME production
is summarised in Table 4.
(3.4)
Increase in the value of equilibrium constant with pressure is due to non-ideality. Thus
if the catalyst is sufficiently active, high conversion of methanol will be obtained at high
pressures and low temperatures. The use of high pressure commercially is expensive
both of capital and gas compression. Therefore, with a very active catalyst, it is most
economical to use lower pressure and obtain the same conversions as at high pressures
but at lower temperatures. Figure 9 shows a variation of equilibrium constant with
temperature and pressures. It shows that a catalyst which is only active at 350°C or
above such as the ZnO/Cr catalyst will require an operating pressure of 300 bar to
achieve a conversion to methanol of 3% while a more active catalyst such as the
Cu/ZnO/Al2O3 catalyst will obtain the same conversion at 50 bar [iv].
3.4. Selectivity
Carbon monoxide and carbon dioxide can also react with hydrogen to produce by-
products such as ethers, hydrocarbons and higher alcohols.
These reactions (equation 3.7-3.9) are more exothermic than the methanol synthesis
reactions and their formation involves larger negative change of free energy. Methanol
is thermodynamically less stable and less likely to be formed from carbon monoxide and
hydrogen than the other possible products such as methane. Kinetic factors are used to
determine the product formed. A selective catalyst is used to favour a reaction path
leading to the desired product (methanol) with a minimum of by-products [iv].
b Catalysts based on Group VIII metals, The by-products are mainly hydrocarbons.
In recent years, some new catalysts and process configuration has been proposed.
Although not yet commercially viable, some aspects may form the basis of methanol
synthesis in the future. Two novel supported catalysts have been reported. ‘Raney
The surface reaction between one chemiadsorbed molecule of carbon monoxide and
two hydrogen molecules to produce one molecule of methanol chemiadsorbed on the
solid catalyst is the slowest intermediate step which controls the whole rate of reaction.
Natta’s wo k ep esents one of the widest anges of conditions in all published
methanol literature. Natta assumed that the rate-determining step was the trimolecular
reaction of carbon monoxide and hydrogen on the surface of the catalyst. From
experimental data, he expressed the correlation between reaction rate, fugacity of
components, and some constants (mainly depending upon the adsorption equilibrium
constants). That led to the correlation in equation (3.10) below.
/
(3.10)
(
Where: r = rate of reaction, f = fugacity, Keq = equilibrium constant and A,B,C and D are
adsorption rate constants.
The pioneering work by Natta has been expanded and improved by many other
researchers. Klier et al., [xxix] assumed that a small amount of carbon dioxide is
/
k (p ) (3.11)
(
Where:
This model is consistent with all the physical characteristics of the CuZnO catalysts and
supports earlier findings that an intermediate oxidation state of the catalyst is its active
state.
Based on the stoichiometry of equation (2.2), Rozovskii [xxx] contends that methanol
forms only via carbon dioxide hydrogenation and proposed the rate equation below:
(3.12)
(3.13)
.
k (P P (P P (3.14)
Where:
The CH-O intermediate was postulated to be the abundant surface intermediate. The
rate determining step was the surface reaction between the adsorbed hydrogen and
methoxy intermediate CH3O-. They also suggested that trace amount of carbon dioxide
detected at the reactor effluent stream was produced from the water gas shift reaction
(equation 3.3) and the redox reaction from the oxidised state to the reduced state of the
catalyst. A carbon dioxide free synthesis gas was used as feed; therefore no term
corresponding to carbon dioxide was incorporated in the rate equation.
The value of the pre-exponential factor and the overall activation energy at 523k are
13600 mol/(s atm gcat) and 34000 cal/gmol respectively [xviii].
.
kp P (1 ) (3.15)
In 1991, they further investigated the kinetics of methanol synthesis over commercial
copper/zinc oxide/alumina catalysts at a temperature between 187-277°C and pressure
between 30-90 bar. A wide range of parameters was applied, especially that of the inlet
concentrations of reactant. They concluded that methanol synthesis occurs from CO2
rather than from CO and that the basic reactions are:
They also demonstrated experimentally that methanol cannot be formed from hydrogen
and carbon monoxide without the presence of water.
Langmuir-Hinshelwood mechanism where CO2 and H2 react on the surface with few
intermediate steps was used. The rate determining step came out to be
( ( )( ))
(3.19)
( ( )( ))
(3.20)
den 1 p p p p p (3.21)
This kinetic model is based on measurements on a deactivated catalyst, and the effect of
deactivation is not accounted for. Hence, the reaction rates are probably too slow [xxxi].
(3.22)
(3.23)
(3.24)
(3.25)
.
Where : ln 29.07 (3.26)
.
ln 5.639 (3.27)
Skrzypek Cu/ZnO/Al2O3 .
(1 )
Lim Cu/ZnO/Al2O3/ZrO2
. ( )
(1 . .
(1
4.1. To develop a kinetic model for the synthesis of methanol from the synthetic
rate data given in Appendix 1
The above will be carried out by deducing a rate equation consistent with the provided
experimental data using the Langmuir-Hinshelwood kinetics. From the rate equation
deduced, the dimension of the reactor will be determined using the design equation of a
plug flow reactor (PFR) and the given specification.
The kinetic modelling will be repeated, and this time the experimental data will be
incorporated into suitable kinetic models from literature. The rate of the reaction and
the weight of catalyst required which will be deduced and this will then be used to work
out the reactor dimension and other properties of the reactor including the catalyst bed
characteristics and the sensitivity to pressure drop.
Hence, (4.3)
(4.4)
The following assumptions will be used to deduce rate law consistent with the
experimental data provided.
Conclusion can be drawn from the rate of disappearance of H2, on the partial
pressure of hydrogen, carbon monoxide and methanol.
.
k (P P (P P (4.6)
(
[ ] (4.9)
(
[ ] (4.10)
∫ (4.11)
(
Where:
The weight of the catalyst calculated by simultaneous numerical solution of the material
and energy balance will be used to calculate the reactor dimension by following the
steps below:
7. Repeat step (1) to (6) for values of conversion X between 0 and 0.9
8. Calculate ∑ (4.13)
Where G* is the average of two successive values of G and is the increment.
9. Plot the results with temperature on the y-axis and conversion on the x-axis.
Find FAo , CAo and which a e some of the values needed to find the eacto
dimension.
Space velocity = ̅
= hence, = ̅
(4.15)
̅
= 10000m3/hr , ̅ = 1 * 10-4
V = 1m3
v = ̅̅̅̅̅̅̅̅̅̅
v = 10000 2.78
PV = nRT (4.16)
n
P
P = ΣPi (4.17)
where:
The volume of the reactor will be determined from the catalyst weight using the
equation: VC = WC/ρC = 1/3VReactor (4.21)
Where:
om the volume, the eacto length, diamete and the catalyst bed’s cha acte istics can
be determined.
The total volume of reactor is the volume of cylindrical section + volume of dome
closures.
D = diameter of reactor
= length of reactor
(Note: The reactor volume does not include the volume occupied by the dome head
closures).
Assumption
Hence: 4 (4.23)
VR = 4 (4.24)
VR πD3 (4.25)
Rearrange to get D
D= √ (4.26)
1. Torispherical heads.
2. Hemispherical heads.
3. Ellipsoidal heads.
4. Flat plates and formed flat heads.
The dimensions of hemispheres are very simple, since it is half of a circle; the radius
from the centre of the circle to all edges of the hemisphere will be the same.
r r
Volume of hemispherical head closure = (4.27)
For a spherical particle, the effective particle diameter d’p= diameter of particle dp =
0.0381m
( (
Friction factor, f [1.7 ] (4.33)
( )
Fluid density ρ (4.34)
(
(4.38)
(
The adiabatic reactor can be controlled by the inlet composition of the reaction mixture
and the inlet temperature (473K). The composition of the inlet mixture for the
methanol synthesis given in the specification sheet is 70mol% H2; 30mol% CO.
A kinetic model will be selected and modelled on ASPEN using the data for kinetic
analysis provided. The composition and the reactor inlet temperature will be varied in
order to test the performance of the reactor. A sensitivity analysis will also be carried
out to check the effect of feed temperature on methanol production.
Langmuir – Hinshelwood model can be used to deduce a rate law consistent with
experimental observation. Combining surface reaction rate laws with the Langmuir
The following assumptions will be used to deduce rate law consistent with the
experimental data provided in Table 6 above.
Conclusion can be drawn from the rate of disappearance of H2, on the partial
pressure of hydrogen carbon monoxide and methanol.
Experiments 1-8:
4 fold decrease in methanol concentration (partial pressure) almost doubled the rate
(experiment 1 compared to 5) as shown in Table 7 below.
[
(5.8)
.
i.e. 1 (5.9)
Table 9. Effect of decreasing the partial pressure of hydrogen on the rate of reaction.
Combining equations 5.8, 5.9 and 5.10 suggests that the rate law is of the form:
[
(5.11)
Where:
To evaluate the reaction rate constant, k and the rate law parameters and
(5.13)
(5.14)
Appropriate data points will be selected from the experimental data available on Table
6 to plot a graph of y against x
Where:
y , P /P (5.16)
c (5.17)
Since the reaction rate constant and adsorption parameters, Ki are functions of
temperature, they should be found at constant temperature.
y-axis X-axis
T PH2/-rH2 PH2 PM
(kPa) (kPa)
475 4812.783 8509 1013
475 3009.904 8509 253
6000
5000
y = 2.3722x + 2409.7
4000
PH2/-rH2
3000
KM
Linear (KM)
2000
1000
0
0 200 400 600 800 1000 1200
PM
y = 2.3722x + 2409.7
1
2409.7
1
2. 7
1
2. 7
4.1 10
2. 7 4.1 10 9.84 10
y-axis X-axis
T PH2/-rH2 PH2 PM
(kPa) (kPa)
475 5249.229 8509 1013
475 4567.672 5906 1013
5300
5200
y = 0.2618x + 3021.3
5100
5000
PH2/-rH2
4900
KH2
4700
4600
4500
0 2000 4000 6000 8000 10000
KH2
y = 0.2618x + 3021.3
1
k2 . 1 10 mol kpa m s
021.
m 0.2618
k2
0.2618
. 1 10
0.2618 . 1 10 8.67 10
The value of k will lie between k1 and k2, hence k = (k1 + k2)/2
The spread sheet used for the calculation has been attached to the appendix.
The kinetic model developed above will be used to simulate a plant scale catalytic
reactor using the specified reaction conditions, thermodynamic and physical data
provided below [xxxiv].
Reactor:
Coolant: boiling water is on shell side; assume coolant temperature constant at 483K
Catalyst Description:
CE4005 | Results and Discussion 51
Shape: Approximately spherical
Diameter: 2.87mm
Process Conditions:
Feed gas:
Space velocity: 10,000 standard cubic meters per hour per cubic meter of reactor
volume.
The continuity equation for a pseudo homogeneous, one-dimensional plug flow is:
(
( 0
since
(1
( ( )
(
0
Where:
U is linear velocity,
CA is concentration,
v0 is volumetric flow,
FA is final molar flow ,
FAo is inlet molar flow,
XA is fractional conversion of A,
-rA is rate of reaction,
ρB is bulk density of the bed,
r is reactor cylindrical section radius,
But, ρ ρ π and d
The design equation for an FBCR is of the same form as equation for the volume V of a
PFR ( ∫ ) [xxxiv].
Space velocity = ̅
= hence, = ̅
̅
= 10000m3/hr , ̅ = 1 * 10-4
V = 1m3
= = 10000 2.78
CAo = 21 9.4 /
.
The values of VO , CA0, FA0 and fo e periment 1-27 are tabulated below.
Experimental 12 data (in bold on Table 12) was used to simulate the plan-scale catalytic reactor.
0.9
[
0
PH2 PM k KH2 KM U h Ts ∏
(kpa) (kpa) (mol kpa-1 m-3 s-1) (W/m2) (m) (K)
5906 1013 0.00037 8.66514E-05 0.00098 631 12 483 3.1415
.
0.877982 mol/m3.s
. .
.
[ 0.9 6096.82m
.
Values of X between 0 and 0.9 were tabulated in order to see the volume needed at
different conversions and the reaction temperature for adiabatic and non-adiabatic
setup. The results are tabulated on Table 15 below.
( ( . .
[ ] 47 [ ] 0.9 781.97
. .
( ( . .
[ ] 48 [ ] 0.9 01. K
( ( . .
Where:
700
600
500
400 Adiabatic
300 Nonadiabatic
200
100
0
0 0.2 0.4 0.6 0.8 1
Conversion
Figure 10. Reaction temperature profile of adiabatic and non-adiabatic set up at conversion between 0 and 0.9
The adiabatic temperature rise is one of the most important characteristics of a reaction
mixture. It is the temperature difference by which the reaction mixture would increase
if the mixture reacted adiabatically from zero to unit degree of conversion. The graph
above shows that for the adiabatic configuration, the temperature increases with
conversion down the length of the reactor as expected for an adiabatic PFR when the
reaction is exothermic. There is no heat exchange device in the adiabatic configuration
so the heat released by reaction will be absorbed by the reaction mixture (no heat
exchange with the surroundings) which is what lead to the temperature increase.
For the non-adiabatic configuration, the temperature down the length of the reactor
remains constant. This can achieved by using a cooling medium which takes out the
heat generated from the exothermic reaction (equation 2.1).
Assumptions
(Note: The reactor volume does not include the volume occupied by the dome head
closures).
Given that the reactor is cylindrical, the volume of the reactor was calculated to be
101.61 m3
From this, the length of the reactor can be calculated. The relationship between the
Where:
D = diameter of reactor
l = length of reactor
VR = 4D
VR πD3
Rearrange to get D
Length = 4D.
The dimensions of hemispheres are very simple, since it is half of a circle; the radius
from the centre of the circle to all edges of the hemisphere will be the same. The reactor
diameter was calculated earlier to be 3.19 metres; hence the radius of the hemisphere
will be 1.595 metres. The dimension of the hemispherical head closure is shown below
accordingly.
Volume of Hemisphere =
r = 1.595m
There are 2 closures (top and bottom) so total volume of closures = 8.49 m3 * 2 = 16.98
m3
The total volume of reactor = volume of the cylindrical section + volume of dome
closure = 101.61m3 +16.98 m3 = 118.59m3
.87
N π 2489 tubes
4 0.0 8 12
d G 0.00287 7.29
e 1 08
1.6 10
Re < 2000 hence the flow will be laminar and the profile of velocity will be parabolic.
Pressure drop ( P
( )
Fluid density ρ
= 756.86 kg/s
R = 8.314 J/mol/K
T = 473K
8.28
10.1 10 ( )
ρ 947.66 2 .24 kgm
8. 14 47
G u ρ
G 7.29
u 0.29ms
ρ 2 .24
. . . .
Hence, Pressure drop ( P 467.97pa = 0.53 bar
.
Pressure drop, ( P
( . .
Bed depth, L 4.2 m
. . .
D √ √ .18m
.
Ranges of pressure drop have been selected around the calculated pressure drop. The
sensitivity result is tabulated in Table 19 below.
Figure 13 below shows the sensitivity of the reactor dimension to pressure drop.
Diameter (D) decreases and the bed depth (L) increases. This suggests that for a given
amount of catalyst, a reduced pressure drop can be obtained by reducing the bed depth
at the expense of increasing the bed diameter. Although reducing the pressure drop will
reduce the operating power cost, it will increase the vessel cost.
60000
40000 Diameter
20000 Bed depth
0
0 2 4 6 8
Skrzypek Cu/ZnO/Al2O3 .
P
kp P (1 )
k P P
Lim Cu/ZnO/Al2O3/ZrO2 P
. (P P )
(1 . .
P (1 P P
Developed Kinetic Kinetic Models from literature Kinetic Models from literature
Model Adiabatic Non-Adiabatic
Agny and Skrzypek Lim Agny and Skrzypek Lim
Takoudis Takoudis
Scaling factor to meet specification - 50 500 1000 100 750 800
Catalyst Weight (kg) 37257 39377 37875 37977 38626 38859 38304
Catalyst Bed Volume (m3) 33.87 35.79 34.43 34.52 35.11 35.33 34.82
Reactor Volume excluding dome closure 101.61 107.39 103.29 103.57 105.34 105.98 104.46
(m3)
Reactor Length (m3) 12.76 12.98 12.81 12.83 12.89 12.92 12.86
Reactor Diameter (m3) 3.19 3.25 3.20 3.20 3.22 3.23 3.22
Catalyst Bed Depth (m) 4.25 4.33 4.27 4.28 4.29 4.31 4.29
Number of catalyst tubes 2500 2600 2500 2500 2600 2600 2500
Mass velocity (kg/m2.s) 7.29 7.05 7.23 7.22 7.14 7.10 7.18
Reynolds number 1308 1264 1297 1295 1280 1275 1287
Pressure drop (bar) 0.53 0.51 0.53 0.52 0.52 0.51 0.52
Number of catalyst tube (Nt) is approximated to the nearest hundred and other values in Table 21 above are rounded up to two decimal
places where appropriate (non-rounded figures are available in the appendix).
The Agny and Takoudis kinetic model came out to be the best fit with the experimental
data as it required the least scaling factor (*50) in order to be similar to the results from
the simulation using the developed kinetic model. Agny and Takoudis model will
therefore be examined in detail and used later for Aspen modelling. The full results from
Skrzpek and Lim kinetic model can be found in appendix 6.
Using experiment 12 from the provided kinetic data, and following the steps in the
methodology (section 4.1.2), the kinetic simulation using the Agny and Takoudis kinetic
model is given in Table 22 below. The catalyst bed characteristics and sensitivity to
pressure drop will not be shown here as they are similar to those calculated in chapter
5.2 above (same trend and therefore same justification) but have been attached to
appendix 6. Values in Table 22 have been rounded up to two decimal place where
appropriate and therefore slightly differs from the corresponding table in the appendix.
Table 22 shows the evaluation of the kinetic parameters which was used to calculate the weight of catalyst required. The results from
this table will be used to investigate the effect of conversion on the adiabatic temperature rise and the rate of reaction. A maximum rate
was observed at a conversion of 0.4. After a conversion of 0.6, the rate started to become negative which means there is a shift in
equilibrium which favours the backward reaction of equation 2.1 (carbon monoxide hydrogenation).
Following the steps in the methodology for a chosen conversion of 0.5 (in bold on
Table 22) and experiment 12 data,
( ( . .
Adiabatic temperature rise, [ ] 47 [ ]
. .
0. 646
. .
k (P P (P P 0.000 ( 9.9 8 .98 – ( 9.9
.
. .
8 .98 = 0.026 mol/(gcat.s).
.
G 2287 6.1 g
( .
Note : The differences in value is as a result of approximation used in the table above.
non approximated values are in the tables available in the appendix.
rate (mol/(gcat s)
0.3
Temperature (K)
0.025 0.5
600 0.2
0.02
400 0.1
0.015 Rate vs
0
200 T Vs X 0.01 Conversion
0.005
0 0 0.6
0 0.2 0.4 0.6 0.8 1 0 0.5 1
Conversion conversion
Figure 14. Reaction rate as a function of degree of conversion in the Figure 15. Relationship between temperature and degree of conversion in
adiabatic reactor. the adiabatic reactor.
In exothermic reactions, increasing the degree of conversion decreases the concentration of the reactants while the concentration of the
product increases, this leads to a decrease in the rate of reaction as shown in Figure 14 above. On the other hand, because the heat of
reaction is being absorbed by the reaction mixture, temperature increases with increase in the degree of conversion as shown on Figure
15 and thereby enhances the reaction. These opposite influences lead to the maximum observed on Figure 14 above. At low
conversions, the reaction rate increases with the degree of conversion. On the other side of the maximum, the reaction rate decreases
with the degree of conversion because the controlling effect is that of the shortage of reactants in the reaction mixture. Increase in
temperature can no longer offset the shortage of reactants at these high degrees of conversion.
To (K) Ts (K) H (kJ/mol Fao (mol/s) (kg/s Cp (kJ/Kg mol.K) PCO (atm) PH2 (atm) PCH3OH (atm) R (J/mol/K) U (W/m2)
475 483 97.97 5947.66 58.29 29.31 39.99 83.9 2.49 8.314 631
h ∏
12 3.142
XA T (K) k [mol/(s atm gcat)] log10Keq Keq Rate Rate G (g) G* (g) G* (g G* (kg
(mol/(gcat s) (mol/(kgcat s)
0 483 0.000103 -1.94 0.012 0.0135 1.35E-05 440520.1
0.1 483.6 0.000104 -1.95 0.011 0.0135 1.36E-05 437945.7 439232.9 43923.29 43.92
0.2 484.2 0.000104 -1.96 0.010 0.0137 1.37E-05 435393.2 436669.4 43666.94 43.67
0.3 484.9 0.000105 -1.98 0.010 0.0137 1.37E-05 432862.5 434127.8 43412.78 43.41
0.4 485.5 0.000106 -1.992 0.010 0.0138 1.38E-05 430353.2 431607.8 43160.78 43.16
0.5 486.1 0.000106 -2.005 0.0099 0.0139 1.39E-05 427865.3 429109.2 42910.92 42.91
0.6 486.7 0.000107 -2.018 0.0095 0.0139 1.39E-05 425398.4 426631.8 42663.18 42.66
0.7 487.4 0.000108 -2.032 0.0092 0.0141 1.41E-05 422952.4 424175.4 42417.54 42.42
0.8 487.9 0.000108 -2.045 0.0090 0.0141 1.41E-05 420527 421739.7 42173.97 42.17
0.9 488.6 0.000109 -2.058 0.0087 0.0142 1.42E-05 418122 419324.5 41932.45 41.93
Catalyst Weight: ∑ 386.26
rate (mol/(gcat s)
0.012
Temperature (K)
400 0.01
0.008
300
0.006 Rate vs Conversion
200 T vs X
0.004
100 0.002
0 0
0 0.2 0.4 0.6 0.8 1 0 0.5 1
Conversion conversion
Figure 16. Reaction rate as a function of degree of conversion in the non-adiabatic Figure 17. Relationship between temperature and degree of conversion in the non-
reactor. adiabatic reactor.
Unlike in the adiabatic reactor where there is no heat loss to the surrounding, non-adiabatic reactors have heat exchange devise which
helps to take out the heat of reaction. A cooling medium can be used to maintain the heat of reaction and hence keep the temperature in
the reactor constant as the reacting mixture will not absorb the heat produced from the reaction. The temperature will be constant
down the length of the reactor as suggested by Figure 16 and this will also keep the rate of the rate of reaction constant because the rate
of reaction is a function of the degree of conversion and temperature. See Figure 17. At higher conversion, the rate of reaction is greater
in the non-adiabatic setup than in the adiabatic set up.
XA Tad Keq Xe
(K)
0 475 0.017 0.89
0.1 509 0.003 0.63
0.2 543 0.0007 0.29
0.3 577 0.0002 0.11
0.4 611 6.61E-05 0.04
0.5 646 2.32E-05 0.01
0.6 680 9.02E-06 0.0060
0.7 714 3.81E-06 0.0027
0.8 748 1.74E-06 0.0013
Sample Calculation
Table 24 above shows that as the inlet temperature increase due to the adiabatic
temperature rise, the adiabatic equilibrium conversion decreases. The results are
plotted on the graph in Figure 18 below.
0.9
0.8
0.7
0.6
Xeq, X
0.5
Xe against T
X against T
0.4
0.3
0.2
0.1
0
0 100 200 300 400 500 600 700 800
Temperature (K)
Interstage cooling can be used to get the best result from the reaction rate and reactant
conversion. Conversion is much less at lower temperature, this means catalyst mass and
volume must be much greater. It is very expensive to operate reactors at high
temperature and pressure, so smaller volume of reactor will be cost effective. The
cooler allows the temperature during a reaction to drop whilst not affecting the
pressure or the stream composition. This significant property is a good way of
increasing conversion and maximising productivity without an increase in overall
reactor volume [xxxvii].
The flow sheet and the stream results from the simulation for a feed composition of
70% H2 and 30% CO entering the reactor at 473K (200 C) is given below.
1 2 3 4
Figure 21. Flow sheet with heat and material balance for ASPEN simulation at a feed inlet temperature of 473K (200 C)
An adiabatic reactor can be controlled by either the composition of the feed or the feed
temperature. Varying the composition showed that a feed composition of 70% H2 and
30% CO is optimum for methanol synthesis under the specified conditions. A conversion
of 29% was achieved (mole flow of methanol produced/ mole flow of feed *100 =
[{6238.968/21412.800} *100]) the results of varying the feed composition and the
temperature and composition profile resulting from such variation has been attached to
the appendix. In order for the reaction to occur, the molar composition of H 2 must
always be greater than that of CO following from the stoichiometry of equation 2.1
(carbon monoxide hydrogenation).
The temperature profile above shows that most of the reaction occurs at the entrance of the reactor. This points towards the need for a
cooling medium to cool the reactant down so that conversion to methanol can occur slowly along the length of the reactor. The adiabatic
temperature rise in this simulation is very high and therefore, there is a need to understand the effect that various feed temperature will
have on this simulation. This vital information can be obtained from a sensitivity analysis with varying feed temperature.
The sensitivity analysis shows that increasing the feed temperature will lead to
decrease in methanol production and vice versa. The optimum temperature from the
graph is 100 C (373K). This results follows from the strong exothermic nature of the
methanol synthesis. At equilibrium, the rate of backward reaction will increase more
relative to the rate of backward reaction with temperature rise which means there will
be less conversion of the reactants to products.
he high tempe atu e ise obse ved f om this simulation that’s illust ated on Figure 22
(almost double that of simulation on excel which might be due to error in the kinetics
specification on ASPEN) suggests that an adiabatic reactor running at the specified
condition is not suitable for the methanol synthesis process and therefore an operation
with an heat exchange medium should be considered. More results that validates the
suggestion for a cooling medium have been attached to the appendix. The simulation
also shows a conversion range between 20%-30%, as discussed earlier, interstage
cooling can be used to improve this conversion.
A continuous adiabatic plug flow reactor (PFR) does not have the effect of macro kinetic
properties, hence the size and shape of the reactor is immaterial from the viewpoint of
chemical reaction. This makes direct data transfer possible i.e. the possibility to carry
out an experiment in a small laboratory scale reactor and transfer the result to a full
plant-scale industrial reactor of the same type preserving identical external reaction
conditions and inlet composition of the reaction mixture [xxxviii].
With regards to the developed kinetics, it was assumed that the reaction is irreversible
which isn’t the case as the methanol synthesis eaction is indeed eve sible. At the
operating conditions used for the methanol synthesis, the ideality assumed will be
invalid due to the non-ideal behaviour of gases at these conditions, the non ideality will
require fugacity parameters to be included in the kinetic rate equation to be in the
formed developed by Natta et.al (1953). Other side reactions discussed in the literature
review such as the water gas shift reaction and formation of DME are also very likely to
occur and these will have an impact on the rate of reaction. These factors put a lot of
limit to the developed kinetic rate equation and hence the performance of the reactor
simulated from that kinetic model.
Plug flow is an idealised flow of fluids under which all particles on a given cross section
will have identical velocity and direction of motion. This excludes mixing in the
direction of motion. Ideal gas law was assumed for all calculations in this report. Under
plug flow, particles of different age do not mix, as the particles that enter the reactor at
the same time must leave simultaneously. In real reactors, the flow of fluids can only
approximate to plug flow. The Reynolds number was calculated to be less than 2000 (Re
< 2000) which means the flow is laminar and this will result in a velocity p ofile that’s
parabolic. In a parabolic velocity profile, the molecules on a given cross section do not
move at the same velocity so particles of different age will therefore mix to some extent.
The effect of mixing can be regarded as negligible if the mixing does not significantly
alter the concentration field induced by chemical reaction given that there are no
appreciable longitudinal gradients of conversion within the reactor. However, because
the length of the tube along which the major portion of the reactant has been converted
to methanol is much larger than the tube diameter (ratio of 1:315), the concept of plug
flow is realistic. The maximum adiabatic temperature on the excel simulation was 748K,
when the simulation was repeated on ASPEN, this value doubled for the same feed
composition and specification. It is not advisable to use adiabatic reactors for reactions
whose adiabatic temperature rise is very large. Isothermal operation will be preferable
as this will allow the reaction to take place at a lower temperature which is more
favourable from the point of view of chemical equilibrium. The reactor was also
modelled to operate non-adiabatically and higher rate was observed at higher
conversion values than in the adiabatic setup. The non-adiabatic temperature profile
which allows for heat transfer agrees more with the admissible temperature range from
literature and the temperature at which the experimental data used was carried out.
The equilibrium conversion for the earlier simulation for the adiabatic setup was 23%
CE4005 | Conclusion 82
for a feed temperature of 473K. ASPEN confirms this result as the range of methanol
conversion lies between 20% and 30 %. Interstage cooling was suggested in order to
achieve higher conversion of the reactants to methanol. Adiabatic plug flow reactor can
only be used if the temperature rise corresponding to the outlet degree of conversion
remains smaller than the operating temperature region of the reactor. The operating
temperature of the methanol synthesis is between 400-700K from literature, see Table
2. The adiabatic temperature rise from the reactor simulation exceeds this value at the
specified conditions. It is important to optimise the temperature regime due to the
effect of temperature on the rate of reaction. Optimisation of the temperature regime
will be discussed further under the recommendation section.
The objectives of this research project were met and I had the opportunity to develop
kinetic modelling methods and approaches, on this basis this research can be concluded
as being successful.
CE4005 | Conclusion 83
7. Recommendations
At equilibrium, the rate of forward reaction is equal to the rate of backward reaction.
For exothermic reactions, the rate of backward reaction will increase more relative to
the rate of backward reaction with temperature rise, therefore lowering the equilibrium
conversion and subsequently the rate of reaction. For a gas reversible exothermic
reaction such as the methanol synthesis, the productivity of the reactor for a given inlet
composition is at its maximum if the state of the reaction mixture follows the path of
maximum productivity. This path is approached neither by the adiabatic nor the
isothermal temperature regime. For the adiabatic setup, increase in temperature of the
reaction mixture favours the rate of the reaction but the productivity is low because the
reaction mixture rapidly approaches the region of the effect of thermodynamic
equilibrium at high temperature. In an isothermal reactor, the reaction can take place at
lower temperature which is more favourable from the point of view of chemical
equilibrium. However the reactor productivity will remain low because of the low
reaction rate in the region free of the effect of chemical equilibrium.
In a eacto that’s neither adiabatic nor isothermal, the temperature profile can be
adjusted such that the reaction mixture is allowed to be heated by the heat of reaction in
the region free of the effect of chemical equilibrium, to be later cooled by heat exchange
in the region affected strongly by chemical equilibrium. This leads to interstage cooling.
Low conversion is sometimes overcome by using several adiabatic reactors with
interstage cooling. Several reactors, with heat exchangers for cooling between them, are
run up to near the maximum reaction rate until satisfactory conversion is attained. This
is a common technique used in methanol synthesis from syngas. Interstage cooling
helps to achieve high conversion and extract reaction heat. Usually, up to three adiabatic
reactors with interstage cooling are sufficient to achieve good conversion [xxxix].
The optimum temperature regime for the methanol synthesis and other reversible
exothermic reaction will be that which approaches as closely as possible to the path of
maximum productivity without exceeding either the upper or the lower limit of the
admissible temperature range.
One of the advantages of the plug flow reactor which makes it suitable for gas phase
reactions is that it has no moving parts and therefore easy to maintain. Also, plug flow
reactors produce the highest conversion per reactor volume of any of the flow reactors.
CE4005 | Recommendations 84
However, for exothermic reactions, the temperature control is difficult and hotspots
might occur. Although the cost of the reactor and catalyst regeneration is high, using a
fluidised bed reactor can eliminate problems with hotspots as the contents in a fluidised
bed reactor are well mixed, resulting in a uniform temperature. A fluidised bed reactor
can handle large amounts of feed and solids and therefore will be suitable for the
methanol synthesis.
Finally, the method of obtaining the kinetic parameters can be improved by solving
them numerically with software package such as POLYMATH or MATLAB. This will give
an improved kinetic model and hence reduce errors in the reactor design and
performance.
CE4005 | Recommendations 85
8. Nomenclature
Symbol Definition Unit
ρB Catalyst bed bulok density kg/m3
C Concentration mol/m3
Co Initial concentration mol/m3
ρC Bulk density of catalyst kg/m3
D Diameter m
d’p Effective particle diameter m
dp Particle diameter m
dx Differential of x
Bed voidage
f Friction factor
FA Molar flow mol/s
FAo Inlet molar flow mol/s
fi Fugacity of component i atm, bar
Fluid density kg/m3
G ratio of molar flow to rate of reaction g, kg
G* average of two successive values of G same unit as G
ΔG° Measure of free energy kJ/mol
h Height m
ΔH Heat of reaction kJ/mol
k Reaction rate constant mol/(gcat.s atm)
ka Adsorption rate constant
kd Desorption rate constant
Ki Adsorption rate constant of component i
Kp, Keq Thermodynamic equilibrium constant dimensionless
l Length m
L Bed depth
Specific mass flow rate kg/s
n Number of moles mol
n Empirical constant
Nt Number of catalyst tubes
action of the su face cove ed by adso bed species
P Pressure atm/Pa/kPa/bar
Pi Partial pressure of component i atm/Pa/kPa
Pressure drop Pa/kPa/bar
r Radius m
-rA Rate of reaction mol A / (kg cat.s)
R Molar gas constant J/mol/K
Re Reynolds number
T Temperature K
Tad Adiabatic temperature rise K
TO Reactor inlet temperature K
Ts Surrounding temperature/temperature of coolant K
̅ Mean residence time s
u velocity m/s
U Overall heat transfer coefficient W/m2K
V Volume m3
Vc Volume of catalyst m3
v0 Volumetric flow m3/s
VR Volume of reactor m3
Wc Weight of catalyst g, kg
X Conversion
CE4005 | Nomenclature 86
Xe Equilibrium conversion
9. References
i George A. Olah (2005). "Beyond Oil and Gas: The Methanol Economy". Angewandte
Chemie International Edition 44 (18): 2636–2639.
iii How is Methanol Made? - Methanol Institute . 2012. How is Methanol Made? -
Methanol Institute . [ONLINE] Available at: http://www.methanol.org/Methanol-
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