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Kelvin Oba
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SEE PROFILE
2013
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.
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 (
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
3.
2.1.
2.2.
3.2.
3.2.1.
3.2.2.
3.3.
3.4.
Selectivity ................................................................................................................. 22
3.5.
Catalysts ................................................................................................................... 23
3.5.1.
3.5.2.
3.6.
4.
Kinetic Models.......................................................................................................... 26
3.6.1.
3.6.2.
3.6.3.
3.6.4.
3.6.5.
3.6.6.
4.1.2.
4.2.
4.2.1.
4.2.2.
4.2.3.
4.2.4.
4.3.
4.4.
5.
4.5.
4.6.
5.1.1.
5.1.2.
5.1.3.
5.1.4.
5.2.
5.2.1.
5.3.
5.4.
5.5.
5.6.
6.
Conclusion ....................................................................................................................... 82
7.
Recommendations .......................................................................................................... 84
8.
Nomenclature ................................................................................................................. 86
9.
References ....................................................................................................................... 87
10. Appendices
10.1 Appendix 1: Data for Kinetic Analysis
10.2 Appendix 2: Possible Routes to Methanol
10.3 Appendix 3: Deriving non-adiabatic energy balance
10.4 Appendix 4: ASPEN Simulation Results
10.5 Appendix 5: Improved Gantt Chart
10.6 Appendix 6: Reactor Simulation Summary
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 Lurgis 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 ........... 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 onedimensional, plug-flow, pseudo homogeneous, nonisothermal reactor model.
The
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.
(2.1)
(2.3)
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 400C 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 - 280C) 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
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
The design Equation of a PFR (plug flow reactor) operating at steady state is given
below.
CE4005 | Background 12
Where:
Co is the concentration in
C is concentration out.
Design Equation:
(2.
Stoichiometry: v=v0
(2.7)
(2.8)
v
(2.9)
CA=CA0 (1-X)
(2.10)
(2.11)
(2.12)
(2.13)
(2.14)
(2.15)
(2.16)
Equation 2.16 above is the design equation for a plug flow reactor.
Knowing that
v and dX = -dCA/CAo
V/vo = CAo
(2.17)
V/vo
t=
(2.18)
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 nonisothermal 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
Catalysts
Methanol distillation
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
CE4005 | Literature Review 15
synthesis reactors with internal cooling. The synthesis gas used in the production of
methanol is a mixture of CO, CO2 and H2. This synthesis gas can be produced from
various feedstock such as natural gas, higher hydrocarbons and coal. The synthesis gas
is produced conventionally via the steam reforming process but it can also be produced
from CO2 reforming, partial oxidation and auto thermal reforming. Figure 7 below
shows the essential steps of Lu gis Low Pressure Methanol Process with combined
reforming of oil associated natural gas. In the Lurgi reactor with typical operating
conditions of 523 K and 80 bar, the catalyst is packed in vertical tubes surrounded by
boiling water. Reaction heat is transferred to the boiling water to produce steam. Due to
the efficient heat transfer, very little temperature gradient is observed along the reactor.
The pressure of the boiling water helps to control the reactor temperature.
Figure 7. Essential p ocess steps in Lu gis 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.):
Steam reforming parts of the methane gas are converted to synthesis gas by
the highly endothermic steam reforming reaction, reaction energy is supplied by
the burning of natural gas outside the catalyst tubes in a multitubular reactor.
nCO + (
CH4 + H2O
CH4 +
(3.1)
(3.2)
(3.3)
The water gas shift (equation 3) occurs in all the reforming steps.
In the methanol synthesis, synthesis gas is converted to methanol over a Cu/Zn/Al2O3
catalyst. Figure 8 below shows the Lu gis [xii] methanol synthesis loop.
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
CE4005 | Literature Review 17
the volatility between ethanol and methanol. Firstly, the dissolved gases are separated
from the crude methanol by flashing at low pressure. Low and high boiling by-products
are removed in energy integrated three column distillation sequence. Ethanol is
removed in the side stream of the third of these columns [xiii].
(3.4)
The presence of the surface-bonded formaldehyde was verified by others such as
Tawarah and Hansen [xx] and Edwards and Schrader [xxi].
CE4005 | Literature Review 18
Transmission infrared spectroscopy was used by Edward and Schrader to develop the
mechanism. However, they speculate that the formaldehyde might be formed by carbon
monoxide insertion into an adsorbed hydroxyl group to form a bidentate formate
species. The infrared studies conducted under reaction conditions also showed that the
CO is adsorbed on the Cu(I) sites of the catalyst used, but much of the reaction occurs on
the zinc oxide component [xxi].
3.2.2. Mechanisms Involving CO2
The thermodynamics of the reaction of carbon dioxide to methanol are very
unfavourable at typical reaction conditions. This made Kung et al. reach a conclusion
that it is very unlikely for any proposed mechanism involving carbon dioxide
hydrogenation to be the predominant one [xvii]. Nevertheless, a series of studies by
Kagan and Rozovskii [xxii,xxiii] led them to conclude that methanol forms only via
carbon monoxide hydrogenation, and that direct synthesis of methanol from carbon
monoxide and hydrogen does not occur at all. Chinchen et al., [xxiv] confirmed this
when he repeated the work of Kagan and Rozovskii.
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.
Recent studies by the department of chemical engineering at Ajou University in Korea
investigated the influence of CO2 on hydrogenation. A kinetic model was developed for
methanol synthesis over Cu/ZnO/Al2O3/ZrO2 catalyst to evaluate the effect of carbon
dioxide on the rate of reaction due to its high activity and stability.
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
CE4005 | Literature Review 19
determining step for CO and CO2 hydrogenations and the water gas shift reaction,
respectively. The result showed that the rate of CO2 hydrogenation is much lower than
that of CO hydrogenation and this affects the methanol production 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.
Figure 9. Thermodynamics of methanol synthesis. Variation of equilibrium constant kp with temperature and pressure
[iv]
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 350C 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].
Thermodynamic equilibrium limits the maximum yields of carbon oxides to methanol.
Due to the strongly non ideal behaviour of gases at conditions used commercially,
equilibrium equations necessarily involve fugacity. The equilibrium composition of any
mixture of carbon oxides, water, methanol, hydrogen and inert can be calculated using
the equations below. These equations corresponds to reactions in equation 3.1 and 3.3.
Kf1 = fCH3OH/fCOfH2
(3.5)
Kf2 = fCO2fH2/fCOfH2O
(3.6)
3.4. Selectivity
Carbon monoxide and carbon dioxide can also react with hydrogen to produce byproducts such as ethers, hydrocarbons and higher alcohols.
CO +3H2
CH4
+H2O
(H298K
-206.17kJ/mol,
G=
-142.25kJ/mol)
(3.7)
2CO +4H2
CH3OCH3 +H2O
(3.8)
2CO +4H2
C2H5OH +H2O
(H298K = -2
. 8kJ/mol, G= -122.55kJ/mol)
(3.9)
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].
3.5. Catalysts
The catalysts used for methanol synthesis can be divided into 2, high-pressure and lowpressure catalysts.
Table 1. Catalysts proposed or used for industrial process [iv].
Catalyst Composition
ZnO
ZnO
Original
synthesis
catalyst,
short life.
ZnO/Cr2O3
ZnO
Standard
high-pressure
catalyst
ZnO/MnO/Cr2O3 + alkali
Standard
high-pressure
Cu
Cu ZnO/Cr2O3
Cu ZnO/Al2O3
Cu
Industrial
low-pressure
catalyst
Pd/SiO2
Pd
Pd/basic oxides
Rh/SiO2
Rh
Rh/basic oxides
Rh complexes
Rh complex
Low
activity;
poorer
selectivityc
a
There is evidence that the active phases in the Cu, Pd and Rh catalysts, essentially the
c homogeneous
a good catalyst for methanol synthesis at high temperature and temperatures above
350C, it was not stable and it quickly lost it activities which means it has to be replaced
frequently. Through research, it was found that chromia acts as a stabilizer for zinc
oxide by preventing the growth of the zinc oxide crystals and by so doing preventing die
off. The Zinc oxide/chromia catalyst was tolerant of the impure synthesis gas and could
have a plant life of several of years. This catalyst was not very selective and depending
on synthesis conditions as much as 2% of the inlet carbon oxides could be converted to
methane and a similar proportion to dimethyl ether. The very exothermic nature of the
side reaction calls for a careful control of catalyst temperature [iv].
3.5.2. Low-pressure Catalysts
The low-pressure process is based on high activity catalysts. Copper oxide was found to
be very effective for methanol synthesis when added to zinc oxide. The zinc
oxide/chromia catalysts also showed increase in activity when Copper oxide was added
to it, so it could be used at temperatures as low as 300C. However catalysts containing
copper were not stable and lost activity e.g. a Zn/Cu/Cr catalyst in atomic proportions
of 6: 3 : 1 lost 40% of its activity in 72 hours. The work of ICI on methanol synthesis
resulted in the production of more stable copper catalysts. In the modern copper/zinc
oxide/alumina synthesis catalysts, high activity and stability are obtained by optimizing
the composition and producing very small particles of the mixture in a very intimate
mixture precipitated at controlled pH in which the acidic and alkaline solutions are
mixed continuously. Catalysts made by the continuous process were used in the first
(1966) low-pressure methanol synthesis plants operating at 50 bar and they had lives
of more than 3 years as well as producing methanol of a higher purity than the highpressure process. Further development resulted in catalysts suitable for operation at
100 bar, around the optimum operating pressure for plants capable of producing 1000
tonnes per day of methanol. Zinc oxide/alumina is not sufficiently refractory as a
support at 100 bar, but a more refractory support is provided by using some of the zinc
component as a compound with the alumina component; as zinc spinel (ZnO.Al2O3),
which is produced in a finely divided state.
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
CE4005 | Literature Review 24
(3.10)
Where: r = rate of reaction, f = fugacity, Keq = equilibrium constant and A,B,C and D are
adsorption rate constants.
The established correlation allows calculating the quantity of methanol produced, as a
function of temperature, space velocity, and composition of feed gas [xxviii].
3.6.2. Rozovskii (1980) and Klier (1982)
Since Nattas
esulting in
methanol synthesis plants that operate at lower pressures and temperatures. In recent
time, much kinetics have been proposed but unfortunately, difference in operating
conditions, catalyst used and feed gas composition has made it difficult to arrive at a
final conclusion on the kinetics and reaction mechanism.
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
CE4005 | Literature Review 27
hydrogenated directly to methanol and the remaining carbon dioxide competes for
active sites on the surface of the catalyst with other reactants. They attempted to
formulate a mechanism and rate law encompassing all surface phenomena. The rate law
formulated based on those assumptions is given below:
/
(
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)
According to Rozovskiis mechanism, carbon dioxide also participates in the reverse
water-gas shift reaction as shown in equation (2.3) with the rate equation given below:
(3.13)
Values of rate constants A-D are still undetermined [xxx].
3.6.3. Agny and Takoudis (1985)
Using a U shaped fixed bed reactor and a CuO/ZnO/Al2O3 catalyst operated at a
pressure between 0.3 to 1.5Mpa and temperature between 523-563K, Agny and
Takoudis [xviii] made use of the Langmuir-Hinshelwood kinetic model, they proposed
CE4005 | Literature Review 28
that that the adsorbed CO molecule dissociatively adsorbs a hydrogen molecule to form
the formyl intermediate CHO- with H2/CO ratio of 0.5/1 which is present in the
.
term of the kinetic equation they came up with equation 3.14 below. n was
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].
3.6.4. Skrzypek's (1985 and 1991)
Skrzypek et.al (1985) [ xxxi ] carried out the Analysis of the low-temperature methanol
synthesis in a single commercial isothermal Cu-Zn-Al catalyst pellet using the dusty-gas
diffusion model. They came up with a rate equation of
kp
P (1
(3.15)
Where:
is
the
reaction
rate
constant
0.830
exp
(-23750/RT)
(3.16),
In 1991, they further investigated the kinetics of methanol synthesis over commercial
copper/zinc oxide/alumina catalysts at a temperature between 187-277C 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:
CO2+3H2CH3OH+H2O and CO2+H2CO+H2O
(3.17)
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
CO2* + H2 * H2CO2*
(3.18)
(* denotes adsorbed species). The resulting rate equations this time around based on
equation 2.2 and 2.3 are:
(
)(
))
(3.19)
)(
))
(3.20)
den
(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].
over
Cu/ZnO/Al2O3/ZrO2 catalyst that was developed and selected to evaluate the effect of
carbon dioxide on the reaction rates due to its high activity and stability.
A kinetic mechanism where CO and CO2 are assumed to adsorb on different sites of Cu
was suggested for the development of hydrogenation reaction rates, while hydrogen is
supposed to be adsorbed on the site of ZnO. Since each overall reaction is made up of
several elementary steps, they developed various rate determining steps and estimated
to find the best fit model for methanol synthesis by using experimental data. The
experimental data in their study suggested the augmentation of additional reactions
other than the three main reactions (Equation 2.1, 2.2 and 2.3).
The resulting rate equations from this study is given below.
(3.22)
(3.23)
(3.24)
(3.25)
Where : ln
ln
29.07
5.639
(3.26)
(3.27)
(3.28)
CE4005 | Literature Review 31
(3.29)
Table 4. Reaction rates for methanol synthesis reaction and DME production [xxvi].
Model
Catalyst Used
Cu/ZnO/Al2O3
Skrzypek
Cu/ZnO/Al2O3
Lim
Cu/ZnO/Al2O3/ZrO2
Rate Equation
(
.
(1
(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.
4.1.1. Developing Langmuir-Hinshelwood Kinetic Model from Experimental Data
Langmuir Hinshelwood model can be used to deduce a rate law consistent with
experimental observation. Combining surface reaction rate laws with the Langmuir
expression gives the Langmuir-Hinshelwood (LH) rate laws for surface catalysed
reactions [ix].
e.g. for the overall reaction: A
(4.1)
(4.2)
Hence,
(4.3)
Where
(4.5)
The following assumptions will be used to deduce rate law consistent with the
experimental data provided.
1. Surface reaction is first order.
2. Reaction is essentially irreversible.
Conclusion can be drawn from the rate of disappearance of H2,
on the partial
(P P
(4.6)
(4.7)
(4.8)
T is temperature.
(4.9)
(4.10)
(4.11)
Where:
T is reaction temperature,
W is weight of catalyst,
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:
1. Choose a value of conversion, X.
2. Depending on the desired reactor set up, calculate T from equation 4.9 for adiabatic
and 4.10 for non-adiabatic.
CE4005 | Work Plan and Methodology 37
3. Calculate the kinetic parameters k and Keq from equation 4.6 and 4.7. (Other kinetic
model will have different kinetic parameters).
4. Substitute the partial pressure, Pi values into the kinetic model rate equation
5. Calculate rA (rate of reaction) using the kinetic model rate equation
6. Calculate (
(4.12)
7. Repeat step (1) to (6) for values of conversion X between 0 and 0.9
8. Calculate
(4.13)
is the increment.
9. Plot the results with temperature on the y-axis and conversion on the x-axis.
dimension.
From the material balance, FAo = voCAo
(4.14)
hence,
(4.15)
= 10000m3/hr , = 1 * 10-4
V = 1m3
v =
v = 10000
2.78
PV = nRT
(4.16)
P = Pi
and
(4.17)
= CAo
(4.18)
Hence, CAo =
(4.19)
(4.20)
where:
V is reactor volume,
T is temperature.
4.2.1. Reactor Volume
For the shell and tube reactor, assuming the catalyst bed occupies 1/3 of the reactor
volume i.e. 1/3VReactor = VCatalyst, i.e. the catalyst will occupy a third of the reactor
volume. Another third of the reactor volume will be occupied by the shell space and the
final third will be occupied by the space between the catalyst bed and the top and
bottom dome heads. This assumption will help to calculate the dimension of reactor
needed without too much complication.
The volume of the reactor will be determined from the catalyst weight using the
equation: VC = WC/C = 1/3VReactor
(4.21)
Where:
WC is weight of catalyst,
om the volume, the eacto length, diamete and the catalyst beds cha acte istics can
be determined.
The total volume of reactor is the volume of cylindrical section + volume of dome
closures.
4.2.2. Reactor Length and Diameter
For a cylindrical vessel, the relationship between the length and the volume of a
cylinder is given as: VR =
(4.22)
Where:
VR = volume of the reactor
D = diameter of reactor
= length of reactor
(Note: The reactor volume does not include the volume occupied by the dome head
closures).
Total length of reactor = length of cylindrical section + length of hemispherical head
closure
Assumption
Assuming a diameter to length ratio (D : ) of 1:4
Hence:
(4.23)
4
D3
(4.24)
(4.25)
Rearrange to get D
D=
(4.26)
4.2.3. Reactor Dome Closure
The reactor is cylindrical and there are four principal types of ends used for a cylindrical
vessel.
1. Torispherical heads.
2. Hemispherical heads.
3. Ellipsoidal heads.
4. Flat plates and formed flat heads.
The reactor has a top and bottom head closure, the choice of head closure used in this
design is the hemispherical type. These have been chosen as they can withstand very
high pressure, and since the reactor design pressure will be higher than the operating
pressure, it is viable to use this type of head closure [xxxiii].
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
Volume of hemispherical head closure =
(4.27)
i. d
(4.28)
(4.29)
u
(4.30)
For a spherical particle, the effective particle diameter dp= diameter of particle dp =
0.0381m
eynolds numbe , e
(4.31)
CE4005 | Work Plan and Methodology 42
Pressure drop (
Friction factor, f
[1.7
(4.32)
Fluid density
(4.33)
(4.34)
(4.35)
Choose values of
Plot a graph of
(4.36)
(4.37)
CH3OH
H298K = -90.64kJ/mol) there is a need to take out the heat of the reaction. Cooling
water can be used to take out the heat of the reaction. The temperature of the cooling
water required can be found graphically by following the steps below.
(4.38)
relationships
suggests
reasonable
coolant
temperature for the shell side in order to achieve the equilibrium conversion.
conditions. The final data set is from a statistically designed, central composite set of
simulated experiments, to which 5% random error was added. It comprises a total of 27
simulated esults[xxxiv].
2H2 + CO
CH3OH
(5.1)
Experiment
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Rate
mol/m3.s
6.573
4.819
6.27
4.928
10.115
7.585
9.393
7.124
1.768
1.177
1.621
1.293
2.827
2.125
2.883
2.035
4.03
3.925
3.938
10.561
1.396
2.452
5.252
3.731
3.599
5.085
3.202
Temp
(K)
495
495
495
495
495
495
495
495
475
475
475
475
475
475
475
475
485
485
485
500
470
485
485
485
485
485
485
CO
4052
4052
1530
1530
4052
4052
1530
1530
4052
4052
1530
1530
4052
4052
1530
1530
2533
2533
2533
2533
2533
2533
2533
4862
1276
2533
2533
Hydrogen
8509
5906
8509
5906
8509
5906
8509
5906
8509
5906
8509
5906
8509
5906
8509
5906
7091
7091
7091
7091
7091
7091
7091
7091
7091
9330
5369
Langmuir Hinshelwood model can be used to deduce a rate law consistent with
experimental observation. Combining surface reaction rate laws with the Langmuir
CE4005 | Results and Discussion 45
expression gives the Langmuir-Hinshelwood (LH) rate laws for surface catalysed
reactions [ix].
The following assumptions will be used to deduce rate law consistent with the
experimental data provided in Table 6 above.
on the partial
(5.7)
..
Experiment
Rate
Temp
mol/m3.s
(K)
CO
Hydrogen
6.573
495
1013
4052
8509
10.115
495
253
4052
8509
This result suggests that methanol is adsorbed on the catalyst surface i.e.
[
.
(5.8)
Experiment
Rate
Temp
mol/m3.s
(K)
CO
Hydrogen
6.573
495
1013
4052
8509
6.27
495
1013
1530
8509
10.115
495
253
4052
8509
9.393
495
253
1530
8509
Experiments 1 and 3, 5 and 7, 9 and 11 shows that almost 3 folds increase in the partial
pressure of carbon monoxide has little effect on the rate of the reaction. This suggests
that carbon monoxide is very weakly adsorbed or goes directly into gas phase.
i.e.
(5.9)
Experiment
Rate
Temp
mol/m3.s
(K)
CO
Hydrogen
6.573
495
1013
4052
8509
4.819
495
1013
4052
5906
This suggests that hydrogen is strongly adsorbed on the catalyst surface, hence
[
(5.10)
Combining equations 5.8, 5.9 and 5.10 suggests that the rate law is of the form:
[
(5.11)
whe e
(5.12)
Where:
The rate law deduced from the experimental data provided (equation 5.12) is given
below:
To evaluate the reaction rate constant, k and the rate law parameters
and
(5.15)
Appropriate data points will be selected from the experimental data available on Table
6 to plot a graph of y against x
Where:
y
c
P /P
(5.16)
(5.17)
(5.18)
Since the reaction rate constant and adsorption parameters, Ki are functions of
temperature, they should be found at constant temperature.
To find k and
and keep
constant.
y-axis
T
PH2/-rH2
X-axis
PH2
PM
(kPa)
(kPa)
475
4812.783 8509
1013
475
3009.904 8509
253
6000
5000
y = 2.3722x + 2409.7
PH2/-rH2
4000
3000
KM
Linear (KM)
2000
1000
0
0
200
400
600
800
1000
1200
PM
y = 2.3722x + 2409.7
1
1
2409.7
CE4005 | Results and Discussion 49
1
2409.7
4.1
10
2. 7
2. 7
2. 7
To find k and
4.1
4.1
1
10
10
9.84 10
and keep
constant.
y-axis
T
PH2/-rH2
X-axis
PH2
PM
(kPa)
(kPa)
475
5249.229 8509
1013
475
4567.672 5906
1013
5300
5200
y = 0.2618x + 3021.3
PH2/-rH2
5100
5000
4900
KH2
Linear (KH2)
4800
4700
4600
4500
0
2000
4000
6000
8000
10000
KH2
y = 0.2618x + 3021.3
CE4005 | Results and Discussion 50
1
k2
c
k2
1
021.
021.
. 1 10 mol kpa m s
0.2618
0.2618
0.2618
k2
. 1 10
. 1 10
8.67 10
The value of k will lie between k1 and k2, hence k = (k1 + k2)/2
k = (4.1
10
. 1 10 )/2 = .7
10
mol kpa m s
The spread sheet used for the calculation has been attached to the appendix.
0
CE4005 | Results and Discussion 52
(
(
Where:
U is linear velocity,
CA is concentration,
v0 is volumetric flow,
XA is fractional conversion of A,
But,
So,
and d
0 or w
) [xxxiv].
hence,
= 10000m3/hr , = 1 * 10-4
V = 1m3
=
= 10000
CAo =
2.78
21 9.4
21 9.4
/
/
= 5947.66mol/s
Table 12. Experimental data table modified to include values of VO , CA0, FA0 and
Expt
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Rate
(mol/m3.s)
6.573
4.819
6.27
4.928
10.115
7.585
9.393
7.124
1.768
1.177
1.621
1.293
2.827
2.125
2.883
2.035
4.03
3.925
3.938
10.561
1.396
2.452
5.252
3.731
3.599
T
(K)
495
495
495
495
495
495
495
495
475
475
475
475
475
475
475
475
485
485
485
500
470
485
485
485
485
Pi (atm)
CH3OH CO
9.99 39.99
9.99 39.99
9.99 15.09
9.99 15.09
2.49 39.99
2.49 39.99
2.49 15.09
2.49 15.09
9.99 39.99
9.99 39.99
9.99 15.09
9.99 15.09
2.49 39.99
2.49 39.99
2.49 15.09
2.49 15.09
5.00 24.99
5.00 24.99
5.00 24.99
5.00 24.99
5.00 24.99
15.00 24.99
1.69 24.99
5.00 47.98
5.00 12.59
H2
CH3OH
83.97 1013000
58.28 1013000
83.97 1013000
58.28 1013000
83.97
253000
58.28
253000
83.97
253000
58.28
253000
83.97 1013000
58.28 1013000
83.97 1013000
58.28 1013000
83.97
253000
58.28
253000
83.97
253000
58.28
253000
69.98
507000
69.98
507000
69.98
507000
69.98
507000
69.98
507000
69.98 1520000
69.98
172000
69.98
507000
69.98
507000
Pi (Pa)
pi (pa
Vo
CA0 (mol/m3) FA0
(m3/s)
CO
H2
4052000 8509000 13574000
2.78
3298.32 9169.33
4052000 5906000 10971000
2.78
2665.82 7410.98
1530000 8509000 11052000
2.78
2685.50 7465.69
1530000 5906000
8449000
2.78
2053.00 5707.36
4052000 8509000 12814000
2.78
3113.65 8655.94
4052000 5906000 10211000
2.78
2481.15 6897.59
1530000 8509000 10292000
2.78
2500.83 6952.31
1530000 5906000
7689000
2.78
1868.34 5193.97
4052000 8509000 13574000
2.78
3437.19 9555.40
4052000 5906000 10971000
2.78
2778.07 7723.02
1530000 8509000 11052000
2.78
2798.58 7780.04
1530000 5906000
8449000
2.78
2139.45 5947.66
4052000 8509000 12814000
2.78
3244.75 9020.40
4052000 5906000 10211000
2.78
2585.62 7188.02
1530000 8509000 10292000
2.78
2606.13 7245.04
1530000 5906000
7689000
2.78
1947.0 5412.67
2533000 7091000 10131000
2.78
2512.47 6984.66
2533000 7091000 10131000
2.78
2512.47 6984.66
2533000 7091000 10131000
2.78
2512.47 6984.66
2533000 7091000 10131000
2.78
2437.09 6775.12
2533000 7091000 10131000
2.78
2592.65 7207.58
2533000 7091000 11144000
2.78
2763.69 7683.06
2533000 7091000
9796000
2.78
2429.39 6753.70
4862000 7091000 12460000
2.78
3090.06 8590.35
1276000 7091000
8874000
2.78
2200.74 6118.04
89.85
72.62
73.16
55.93
84.82
67.59
68.13
50.90
93.64
75.68
76.24
58.28
88.39
70.44
71.00
53.04
68.45
68.45
68.45
66.39
70.63
75.29
66.19
84.19
59.96
26
27
5.085
3.202
485
485
5.00
5.00
24.99
24.99
92.07
52.98
507000
507000
2533000
2533000
9330000
5369000
12370000
8409000
Experimental 12 data (in bold on Table 12) was used to simulate the plan-scale catalytic reactor.
2.78
2.78
3067.74
2085.42
8528.31
5797.46
83.58
56.82
The rate law deduced from the experimental data provided (equation 5.12) is given
below:
0.9
0
To (K)
H (kJ/mol
475
Fao (mol/s)
97.97
(kg/s
Cp (kJ/Kg mol.K
5947.66
58.28
29.31
PH2
(kpa)
5906
PM
(kpa)
KH2
(mol
kpa-1
1013
KM
m-3 s-1)
0.00037
8.66514E-05
0.00098
Ts
(W/m2)
(m)
(K)
631
12
483
3.1415
.
.
0.9
0.877982 mol/m3.s
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.
Table 15. Reactor volume and temperature profiles for adiabatic and non-adiabatic setup at conversion between 0 and
0.9
-rH2(mol/m3.s)
V(m3)
Adiabatic T (K)
Non-Adiabatic T(K)
0.88
475
483
0.1
0.88
677.42
509.10
485.04
0.2
0.88
1354.85
543.22
487.08
0.3
0.88
2032.27
577.32
489.12
0.4
0.88
2709.69
611.43
491.16
0.5
0.88
3387.12
645.54
493.19
0.6
0.88
4064.54
679.65
495.23
0.7
0.88
4741.97
713.75
497.27
0.8
0.88
5419.39
747.86
499.31
0.9
0.88
6096.82
781.97
501.35
47
.
.
] 0.9
781.97
48
] 0.9
01.
Where:
XA is fractional conversion,
900
800
700
600
500
400
Adiabatic
300
Nonadiabatic
200
100
0
0
0.2
0.4
0.6
0.8
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).
5.2.1. Reactor Dimension
To get a reactor dimension in the specified range, the reactor volume in Table 15 above
will be scaled down by 60.
The new reactor volume will be 6096.82/60 = 101.61m3.
Catalyst bed
Reactor
Reactor
Volume(m3)
Volume (m3)
Diameter (m)
Length (m)
(m)
101.61
33.87
3.19
12.76
3.19
Assumptions
4D
Where:
VR = volume of the reactor
D = diameter of reactor
l = length of reactor
The volume of the reactor can be rewritten as:
VR =
VR
4D
D3
Rearrange to get D
= 3.19m
Length = 4D.
Hence length of the reactor l = 4*3.19 = 12.76m (cylindrical section)
5.2.1.1.
The reactor has a top and bottom head closure, the choice of head closure used in this
design is the hemispherical type. These have been chosen as they can withstand very
high pressure, and since the reactor design pressure will be higher than the operating
pressure, it is viable to use this type of head closure [xxxv].
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
Volume of hemispherical head closure =
(1. 9
= 8.49m3
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
5.2.1.2.
5.2.1.2.1.
Catalyst Weight
Assuming a Cu/ZnO/Al2O3 catalyst is used, The bulk density, b of the catalyst is 1100
kg/m3 [xxxvi ]
WC = VC * b = 33.87 m3 * 1100 kg/m3 = 37257kg
Where: WC is weight of catalyst; VC is volume of catalyst and b is the catalyst bulk
density.
5.2.1.2.2.
N
i. d
.87
4 0.0 8 12
2489 tubes
5.2.1.2.3.
Bed Depth
Weight of catalyst, Wc = 37257kg
Diameter of the reactor (D) = Catalyst bed diameter= 3.19m,
atalyst bulk density,
1100kg/m3
Bed depth, L
4.2 m
5.2.1.2.4.
Mass Velocity
.
Mass velocity, G
5.2.1.2.5.
7.29 kgs
Reynolds Number
For a spherical particle, the effective particle diameter, dp= diameter of particle, dp =
0.00287m [ix]
e
d G
0.00287 7.29
1.6 10
1 08
Re < 2000 hence the flow will be laminar and the profile of velocity will be parabolic.
5.2.1.2.6.
Pressure drop (
Pressure Drop
P
CE4005 | Results and Discussion 63
Friction factor, f
[1.7
(
Fluid density
[1.7
.
.
17.0
8.28
)
947.66
8. 14 47
10 (
G
G
u
Hence, Pressure drop (
2 .24 kgm
u
7.29
2 .24
0.29ms
.
Catalyst bed
Weight (kg)
depth, L (m)
37257
b (kg/m3)
No. of tubes
dp
Nt
4.25
1100
2489 0.00287
25.24
Mass Velocity,
Reynolds
Friction
Superficial
Pressure
Pressure
G (kg/m2.s)
Number, Re
factor, f
linear
drop (Pa)
drop
velocity
(bar)
u (m/s)
7.29
1308
17.05
0.29
53467.97
0.53
5.2.1.2.6.1.
The sensitivity of the reactor dimension to a given pressure drop can be used for
operating power cost and vessel cost studies. Therefore a sensitivity analysis will be
carried out for the rector dimension obtained from the plant-scale catalytic reactor
simulation.
Pressure drop, (
Bed depth, L
P
(
.
.
.
.
4.2 m
.18m
Ranges of pressure drop have been selected around the calculated pressure drop. The
sensitivity result is tabulated in Table 19 below.
Table 19. Reactor dimension sensitivity to pressure drop
Pressure drop
Bed Depth
(Pa)
L (m)
D^2
Diameter
D (m)
10000
0.795122107
54.23839605
7.364672162
20000
1.590244214
27.11919802
5.207609627
30000
2.385366321
18.07946535
4.251995455
40000
3.180488428
13.55959901
3.682336081
53467.97
4.251356496
10.14409114
3.184978985
60000
4.770732642
9.039732675
3.00661482
70000
5.565854749
7.748342293
2.783584432
80000
6.360976856
6.779799506
2.603804813
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.
CE4005 | Results and Discussion 65
100000
80000
60000
40000
Diameter
20000
Bed depth
0
0
Model
Developed
Catalyst Used
kP
P
kinetic Cu/ZnO/Al2O3
model
(assumed)
Cu/ZnO/Al2O3
Skrzypek
Cu/ZnO/Al2O3
Lim
Rate Equation
1
P
k (P P
kp
P (1
Cu/ZnO/Al2O3/ZrO2
(1
(1
P
(P P
P
k P P
(P P
.
)
P
)
P
Developed Kinetic
Model
Scaling factor to meet specification
Catalyst Weight (kg)
Catalyst Bed Volume (m3)
Reactor Volume excluding dome closure
(m3)
Reactor Length (m3)
Reactor Diameter (m3)
Catalyst Bed Depth (m)
Number of catalyst tubes
Mass velocity (kg/m2.s)
Reynolds number
Pressure drop (bar)
37257
33.87
101.61
12.76
3.19
4.25
2500
7.29
1308
0.53
12.98
3.25
4.33
2600
7.05
1264
0.51
12.83
3.20
4.28
2500
7.22
1295
0.52
12.81
3.20
4.27
2500
7.23
1297
0.53
12.89
3.22
4.29
2600
7.14
1280
0.52
12.92
3.23
4.31
2600
7.10
1275
0.51
Lim
800
38304
34.82
104.46
12.86
3.22
4.29
2500
7.18
1287
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).
Experiment 12 data (see Table 13 and Table 14) was used to simulate a plant scale
catalytic reaction at the specified reaction conditions, thermodynamic and physical
property.
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. Summary of Agny and Takoudis model for an adiabatic reactor using the provided experimental data
To (K)
H (kJ/mol
475
FA0 (mol/s)
(kg/s)
58.29
Cp
(kJ/Kg mol.K)
29.31
PCO
(atm)
PH2 (atm)
PCH3OH (atm)
83.98
2.49
Keq
G
(g)
475600.1
G*
(g)
0.017
rmethanol
(mol/(gcat s)
0.013
97.97
5947.66
log10Keq
475
k
[mol/(s atm gcat)]
9.56E-05
0.1
509
0.00013
-2.48
0.003
0.017
349246.6
412423.32
41242.332
41.24
0.63
0.2
543
0.00017
-3.11
0.0007
0.022
268466.3
308856.44
30885.644
30.89
0.29
0.3
577
0.00022
-3.68
0.0002
0.027
217945.1
243205.69
24320.569
24.32
0.11
0.4
611
0.00027
-4.18
6.61E-05
0.031
194828.5
206386.77
20638.677
20.64
0.04
0.5
646
0.00033
-4.63
2.32E-05
0.026
225302.9
210065.7
21006.57
21.01
0.01
0.6
680
0.00039
-5.04
9.02E-06
0.00092
6468631
3346966.9
334696.69
334.69
0.0060
0.7
714
0.00045
-5.42
3.81E-06
-0.078
-76068
3196281.4
319628.14
319.63
0.0027
0.8
748
0.00052
-5.76
1.74E-06
-0.279
-21313.9
-48690.98
-4869.0979
-4.867
0.0013
XA
Tad
(K)
-1.76
39.99
R
(J/mol/K)
8.314
G*
(g
G*
(kg
Xe
0.89
Catalyst Weight :
787.55
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).
Sample Calculation
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,
0.
47
.
.
646
(P P
0.000
( 9.9
8 .98
.
.
( 9.9
= 0.026 mol/(gcat.s).
.
2287 6.1 g
is the increment.
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.
800
600
400
T Vs X
200
0
0
0.2
0.4
0.6
Conversion
0.8
rate (mol/(gcat s)
Rate vs Conversion
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
0.3
0.4
0.5
0.2
0.1
Rate vs
Conversion
0
0.6
0
0.5
conversion
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.
Table 23. Summary of Agny and Takoudis model for non-adiabatic reactor setup using the experimental data provided
To (K)
Ts (K)
475
XA
483
T (K)
H (kJ/mol
Fao (mol/s)
97.97
5947.66
log10Keq
(kg/s
58.29
Keq
Cp (kJ/Kg mol.K)
29.31
PCO (atm)
PH2 (atm)
PCH3OH (atm)
R (J/mol/K)
83.9
2.49
8.314
39.99
Rate
(mol/(kgcat s)
1.35E-05
G (g)
G* (g)
U (W/m2)
631
12
3.142
483
0.000103
-1.94
0.012
Rate
(mol/(gcat s)
0.0135
G*
(g
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
(kg
440520.1
Catalyst Weight:
G*
386.26
Rate vs Conversion
0.016
0.014
500
400
300
T vs X
200
100
rate (mol/(gcat s)
Temperature (K)
600
0.012
0.01
0.008
0.006
Rate vs Conversion
0.004
0.002
0
0
0.2
0.4
0.6
Conversion
0.8
0.5
conversion
Figure 17. Relationship between temperature and degree of conversion in the nonadiabatic 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
(K)
Keq
Xe
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
At a fractional conversion XA = 0.5,
(
.
(
= 0.01
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.
Xeq, X
0.6
0.5
Xe against T
X against T
0.4
0.3
0.2
0.1
0
0
100
200
300
400
500
600
Temperature (K)
Figure 18. Plot of equilibrium conversion as a function of temperature.
700
800
Figure 18 shows that for a feed temperature of 475K, the adiabatic temperature
equilibrium is about 550K and the equilibrium conversion is 23% therefore a cooling
water temperature of 550K will be required on the shell side of the reactor to keep the
reaction at the equilibrium conversion (highest conversion that can be achieved) .
Cooling the feed down to 400K will shift the energy balance line to the left and increase
the equilibrium conversion. Interstage cooling can be used to achieve higher
conversions.
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.
PFR
B2
B3
Temperature
Pressure
bar
199.8
199.8
1182.7
1182.7
101.300
101.300
101.300
100.800
1.000
1.000
1.000
1.000
21412.800
21412.800
8934.864
8934.864
210150.271
210150.271
210150.271
210150.271
Vapor Frac
Mole Flow
kmol/hr
Mass Flow
kg/hr
Volume Flow
cum/hr
8977.323
8977.323
11067.410
11120.577
Enthalpy
Gcal/hr
-142.218
-142.218
-142.218
-142.218
Mole Flow
kmol/hr
CO
6423.840
6423.840
184.872
184.872
H2
14988.960
14988.960
2511.024
2511.024
6238.968
6238.968
CH4O
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).
Figure 22. Temperature profile of the reactor at a feed composition of 70% H2 and 30% CO
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.
CE4005 | Results and Discussion 79
A sensitivity analysis was performed to see the effect of feed temperature on the
production of methanol.
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 thats 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.
6. Conclusion
The primary objectives of this research project is to develop a kinetic model and reactor
design for the synthesis of methanol. Using the kinetic analysis data provided for
methanol synthesis, a Langmuir-Hinshelwood type of kinetics was developed. The
developed kinetic rate equation was used to simulate a plant scale catalytic reactor at
specified reaction conditions similar to that used in the chemical industry for methanol
synthesis. The reactor was simulated as a simple, one-dimensional, plug-flow, pseudo
homogeneous, nonisothermal reactor 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 thats
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 thats 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
B
C
Co
C
D
dp
dp
dx
f
FA
FAo
fi
G
G*
G
h
H
k
ka
kd
Ki
Kp, Keq
l
L
n
n
Nt
P
Pi
r
-rA
R
Re
T
Tad
TO
Ts
u
U
V
Vc
v0
VR
Wc
X
Definition
Catalyst bed bulok density
Concentration
Initial concentration
Bulk density of catalyst
Diameter
Effective particle diameter
Particle diameter
Differential of x
Bed voidage
Friction factor
Molar flow
Inlet molar flow
Fugacity of component i
Fluid density
ratio of molar flow to rate of reaction
average of two successive values of G
Measure of free energy
Height
Heat of reaction
Reaction rate constant
Adsorption rate constant
Desorption rate constant
Adsorption rate constant of component i
Thermodynamic equilibrium constant
Length
Bed depth
Specific mass flow rate
Number of moles
Empirical constant
Number of catalyst tubes
action of the su face cove ed by adso bed species
Pressure
Partial pressure of component i
Pressure drop
Radius
Rate of reaction
Molar gas constant
Reynolds number
Temperature
Adiabatic temperature rise
Reactor inlet temperature
Surrounding temperature/temperature of coolant
Mean residence time
velocity
Overall heat transfer coefficient
Volume
Volume of catalyst
Volumetric flow
Volume of reactor
Weight of catalyst
Conversion
Unit
kg/m3
mol/m3
mol/m3
kg/m3
m
m
m
mol/s
mol/s
atm, bar
kg/m3
g, kg
same unit as G
kJ/mol
m
kJ/mol
mol/(gcat.s atm)
dimensionless
m
kg/s
mol
atm/Pa/kPa/bar
atm/Pa/kPa
Pa/kPa/bar
m
mol A / (kg cat.s)
J/mol/K
K
K
K
K
s
m/s
W/m2K
m3
m3
m3/s
m3
g, kg
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): 26362639.
ii John J. McKetta Jr. Encyclopedia of Chemical Processing and Design. Volume 1:
Abrasives to Acrylonitrile. 1 Edition. CRC Press, 1976, pp. 418-451.
iii How is Methanol Made? - Methanol Institute . 2012. How is Methanol Made? Methanol Institute . [ONLINE] Available at: http://www.methanol.org/MethanolBasics/Overview/How-is-Methanol-Made-.aspx. [Accessed 29 October 2012].
iv Martyn V. Twigg. Catalyst Handbook. 2nd Edition., CRC Press, 1989, pp.442.
v F. Marschner and F. W. Moeller in Applied Industrial Catalysis, Vol. 2, Academic, New
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