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CHAPTER 1. INTRODUCTION..............................................................................................1
1.1
SIGNIFICANCE.........................................................................................................2
1.2
OBJECTIVE OF THESIS...........................................................................................3
1.3
ORGANISATION OF THESIS...................................................................................4
List of Figures
Figure 1. Relation between reaction pressure and CO2 conversion and methanol yield from
experimental results and thermodynamic predictions .............................................................13
Figure 2. Relationship between reaction temperature and CO 2 conversion amd yield of
methanol from experimental results and thermodynamic predictions.....................................14
Figure 3. Relationship between space velocity and CO2 conversion and methanol yield ......15
Figure 4. Rates of methanol formation as a function of space velocity for methanol
synthesis over Cu/ZnO/Al2O3catalyst with synthesis gas containing 10 vol% CO2................15
Figure 5. Aspects to be dealt with in the modelling of fixed bed reactors...............................25
Figure 6. Model Results of various parameters at T=498 K & P=50 bar (a) Production of
methanol (b) Yield of methanol w.r.t. C (c) Conversion of carbon monoxide
(d) Conversion of hydrogen and (e) Temperature along the length of the reactor.................37
Figure 7. Effect of Pressure on the molar flow rates of methanol...........................................38
Figure 8. Effect of Pressure on the conversion of carbon monoxide.......................................39
Figure 9. Effect of Pressure on the yield of methanol w.r.t.C .................................................40
Figure 10. Effect of Pressure on the yield of methanol w.r.t. H2..............................................41
Figure 11. Effect of Pressure on the conversion of Carbon Dioxide.......................................42
Figure 12. Effect of Pressure on the conversion of Hydrogen.................................................43
2
List of Tables
Table 1. Various kinetic models along with their experimental reaction conditions..................7
Table 2. Various catalysts used along with the reactions, reactor used and the reaction
conditions.................................................................................................................................23
Table 3. Frequency Factors of Kinetic Equation......................................................................31
Table 4. Frequency Factors of Enthalpy Equation...................................................................33
Table 5. Industrial Reactor Specification, Catalyst Properties and Feed Conditions...............34
Table 6. Comparison of results with simulated results given by Panahi et al..........................36
Table 7. Comparison of Temperature Effect in Methanol Synthesis........................................49
CHAPTER 1. INTRODUCTION
(1)
(2)
(3)
unified conclusion on one scheme. The role of CO 2 in the synthesis of methanol and the role
of the ZnO catalyst are still some areas where voids in exact knowledge exist [4, 5 and 6].
Several efforts have been made for improving the synthesis of methanol after its
foundation by B.A.S.F. (Baden Aniline and SODA Factory). They developed new reactor
configurations, new, stable and more efficient catalysts, and optimized the reaction
parameters viz temperature, pressure and space velocity. The development of catalysts
involves efficacious supports ZnO and ZrO2, enhancers viz zirconia, alumina and various
contenders like cobalt, gallium, magnesium and boron for enhancing the catalysts activity at
changing heat and heating conditions [2, 4]. Since the manufacture of methanol is heat
producing exothermic reaction, increased temperatures can improve the amount of methanol
produced but because of thermodynamic limitations it can enhance it up to an optimal
temperature. Because of these limitations the equilibrium yield decreases with increasingly
high temperatures. Hereby, new and improved methods have been developed which prefer
synthesis of methanol at low temperatures [2]. However, there is still debate on the reaction
mechanism and is still explored.
1.1 SIGNIFICANCE
The manufacture of methanol is of great significance industrially. The worldwide
methanol product was around 44 MMT per year in 2010 which increased to 84 MMT per
year in 2012. The World Methanol Cost Study report of the Chemical Market Associates in
2010 stated that the international methanol industry is half-way of the maximum ability build
on its past [7]. Another report, in 2011, stated that international methanol consumption
increase had been very strong in 2010 and was anticipated to increase at the same rate [8]. It
caters to a very wide variety of applications due to its very high demand. It is used as a raw
material in the synthesis of very important chemical viz methyl tert-butyl ether,
formaldehyde, chloromethane and acetic acid which can be in succession can be used in
many application like plastics, paints and plywood to explosives. [9]. Methanol is also used
as a transportation fuel in two ways, as methanol as it is or by blending it in petrol.
It is an excellent promising alternating energy source since it has several advantages such
as low emissions, clean burning properties, high energy density, high octane rating, easy
transport, high volatility, and has abilities of incorporating in the existing engines with minor
infrastructural modifications [3, 10, and 11]. In the fuel cell research applications, methanol is
the fuel for direct methanol fuel cells [11].
The world global economy is strongly affected by the methanol industry. It is
generating $12 billion in annual economic activity thereby creating vast openings of
employment. Another important horizon is the methanol manufacture by addition of
hydrogen to carbon dioxide which helps in utilizing the excess atmospheric carbon dioxide
and thereby removing one of the main cause of global warming by the reduction of one of the
major greenhouse gases [3, 9]. So enhancing the production of methanol and optimizing it by
modelling its reaction kinetics is of significant importance due to its numerous benefits as a
source of alternative energy and its use in a variety of applications. The disagreement on the
reaction scheme for methanol synthesis leads development of new and efficacious kinetic
models which can improve the production of methanol and can result in obtaining high yields
of methanol with huge profits.
Temperature
Pressure
Finding the optimal parametric conditions for the maximum production of methanol
2.1 OUTLINE
The manufacture of methanol has been accomplished by BASF in 1920. Because of its wide
range of applications to which it caters it holds great industrial significance. The worldwide
methanol consumption increased from 40.4 MMT in 2007 to 58.6 MMT in subsequent 5
years [12].
explorations have been carried out for improving the production of methanol. A large number
of experimental studies have been carried out since decades but some doubts and questions
are still unanswered. The main dispute revolves around the identity of active sites and the
reaction mechanism (role of CO and CO 2). The following aspects of methanol synthesis
kinetics are analysed in the literature review.
Kinetic Models
Reaction Mechanism
Reaction Conditions
Catalyst
One of the kinetic models was given by Graaf et al. (1988) in which carbon
monoxide and carbon dioxide hydrogenation was taken into account. They got around 48
reaction pathways by appropriate assumptions of various basic reactions to be rate controlling
and next, by using statistical discrimination they selected the best possible kinetic model.
Also the water gas shift reaction was considered along with above motioned reactions. [16].
Mcneil et al. (1989) derived a CO2 expression rate which was rooted on more
mechanist data and conditions written in literature. [17]. Skyzypek et al. (1991) showed
through experiments that the production of methanol chooses CO 2 upon carbon monoxide as
the carbon source and hence developed their kinetic models based on the reactions (2) & (3)
[18].
Askgaard et al. (1995) gave a kinetic model for synthesis of methanol and evaluated
the kinetic parameters using the surface science studies and gas phase thermodynamics. They
discovered out that the calculated rates compared well with the measured rates when they
were extrapolated to actual working conditions [19].Froment and Buschhe (1996) developed
a steady state kinetic model by conducting experiments which were supported by a
comprehensive reaction path and network considering carbon dioxide to be the primary feed
of carbon in the process of methanol synthesis. The models took into accounted the effect of
various parameters such as pressure, gas phase composition and temperature and on the
production rates of methanol even beyond their own experimental conditions [13]. Kutoba et.
al (2001) also developed the kinetic equations for the synthesis of methanol assuming the
hydrogenation of carbon dioxide to be the principal reaction. The authors propounded that
that yield values obtained from their equations compared well with the experiments
conducted in a test plant so their equations were reasonably accurate [20]
Setnic and Levec (2001) put forward model for kinetics of liquidized phase of
methanol manufacture. They demonstrated that the yield of methanol is directly related to the
CO2 amount only [21].
Rozovskii and Lin (2003) propounded a couple of reaction steps for building
hypothetical model for kinetics that satisfy the data from experimentation as well. Two
separate compositions of gas were used, one rich carbon monoxide and second with CO 2 for
testing their models applicability of their. They propounded that both the schemes were
efficacious with a carbon dioxide enriched mixture but the scheme 1 kinetic model failed in
matching the experimental data when a carbon monoxide enriched mixture was used. [22].
Lim et al. (2009) derived an inclusive kinetic model which consisted of forty-eight reaction
rates which were based on the various possible rate controlling reactions. By estimating the
parameters they demonstrated, from the forty-eight rate of reactions, methoxy species surface
reaction step was controlling for addition of hydrogen to CO, formate intermediates
hydrogenation was controlling for the hydrogenation of CO 2 and formate intermediate
formation
was
controlling
step
for
reverse
water
gas
shift
reaction
using
Table 1. Numerous kinetic models along with their experimental reaction conditions.
Operati
Autho
ng
Kinetic Model
Conditio
r,
Refere
nce
Year
ns
493-533
K;
r CH OH =k
3
40-55
0.5
p CO p H
0.34
0.66
pCH
OH
pCH OH
3
0.4
p CO pH K 2
2
Leonov
et al.,
13
1973
atm
K
498-523
r CH OH =const
3
K;
75 atm
3
redox
pCO
pCO
( )(
( )] (
1+ K redox
pCO p H
pCO
K2
)
n
F + K CO pCO )
2
pCH OH p H
3
p3H
p CH OH
p CO
( )(
1
+ K ' pCO
K1
2
2O
))
Klier
et al.,
1982
14
f CO f 2H
f CH OH
3
K 2
r CH OH =
3
( A+ B f CO+C f H +G f CO )
2
Villa
N/A
et al.,
r RWGS =
f CO f H f CO f H
2
1985
O K 3
Operati
Autho
ng
Kinetic Model
Conditio
r,
Year
ns
k 1 K CO c CO c3H/2
r CH OH =
c CH OH
c
1 /2
( 1+k CO c CO + k CO c CO ) c H
2
K;
k 2 k CO cCO c H
2
( )
O
1 /2
H2
cH
1/ 2
2
bar
KH
r CH OH =
( )
2
K 1/H 2
c CH OH c H
3
et al.,
cH O
1988
1 /2
( 1+k CO c CO + k CO c CO ) c H
2
)
( )
3 /2
H2
eq
3
KH
K
nce
Graaf
k 1 K CO c CO c3H/2
Refere
K eq
2
( 1+ k CO cCO +k CO cCO ) c H
2
KH
c H O c CO
r H O=
15-50
K eq
1
1 /2
H2
483-518
15
1 /2
H2
cH
16
k '1 K CH K 2H K 2H K CO pCO p 2H
2
r=
483-513
3 /2
p CH OH
K eq
3
3/ 2
)
'
K CH K H K H K CO p CO p CO + K CO pCO + K H p H
2
K;
2.89-
McNeil
} {p} rsub {{H} rsub {2}} rsup {2} right )} right ]} over {{{K}
et al.,rsub {{H}
17rsub {2}} rsup {1
4.38
1989
MPa
+=k11 K
3 /2
5
1
8
K 9 K 10 K 11
483-563
K;
1-4 bar
pH
po
3/ 2
p CO 2
po
( )( )
2
Askgaar
1 pCH OH pH O 2
=k 11 K 35 / 2 K 1
8 K 9 K 10 K 11
K G p 3/H 2 p1o /2
r
3
et al.
1995
1 pCH OH p H
K
p3H pCO
( )
r MeOH =
453-553
((
KH O
1+
K8 K9 K H
2
pH O
+ K H p H K H O pH O
pH
)( )
K;
[ (
k '1 pCO 1K 3
bar
r RWGS =
((
KH O
1+
K8 K 9 K H
2
p H O p CO
p H pCO
2
Conditio
)]
pH O
+ K H pH K H
pH
and
)( )
2
1996
3
pH
Autho
Kinetic Model
r,
Year
ns
13
Operati
ng
Froment
Bussche
15-51
19
Refere
nce
k M P ( CO 2 ) P ( H 2 )
R M=
P ( CH 3 OH ) P ( H 2 O )
[K
P ( H 2)]
2
[ 1+ K CO P ( CO 2 ) + K H O P ( H 2 O ) ]
473-548
Kubota
et al.,
K;
4.9MPa
k R P ( CO 2)
RR =
P ( CO ) P ( H 2 O )
[K
P2 ( H 2 ) ]
2001
[ 1+ K CO P ( CO2 ) + K H O P ( H 2 O ) ]
2
(e ERT )
c CO ( c H c H
Me
r Me= A Me
473-513
(1+ A
,eq
)
2
( )c
e
EW
RT
H2 O
Setinc
K;
and
34-41
Levec,
bar
20
r H O =A H O
2
(
e
EH O
RT
2
(1+ A
2001
( )c
EW
RT
H2O
21
Rozovsk
r=
513 K;
K 3 p H ( 1 pm p H O )
2
1+ K2 p H O +
5.2 MPa
K 2 p H O
And
( K 1 pCO )
Lin,
526-533
k A K CO K H 2 K CH , CO p CO p 2H
K;
r A=
5 MPa
et al.,
0.5
( 1+k CO p CO ) (1+ K 0.5
H pH + K H O pH O)
2
k B K CO
rB=
pCH OH
K PA
2003
Lim
K 0.5
H p CO p H
2
pH
2009
pCO p H O
K PB
2
0.5
2
0.5 0.5
( 1+ k CO pCO ) (1+ K H p H + K H O p H O ) ( 1+k CO p CO )
2
10
22
k C K CO K H K CH ,CO
2
rC=
(1+ K
0.5
H2
0.5
H2
pCO p2H
2
p CH OH p H O
K PC
3
pH
p + K H O pH
2
) ( 1+ k CO p CO )
2
11
obtained. They demonstrated that on increasing the CO2 pressure the formation rate of
methanol also increased. Later on in the next year, they demonstrated a fine study and
propounded that the hydrogenation of carbon dioxide as main step in the methanol
production at low conditions of temperature, conversion and if the water is absent but at
increased conditions of conversion, temperature, and presence of water, methanol was
mainly a product of hydrogenation of carbon monoxide [25].
Chinchen et al. accounted that carbon dioxide is the main reactant in the synthesis of
methanol by utilizing
14
methanol synthesis was derived by Takagawa and Ohsugi in 1987 under various experimental
conditions. They demonstrated that in the beginning of the reaction the synthesis rate with the
increase in CO2/CO proportion but later it decreased with the increasing ratio and started
forming water. They asserted that their results were very similar with both Liu et al. and Klier
et al. [15]. The experimental study by McNeil et al. demonstrated that the feed containing 2
mole % carbon dioxide in the feed yields an optimum production rate of methanol. The also
propounded that at lower temperatures there is more contribution of CO 2 to formation of
methanol. Unlike earlier studies, they derived a mechanistic information based rate
expression. It included the study of CO2 affecting the rate as a producer as well as an inhibitor
[17].
A class of researchers headed by Rozovskii et al. demonstrated that carbon monoxide doesnt
hydrogenate directly to methanol. In earlier work, by use of 14C labelling and in a recently
conducted work utilizing the technique of Temperature Programmed Desorption they
reported that the synthesis of methanol takes place through CO 2 hydrogenation [22]. Fujita et
al. conducted a methanol synthesis study in a flow reactor at atmospheric pressure. They
found that methanol produced from CO 2 via formate species hydrogenation appeared on Co
and Cu formed methanol via formate species hydrogenation formed on ZnO. The rates of
carbon dioxide hydrogenation came out much intense as compared to the hydrogenation of
CO. The study accounted that existence of H2O and former reactivity differences and the later
discussed formate species primarily were behind the change in the synthesis rates of
methanol from CO2 & CO.
Sun and co-workers in 1988 analysed synthesis of methanol & water gas shift reaction
utilizing IR technique, subsequently concluded that the major pathway in the synthesis of
methanol was the hydrogenation of carbon dioxide and CO 2/CO hydrogenation reactions.
12
Hydrogenation of formate species was found to be the rate determining step. They
recommended that the addition of carbon monoxide brings down the production process
activation energy, in addition to influencing the path of reaction [5]. In the other study by
Sahibzada et al. they demonstrated that the basic rate for the hydrogenation of carbon dioxide
was 20 times than the hydrogenation of CO and at CO 2> 1%, was the primary source for
methanol synthesis. They accounted for production of methanol increased linearly with
increase in amount of CO2 in the products absence [26]. Further, Ostrovskii established the
part played by carbon dioxide in the production of methanol analysed the mechanism of
formation of methanol on Cu/Zn comprising promoter in various experimental setups and
demonstrated that main feed for production of methanol was CO2 [27].
Thereafter, Lim et al. performed an inclusive study in which they assumed CO 2 and
CO to get absorbed on various Cu spaces and adsorbing H2O on a ZnO site. It was
propounded that the rate of hydrogenation of CO 2 was slower than the rate of hydrogenation
of CO which brought down the rate of methanol formation but since carbon dioxide decreases
the rate of water-gas sift reaction, therefore the production of DME decreases, which is a byproduct of methanol. It was henceforth summarized that the synthesis rate of methanol can be
secondarily improved by finding an optimal concentration of CO 2. Among the various
studies, they affirm to be the first one reporting the carbon dioxide role in the production of
methanol, recommending a kinetic mechanism relating the hydrogenation reactions of CO
and CO2 [3]. In a neoteric study by the same authors, they evaluated the effect of CO 2 fraction
on the methanol yield by using the kinetic model developed by them and they even
formulated a way for optimizing and maximizing the formation rate of methanol including
CO2 fraction and temperature profile into the account [28].
2.4.1 Pressure
The formation of methanol was carried in beginning at extremely increased pressures
when BASF incepted it in 1920s. Lately, ICI reduced the pressures from 50-100 atm utilizing
13
a catalyst based on Cu/ZnO/Al2O3 [9]. Graaf et al.in 1988 analysed the kinetic model for
methanol formation from carbon dioxide, carbon monoxide and hydrogen over the similar
catalyst and thereby formulated a kinetic model which was carried out at pressures of 15-50
atm. They affirmed that the low pressure kinetic model for the synthesis of methanol to be
more accurate in representing and comparing the experimental values to the models proposed
previously [29]. Deng et al. reported that the synthesis of methanol could also be operated at
20 atm using the catalyst based on Cu/ZnO/Al2O3 [9].
Xin et al. propounded that it is beneficial to use high pressure for the hydrogenation of
carbon dioxide as represented by Figure 1 [31].
Figure 1. Relation between reaction pressure and CO2 conversion and methanol yield
from experimental results and thermodynamic predictions [30].
However, the production cost tends to increase with very high pressures and are also unsafe.
Therefore, current efforts are being going on to decrease pressure by developing novel
catalysts without affecting the methanol yield.
14
2.4.2 Temperature
Synthesis of methanol is generally at 493-573 K [17, 19]. Since, CO 2 and CO
hydrogenation steps are exothermic; with increase in temperature their rate increase but only
up to a limited temperature. The rates start to decline at higher temperatures due to reduction
in the equilibrium constant with the reduction in temperature. Hereby extremely high
temperatures are unsuitable. Bill et al. showed that the yield of methanol increases with the
temperature but only up to 493 K [9]. Likewise, Xin et al. founded that highest yield and
carbon dioxide conversion could be achieved nearly around 523 K. In addition to this
asserted that the formation of methanol prone to the temperature of reaction as compared to
WGS reaction. The temperature dependence of carbon dioxide conversion and methanol yield
is shown by Figure 2 [30].
formate to methanol steps in place of formate to methoxy to methanol route. It was also
stated that the production at low temperature led to increased conversions (50-80%) and also
reducing the cost of production without any thermodynamic equilibrium [9].
16
Figure 3. Relationship between space velocity and CO2 conversion and methanol yield [30]
17
In the other study by Lee and co-workers, they founded that the yield of methanol
increased at less space velocity along with limitation to specific carbon dioxide amounts on
crossing which it starts to go down. It was stated that the topmost synthesis rate can be
reached with an optimal value of space velocity, as illustrated in Figure 4 [31].
2.5 CATALYST
A brief summary of the catalysts used in the formation of methanol is accounted in
this section. First section discusses about the foundation concepts about the process of
catalysis, then a short overview of the industrially utilized catalysts which are supported on
Cu. In the remaining section, the studies aiming for finding more appropriate catalysts for the
formation of methanol from carbon dioxide are discussed.
18
The structural aspects of catalyst are of utmost importance regarding in concern with its
usefulness. The fluid flow through the bed of the catalyst is influenced by the shape and size.
Its mechanical strength helps to ensure its long enough lifetime. High selectivity and activity
are ascertained by high enough surface area and correct chemical components. The addition
of components helps to achieve stable operation of the catalysts. There are typically thee
components of the catalysts:
Support
Promoters
Active components
The active sites holds the sole responsibility for the occurrence of chemical reactions. The
active species are placed over the support which is the basis of the catalyst. To avoid
undesired sintering, the catalyst must render an adequate surface area for the active species so
that they can be evenly distributed. The support should have no active sites like the catalysts.
The promoters enhance or inhibit the activity of the catalyst. To obtain the desired selectivity,
activity and stability property only requires the addition of small quantity of promoters [32].
Catalyst preparation is to be paid great attention as final properties are affected by it.
The procedure for preparing the catalyst is generally acquired through the experimental
studies which are very time consuming. Impregnation and precipitation are the most widely
methods which are used for the preparation of the heterogeneous catalysts. In the method of
impregnation, the catalyst support is forged to little cylindrical shapes such as spheres, rings
and pellets. Thereafter, the material of the support is bared to a solution with a suitable
compound thereby providing the part that is active to a compound that can be easily be
transformed into the active phase. The preparation of catalyst that can be precipitated out
requires quick mixing of metal salts concentrated solutions which lead to precipitates in a
form of high surface area. Filtering and washing is then followed after the precipitation step.
Thereafter the conversion of precipitate takes place by drying and heating into appropriate
oxides [33].
The reduction in the catalysts activity is deactivation. There may be chemical, thermal
and mechanical reasons of the deactivation. Catalysts poisoning is due to the impurities
adsorption on the surface of the catalyst and thereby blocking the passage to the active sites
[34]. The catalyst can get fouled by unfavourable association of catalysts with reaction
species [35]. This interaction is very usual cause of the catalysts deactivation. The sintering
19
process causes the cluster particles of active metal to form bigger particles which causes more
reduction in the number of active sites and hence there is loss of active sites [36].
20
out an active catalyst for CO2 rich feed. Therefore catalysts based on Cu with metallic
additives have been examined to accomplish this purpose.
Saito et al. propounded that the catalysts based on Cu/ZnO operate well with the feed
rich in monoxide but loses their activity when carbon dioxide amount is increased. It was
observed that this loss in activity was because due to formation of water, formed during the
hydrogenation of carbon dioxide along with the formation of methanol [46]. Novak et al.
acquired results which proved that the activity loss of CuO/ZnO-Al2O3 catalyst is due to
water formation [47]. Wu et al. proved the harmful effect of H2O to the Cu/ZnO catalyst by
using various feed compositions [39]. They found that the yield of water increases and the
yield of methanol decreases with increasing quantity of carbon dioxide in the feed. They
came to the conclusion that reduction in activation of the Cu/ZnO based catalysts is
accelerated in presence of water. They also assumed that on adding silica to the catalyst based
on Cu/ZnO could hinder the harmful effect of H2O and thereby permitting the formation of
methanol from the feed rich in carbon dioxide with the catalysts based on Cu/ZnO-based.
According to Twigg & Spencer, poising due to chloride and sulphur, physical injury, thermal
sintering and carbon deposition may bring down the activity of the catalyst based on Cu [48].
Quinn et al. propounded that arsine significantly deactivates the CuO/ZnO/Al2O3 based
catalyst may be in the feed during three-phase methanol synthesis [49].
Yang
et
al.
propounded a newer method for the low-pressure methanol formation which uses alcohol
promoted Cu/ZnO catalysts [2, 50]. Yang et al. and Reubroycharoen et al. utilized a Cu/ZnOAl2O3 catalyst while Zhang et al. utilized a Cu/ZnO catalyst. In all these researches propanol,
butanol and ethanol were analysed as alcohol promoters. This newer method was carried out
at a pressure of 3.0 MPa and a temperature of 443 K. This low reaction temperature led to
high conversion of carbon monoxide (50-80%) [2].
Zn oxides have also been tested as an additives to the catalysts based on Cu. Huang et
al. analysed the impact of oxide additives viz Cr, Co and Zn to the catalysts based on Cu.
They perceived remarkable enhancements in the activity of the catalysts for the methanol
formation and WGS reaction by adding Cr 2O3 to a Cu catalyst whereas by the addition of
CoO addition no remarkable changes were perceived [51]. In addition, the influence of SiO2
on the activity of the catalysts which are based on Cu has also been analysed [52, 53]. They
also noticed that the catalytic activity for the production of methanol from carbon dioxide
increased with the addition of SiO2.
21
22
H2/CO2, high space velocity and low temperature are advantageous for the synthesis of
methanol [59]. The influence of Zr oxide and Ce addition to the catalysts was also studied
was Pokrovski et al. They made and examined the Cu/CexZr1-xO2 with differing content of Ce
and observed that the catalyst activity for the formation of methanol through the
hydrogenation of carbon dioxide increase with the addition of Ce. The optimum amount of
Ce needed in the catalyst was also determined. [56].
The effect of metal oxide additives viz Mn, Mg, Ga, Gd, B and In on Cr/ZnO/ZrO 2
catalyst was analysed by Sloczynski et al. They propounded that the catalyst activity was
greatly influenced by the oxide additives. Highest yield of methanol was obtained with Ga
addition whereas there was severe loss of activity on the addition of In. Toyir et al. accounted
the persistency of Ga as an efficacious catalyst. The experiments were conducted using a
catalyst based on Cu/ZnO/Ga2O3 in the formation of methanol by hydrogenation of carbon
dioxide [60]. Liu et al. also analysed catalysts with oxide additive which are based on Cu but
they mainly concentrated on the advantageous effect of the addition of nanocrystalline Zr on
the activity of the catalyst [61].
Saito et al. observed the supporting action of the oxide of Ga to the catalyst in case
when CO2was used to give methanol. They investigated with the additives of Zr, Cr, Al, and
Ga. On the basis of their investigations, they manufactured two multicomponent catalysts
(Cu/ZnO/ZrO2/Al2O3/Ga2O3 & Cu/ZnO/ZrO2/Al2O3) and observed that the catalyst activity
was greater than that of the traditions Cu-based catalysts [20]. In the investigations of Saito et
al. & Wu et al., they defined the optimal conditions for preparation of multicomponent
catalysts. Saito et al. also accounted that the multicomponent catalyst which were developed
were highly stable and effective for methanol production from CO 2 [39]. Omata et al. also put
forward a similar type of multicomponent catalyst with various amount of substances
measuring their activities. They prepared a neural network for predicting the activity on basis
of the amount which had been then utilized for finding the optimum catalyst composition
[62].
23
24
Table 2. Various catalysts used along with the reactions, reactor used and the reaction
conditions
Author
Catalysts
Reaction
Feed
[mol%]
[K]
Klier
CuO-ZnO
CO +2H2 CH3OH
CO: 0-30
et al.
30-70 metal
CO2: 0-30
(1982)
Atomic %
H2O
H2: 70
498523
P
[bar
]
Type of
Reactor
Tubular
75
Integral
Fixed bed
Al2O3
et al.
Haldor
(1988)
Topsoe
Mk 101
CO +2H2 CH3OH
CO: 0-22
CO2: 1-26
483-
H2O
H2: 67, 4-
518
CO + H2O CO2 + H2
90
Gradientless
15-50
spinning
basket
CO: 0-30
Bussche
And
CuO-ZnO-
Froment
Al2O3
(1996)
Wedel
et al.
(1988)
Ledako
wicz
et al.
(1992)
BASF S3-85
< 60m
CO2: 0-30
H2: 70
453-
pCO2/pCO
553
Tubular
:
0-4
CO: 17-50
CO +2H2 CH3OH
15-51
CO2: 1-5
H2: 31-65
493523
20-60
Grdientless
Autoclave
Stirred
BASF S3-85
And BT-d
CO: 17-50
CO +2H2 CH3OH
< 63m
CO2: 1-5
H2: 31-65
490533
autoclave and
20-60
bubble
column
slurry reactor
25
Author
Catalysts
Reaction
Feed
[mol%]
[K]
P
[bar
]
Type of
Reactor
CuO-ZnOAl2O3
Commercial
Skrzypek
Blasiaks
CO: 0-20
et al
catalyst
H2O
CO2: 5-35
(1991)
CuO: 62,
CO2 + H2 CO + H2O
H2: 10-80
460550
Integral fixed
30-90
ZnO: 30 and
Al2O3
: 7 wt%
CO +2H2 CH3OH
Coteron
and
Cu70Zn30 and
Hayhurst
Cu70Zr30
(1994)
CO + CO2 + H2 CH3OH
CO: 10-40
+ H2O
CO2: 0-10
H2: 40-70
473523
Continuous
10
tubular,
differential
mechanism propounded
by Chinchen et al.
Setinc
Commercial
and
Cu/ZnO/
Levec
(2001)
CO: 10-20
473-
CO +2H2 CH3OH
CO2: 10-
513
Al2O3
20
(C79 5GL;
H2O
H2: 60-80
26
34-41
Slurry reactor
Sud Chemie
AG)
CO + H2O CO2 + H2
27
dT
U
=(H ) r A B 4 ( T T r ) 3.1.1 .2
dz
dt
28
d pt
g u 2s
=f
3.1.1 .3
dz
dp
With the initial conditions: at z=0, CA=CA0, T=T0, pt = pt0. In (3.1.1.3), dp is the equivalent
particle diameter. In the specific cases g, cp, and cp may be considered to be constant. This
system of ordinary differential equations is integrated by means of Runge-Kutta method. The
integration purpose can be the design of a new reactor or the simulation of an existing reactor.
Equation (3.1.1.1) can be obtained from material balance on a reference component
(say A) over an elementary cross section of a tubular reactor containing dW amount of
catalyst. To eliminate the bed density, the rate equations of homogeneously catalysed
reactions are based on unit catalyst weight, rather than the basis on reactor volume.
Over an elementary weight of catalyst, the material balance for A on the conversion basis
may be written as:
r A dW =F A 0 dx A 3.1 .1 .4
Where FA0 is the molar feed rate of A, or
r A B dz=F A 0 dx A 3.1 .1.5
From which (3.1.1.1) can be easily obtained. U in (3.1.1.2) is overall heat transfer coefficient.
It is defined by
1 1 d Ab 1
= +
+ 3.1.1 .6
U j Am u
where
29
i, for heating up the reaction mixture may be based on Levas correlation (1949):
jd p
d G
=0.813 p
g
0.9
( )
e6 d
/dt
For cooling
3.1.1.7
jd p
dp G
=3.50
g
0.7
( )
4.6 d p / dt
where
dp = equivalent particle diameter (m)
dt = tube diameter (m)
However, a linear relation between the Reynolds numbers and Nusselt numbers (1972):
j d p 0j d p
c d pG
=
+0.033 p
3.1.1 .8
g
g
g
( )
The impact of the catalyst properties and the tube diameter enter the correlation through j0
called static contribution:
0
0j =
where
10.21 e
4/ 3
dt
0e
The parameter which now remain to be specified is friction factor f. Special attention
is required by the pressure drop equation (3.1.1.3). It is different from the from the Fanning
equation. Special care has to be taken for checking the pressure drop relation from which f
was derived. Ergun equation (1952) is the most popular equation for determining the pressure
30
drop through packed beds. He considered that the packed bed consist of a bundle of nonconnecting parallel channel with the hydraulic radius Rh (ratio of void fraction , to surface of
solid per m3 of bed av):
R h=
av
Equivalent particle diameter dp is the sphere diameter having the same surface area per unit
volume as that of the actual particle, Sv:
S v=
av
1
So that
d p=
6 ( 1 )
3.1 .1.9
av
The pressure drop for laminar flow in an empty conduit given by Hagen Poiseuille when
written in the form of (3.1.1.3) gives a friction factor
(1 )2 36
f=
3.1.1 .10
3 ( d p G/ )
Since the packed bed reactor channels are not straight, a correlation factor of 25/6 has to be
introduced by Ergun to fit the experimental data, so that (3.1.1.11) becomes
f=
(1 )2 150
3.1.1 .11
3 ( d p G/ )
For highly turbulent flow, the Burke & Plummer equation gives a friction factor
f =1.75
1
3.1 .1.12
3
Adding both
f=
b ( 1 )
1
a+
3.1.1 .13
3
31
( 1 )1.2 0.2
f =6.8
3.1 .1 .14
3
The values of a and b drastically change at dt/dp below 5. Reichelt and Blasz (1957) proposed
an equation of equivalent particle diameter for hollow rings:
d p=6
V (cylinder )
Em
S(external cylinder )
where
E=
m=
d e /d i
d 2e
0.4
( )
d 2i
d 2e
0.75
( )
+ 0.010
d 2i
where de and di are the external diameters of the hollow cylinders respectively.
Haughey and Beveridge (1969) correlated the void fraction in packed beds of spheres as:
( d t /d p 2 )
=0.38+0.073 1+
3.1 .1.16
2
( d t /d p )
32
CO +2H2 CH3OH
(1)
(2)
CO + H2O CO2 + H2
(3)
The model uses the kinetic equation propounded by Vanden Bussche and Froment (1996)
[13].
k 1 pCO p H 1
2
CH 3 OH
K p CO p
H2
RWGS
eq
2
)
)
k3 pH O
1+
+ k 4 pH +k 5 p H O
PH
k 2 pCO 1K eq
3
pCH OH p H
p H O pCO
p CO pH
2
)]
k3 pH O
1+
+ k 4 pH +k 5 p H O
pH
2
33
In the above equation all the constants (kj) follow Arrhenius equation and equilibrium
constants were acquired from the studies that are listed in Table 1 [69].
( RTB )
k j= A j exp
A
B
A
B
A
B
A
B
A
B
eq
K2
1.07
36696
3453.38
0.499
17197
6.62*10-11
124119
1.22*1010
-94765
10
3066
10.592
T
2073
+2.029
T
eq
K2
10
34
( H j) c ( r i ) A
dFi
i
=
dl
FiC p
i
component &
Fi
Cp
is the ith component molar flow rate. The relationship between the partial
pressure and the molar flow of components assuming the gas to be ideal is illustrated by
Pi=P
Fi F
= F i
Ft t
i
Where Pi is ith component partial pressure, P is the total pressure, Fi the ith component molar
flow rate and Ft is total molar flow rate.
The components molar heat capacity in the reactor is propounded from the following
equation along with the information provided in Table 2
35
Cp
= Ai + Bi T +C i T 2+ D i T 2
R
where, R is the gas constant, Cp is the molar heat capacity and Ai, Bi, Ci and Di are constants
H = H
o
298
+ C p dT
298
103B
106C
10-5D
2.211
3.47
3.249
5.457
3.376
12.216
1.45
0.472
1.045
0.557
-3.450
-
0.121
0.081
-1.157
-0.031
36
With the inbuilt subroutines, the solver (ode45) checks for required tolerance, relative error
and absolute error in the calculations. Thus, it keeps on solving for every step interval, until it
reaches the final length of the reactor.
Finally, the whole of reactor data is saved in Microsoft Excel file for further analysis. The
reactor data is compared and analysed for best reactor configuration.
Table 5. Catalyst Properties, Feed Conditions and Industrial Reactor Specification
Parameter
Value
Unit
H2
80
CO
4.76
CO2
2.95
CH3OH
0.3
H2O
0.06
N2
0.01
CH4
11.92
Inlet temperature
498
Inlet pressure
50
Bar
Number of tubes
5947
Diameter of tube
0.04
47400
Kmol hr -1
10
1063
kg m-3
37
The results of modelling and simulation done with the help of MATLAB code is
showed here. The effects of various parameters like the inlet temperature of the reactor,
reactor pressure and H2/CO2 mole ratio on the synthesis of methanol are studied. Molar flow
rate profile of the components hydrogen, carbon monoxide, carbon dioxide, methanol and
steam against the tube length has been tabulated and graphed. In addition to the molar flow
rate profiles of the components, graphs showing the yield of methanol, conversion of
hydrogen and conversion of carbon dioxide along the tube length are also provided.
Four definitions are commenced to study the conversion of CO, conversion of hydrogen and
yield of DME through the reactor length:
X CO
XH
F CO
FCO out
2
F CO
FH
F H out
2
FH
YieldCH OH (H )=
3
YieldCH OH (C )=
3
100
100
FCH
FH
F CH
OH
* 100
OH
( FCO + F CO ) * 100
2
Where FCO
FH
YieldCH
F H out
2
XH
conversion of hydrogen ,
synthesis gas and
OH (C )
gas. The reactor conditions have been tried to be optimized for the maximum conversion of
carbon dioxide.
39
Matlab Model
Percentage Error
CO2 Conversion
49.15
47.855
2.634 %
Temperature
528.2
515.25
2.452 %
40
(a)
(b)
(c)
41
(d)
(e)
Figure 6. Model Results of various parameters at T=498 K & P=50 bar (a) Production of
methanol (b) Yield of methanol w.r.t. C (c) Conversion of carbon monoxide
(d) Conversion of hydrogen, and (e) Temperature along the length of the reactor
42
(a)
(b)
(c)
(a)
(b)
(c)
(a)
(b)
(c)
(a)
(b)
(c)
(a)
(b)
(c)
(a)
(b)
(c)
49
(a)
(b)
50
(a)
(b)
51
(a)
(b)
52
(a)
(b)
53
54
55
The above table shows the effect of variation in temperature during the production of methanol. It is developed using the methanol studies performed by
various researchers using different catalysts and kinetics. It is propounded that the kinetics used by various researchers for methanol production shows a very
negligible effect on the conversion of carbon monoxide, carbon dioxide and the yield of methanol. So from the above table it can be concluded that the
temperature does not have a very significant effect in the production of methanol.
56
(a)
(b)
CONCLUSION
58
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68
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69