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Iranian Journal of Chemical Engineering

Vol. 10, No. 4 (Autumn), 2013, IAChE

Kinetic Study of Methanol to Propylene Process


on High Silica H-ZSM5 Catalyst
N. Hadi1, A. Niaei1, S.R. Nabavi2∗, A. Farzi1
1- Department of Chemical Engineering, University of Tabriz, Tabriz, Iran
2- Department of Applied Chemistry, University of Mazandaran, Babolsar, Iran

Abstract
A series of experiments were carried out by mixture of methanol and water as feed of
the methanol to propylene (MTP) process in temperature range of 623-823 K. The H-
ZSM5 catalyst with the Si/Al ratio of 200 was applied for carrying out the experiments.
A novel lumped kinetic scheme was proposed for methanol to propylene (MTP) process.
The reactor was mathematically modeled by assumptions of being isothermal, fixed
bed, plug flow and the hybrid genetic algorithm was applied for estimating the kinetic
parameters. The temperature dependency of the kinetic parameters was determined,
using the modified Arrhenius relation. A good agreement was observed between the
experimental and the calculated data. Effect of temperature on propylene and ethylene
selectivity was investigated. It was found that the propylene selectivity increases with
temperature until 773.15 K, but after that it decreases.

Keywords: Kinetic Study, Methanol to Propylene Process, Lumped Mechanism,


Hybrid Genetic Algorithm, High silica H-ZSM5 Nano Catalyst

1. Introduction produced as a byproduct and the rate of


Since propylene is an essential feedstock for propylene production is low. These old
production of vast types of polypropylene methods could not afford the future growing
plastics and these types of plastics are demand for propylene. In recent years, the
applied widely in many aspects of people’s conversion of methanol to propylene (MTP)
lives, it plays an important role in gas process has been launched as a new
conversion industries nowadays. Obviously technology for propylene production
the demand for propylene and its derivatives generated from the methanol to olefins
is increasing fast [1]. Old methods of (MTO) process [3]. The feed of the MTP
propylene production, such as steam cracking process consists of methanol which is mostly
and fluid catalytic cracking (FCC) of crude synthesized from synthesis gas (mixture of
oil consume enormous amounts of petroleum CO and H2). The synthesis gas is obtained
resources [2]. In these methods propylene is from steam reforming of natural gas or

∗ Corresponding author: srnabavi@umz.ac.ir

16
Hadi, Niaei, Nabavi , Farzi

gasification of coal. Furthermore, large MTO/MTP processes are lumped models. A


amounts of methanol can also be produced brief review of kinetic models that have been
by biomass [4, 5]. The economical aspect of proposed for MTO/MTP processes is given
the MTP process is that, by using this here.
process, the need for crude oil will be The reaction path for methanol conversion to
removed. Because of plentiful amounts of hydrocarbons has been expected to involve
natural gas and coal resources to produce the sets of steps which are shown in Fig. 1 [9].
synthesis gas and also renewable resources of The initial reversible step of dimethyl ether
biomass, the MTP process can be considered (DME) formation has been proven to be
as a novel process for production of rapid and mainly at equilibrium under the
propylene [6]. conditions of hydrocarbon formation [9-11].
Kinetic models are essential for reactor Chang and Silvestri [12] proposed a
design, modeling and optimization of mechanism involving carbenoid
processes. They are implemented in intermediates. Chen and Reagan [13], who
mathematical models of various reactors for observed evidence of autocatalytic behavior
estimation of product selectivity, product of methanol conversion over ZSM5 zeolites,
distribution and determination of the supported the mechanism of Chang and
dimensions of the reactor. These models Silvestri [12]. Ono and Mori [14]
form the quantitative basis for comparison of demonstrated the selectivity behavior of
different reactor types and selecting the C2-C5 olefins during the initial stages of the
optimum type of the reactor to maximize the reaction. Chang [9] modified the model of
most valuable product in a particular process Chen and Reagan [13]. The model proposed
[7]. The kinetic models are categorized into by Chang [9] was based on the reactivity of
two main groups: (a) lumped models in carbene species, which was generated via α-
which the detailed chemical species are elimination of water. Bos et al. [7] developed
summarized in larger groups and represent a kinetic model for the MTO process based
the reality of process, (b) detailed model that on the SAPO-34 molecular sieve. The final
takes into account single event reaction steps scheme consisted of 12 reactions involving 6
which consist of molecules, ions and product lumps plus coke. The other kinetic
unstable intermediates. Because of the model on the SAPO-34 was proposed by
complexity of type (b) models, for design Gayubo et al. [15]. The kinetic parameters of
purposes type (a) is applied in most cases [8]. this model were obtained by experiments that
Due to the complexity of the reaction were carried out in a fixed bed isothermal
network of the methanol conversion into reactor.
light olefins, most of the kinetic models in
⎧ Paraffins
− H 2O
− H 2O ⎪
2 CH 3OH R CH 3OCH 3 ⎯⎯⎯
→ LightOlefins → ⎨CycloParaffins
+ H 2O
⎪ Aromatics

Figure 1. Reaction scheme proposed by Chang [9].

Iranian Journal of Chemical Engineering, Vol.10, No. 4 17


Kinetic Study of Methanol to Propylene Process on High Silica H-ZSM5 Catalyst

Another lumped kinetic model for the recently, Hadi et al. [27] suggested a kinetic
MTO/MTP processes, known as model for the MTP process on Mn/H-ZSM5
"Hydrocarbon pool" has been introduced [16- based on the theory of the hydrocarbon pool
21]. This kinetic model mainly contains a and the conjugate methylation/cracking
central complex chemical species. Nuclear reactions using a fixed bed reactor. This
magnetic resonance (NMR) studies kinetic model consists of 17 reactions and 14
demonstrated that the complex molecules chemical species in which initially methanol
form initially in the later stages of the dehydrates to form higher olefins. The higher
process undergo cracking to produce the light olefins undergo the methylation reactions.
olefins [22, 23]. Hexene and heptene crack to form light
In all of the above works, the MTO process olefins: ethylene and propylene.
has been emphasized. The objective of the There exist some single event kinetic models
MTO process is to increase the selectivity of for the MTO process. Mihail et al. [28]
ethylene, while in the MTP process only developed a complex model for the MTO
propylene is valuable and attempts are process on a modified synthetic mordenite
focused on increasing propylene selectivity. catalyst. The model contained individual
Few researches exist in the kinetic study of steps up to 53 reactions and about 37
the MTP process. For instance, Mei et al. chemical species including radicals and
[24] developed a simple lumped model for molecules. Park and Froment [29-30]
the MTP (Fig. 2). developed a detailed kinetic model based on
elementary steps of carbenium ion chemistry
in which ethylene and propylene were the
main products. H-ZSM5 catalyst with Si/Al
ratio of 200 was applied and activation
energies for each elementary step were
obtained through the Evans-Polanyi
Figure 2. The reaction pathway for the MTP process relationship.
proposed by Mei et al. [24].
In the present work due to kinetic study, the
activity of the high silica H-ZSM5 catalyst
Wu et al. [25] proposed a kinetic model for
on selectivity of propylene was examined at
the MTP process over a high silica H-ZSM5
several WHSV (Weight Hourly Space
catalyst. The kinetic model included a cycle
Velocity) and reaction temperatures. A
methylation from C4= through C5= to C6= and
lumped kinetic model with 10 reactions was
further to C7=. The β-scission of C6= and C7=
proposed for the MTP process. The kinetic
causes propylene production. Guo et al. [26]
parameters were estimated by modeling of a
applied the reaction mechanism suggested by
fixed bed, plug flow reactor using hybrid
Wu et al. [25] and carried out some
genetic algorithm. The model of the reactor
experiments using the monolithic and packed
was derived by solving mass conservation on
bed reactors for estimation of the kinetic
each chemical species, consequently a
parameters in the MTP process. More
heterogeneous model in which the reaction

18 Iranian Journal of Chemical Engineering, Vol. 10, No. 4


Hadi, Niaei, Nabavi , Farzi

was assumed to occur in the solid catalytic over a plug of quartz wool and inserted into
bed was obtained. the reactor. The length of the bed was 100
mm in the reactor. The reactor was placed in
2. Experimental an electrical furnace controlled by a
2-1. Catalyst preparation proportional–integral-derivative controller
The starting material for preparation of (PID), (Fig. 3). Feed of the process (the
catalyst was Na-ZSM5 with a Si/Al ratio of mixture of methanol and water) was passed
200(JCPDS. 44-0003), BET surface area of through the preheater, mixed by carrier gas
400 (m2/g) and pore volume of 0.16 (cm3/g) (N2) and fed to the reactor bed. In order to
which was supplied by ZEOCHEM® delay the catalyst deactivation, and also to
(Switzerland). The samples in the NH4-form increase the selectivity of propylene, the feed
were prepared by ion-exchange with NH4Cl consisted of 20 mol% of methanol and 80
(Merck®, Germany) solution (1M) at 50˚C mol% of water. The experiments were
for 24 h. The H-ZSM5 zeolites were obtained carried out at 350, 375, 400, 425, 450, 500
through calcination of the NH4-zeolites in air and 550°C. The required pressure for the
at 500ºC for 5 h. reaction was supplied by N2 inert gas. The
inlet pressure of the reactor was 1.5bar.
2-2. Catalyst characterization Because of the large porosity of the quartz
X-ray diffraction pattern of the catalyst was wool, the pressure drop in the reactor was
taken in order to characterize the phases and negligible. The product was condensed and
crystallinities of the H-ZSM5 zeolite. The analyzed by Shimadzu® 2010 plus model gas
prepared catalyst was analyzed at room chromatograph.
temperature by X-ray diffraction using a The GC analyzer (Shimadzu 2010 plus
Siemens® D500 X-ray diffractometer with model) was equipped with a HP-PLOT
monochromatic Cu-Kα radiation (wavelength Al2O3S, Agilent capillary column (length:
λ = 0.154 nm at the range of 2θ from 4o to 50m and internal diameter: 0.53mm) and
70o and at the scanning rate of 2o/min). The Flame Ionization Detector (FID). Helium
surface morphology of the sample was was applied as the carrier gas of the GC
determined by scanning electron microscopy analyzer.
(SEM) recorded on a Vega TESCAN®
microscope. In order to provide evidence 2-4. Modeling of the reactor
about nanostructure of the zeolite, The model of the reactor was obtained by
transmission electron microscopy (TEM) mass conservation equations on each
image of the catalyst was taken with a chemical species. The result is a
Philips® CM 200 FEG instrument. heterogeneous model in which the reaction
was assumed to occur in the solid catalytic
2-3. Set up and catalyst test bed. In this model, the space time of the feed
A fixed bed plug flow reactor was applied to (W/FOxy.) is considered as independent
test the catalyst activity. The reactor was a variable and the weight fractions (ωi) of
pyrex tube with 900 mm length and 9 mm in chemical species are considered as dependent
diameter. The catalyst powder was placed ones.

Iranian Journal of Chemical Engineering, Vol.10, No. 4 19


Kinetic Study of Methanol to Propylene Process on High Silica H-ZSM5 Catalyst

Figure 3. Experimental set up for the MTP process.

r j = k j ∏ i =1 ωi
m
j = 1, 2 ,..., number of reactions (2)
dωi n
= ∑ rj i = 1, 2,..., number of components
d(W / Foxy. ) j=1
(1) 3. Results and discussion
3-1. Catalyst characterization
Where ωi indicates the weight fraction of The XRD pattern of the catalyst which
represents the phases and crystallinities of
chemical species (g i .g −total
1
) , W/FOxy. is the
the H-ZSM5 (Si/Al=200) is shown in Fig. 4.
−1
space time of the feed (g catalyst .h.g oxy. ) . The This pattern represents distinct broad
term rj indicates the rate of jth reaction. All diffraction peaks in 8-10 and 20-25 in 2θ
reactions were assumed elementary and ranges [31]. The XRD pattern indicates no
pseudo first order reactions. remarkable damage of the ZSM-5
(JCPDS.44-0003) structure.

Figure 4. XRD pattern of the H-ZSM5 catalyst with Si/Al=200.

20 Iranian Journal of Chemical Engineering, Vol. 10, No. 4


Hadi, Niaei, Nabavi , Farzi

SEM image shows the surface morphology Methanol is at equilibrium with dimethyl
and crystallite size of the H-ZSM5 catalyst ether (DME). So the equilibrium mixture of
with Si/Al=200. According to the SEM methanol and DME can be assumed as a
image, distribution of the particles size seems chemical species named 'Oxygenate' [13, 14,
to be rather uniform and the external surface 15, 24]. Iso-butane and n-butane are the
of the H-ZSM5 zeolites seems clear and structural isomers of butanes and summation
smooth. TEM image confirms the was considered for these products which are
nanostructure of H-ZSM5 (Fig. 6). mentioned as 'C4H10' chemical species. The
different isomers of butene such as: Trans-2-
butene, Cis-2-butene, Iso-butene and 1-
butene were gathered together as 'C4H8'
chemical species. Also, the different isomers
of pentene such as trans-2-pentene, 1-
pentene, Cis-2-pentene were counted as
'C5H10' chemical species. The rest of the
hydrocarbons, for example, pentanes,
Aromatics (benzene, toluene, xylenes) and
other heavier hydrocarbons were listed as
C5+' chemical species [7, 15].
Because the feed was enriched with water;
the formation of coke was low. Existence of
water provided a way to increase the
Figure 5. SEM image of the H-ZSM5 catalyst.
selectivity to light olefins by decreasing the
selectivity of aromatics [14]. The reaction
scheme, which containins 10 reactions and 9
chemical species, is outlined in Fig. 7. It was
supposed that oxygenate was directly
converted to light olefins such as ethylene
and propylene. Light olefins tend to generate
the higher olefins such as butenes and
pentenes [25]. Some paraffins such as
methane, ethane, propane, butanes and
pentanes were formed directly via oxygenate
[18]. The final reaction step led to the
formation of higher hydrocarbons. For
example, pentenes tend to form heavier
Figure 6. TEM image of the H-ZSM5 catalyst.
hydrocarbons such as higher paraffins and
aromatics which were shown as 'C5+'
3-2. Kinetic study
chemical species in reaction scheme (Fig. 7).
A lumped kinetic model was proposed based
on the following simplification assumptions:

Iranian Journal of Chemical Engineering, Vol.10, No. 4 21


Kinetic Study of Methanol to Propylene Process on High Silica H-ZSM5 Catalyst

Figure 7. Proposed scheme of reaction.

3-3. Kinetic modeling Where ωi,j(calc.) are the values of the


According to the equation 2, the rates of calculated weight fraction that were obtained
reactions are elementary and pseudo first by solving the mass conservation equations
order and by considering the reaction for component i in the experimental point j
pathway of Fig. 7, the equations shown in that correspond to a specified value of space
Table1 can be driven for reaction rates. The time, ωi,j are the values of the experimental
method for estimation of the kinetic weight fraction that were obtained for seven
parameters consisted of solving the mass different temperatures with different space
conservation equations for each chemical time of feed. To reduce the calculation of the
species mentioned in the kinetic scheme. For kinetic parameters, reparametrization was
parameter estimation, the rates of reactions carried out for estimation of the pre
were considered as a power law relation. By exponential factor (k0) and the activation
using equation 1, the relations which are energy (E). The reparametrized relationship
shown in Table 1 can be written for each between the kinetic parameters and
chemical species. The differential equations temperature is according to the modified
corresponding to the mass conservation Arrhenius equation:
equations of chemical species were solved by
ode15s function in MATLAB®. The kinetic −E 1 1
parameters were estimated using hybrid k i = k oi exp[ ( − )] (4)
R T Tm
genetic algorithm (GA) in MATLAB®
optimization Toolbox. The objective function
Thus the kinetic parameters for each reaction
which was applied to minimize the deviation
involved in the reaction scheme are
between the experimental and the calculated
optimized at a reference temperature,
weight fraction of chemical species was
Tm=708.86 K. The optimal parameters which
according to the equation 3.
were applied in GA running were as follows:
population size=100; generation=200;
m p
of = ∑∑ ( ωi , j −ωi , j ( calc.) 2 / mp (3) crossover fraction=0.5; crossover function:
i =1 j =1 crossover arithmetic. The other parameters in
GA were held on their default values. The

22 Iranian Journal of Chemical Engineering, Vol. 10, No. 4


Hadi, Niaei, Nabavi , Farzi

hybrid function (fminsearch) existing in the ethylene. At Tm the kinetic parameters


MATLAB® optimization Toolbox was corresponding to the formation of propylene
applied to optimize the kinetic parameters from oxygenates and from ethylene are:
end of GA run. The average corresponding k6=2.345 h-1 and k7=1.256 h-1, respectively.
value of the objective function, equation 3, Low reaction rate of steps 1, 2 and 4 which
was 4.392×10-5. The respective spans for the refer to formation of paraffins such as
95% confidence intervals of each of the methane, propane and chemical species of
estimated parameters have been calculated C5+ is also notable. Their kinetic parameters
by regression analysis using GA. According at Tm are k1=0.08 h-1, k2=0.291 h-1 and
to the equation 4, the values of the pre k4=0.454 h-1. The greatest value for
exponential factor and the activation energy activation energy (E) belongs to the 5th
of each reaction with their 95% confidence reaction and demonstrates that the formation
intervals are reported in Table 1. of ethylene is sharply dependent on
From the values of the kinetic parameters, it temperature. The calculated correlation
is concluded that the formation of propylene coefficient between E and k0 values is 0.084
takes place mainly from the chemical species which shows there is no significant
of oxygenates and a lesser value from correlation between these parameters.

Table 1. The reaction rates and the mass conservation equations for each chemical species.
Mass conservation equations
Reaction rate Kinetic parameters according to equation 4
for chemical species
d ωexy ,cnatc 02953( ±36 ) 1 1
= −( r2 + r2 + r2 + r4 + r6 + r8 ) r2 = k 2ωexy ,cnatc k 2 = 0.038( ±0.005 )exp [ ( − )]
d ( w / Foxy .) R T 708.86
d ωC 2 M 4 r2 = k 2ωexy ,cnatc −4537( ±55 ) 1 1
= r2 k 2 = 0.291( ±0.014 )exp [ ( − )]
d ( w / Foxy .) R T 708.86

r2 = k 2ωexy ,cnatc 01461( ±48 ) 1 1


d ωC 2 M 6 k 2 = 0.971( ±0.009 )exp [ ( − )]
= r2 R T 708.86
d ( w / Foxy .)
r4 = k 4ωexy ,cnatc −3665( ±37 ) 1 1
k 4 = 0.454( ±0.012 )exp [ ( − )]
d ωC 4 M 10 R T 708.86
= r2
d ( w / Foxy .) −6039( ±94 ) 1 1
r5 = k 5ωexy ,cnatc k 5 = 2.039( ±0.053 )exp [ ( − )]
d ωC 2 + R T 708.86
= r2 + r20
d ( w / Foxy .) r6 = k 6ωexy ,cnatc −1950( ±28 ) 1 1
k 6 = 2.356( ±0.047 )exp [ ( − )]
R T 708.86
d ωC 2 M 6
= r5 − r7 03297( ±48 ) 1 1
d ( w / Foxy .) r7 = k 7ωC 2 ,M 4
k 7 = 1.256( ±0.002 )exp [ ( − )]
R T 708.86
d ωC 2 M 6 −1483( ±38 ) 1 1
= r6 + r7 − r8 r8 = k 8ωC 2 ,M 6 k 8 = 2.555( ±0.060 )exp [ ( − )]
d ( w / Foxy .) R T 708.86
d ωC 4 M 6 −4637( ±123 ) 1 1
= r5 − r0 r9 = k 9ωC 4 ,M 8 k 9 = 3.432( ±0.058 )exp [ ( − )]
d ( w / Foxy .) R T 708.86

d ωC 2 M 10 −5353( ±79 ) 1 1
= r0 − r20 r10 = k 10ωC 2 ,M 10 k 10 = 0.777( ±0.004 )exp [ ( − )]
d ( w / Foxy .) R T 708.86

Iranian Journal of Chemical Engineering, Vol.10, No. 4 23


Kinetic Study of Methanol to Propylene Process on High Silica H-ZSM5 Catalyst

Fig. 8 represents the main product Effect of temperature on the propylene mole
distribution versus space time of the feed at fraction is shown in Fig. 9. The mole fraction
seven temperatures. The experimental and of propylene increases when the temperature
calculated values were shown by points and increases to 773.15 K but decreases at higher
lines respectively. A good agreement is than this temperature. The propylene mole
observed between the experimental and the fraction is higher than ethylene in all
calculated data obtained from kinetic model. temperatures except at 623.15K.

-1 -1
(W /Foxy. ); g catalyst.h.g oxy. (W /Foxy. ); g catalyst.h.g oxy.

-1 -1
(W /Foxy. ); g catalyst.h.g oxy. (W /Foxy. ); g catalyst.h.g oxy.

-1 -1
(W /Foxy. ); g catalyst.h.g oxy. (W /Foxy. ); g catalyst.h.g oxy.

-1
(W /Foxy. ); g catalyst.h.g oxy.

Figure 8. Weight fraction of each olefin and oxygenate versus space time of feed for different values of reaction
temperatures. Points: experimental results. Lines: calculated with the kinetic model.

24 Iranian Journal of Chemical Engineering, Vol. 10, No. 4


Hadi, Niaei, Nabavi , Farzi

Figure 9. Effect of temperature on mole fractions of propylene and ethylene.

4. Conclusions "Synthesis gas conversion into


• A new lumped kinetic model was hydrocarbons (gasoline range) over
proposed for methanol to propylene bifunctional zeolite containing catalyst:
Experimental study and mathematical
process on high silica HZSM-5
modeling", Chem. Eng. J., 107, 63,
(Si/Al=200) catalyst.The kinetic
(2005).
parameters were estimated successfully [3] Hadi, N., Shirazi, M.N., Niaei, A.,
using hybrid gentic algorithm. Farzi, A. and Khoshbakhti, R.,
• A good agreement was observed between "Investigation of optimum flow rate
experimental and calculated profiles of and reaction temperature for production
the species.The mole fraction of of propylene on modified Mn/H-ZSM-5
propylene is increased gradually with nano catalyst: Methanol to propylene
(MTP) process", Proceedings of the 4th
increasing of temperature but it decreases
Int. Conf. on Nanostructures (ICNS4),
higher than 773.15 K.
Kish, Iran, pp. 1100-1102, (2012).
[4] Zhang, L., Xu, C. and Champagne, P.,
References "Overview of recent advances in
[1] Shirazi, M.N., Hadi, N., Niaei, A., thermo-chemical conversion of
Salari, D. and Nabavi, S.R., "Effect of biomass", Energ. Convers. Manag., 51,
phosphorous and impregnation method 969, (2010).
on propylene selectivity from methanol [5] Baliban, R.C., Elia, J.A., Weekman, V.
over HZSM-5 nano catalysts", and Floudas, C.A., "Process synthesis
th
Proceedings of the 7 Int. Chem. Eng. of hybrid coal, biomass, and natural gas
Cong. (IChEC), Kish, Iran, 1, (2011). to liquids via Fischer–Tropsch
[2] Mysov, V.M., Reshetnikov, S.I., synthesis, ZSM-5 catalytic conversion,
Stepanov, V.G. and Ione, K.G., methanol synthesis, methanol-to-

Iranian Journal of Chemical Engineering, Vol.10, No. 4 25


Kinetic Study of Methanol to Propylene Process on High Silica H-ZSM5 Catalyst

gasoline and methanol-to-olefins/ over ZSM-5 zeolite", J. Chem. Soc.


distillate technolo-gies", Computers Faraday Trans., 77, 2209, (1981).
and Chem. Eng., 47, 29, (2012). [15] Gayubo, A.G., Aguayo, A.T., Sanchez,
[6] Liu, J., Zhang, C., Shen, Z., Hua, W., A.E., Tarrio, A.M. and Bilbao, J.,
Tang, Y., Shen, W., Yue, Y. and Xu, "Kinetic modeling of methanol
H., "Methanol to propylene: Effect of transformation into olefins on a SAPO-
phosphorus on a high silica HZSM-5 34 catalyst", Ind. Eng. Chem. Res., 39,
catalyst", Catal. Commun., 10, 1506, 292, (2000).
(2009). [16] Wang, W., Jiang, Y. and Hunger, M.,
[7] Bos, A.N.R., Tromp, P.J.J. and Akse, "Mechanistic investigations of the
H.N., "Conversion of methanol to lower methanol-to-olefin (MTO) process on
olefins kinetic modeling reactor acidic zeolite catalysts by in situ solid-
simulation and selection", Ind. Eng. state NMR spectroscopy", Catal.
Chem. Res., 34, 3808, (1995). Today, 113, 102, (2006).
[8] Keil, F.J., "Review, Methanol-to- [17] Dahl, I.M. and Kolboe, S., "On the
hydrocarbons: Process technology", reaction mechanism for hydrocarbon
Microporous and Mesoporous formation from methanol over SAPO-
Materials, 29, 49, (1999). 34: 2. Isotopic labeling studies of the
[9] Chang, C.D., "A kinetic model for co-reaction of propene and methanol",
methanol conversion to hydrocarbons", J. of Catal., 161, 304, (1996).
Chem. Eng. Sci., 35, 619, (1979). [18] Olsbye, U., Bjørgen, M., Svelle, S.,
[10] Gayubo, A.G., Aguayo, A.T., Olazar, Lillerud, K.P. and Kolboe, S.,
M., Vivanco, R. and Bilbao, J., "Mechanistic insight into the methanol-
"Kinetics of the irreversible to-hydrocarbons reaction", Catal. today,
deactivation of the HZSM-5 catalyst in 106, 108, (2005).
the MTO process", Chem. Eng. Sci., [19] Song, W., Marcus, D.M., Fu, H.,
58, 5239, (2003). Ehresmann, J.O. and Haw, J. F., "An
[11] Mier, D., Aguayo, A.T., Gayubo, A.G., oft-studied reaction that never was:
Olazar, M. and Bilbao, J., "Synergies in Direct conversion of methanol or
the production of olefins by combined dimethylether to hydrocarbons on the
cracking of n-butane and methanol on a solid acids HZSM-5 or HSAPO-34", J.
HZSM-5 zeolite catalyst", Chem. Eng. Am. Chem. Soc., 124, 3844, (2002).
J., 160, 760, (2010). [20] Marcus, D.M., McLachlan, K.A.,
[12] Chang, C.D. and Silvestri, A.J., "The Wildman, M.A., Ehresmann, J.O.,
conversion of methanol and other o- Kletnieks, P.W. and Haw, J.F.,
compounds to hydrocarbons over "Experimental evidence from H/D
zeolite catalysts", J. Catal., 47, 249, exchange for the failure of direct C-C
(1977). coupling mechanisms in the methanol-
[13] Chen, N. and Reagan, W., "Evidence of to-olefin process catalyzed by HSAPO-
autocatalysis in methanol to 34", Angew. Chem. Int. Ed., 45, 3133,
hydrocarbons reactions over zeolite (2006).
catalysts", J. Catal., 59, 123, (1979). [21] Lesthaeghe, D., Van Speybroeck, V.,
[14] Ono, Y., Mori, T., "Mechanism of Marin, G.B. and Waroquier, M.,
methanol conversion into hydrocarbons "Understanding the failure of direct

26 Iranian Journal of Chemical Engineering, Vol. 10, No. 4


Hadi, Niaei, Nabavi , Farzi

C-C coupling in the zeolite-catalyzed [27] Hadi, N., Niaei, A., Nabavi, S.R., Farzi,
methanol-to-olefin process", Angew. A. and Shirazi M.N., "Development of
Chem. Int. Ed., 45, 1714, (2006). a new kinetic model for methanol to
[22] Arstad, B. and Kolboe, S., "The propylene process on Mn/H-ZSM-5
reactivity of molecules trapped within catalyst", J. of Chem. and Biochem. Q.,
the SAPO-34 cavities in the methanol- 28 (1), 1, (2014).
to-hydrocarbons reaction", J. Am. [28] Mihail, R., Straja, S., Maria, G. H.,
Chem. Soc., 123, 8137, (2001). Musca, G. and Pop, G.R., "A kinetic
[23] Svelle, S., Olsbye, U., Joensen, F. and model for methanol conversion to
Bjørgen, M., "Conversion of methanol hydrocarbons", Chem. Eng. Sci., 38 (9),
to alkenes over medium and large-pore 1581, (1983).
acidic zeolites: Steric manipulation of [29] Park, T.Y. and Froment, G.F., "Kinetic
the reaction intermediates governs the modeling of the methanol to olefins
ethene/propene product selectivity", J. process1: Model formulation", Ind.
of Phys. Chem., 111, 17981, (2007). Eng. Chem. Res., 40, 4172, (2001).
[24] Mei, C.S., Wen, P., Liu, Z., Wang, Y., [30] Park, T.Y. and Froment, G.F., "Kinetic
Yang, W., Xie, Z., Hua, W. and Gao, modeling of the methanol to olefins
Z., "Selective production of propylene process: Experimental results, model
from methanol: Mesoporosity develop- discrimination and parameter
ment in high silica HZSM-5", J. Catal., estimation", Ind. Eng. Chem. Res., 40,
258, 243, (2008). 4187, (2001).
[25] Wu, W., Guo, W., Xiao, W. and Luo, [31] Treacy, M.M.J. and Higgins, J. B.,
M., "Dominant reaction pathway for Collection of simulated XRD powder
methanol conversion to propene over patterns for zeolites, 4th ed., Structure
high silicon H-ZSM-5", Chem. Eng. Commission of the International Zeolite
Sci., 66, 4722, (2011). Association, Amsterdam, Netherlands,
[26] Guo, W., Xiao, W. and Luo, M., p. 380, (2001).
"Comparison among monolithic and
randomly packed reactors for the
methanol-to-propylene process", Chem.
Eng. J. 207-208, 734, (2012).

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