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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Preparation of SAPO-34 catalyst and presentation of a

kinetic model for methanol to olefin process (MTO)

Niloufar Fatourehchi a , Morteza Sohrabi a,b,∗ , S. Javid Royaee a,c , S. Mahdi Mirarefin a
a Amirkabir University of Technology, Chemical Engineering Department, Tehran 15914, Iran
b The Academy of Sciences of Iran, Engineering Division, Tehran 19717, Iran
c Refining Technology Development Division, Research Institute of Petroleum Industry, Tehran, Iran

a b s t r a c t

Conversion of methanol to light olefins (MTO) using acidic SAPO-34 molecular-sieve as the reaction catalyst was
studied in a differential fixed bed reactor within the temperature range of 375–425 ◦ C and under 4 bar pressure.
The importance of MTO process is due to the increasing demand for light olefins in recent years. SAPO-34 was
synthesized by hydrothermal method, applying morpholine as the template. The latter compound was then changed
into protonated form by ion exchange method with ammonium chloride at 80 ◦ C. A simple stoichiometric scheme
has been presented for MTO. In addition a mechanism for this process based on Langmuir–Hinshelwood formulation
has been put forward and the kinetic parameters have been evaluated as functions of temperature.
© 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Methanol to olefin (MTO); SAPO-34; Catalytic reaction; Kinetic model

1. Introduction The production of light olefins from methanol was first

Methanol is a major chemical building block used to manufac-
ture formaldehyde, MTBE, acetic acid and a wide range of other
chemical products. The reduction in MTBE demand, mainly
due to the decision taken by some of the states in the US and
certain countries in the world to eliminate its use in the gaso-
line, is causing some of the producers in the world to explore
alternate applications for their existing methanol plants. One
such utilization is the conversion of methanol to olefins (MTO)
(Al Wahabi, 2003).
Olefins can be produced using several processes and feed
stocks. In every process a range of products and byproducts
are formed. The percentage of the different output products
depend on the process and the feedstock used. Currently,
there are three main industrial methods for olefins forma-
tion, steam cracking of hydrocarbons (naphtha, ethane, gas oil
and LPG), fluid catalytic cracking in oil refineries and paraffin
dehydrogenation. In addition to these commercial processes,
there are some non-commercial technologies under various
phases of development such as oxidative coupling of methane
(OCM), oxidative dehydrogenation of paraffins and methanol
to olefins (MTO) process (Al Wahabi, 2003).
realized around 1977, during the development of Mobil’s
methanol to gasoline (MTG) process. In the MTG process,
where ZSM-5 is used as a catalyst, methanol is first dehydrated
to dimethylether (DME). The equilibrium mixture of methanol,
DME and water is then converted to light olefins. A final reac-
tion step leads to a mixture of higher olefins, n/iso-paraffins,
aromatics and naphthenes (Al Wahabi, 2003).
Methanol to olefin (MTO) process provides a conventional
method for production of ethylene and propylene. This pro-
cess has some advantages over the current steam cracking of
NGL, naphtha or other light fractions of petroleum, due to the
fact that MTO can provide a wider and more flexible range of
ethylene to propylene ratio relative to those of conventional
processes to meet market demand. In addition, methanol may
be produced from synthesis gas, that can be formed from any
source of carbon-containing materials such as coal, petroleum
residue, biomass and natural gas (Eng et al., 1998a,b; Vora et
al., 1997).
A number of molecular sieve catalysts have been exam-
ined for the MTO process. However, SAPO-34 was observed to
be a more efficient catalyst in terms of activity and selectiv-
ity for light olefins (Wilson and Barger, 1999). Several studies

∗
Corresponding author at: Department of Chemical Engineering, Amirkabir University of Technology, Tehran 15914, Iran.
E-mail address: sohrabi@aut.ac.ir (M. Sohrabi).
Received 3 October 2009; Received in revised form 7 August 2010; Accepted 5 October 2010
0263-8762/$ – see front matter © 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2010.10.007

Please cite this article in press as: Fatourehchi, N., et al., Preparation of SAPO-34 catalyst and presentation of a kinetic model for methanol to
olefin process (MTO). Chem Eng Res Des (2010), doi:10.1016/j.cherd.2010.10.007
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Nomenclature
E activation energy (J)
F0 molar rate of feed (mol/h)
kr kinetic parameter of dimethylether production
(mol/g h)
ke kinetic parameter of ethylene production
(mol/g h)
kp kinetic parameter of propylene production
(mol/g h)
kparaffin kinetic parameter of paraffin production
(mol/g h barn )
k0 Arrhenius constant
Kd equilibrium constant of dimethylether produc-
tion
Km equilibrium constant of methanol production
Pw partial pressure of water (bar)
Pmethanol partial pressure of methanol (bar)
n order of reaction
rdimethylether rate of dimethylether production (mol/g h)
rEthylnene rate of ethylene production (mol/g h)
rPropylene rate of propylener production (mol/g h)
rParaffin rate of paraffin production (mol/g h)
U0 inlet gas velocity (m/s)
Umf minimum fluidizing velocity (m/s)
Wcat weight of catalyst (g)
on MTO process using chabazite and ZSM-5 have been also
conducted. Single event kinetics was used to build a kinetic
model for MTO on ZSM-5. Since SAPO-34 seems to be a desir-
able catalyst for MTO, and this process has a great potential for
commercialization, detailed research on the products change
with the reaction conditions applying SAPO-34 catalyst would
be important and beneficial (Wu et al., 2004).
In the present study, SAPO-34 has been synthesized and
the activity of the latter has been measured applying a differ-
ential fixed bed reactor. In addition, a kinetic model has been
proposed and the kinetic parameters have been evaluated.
2. Methods and materials
2.1. Materials
The materials applied in this study were all analytical grades.
2.2. Catalyst preparation
The catalyst was prepared according to the hydrothermal
method outlined by Song (Song, 2001; Lok et al., 1984) and
Prakash and Unnikrishnan (1994) using aluminum isopropox-
ide, phosphoric acid, fumed silica and morpholine. The first
step was hydrolysis of isopropoxide. Specified amount of
aluminum isopropoxide [98% Al(O-i-C3 H7 )3 , Alfa Aesar (Karl-
sruhe, Germany)] was mixed with distilled water. The mixture
was heated to 80 ◦ C to accelerate the hydrolysis. The hydrol-
ysis was completed in 2 h with vigorous stirring, resulting in
a homogeneous white gel. Isopropyl alcohol, the product of
the hydrolysis, was left in the gel without further treatment.
The second step was to mix phosphoric acid [85% H3 PO4 , Alfa
Aesar (Karlsruhe, Germany)] with the white gel. Phosphoric
acid was added drop wise to aluminum gel within 5 min with
stirring. The resulting white homogenous gel comprised part
Please cite this article in press as: Fatourehchi, N., et al., Preparation of SAPO-34 catalyst and presentation of a kinetic model for methanol to
olefin process (MTO). Chem Eng Res Des (2010), doi:10.1016/j.cherd.2010.10.007
(A) of the final mixture. The second step was to prepare part
(B) of the final mixture. Morpholine [99% C4 H9 O, Merck (Darm-
stadt, Germany)] was mixed with specified amount of fumed
silica [95% SiO2 , Alfa Aesar (Karlsruhe, Germany)]. The mix-
ture was stirred until a homogenous solution was formed.
Part B was then added to part A with stirring. The final mix-
ture was further stirred for 2 h, resulting in a semi-transparent
homogenous white gel. The final gel mixture having the pH 8
was transferred into a high-pressure stainless steel autoclave.
The autoclave was sealed and maintained at 200 ◦ C for 48 h
without stirring. The pressure inside the autoclave was equal
to the autogeneous pressure of water at 200 ◦ C. The autoclave
was slowly cooled down after 48 h. As-synthesized SAPO-34
was recovered from the autoclave; washed three times with
200 ml distilled water; dried at 120 ◦ C for 24 h and calcined at
600 ◦ C for 10 h. The product was then transformed into pro-
tonated form by ion exchange process with 2-M ammonium
chloride solution at 80 ◦ C. The synthesized catalyst dried at
120 ◦ C for 24 h and calcined at 500 ◦ C for 10 h.
2.3. Packed bed reactor
A differential fixed bed reactor was applied to investigate the
kinetic of the reaction and to present a suitable rate model. The
reactor consisted of a 70 cm high cylindrical tube with 1.6 cm
internal diameter. The depth of the catalyst bed in the reactor
was 1.5 cm. The heat transfer to the reactor was provided by
an electric jacket wrapped around the reactor. Reaction tem-
perature was controlled by a PID controller and measured by
a thermocouple (PT100) housed in a thermo well located at
the center of the catalyst bed. The reactor’s pressure was reg-
ulated by a backpressure system. A schematic diagram of the
experimental set-up is shown in Fig. 1.
2.4. Feed
To increase the olefin’s selectivity and reduce the rate of cata-
lyst’s deactivation, the feed was enriched with water vapor.
Thus, a feed consisted of 50 mol% methanol and 50 mol%
water was applied. Flow of liquid feed was controlled by a
dosing pump (Milton Roy model H94X (Ivyland, USA)).
2.5. Analytical procedure
In all experimental runs, when steady state conditions were
established (usually after about 10 mean residence times) a
portion of the gas mixture leaving the reactor was conducted
to a GC apparatus connected on line to the reactor’s exit port.
Such a procedure was repeated at regular time intervals of
7 min.
The GC analyzer (Agilent model 6890, (CA, USA)) was
equipped with a 30 m capillary column made of silica with
polyamide coating, 0.53 mm internal diameter. Helium was
used as the carrier gas and thermal conductivity detector was
applied. The column temperature was increased linearly from
60 to 150 ◦ C with a rate of 30 ◦ C/min.
3. Results and discussion
3.1. Catalyst synthesis
H-SAPO34 was synthesized according to Section 2.2 of the
present paper. SEM image and XRD pattern of the catalyst are
given in Figs. 2 and 3.
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Fig. 1 – Experimental set-up.

(b) The adsorbed molecules diffuse across the surface and

interact when they are close.
(c) A product molecule is formed and desorbs into the fluid
phase.

A schematic diagram of this mechanism is shown in Fig. 4.

According to such a mechanism, methanol molecules
adsorbed at the active site of the catalyst and diffused across
the surface, leading to formation of CH3 OH·S. Intermediate
CH3 OH·S was then interacted with another CH3 OH·S species
forming DME·S. Three different paths could be assumed for
decomposition of DME·S, i.e., DME·S could leave the active
Fig. 2 – SEM image of catalyst. site and forms dimethyl ether, or may either convert to ethy-
lene or reacts with another CH3 OH·S intermediate to produce
propylene. Thus, the mechanism may be presented as follows:
Prior to application, the catalyst was regenerated by
100 ml/min nitrogen gas in 500 ◦ C for 2 h. Flow of nitrogen km
CH3 OH + S  CH3 OH · S (1)
was controlled by a mass flow controller (MFC) (Brooks model km
5850E, USA).
kd
3.2. Kinetic study 2CH3 OH · SCH3 OCH3 · S + H2 O + S (2)
k
d

In developing a mechanism for light olefins formation, a sim-

Dimethylether production:
ple stoichiometric relation was first presented for this process
as follows:
Ethylene

Higher olefins
Methanol Dimethylether (minute amounts)

Paraffin Propylene
It was further assumed that the reaction mechanism fol-
lows the Langmuir–Hinshelwood formulation.
kr
The Langmuir–Hinshelwood–Hougen–Watson (LHHW) CH3 OCH3 · S−→CH3 OCH3 + S (3)
mechanism is based upon the following assumptions:
Ethylene production:
(a) Reactants’ molecules adsorb onto the surface of the cata-
ke
lyst. CH3 OCH3 · S−→C2 H4 + H2 O + S (4)

Please cite this article in press as: Fatourehchi, N., et al., Preparation of SAPO-34 catalyst and presentation of a kinetic model for methanol to
olefin process (MTO). Chem Eng Res Des (2010), doi:10.1016/j.cherd.2010.10.007
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Fig. 3 – XRD pattern of catalyst.

Fig. 4 – Langmuir–Hinshelwood mechanism.

Propylene production: assuming a combination of different steps as the rate limiting

relations. The kinetic models deduced from such assumptions
kp all provided poor correlations with the experimental data and
CH3 OCH3 · S + CH3 OH · S−→C3 H6 + 2H2 O + 2S (5)
were thus discarded.

The following kinetic model was derived by taking relations

kr Kd Km
2 P2
methanol
(3)–(5) as the rate determining steps. These reactions were rdimethylether = (6)
selected after a number of unsuccessful attempts made by Pw (1 + Km Pmethanol + (Kd Km
2 P2 /P ))
methanol w

Table 1 – Kinetic data at different operating conditions.

Temperature Wcat /F0 PMethanol PDimethylether PEthane PEthylene PPropane PPropylene PWater
(◦ C) (g h/mol) (bar) (bar) (bar) (bar) (bar) (bar) (bar)

375 2.531646 1.91095 0.009938 0.001473 0.011372 0.005877 0.013905 2.047521

3.375527 1.88575 0.011174 0.002216 0.015331 0.007749 0.019608 2.059071
5.063291 1.83887 0.012642 0.005673 0.022119 0.013345 0.028786 2.079408
6.751055 1.79102 0.014052 0.009037 0.031566 0.014945 0.036641 2.103402
8.438819 1.74814 0.015019 0.013638 0.035049 0.023098 0.046048 2.119609
10.12658 1.70306 0.015050 0.017290 0.041218 0.028234 0.055113 2.140771
400 2.531646 1.90852 0.009852 0.003265 0.011381 0.010256 0.011728 2.043763
3.375527 1.87855 0.011069 0.006417 0.017741 0.011569 0.017714 2.057639
5.063291 1.82771 0.012472 0.010151 0.025876 0.019882 0.026435 2.078024
6.751055 1.77315 0.013819 0.013282 0.037101 0.026015 0.033846 2.103788
8.438819 1.72727 0.014745 0.019169 0.041422 0.035386 0.041932 2.120970
10.12658 1.67528 0.014605 0.024854 0.048290 0.039526 0.052414 2.145870
425 2.531646 1.90059 0.009395 0.008054 0.016278 0.012082 0.009585 2.044520
3.375527 1.87089 0.009999 0.008654 0.021151 0.018325 0.014876 2.057207
5.063291 1.81211 0.011364 0.014621 0.029680 0.027385 0.024176 2.080817
6.751055 1.75732 0.012641 0.020339 0.042622 0.036035 0.030171 2.102169
8.438819 1.70816 0.014010 0.026990 0.048921 0.038950 0.039896 2.123770
10.12658 1.65798 0.014448 0.031675 0.055216 0.053347 0.046946 2.140423

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olefin process (MTO). Chem Eng Res Des (2010), doi:10.1016/j.cherd.2010.10.007
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Table 2 – Rate of consumption or production of reactants and products.

Temperature (◦ C)  (bar g h/mol) −rMethanol (mol/g h)

ARTICLE IN PRESS
rDimethylether (mol/g h) rParaffin (mol/g h) rEthylene (mol/g h) rPropylene (mol/g h)

375 6 0.01448 0.00410 0.00190 0.002532 0.003032

7.5 0.01431 0.00400 0.00205 0.002531 0.003075
10 0.01400 0.00403 0.00230 0.002500 0.003090
12.5 0.01370 0.00402 0.00255 0.002431 0.003173
15 0.01350 0.00390 0.00280 0.002325 0.003200
17.5 0.01310 0.00388 0.00305 0.002181 0.003175
400 6 0.01590 0.00400 0.00282 0.002460 0.002620
7.5 0.01495 0.00410 0.00300 0.002520 0.002650
10 0.01420 0.00402 0.00330 0.002500 0.002700
12.5 0.01410 0.00406 0.00361 0.002301 0.002763
15 0.01440 0.00395 0.00390 0.002002 0.002801
17.5 0.01455 0.00382 0.00411 0.002101 0.002785
425 6 0.01531 0.00405 0.00402 0.003084 0.001988
7.5 0.01501 0.00401 0.00405 0.003113 0.001984
10 0.01430 0.00403 0.00410 0.003101 0.001981
12.5 0.013780 0.00397 0.00415 0.003001 0.001973
15 0.01350 0.00386 0.00420 0.002851 0.001968
17.5 0.01310 0.00371 0.00424 0.002810 0.001965

5
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Table 3 – Kinetic parameters at different temperatures.

Temp. (◦ C) Parameter

Km Kd kr (mol/g h) ke (mol/g h) kp (mol/g h) kParaffin (mol/g h barn ) n

375 2.22 4.683 0.00045 0.0028 0.0366 0.009268 0.342

400 1.187 3.757 0.00058 0.0035 0.0184 0.010023 0.31
425 0.898 2.601 0.00071 0.0054 0.013 0.004808 0.048

Table 4 – Values of k0 and E for dimethyl ether and 4. Conclusion

ethylene.
It was found that the two step hydrothermal synthesis of
Material k0 E (J)
H-SAPO34 is a convenient method by which such a com-
Dimethylether 0.266335 34295.25 pound may be formed. SAPO-34 was then protonated by
Ethylene 31.785175 50557.43 ion-exchange process into an active catalyst by which trans-
formation of methanol to light olefins was achieved. An
ke Km
2 P2
methanol appropriate kinetic model was presented and the kinetic
rEthylene = (7)
Pw (1 + Km Pmethanol + (Kd Km
2 P2 /P ))
methanol w
parameters were evaluated as functions of temperature using
a differential fixed bed reactor.
3 P3
kp Kd Km methanol
rPropylene = (8)
Pw (1 + Km Pmethanol + (Kd Km
2 P2 /P ))
2 References
methanol w

To simplify calculations, the rate of paraffin production was
considered as a power law relation:
rParaffin = kParaffin PnParaffin
As it was mentioned in Section 2.3, a differential packed bed
reactor (with 1.5 cm depth of catalyst bed) was used to inves-
tigate the kinetic of the reaction. Synthesis of methanol was
carried out at 4 bar pressure and 375, 400 and 425 ◦ C. The feed
was consisted of 50 mol% methanol and 50 mol% water. As the
catalyst depth did not exceed 1.5 cm, the temperature could
be effectively controlled and formation of hot spots or fronts
was avoided. Results obtained from the kinetic studies are
presented in Table 1.
The rates of formation or consumption of the materials
were determined from the slopes of tangents drawn at vari-
ous points on the plots of components concentrations against
time. Rate data are presented in Table 2.
Values for kinetic parameters at various temperatures are
presented in Table 3.
It may be observed from this table that the rate coefficient
for propylene is declined with increase in temperature. This is
probably due to further conversion of propylene to certain by-
products, the rates of which are more temperature sensitive
than that of propylene formation
The temperature dependency of the kinetic parameters (kr ,
ke , kp ) was determined assuming the Arrhenius type relation.
These values are presented in Table 4.
Al Wahabi, S.M., 2003. Conversion of methanol to light olefins on
SAPO-34 kinetic modeling and reactor design. Ph.D. Thesis. A
& M University, Texas.
Eng, C.N., Arnold, E.C., Vora, B.V., 1998a. Integration of the
(9) UOP/HYDRO MTO process into ethylene plants. In: Presented
at the AIChE Spring National Meeting, Session 16,
Fundamental Topics in Ethylene Production, Paper 16g, New
Orleans, Louisiana.
Eng, C.N., Arnold, E.C., Vora, B.V., Fuglerud, T., Kvisle, S., Nilsen,
H., 1998b. Natural gas utilization and UOP/HYDRO MTO
process. In: Presented at the AIChE Spring National Meeting,
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Lok, B.M., Messina, C.A., Patton, R.L., Gajek, R.T., Cannan, T.R.,
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Please cite this article in press as: Fatourehchi, N., et al., Preparation of SAPO-34 catalyst and presentation of a kinetic model for methanol to
olefin process (MTO). Chem Eng Res Des (2010), doi:10.1016/j.cherd.2010.10.007