4116 Ind. Eng. Chem. Res.

2007, 46, 4116-4123

Methanol Conversion to Light Olefins over SAPO-34: Reaction Network and

Deactivation Kinetics

D. Chen,*,† A. Grønvold,‡,§ K. Moljord,‡,⊥ and A. Holmen†

Department of Chemical Engineering, Norwegian UniVersity of Science and Technology (NTNU),
N-7034 Trondheim, and SINTEF Applied Chemistry, N-7034 Trondheim, Norway

The kinetics of the reactions involved in the conversion of methanol to light olefins over SAPO-34, including
deactivation caused by coke deposition, has been studied in an oscillating microbalance reactor between 673
and 823 K, space velocities from 50 to 2000 g/gcat,h and methanol partial pressures from 7 to 83 kPa. The
proposed reaction network involves dimethyl ether as an unstable primary product, all the olefins formed in
parallel as secondary products, and the paraffins formed from further reactions of olefins as stable tertiary
products. The selectivity to ethene increased with increasing coke content and temperature. A kinetic model
including the deactivating effect due to coke deposition has been developed to properly simulate the changes
in activity and selectivity with the coke content. A linear dependency between the coke content and the
reaction rate gave the best representation of the experimental data.

Introduction developed by Bos and Tromp.17 The conversion and the

From synthesis gas, which can be obtained by gasification,
partial oxidation, or steam reforming from raw materials, such
as biomass, coal and natural gas, methanol is synthesized using
a proven technology. The catalytic conversion of methanol to
olefins (MTO) was originally an intermediate step in Mobil’s
process to convert methanol to synthetic gasoline using H-
ZSM-5 as catalyst.1 However, interest has recently shifted
toward the MTO process following the increased demand for
olefins.2 As a consequence of the discovery of aluminophosphate
molecular sieves, especially SAPO-34,3 it is possible to
selectively produce ethene and propene at high methanol
conversions, due to the narrow pores (0.43 nm) extending in
three dimensions and the mild acidity of SAPO-34.4 However,
fast deactivation of the catalyst due to coke formation has been
reported.5-7
Most kinetic studies on methanol conversion have been made
on HZSM-5 catalysts, and a number of simplified kinetic models
have been developed. The complexity of the model varies
according to the degree of lumping proposed.8-12 A very detailed
analysis has been performed by Mihail et al.13-14 in which 33
reactions were used. Single-event kinetic modeling of MTO on
H-ZSM-5 has been performed by Park and Froment15-16 on the
basis of a detailed mechanistic description of the MTO reaction.
Sedran et al.11 tested several alternative kinetic models for
conversion of methanol to hydrocarbons, including an expo-
nential activity function to account for the deactivation of the
catalyst. A common characteristic of the kinetic models is the
autocatalytic effect in the reaction network. However, to our
knowledge, autocatalytic behavior has not been reported for
conversion of methanol to light olefins over SAPO-34.
A kinetic model for MTO over SAPO-34 based on results
obtained in a plug flow fixed-bed reactor at 723 K has been
* To whom correspondence should be addressed. Tel: +47 73593149.
E-mail: chen@nt.ntnu.no.
†
NTNU.
‡
SINTEF Applied Chemistry.
§
Present address: Hydro Oil & Energy Research Center, Box 2561,
N-3907 Porsgrunn, Norway.
⊥ the deactivation due to coke deposition.
Present address: Statoil, Postuttak, N-7005 Trondheim, Norway.
selectivities were studied as a function of the coke content of
the catalyst. An exponential dependency was found to give the
best representation of the effect of coke on the reaction rate.
Unfortunately, direct measurements of coke formation in situ
are not possible in a fixed-bed reactor. The determination of
coke in this case must be done either by burning off the coke
in the reactor or by taking the catalyst out of the reactor for
weighing. Such measurements of coke content in a fixed-bed
reactor may, therefore, introduce additional errors, and it is also
a time-consuming process. The parameters in the model were,
thus, estimated from a limited amount of data. Gayubo et al.18
performed a kinetic study of MTO in SAPO-34-based catalysts
in a fixed-bed reactor, in which the catalysts were prepared by
agglomerating the SAPO-34 (25 wt %) with bentonite (30 wt
%), using fused alumina as the inert charge (45 wt %). The
MTO reaction was studied as a function of time on-stream, and
the initial reaction rates at different conditions were obtained
by extrapolating ration rates to zero time. The authors have
proposed a reaction network of MTO taking into account four
individual steps for the production of ethene, propene, butanes,
and other hydrocarbons (pentenes + paraffins). A kinetic model
for the reaction network was developed; however, kinetics of
coke deposition and deactivation during MTO were not included.
Alwahabi and Froment19 have recently developed a single-event
kinetic model of the MTO reaction on SAPO-34 based on the
experimental data in a fixed-bed reactor. The deactivation caused
by coke formation was modeled by fitting the conversion
changes with time on-stream in the fixed-bed reactor. However,
experimental data of coke formation and the deactivating effects
of the coke formed are missing.
An oscillating microbalance reactor (TEOM) provides an
opportunity to achieve a better quantitative understanding of
the activity and the selectivity changes with the coke forma-
tion.20 The mechanism and kinetics of the coking process have
been investigated in detail in our previous work.21 The present
work will focus on the selectivity to olefins and its changes
with coke formation. A reaction network is proposed, and a
kinetic model for this reaction network is developed, including

10.1021/ie0610748 CCC: $37.00 © 2007 American Chemical Society

Published on Web 12/10/2006

Experimental Section
The setup of the TEOM reactor, the catalysts, and the
experimental methods are identical to those described in our
previous work.22 A more detailed description of the TEOM
reactor can be found in a recent review.23 Calcined SAPO-34
with a unit cell composition of (Si2.88Al18P15.12)O72 was ob-
tained from SINTEF Applied Chemistry. SAPO-34 catalysts
are typically cubic crystals with sizes of ∼2 µm. The SAPO-
34 particles (52-140 mesh) were dried in situ at 773 K in
flowing He for more than 3 h. The MTO reaction was performed
at WHSV ranging from 57 to 2558 g (g of cat)-1 h-1, methanol
partial pressure ranging from 7.2 to 83 kPa, and temperatures
between 673 and 823 K. The runs with different space velocities
were carried out at 698 K and a methanol partial pressure of
7.2 kPa to obtain a relatively low coking rate. The runs with
different methanol partial pressures were also performed at
698 K. The space velocity was adjusted to ensure an identical
conversion when the partial pressure of methanol was increased.
For high methanol partial pressures, very high space velocities
were required as a result of very rapid coke formation.
The conversion and selectivities were calculated on a CH2
basis (CH3OH f CH2 + H2O). The isomers of C4, C5, and C6
were lumped according to their respective carbon numbers, and
the selectivities of C1-C6 hydrocarbons were calculated by
normalization exclusive coke. The yield-conversion plots were
presented on a weight basis, and the formation of DME,
hydrocarbons (C1-C6), and water was included. The water
fraction was calculated from the mass balance. Due to the fast
coke deposition on the catalyst, pulse experiments were used
to study the changes in activity and selectivity with coke content.
Pulses of 3-min duration were used for PmeOH < 30 kPa, whereas
1-min pulses were used at high temperatures (773-823 K). It
has been shown previously that the conversion and selectivity
were not affected by the pulse size.21
Reaction Network
As discussed previously,20 the yield-conversion plot is a
powerful tool for distinguishing the type of product (stable or
unstable, primary or secondary) and the type of deactivation
(selective or nonselective). Selective deactivation has been
illustrated for the MTO reaction over SAPO-34. However, only
a simple reaction model was used previously,20 in which all
the hydrocarbons were lumped together; dimethyl ether (DME)
was treated as a primary product; and the olefins, as secondary
products. The present work differentiates the individual hydro-
carbons according to product types and determines the effect
of coke formation on the distribution of olefins.
In Figure 1, the product yields at different space velocities
are plotted against the conversion at 698 K and a methanol
partial pressure of 7.2 kPa. Initial conversions are obtained by
varying the space velocity, and the different symbols in Figure
1 illustrate different space velocities. For a certain space velocity,
the conversion decreased with increasing coke content. The solid
lines enclosing such loops are OPEs (optimum performance
envelopes20,24), which are obtained from approximately the first
pulse (TOS ) 2 min). Although this treatment is not very
rigorous due to deactivation during the first pulse, it is expected
not to lead to large errors with respect to the selectivity plot in
this case, since the selectivity change with coke content is small
at low coke contents (as shown later in Figure 5). However, it
should be noted that the ethene selectivity changes significantly
at very low coke content, and the uncertainty in determining
Ind. Eng. Chem. Res., Vol. 46, No. 12, 2007 4117
the OPE of ethene formation is, thus, relatively large. From the
OPEs, the types of products can be identified.
The OPE curves for the yield of C2-C6 are almost straight
lines, indicating that the selectivities to olefins are almost
constant on the fresh catalyst, regardless of the conversion. In
other words, the gas-phase olefins formed over SAPO-34 are
quite stable, and the secondary reactions of olefins do not seem
to be very important. It has to be noted that the linear OPE
curves do not pass through zero conversion, which is a
characteristic of secondary products. The hydrocarbons, includ-
ing ethene, propene, C4, C5, and C6, can thus be considered as
stable secondary products formed in parallel from DME at a
methanol conversion less than 100%. Light paraffins (ethane
and propane) are formed only at high conversions, meaning that
paraffins are stable tertiary products. The OPE curve for coke
went through 0 at an almost identical conversion as for the
olefins (10%), and it increased with increasing conversion. Coke
may, therefore, be considered as a secondary plus stable tertiary
product. The detailed mechanism of coke deposition has been
discussed previously.21 Reaction intermediates such as carbe-
nium ions inside the pores of SAPO-34 were considered as the
major coke precursors.
Equilibrium between olefins formed during methanol to
gasoline over ZSM-5 is achieved.25 This is different for SAPO-
34, in which the olefin distribution is far from equilibrium.26
Additionally, equilibrium cannot explain the constant olefin
distribution at different space velocities, since the partial pressure
of olefins (related to the level of oxygenates conversion) has a
profound influence on the equilibrium between olefins.25 Instead,
we believe that the constant olefin distribution is caused by the
low reactivity of olefin and the lower adsorption capacity for
olefins relative to methanol.27 The low olefin reactivity over
SAPO-34 has been demonstrated from the observation that the
reaction rate of propene conversion was almost 100× lower
than the MTO reaction.27 The low reactivity of olefins was also
observed by Dahl et al.28 during ethanol and propanol conversion
over SAPO-34. Salehirad and Anderson29 reported that ethene
conversion was faster on the methylated SAPO-34 than on the
bare catalyst, but the reaction rate of propene was still much
lower than for methanol.
It should be noted that the conversion of methanol was
<100% at the reaction conditions used in this work. The
presence of methanol, DME, and water might to some extent
contribute to the lower reactivity of olefins through competitive
adsorption between polar molecules (methanol, DME, and
water) and less polar olefins. Water is known to suppress the
conversion of olefins and coke deposition.30,31
Figure 1 suggests methane to be a stable primary plus
secondary product. Methane was suggested in the literature29,31,32
as a primary product formed directly from methanol. A
mechanism with surface methoxy species as intermediates has
been suggested to explain the formation of methane:
Another possible path for methane formation has been also
reported29,33 (reaction 2):
4118 Ind. Eng. Chem. Res., Vol. 46, No. 12, 2007

Figure 1. Yields versus methanol conversion during MTO over SAPO-34 at PMeOH ) 7.2 kPa and 698 K. Symbols with lines represent experimental results
at different WHSV (g (g of cat)-1 h-1): 384 (O), 253 (×), 114 (+), 82 (∆), 57 (]). Solid lines: OPE curves obtained from data of the first pulse.

where the hydride source is a large molecule deposited on the

surface of the catalyst, referred to as coke. Both mechanisms
may contribute to the methane formation. However, it is difficult
to discuss the mechanism in more detail, since the yields of
methane in the present work are very low, and a relatively large
error in the analysis is expected.
The reaction network given in Figure 2 is based on the
discussion above. All the hydrocarbons are formed mainly as
parallel products from DME. The methanol molecule might also
contribute to the olefin formation as a methylating agent inserted
into the surface intermediates, yielding a chain growth. However,
it is difficult to determine the degree of olefin formation from
DME and directly from methanol, so Figure 2 illustrates only
the possible pathways for olefin formation from DME. The
reaction network can be explained by the hydrocarbon pool
Figure 2. Reaction network for MTO over SAPO-34.
mechanism,26 regardless of the nature of the “hydrocarbon pool”,
which is still in debate.
Selectivities During MTO on SAPO-34
Effect of Space Velocity. All the OPE lines for the
hydrocarbons in Figure 1 are nearly linear, indicating that the
selectivities are independent of conversion (or space velocity).
This is in good agreement with the results of Liang et al.,5 but
it is different from the observation of Cai et al.34 and Bos et
al.17 These authors observed that the selectivity to ethene

Figure 3. Ethene selectivity with coke content at 698 K but different partial
pressures. ], 15 Kpa, 384 g (g of cat)-1 h-1; O, 30 KPa and 768 g (g of
cat)-1 h-1; ∆, 60 KPa and 1538 g (g of cat)-1 h-1; 0, 83 kPa and 2558 g
(g of cat)-1 h-1.
Figure 4. Selectivity with temperature during the MTO reaction on SAPO-
34 at 7.2 kPa methanol partial pressure, 385 g (g of cat)-1 h-1and a coke
content of 4.6 wt %. [, ethene; 9, propene; b, C4; ×, C5; 2, methane.
decreased with increasing space velocity. One important dif-
ference is the higher space velocity (57-384 h-1) used in the
present work than in the studies of Cai et al.34 and Bos et al.17.
As discussed above, the secondary reactions of olefins are not
important at the conversions studied in the present work, in
which the primary olefin selectivity during MTO over SAPO-
34 is dominant. However, further reactions involving olefins
are more important at the low space velocities of 2-10 g (g of
cat)-1 h-1, as in the study of Cai et al.34 This might explain the
difference in the space velocity dependency on the selectivity
to olefins.
Effect of Partial Pressure. Experiments at identical conver-
sion were achieved by adjusting both the partial pressure of meth-
anol and the space velocity. Product selectivities were found to
be independent of the partial pressure at constant coke content.
An example of the changes in the selectivity to ethene with coke
content at different partial pressures is illustrated in Figure 3.
Effect of Temperature. The effect of temperature on the
product (hydrocarbon) selectivities at a constant coke content
of 4.6 wt % is presented in Figure 4. The selectivity to ethene
and methane increases while the selectivity of propene decreases
with temperature. C4 and C5 selectivities are only slightly
influenced. As shown previously, the coke selectivity increases
significantly with temperature.21
Effect of Coke Deposition. Figure 1 reveals that the selec-
tivities changed with the degree of deactivation due to coke depo-
sition. At a given conversion, the yields of C3-C6 olefins on a
Ind. Eng. Chem. Res., Vol. 46, No. 12, 2007 4119
Figure 5. Selectivity versus the coke content at 698 K, WHSV ) 57 g
(g of cat)-1 h-1and a methanol partial pressure of 7.2 kPa. 9, Methane; b,
ethene; [, propene; 2, butene; ×, C5; +, C6.
Figure 6. Relative selectivities versus coke content at 698 K, WHSV )
57 g (g of cat)-1 h-1 and a methanol partial pressure of 7.2 kPa. b, Ethene;
[, propene; 2, butene; ×, C5; +, C6.
catalyst containing coke were lower than on the fresh catalyst,
whereas the opposite trend was observed for ethene, as shown
in Figure 1. This is an example of selective deactivation,20 in
which each reaction step has its own deactivation rate.
The change in selectivity of different hydrocarbons with the
coke content is shown in Figure 5 for WHSV ) 57 g (g of
cat)-1 h-1. Figure 6 shows variations in relative selectivities at
the same conditions as in Figure 5, where the initial selectivity
was obtained by extrapolation to zero coke content from Figure
5. These results clearly show that the selectivity to ethene
increases with increasing coke content. The following decrease
in selectivity of the olefins with coke content was found.
C6 > C5 > C4, C3
Changes in the product selectivities for a complex reaction due
to coke formation on a zeolite-type catalyst can be caused by
changes in conversion, acidity (including density and strength
distribution), and shape selectivity.20 The linear OPE pattern in
the yield-conversion plots for all the hydrocarbons (Figure 1)
shows constant selectivities at different conversions on the fresh
catalyst. In other words, the change in the conversion level itself
due to the coke deposition should not influence the selectivity
to the hydrocarbons. The heat of adsorption as function of the
site coverage of methanol measured by methanol adsorption on
SAPO-34 indicated a uniform distribution of acid strength,27
which is in good agreement with the result obtained from
ammonia TPD experiments.35 In addition, the number of active
4120 Ind. Eng. Chem. Res., Vol. 46, No. 12, 2007

sites per cage was estimated to be 0.8,36 indicating that a maxi-

mum of 80% of the cages are active for reaction. Each cage
can be considered as a microreactor, and coke deposition reduces
the number of microreactors. The number of active sites in each
accessible microreactor is close to 1; therefore, it is not expected
that the change in the number of total active sites due to coking
influences the product distribution. The change in acidic
properties is, therefore, unlikely to be the main reason, and shape
selectivity is a more likely reason for the selectivity change.
The MTO reaction on differently sized crystals has demon-
strated the importance of the shape selectivity on the selectivity
changes due to coke deposition.37 The results showed almost
no effect of crystal size on the selectivity, but a significant effect
of coke deposition. Therefore, the transition-state shape selectiv-
ity was considered to be dominant at relatively high coke
contents. The formation of larger molecules via a larger-sized
reaction intermediate was significantly suppressed by the
reduced free space in the cavities by coke deposition, hence,
enhancing the ethene formation. The much lower ethene
selectivity at the low coke content (Figure 3) can be explained
by a weak or no effect of the transition-state shape selectivity.37
However, a possible effect of the changes in the reaction
mechanism with coke content cannot be excluded.

Deactivation Due to Coke Deposition

The coke deposition and deactivation of the MTO reaction
at 698 K and PMeOH ) 7.2 kPa for different space velocities
have been discussed in detail in our previous work.21 Deactiva-
tion of zeolites due to coke deposition is normally very
complicated, since intracrystalline diffusion often influences both
activity and selectivity. Coke deposition can reduce the number
of active sites by site coverage or by pore blockage. Coke
deposition can also increase the effective diffusion length and,
thus, decrease the effective diffusivity and the effectiveness
factor. It has been demonstrated that intracrystalline diffusion
plays a key role in determining the activity and the coke
deposition during MTO on SAPO-34 with the crystal size used
in the present work.27,38-40 The role of the intracrystalline
diffusion in MTO has recently been reviewed by Ruthven41 and
Chen et al.;23 however, no attempts have been made to
distinguish between different causes of deactivation in the
modeling in the present work.
Our previous work21 has shown that coke deposition increases
significantly with increasing temperature. Figure 7A shows that
the conversion of the oxygenates decreases more significantly
with time on-stream at the higher temperature; however, Figure
7B indicates a rather similar deactivating effect of coke
molecules formed during MTO at different temperatures. It
means that the rapid deactivation of oxygenates at high
temperatures is a main result of the rapid coke deposition.
A small difference in the initial conversion of oxygenates
with temperature can be observed at lower coke content (Figure
7B). This is mainly due to the high conversions, in which the
conversion is not very sensitive to the change in the activity at
such conditions. In addition, it can partly be a result of diffusion
limitation. It is well-known that diffusion limitations reduce the
observed activation energy.
Kinetic Model of the MTO Reaction Network
It was found that it is difficult to model the formation and
consumption of DME properly. It is expected that the formation
and conversion of DME are influenced by intracrystalline
diffusion, due to the large crystals (∼2 µm) of SAPO-34 used
Figure 7. Changes in conversion of oxygenates with the time on-stream
(A) and the coke content (B) at 425 °C (O), 500 °C (4), and 550 °C (0).
Partial pressure of methane of 14 kPa, WHSV ) 263 g (g of cat)-1 h-1
in the present work. Coke deposition can significantly change
the intracrystalline diffusion resistance, increasing the complex-
ity in modeling of the formation and consumption of DME.
Therefore, methanol and DME are lumped together as oxygen-
ates in our model. The kinetic models for coke deposition and
the conversion of oxygenates were developed in our previous
work,21 in which the conversion of oxygenates was treated as a
first-order reaction. In the present work, the model is explored
to predict the selectivity change with coke formation. The
TEOM reactor is treated as an ideal isothermal plug flow reactor
containing 5-10 mg of catalyst. The integral model for
methanol conversion is used in the present work, but an
approximation has been made to assume uniform distribution
of coke in the catalyst bed. The experimental coke contents were
used to fit the parameters in the deactivation functions. In the
model, all mole fractions are calculated on a dry basis, that is,
on the basis of CH2 equivalents.
The reactor models can be expressed as
b
dx
)b
r (3)
d(W/FMeOH)
The kinetic model for the reaction network presented in Figure
2 is expressed as follows,
ri ) k0i φiy6P0 for i ) 1-5
5
r6 ) ( ∑
i)1
k0i φi)y6P0 (5)
 Ind. Eng. Chem. Res., Vol. 46, No. 12, 2007 4121

Table 1. Reaction Rate Constants, k0i ; Deactivation Rate Constants, ri, at Different Temperatures and Parameters for Arrhenius Equation ki0 )
Ai exp(-Ei/RT)
T, °C
400 425 500 550 Ai (kmol/gcat, kPa, h) E (kJ/mol)
k01 0.22 ( 1 × 10-2 0.25 ( 1 × 10-2 0.55 ( 5 × 10-2 0.755 ( 6 × 10-2 7210 38.4
k02 0.35 ( 1 × 10-2 0.31 ( 1 × 10-2 0.67 ( 5 × 10-2 0.76 ( 6 × 10-2 40 27.0
k03 0.13 ( 1 × 10-2 0.11 ( 1 × 10-2 0.23 ( 5 × 10-2 0.28 ( 5 × 10-2 15 26.9
k04 0.038 ( 2 × 10-2 0.035 ( 2 × 10-3 0.087 ( 1 × 10-2 0.104 ( 2 × 10-2 17 49.8
k05 0.008 ( 9 × 10-3 0.011 ( 6 × 10-3 0.017 ( 1 × 10-2 0.030 ( 9 × 10-3 5 32.4
k07 0 0.006 ( 5 × 10-3 0.020 ( 1 × 10-2 0.028 ( 9 × 10-2 181 59.6
R1 0.038 ( 1 × 10-3 0.049 ( 3 × 10-4 0.054 ( 3 × 10-3 0.063 ( 1 × 10-3
R2 0.041 ( 1 × 10-3 0.052 ( 3 × 10-4 0.059 ( 2 × 10-3 0.066 ( 1 × 10-3
R3 0.040 ( 2 × 10-3 0.052 ( 8 × 10-4 0.054 ( 4 × 10-3 0.058 ( 3 × 10-3
R4 0.050 ( 8 × 10-3 0.060 ( 6 × 10-4 0.060 ( 1 × 10-2 0.062 ( 6 × 10-3
R5 0.115 ( 4 × 10-2 0.114 ( 3 × 10-2 0.059 ( 1 × 10-2 0.065 ( 1 × 10-2
R7 0.066 ( 3 × 10-2 0.066 ( 2 × 10-2 0.057 ( 3 × 10-2 0.072 ( 2 × 10-2

where i ) [ethene, propene, butenes (C4), C5, C6, oxygenates,
ethane + propane]. The formation of paraffins (ethane and
propane) was treated as a secondary reaction of all hydrocarbons.
The rate of formation is described by eq 6,
r7 ) k07φ7(1 - y6)P0
where k0i is the initial rate constant, φi is the deactivation
function, P0 is the initial methanol partial pressure, and yi is
the mole fraction on a CH2 basis.
All rate constants are assumed to depend on the catalyst coke
content, which is taken into account by the deactivation
functions, φi. Different deactivation functions42,43 have been tried
to describe the change in reaction rates with coke content. The
linear function (eq 7) was found to give the best fit to the
experimental data.
B
φ)1-R
bC
C is the weight percent of coke on the catalyst (gcoke/gcat %). It
should be noted that the experimental relationship between the
deactivation and the coke content is not perfectly linear, as
shown in Figure 7B. It follows a curve of a decrease in
effectiveness factor with increasing Thiele modulus. A rigorous
modeling, including intracrystalline diffusion and changes with
coke deposition, will be necessary in the future to perfectly
simulate the deactivation function of this system.
As mentioned above, selective deactivation for the MTO
reaction over SAPO-34 was found. The different reaction steps
have different deactivation rates, that is, different Ri values. The
effect of coke on the selectivity, that is, the ratio of the reaction
rates, can now be modeled by using different values for the
empirical Ri constants.
A fourth-order Rung-Kutta method was used to integrate
the ordinary differential equations. The estimation of the
parameters of the kinetic model has been carried out by the
nonlinear least-squares routine in MATLAB using the Leven-
berg-Marquardt method. The optimum function is given in eq
8,
n m
S) ∑ ∑ wij[(yiPR) - (yiEXP)]
i)1 j)1
individual parameters was tested by t-test, and the standard
deviation of each parameter was also calculated in a 95%
confidence interval.42 All the parameters in the model have been
estimated separately at different temperatures. Reaction and
deactivation rate constants together with their standard deviations
(6) are listed in Table 1. Statistical analysis indicated that the overall
regression is meaningful.
The empirical deactivation rate constant R follows the order
of the molecular size. Larger molecules have larger changes in
selectivity with coke content and, thus, a higher deactivation
rate. This may point out the importance of the effect of
transition-state shape selectivity on the product selectivity.37 The
standard deviation for R5 and R7 is relatively large. It is mainly
due to the relatively large experimental error for the analysis,
since the mole fractions of C6, ethane, and propane are very
low in most of the experiments.
Figure 8 shows an Arrhenius plot of the initial kinetic rate
(7) constants for the formation of the various products. The rate
constants fitted Arrhenius law well. The estimated apparent
activation energies and pre-exponential factors are presented
in Table 1.
Figure 9 shows the comparison between experimental and
predicted mole fractions for each component. The rate constants
were calculated from the Arrhenius equation using the param-
eters presented in Table 1. The model fitted the experimental
results generally well at all temperatures, except for C6. The
reason for the deviation in predicting the C6 mole fraction is at
least partly due to the relatively large experimental error in the
GC analysis, since the mole fraction of C6 is very low, especially
at relatively high coke contents. The same argument also holds
for methane. The mole fraction of methane is very low at the
conditions used in the present work. In addition, a very small
fraction of methane was founded in a few blank experiments,
possibly caused by decomposition of methanol on the metal
(8)

where index i indicates the component considered; index j,

the kinetic run; yiPR and yiEXP are the predicted and experimental
molar fraction for component i; and wij is a weighting factor.
After the parameters was estimated, an extensive statistical
analysis was performed. The significance of the overall regres- Figure 8. Arrhenius plot for reaction rate constants. 9, Ethene; 2, propene;
sion was tested by means of an F-test. The significance of the ×, butenes; [, C5; b, C6.
4122 Ind. Eng. Chem. Res., Vol. 46, No. 12, 2007
Figure 9. Parity plot for mole fraction of olefins. 698 K, methanol partial
pressure of 7.2 kPa and WHSV. 0, 385; ∆, 113; / , 82; ], 57 g (g of
cat)-1 h-1; 773 K, 12 kPa and 266 g (g of cat)-1 h-1, 2; 823 K, 8 kPa bar,
and 268 g (g of cat)-1 h-1, [; 673 K, 7.2 kPa and 385 g (g of cat)-1 h-1,
b.
part in the setup. The reproducibility of the methane mole
fraction is relatively poor. It is expected that the experimental
uncertainty is larger at low conversions, such as high coke
contents and low temperatures. Therefore, kinetic modeling of
methane formation is not reported in the present work.
The apparent activation energies for the olefin formation are
relatively low, as shown in Table 1. As discussed previously,27,37
this is due in part to the intracrystalline diffusion limitation.
The intrinsic activation energy can be estimated by accounting
for the effect of diffusion.42 If we assume that MTO was
controlled completely by intracrystalline diffusion, the activation
energy should be 2× the activation energy measured, namely,
76 kJ/mol. The apparent activation energy for ethene formation
is then expected to be between 38 and 76 kJ/mol. However, for
zeolite-catalyzed reactions, the apparent activation energy also
involves the heat of adsorption.43 The real intrinsic activation
energy for the surface reaction is then estimated43 to be between
68 and 106 kJ/mol, taking into account the measured adsorption
heat of 30 kJ/mol for methanol.27 The presence of intracrystalline
diffusion limitation makes it difficult to compare the activation
energy directly with the literature data.
In addition, it is worth mentioning that the estimated initial
rate constant is only an approximation, and the induction period
during which conversion increased with time on-stream or coke
content is ignored in the present work. Induction periods have
been observed during MTO over SAPO-34, and the length of
the induction period depended on the crystal size, temperature,
and concentration of oxygenates.37 For SAPO-34 used in the
present work, the effect of intracrystalline diffusion cannot be
avoided,27 and thus, the induction period is very short. For
example, the induction period measured at 698 K and 30 kPa
methanol partial pressure was about 15-30 s. Hence, ignoring
the induction period should not create a large error.
Conclusions
A reaction network for the MTO reaction has been estab-
lished, DME is a nonstable primary product, all the hydrocar-
bons are formed in parallel from oxygenates, and ethane and
propane are considered to be stable tertiary products. A relatively
simple kinetic model, in which methanol and DME were
lumped, was developed to describe the change in selectivities
with the coke content. Catalyst deactivation was well-described
by a linear relation between the coke content and the reaction
rate. The experimental data fitted the model generally well in
the temperature range of 673-823 K. The secondary reactions
of olefins were not included in this kinetic model, because their
reactivity was low.
The distribution of olefins was not affected by the partial
pressure of methanol and the space velocity, but increasing
temperature and coke deposition increased the ethene selectivity
significantly during MTO over SAPO-34. The effect of coke
on the selectivities is proposed to be a result of transition-state
shape selectivity, favoring the formation of smaller molecules
as the void volume in the cavities is reduced by coke.
Acknowledgment
The support of this work by the Norwegian Research Council
and Norsk Hydro ASA is gratefully acknowledged.
Nomenclature
Ai ) pre-exponential factor for the reaction rate, k0i , kmol (g of
cat, kPa,h)-1
C ) weight percent of coke on the catalyst (g of coke/100 g of
cat)
E ) activation energy, kJ/mol
FMeOH ) molar flow rate of methanol (mol/h)
i ) 1, 2, 3, 4, 5, 6, 7 represents ethene, propene, butenes (C4),
C5, C6, oxygenates, and ethane + propane, respectively.
j ) number of kinetic run
k0i ) initial rate constant for the formation of component i,
kmol (g of cat, kPa,h)-1
P0: initial methanol partial pressure, kPa
b
r ) [r1, r2, r3, r4, r5, r6, r7]; matrix of reaction rate, kmol (g of
cat, h)-1
ri ) rate of formation of I, kmol (g of cat,h)-1
S ) objective function
W ) catalyst loading, g of cat
wij ) weighting factor.
b
x ) [x1, x2, x3, x4, x5, x6, x7]; matrix of conversion
xi ) conversion to i
yi ) mole fraction of component i on a CH2 basis
yiEXP ) experimental molar fraction for component i
yiPR ) predicted molar fraction for component i
Ri ) empirical deactivation constant for the reaction corre-
sponding the formation of i defined by eq 7
φi ) deactivation function for the formation of component i
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ReceiVed for reView August 15, 2006
ReVised manuscript receiVed October 19, 2006
Accepted October 20, 2006
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