Ind. Eng. Chem. Res.

2001, 40, 4187-4196 4187

Kinetic Modeling of the Methanol to Olefins Process. 2.

Experimental Results, Model Discrimination, and Parameter
Estimation
Tae-Yun Park† and Gilbert F. Froment*,‡
Laboratorium voor Petrochemische Techniek, Universiteit Gent, Krijgslaan 281, B-9000 Gent, Belgium

The methanol to olefin process on ZSM-5 was studied in an integral tubular reactor at
atmospheric pressure and over a temperature range of 360-480 °C. Eight kinetic models based
upon the elementary steps of the conversion of methanol over dimethyl ether into olefins were
tested. They contained more than 30 parameters. The model parameters were transformed to
include the physicochemical constraints in the parameter estimation itself, instead of accounting
for these a posteriori. The estimation was performed by the genetic algorithm, followed by the
Levenberg-Marquardt routine, but in combination with sequential quadratic programming to
account for the constraints. The finally retained model corresponds to a mechanism that proceeds
over oxonium methylide formed from a methoxy ion interacting with a basic site of the catalyst.
The ylide subsequently reacts with dimethyloxonium ions to generate in parallel the primary
products ethylene and propylene. Through steps of carbenium ion chemistry, the latter lead to
higher olefins but also, to a lesser extent, to paraffins and aromatics.

Introduction
In the first part of this work, the chemical pathways
leading from methanol to olefins were detailed in their
elementary steps and eight rival kinetic models were
developed based on the steps leading to the formation
of the primary products: methane, ethylene, and pro-
pylene out of methanol and dimethyl ether (DME).
Higher olefins, paraffins, and aromatics are formed by
a very large number of elementary steps of carbenium
ion chemistry. The kinetics of these steps were written
in terms of single events so as to limit the number of
independent parameters. In this second part, the model
discrimination and parameter estimation is dealt with,
starting from experimental data obtained with a ZSM-5
catalyst.
Catalyst Synthesis and Characteristics
ZSM-5 was synthesized as described by Jacobs and
Martens.1 Reagents were silicon oxide (Aerosil, De-
gussa), NaAl2O2H2O (BHD Chemicals), sodium hydrox-
ide (Baker analyzed reagent), tetrapoly(ammonium
bromide) (TPABr; Fluka), and concentrated sulfuric acid
(Baker). The specific silicon/aluminum ratio was ob-
tained by adjusting the aluminum content in the
synthesis mixture (silicon/aluminum ) 200). The crys-
talline product was dried at 80 °C and calcined in static
air at 550 °C for 12 h. NaHZSM-5 was acidified by ion
exchange with NH4NO3 (1.0 N) for 3 h under total
reflux. The zeolite was identified as highly crystalline
ZSM-5 by X-ray diffraction and by scanning electron
* To whom correspondence should be addressed.
† Present address: Catalytica Energy Systems, Inc., 430
Ferguson Drive, Mountain View, CA 94043-5272. Tel: +1-650-
940-6217. Fax: +1-650-618-1454. E-mail: taeyun@mail.com.
‡ Present address: Department of Chemical Engineering,
Texas A&M University, College Station, TX 77843-3122. Tel:
+1-979-845-3361. Fax: +1-979-845-6446. E-mail: g.froment@
ChE.tamu.edu.
10.1021/ie000854s CCC: $20.00 © 2001 American Chemical Society
Published on Web 06/16/2001
microscopy. The particle size was less than 10 µm. The
surface area was on the order of 400 m2/g. The catalyst
powder was pelletized by pressing it into wafers at 375
kg/cm2. It was then crushed and screened to 0.5-1.0
mm.
Experimental Setup and Procedure
The experimental setup is shown in Figure 1. During
reaction the reactor is immersed in a molten salt bath,
but for the conditioning of the catalyst, it is lifted by an
oil system into an infrared-heated furnace. This com-
bined unit has been described in detail by Lox et al.2
The reactor tube itself has a length of 0.27 m and an
internal diameter of 0.0214 m. For the experiments at
temperatures above 450 °C, a titanium reactor was used
to avoid methanol decomposition. The catalyst bed was
diluted with inert oxide beads (5 vol. of beads inert/1
vol. of catalyst). The catalyst was pretreated by heating
it at 120 °C/h to 550 °C in a nitrogen flow (30 mL/min).
Achieving steady state after a change in operating
conditions took something like an hour. Catalyst de-
activation was slow and not noticed before at least 5 h
of operation. The catalyst was carefully regenerated in
air at 550 °C to avoid excessive hot spots. The initial
activity was completely recovered, even after some 50
regenerations.
The reactor effluent was analyzed on-line by means
of a Carle CGC 500. The C4+ hydrocarbons were
separated on a capillary column RSL-160 with a length
of 30 m and identified by means of a flame ionization
detector. Light hydrocarbons, water, and the internal
standard, nitrogen, were separated by a series of packed
columns and detected by a thermal conductivity detector
(TCD). Hydrogen was quantitatively transferred from
the carrier gas, helium, into a nitrogen flow and detected
by a separate TCD. Peak processing was carried out by
a process and a personal computer. For more detailed
analysis of the isomers, a liquid sample of the C6+
hydrocarbons was analyzed by GC-MS. The use of an
4188 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001

Figure 1. Experimental fixed-bed setup for the kinetic study of the MTO process.

Figure 2. Methanol conversion vs space time at various temper-

atures.

internal standard allowed mass balances to be checked.

In all cases the closure exceeded 97%.
The kinetic data were collected at various settings of
temperature, inlet partial pressures of methanol, and
space time, τ ()W/FMeOH°). The experiments were
performed at five different temperatures in the range
of 360-480 °C. Depending on the temperature, the
space time ranged from 0.1 to 7 gcat‚h/mol. The total
pressure inside the reactor, pt, was 1.04 bar for all of
the experiments. The initial partial pressure of metha-
nol was varied by diluting the methanol feed with
bidistilled water and nitrogen. The total number of
Figure 3. Selectivities for DME, olefins, and parafins + aromatics
as a function of methanol conversion at 440 °C and a total pressure
of 1.04 bar. Feed: methanol.
experiments amounted to 222. A few were duplicated,
mainly for the purpose of collecting statistical informa-
tion. For the selected experimental conditions, internal
and external heat- and mass-transfer limitations were
insignificant, mainly because of the small particle size
of the catalyst. The test calculations3 were based on gas
 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001 4189

Figure 4. Yields of MTO products vs space time.

Table 1. Definition of the Parameters To Be Estimated after the Reparametrization of Rate and Equilibrium Constants
Pi definition Pi definition
P1 ∆SPr°(MeOH)/R - ∆HPr°(MeOH)/RTm P 18 +
Esr(OM;DMO+:R2)/R
P2 ∆HPr°(MeOH)/R P 19 ln Asr(OM;DMO+:R+ + +
3 )-Esr(OM;DMO :R3 )/RTm
P3 ∆SHyd°(R+ +
1 )/R - ∆HHyd°(R1 )/RTm
P 20 Esr(OM;DMO+:R+ 3 )/R
+
P4 ∆HHyd°(R1 )/R P 21 ln APr(O2) - EPr(O2)/RTm
P5 ln AC(R+ +
1 ) - EC(R1 )/RTm
P 22 EPr(O2)/R
P6 EC(R+1 )/R P 23 ∆S̃Pr/R
P7 ln AF(DME) - EF(DME)/RTm P 24 ∆HPr°(O2)/R
P8 EF(DME)/R P 25 ∆HPr°(O3)/R
P9 ∆SPr°(DME)/R - ∆HPr°(DME)/RTm P 26 ∆HPr°(O4r)/R
P 10 ∆HPr°(DME)/R P 27 ∆HPr°(O5r)/R
P 11 ln AF(CH4) - EF(CH4)/RTm P 28 ∆HPr°(O6r)/R
P 12 EF(CH4)/R P 29 ∆HPr°(O7r)/R
P 13 ln Asr(R+ +
1 ;bs) - Esr(R1 ;bs)/RTm
P 30 ∆HPr°(O8r)/R
P 14 Esr(R+1 ;bs)/R P 31 t
ln(CH +Ã)

P 15 ln Asr(OM;H+) - Esr(OM;H+)/RTm P 32 R
P 16 Esr(OM;H+)/R P 33 E°/RR
P 17 ln Asr(OM;DMO+:R+ + +
2 ) - Esr(OM;DMO :R2 )/RTm

mixtures containing methanol, DME, and olefins with Reparametrization

up to eight carbon atoms.
Experimental Results
Figure 2 shows the conversion of methanol as a
function of space time, represented by τ, and Figure 3
typical selectivities (number of moles formed per 100
mol of methanol reacted) of DME, olefins, (from C3 to
C8), and aromatics (from C6 to C10) as a function of
methanol conversion. DME is rapidly formed out of
methanol but also rapidly consumed. The major prod-
To reduce the correlation between preexponential
factors and activation energies, reparametrization has
been applied.6 The Arrhenius form of the rate coefficient
is given by
ki ) Ai exp(-Ei/RT) (1)
After introduction of the mean temperature, Tm, the rate
coefficients for the formation of primary products can
be written as

[( ) ( )]
ucts are olefins, but the selectivity toward olefins
reaches a maximum around a methanol conversion of Ei Ei 1 1
ki ) exp ln Ai - - - (2)
95%. The production of paraffins and aromatics is RTm R T Tm
negligible as long as the methanol conversion is kept
below 70%. Figure 4 shows yields (grams formed per Note that the total concentration of acid and/or basic
100 g of methanol fed) versus the space time based upon t t
sites (CH + or Cbs) is incorporated into the rate coef-
methanol. The main product is propylene, while the ficient given in eqs 1 and 2.
ethylene yield levels off at high space times. Although The rate coefficient (2) can also be written as
it has been reported that methane is one of the main
products at low methanol conversion,4 this is not the
case in this work. Calculations showed that at high
space times the composition of the olefin fraction was
[
ki ) exp P i - P k (1
-
T Tm
1
)] (3)

at equilibrium, confirming literature information.5 in which the temperature-independent parts (ln Ai -

4190 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001

Table 2. List of Physicochemical Constraints for the Parameters of Mechanism a′′

number constraints physical meaning
1 P 25 < P 24 ∆HPr°(O3) < ∆HPr°(O2)
2 P 26 < P 25 ∆HPr°(O4r) < ∆HPr°(O3)
3 P 27 < P 26 ∆HPr°(O5r) < ∆HPr°(O4r)
4 P 28 < P 27 ∆HPr°(O6r) < ∆HPr°(O5r)
5 P 29 < P 28 ∆HPr°(O7r) < ∆HPr°(O6r)
6 P 30 < P 29 ∆HPr°(O8r) < ∆HPr°(O7r)
7 P 3 + P 4/Tm < 0 ∆SHyd°(R+ 1) < 0
8 P 5 + P 6/Tm - ln(kBTminCH t
+/h) < 0 ∆SC°q(R+ 1) < 0
9 P 7 + P 8/Tm - ln(kBTminCH t
+/h) < 0
∆SC°q(DME) < 0
10 P 21 + P 22/Tm - ln(kBTminCH t
+/h) < 0
∆SPr°q(O2) < 0
11 and 12 -S°(MeOH)/R < P 1 + P 2/Tm < -41.8/R -S°(MeOH) < ∆SPr°(MeOH) < -41.8
13 and 14 -S°(DME)/R < P 9 + P 10/Tm < -41.8/R -S°(DME) < ∆SPr°(DME) < -41.8
15 and 16 -S°(O2)/R - ln(σO R2+ O2 R2+
gl /σgl ) < P 23 < - 41.8/R - ln(σgl /σgl )
2 -S°(O2) < ∆SPr°(O2) < -41.8
17 1.4 × 10-3P 2 - (P 1 + P 2/Tm) < 51.04/R 1.4 × 10-3∆HPr°(MeOH) - ∆SPr°(MeOH) < 51.04
18 1.4 × 10-3P 10 - (P 9 + P 10/Tm) < 51.04/R 1.4 × 10-3∆HPr°(DME) - ∆SPr°(DME) < 51.04
19-25 1.4 × 10-3Pj - (P 23 + ln(σO Rir’+
gl /σgl )) < 51.04/R, j ) 22 + i
ir 1.4 × 10-3∆HPr°(Oir) - ∆SPr°(Oir) < 51.04, i ) 2, 3, ..., 8
26∼116 ∆HMe(i,j;P k) < 0, i ) category index, j ) reaction index ∆HMe(i,j) < 0, i ) category index, j ) reaction index
117∼168 ∆HOl(i,j;P k) < 0, i ) category index, j ) reaction index ∆HOl(i,j) < 0, i ) category index, j ) reaction index
169∼259 |∆HMe(i,j;P k)|/R - P 33 < 0, i ) category index, j ) reaction index EMe(i,j) > 0, i ) category index, j ) reaction index
260∼311 |∆HOl(i,j;P k)|/R - P 33 < 0, i ) category index, j ) reaction index EOl(i,j) > 0, i ) category index, j ) reaction index

Ei/RTm) and Ei/R are represented by P i and P k,
respectively. These are the parameters to be estimated,
rather than Ai and Ei.
In a similar way the equilibrium constants involved
in the formation of primary products can be written as
product of R and ∆HMe(i,j). It is known that nonlinear
regression becomes difficult in the presence of nonlinear
constraints.8 To avoid this problem, the rate coefficient
represented in eq 6 was reparametrized as follows:

[
Ki ) exp P l - P m (1
-
T Tm
1
)] (4) kMe(i,j) ) ne(i,j) exp P k - { Pl
T (
Pm-
|∆HMe(i,j)|
R )}
(7)
with P l and P m based on the enthalpy and entropy
changes between reactant(s) and product(s) of the given where P k ) ln(CH t
+Ã), P l ) R, and P m ) E°/RR. The
reaction, i.e. constraint for satisfying positive activation energy now
∆S° ∆H° ∆H° becomes linear:
Pl ) - , Pm) (5)
R RTm R
|∆HMe(i,j)|
The rate coefficients for the formation of higher olefins Pm> (8)
were reparametrized in a different way. They were R
written in terms of the single-event approach and the
Evans-Polanyi relation.7 For instance, the rate coef- The protonation equilibrium constant for the various
ficient for the ith category and the jth methylation is reference olefins is expressed as follows:
given by
σO ir
1
KPr(Oir) )
gl

σRglir'
+ ( )
exp P j - P k , i ) 2, 3, ..., 8
T
(9)

where P j ) ∆S̃Pr/R and P k ) ∆HPr°/R.

The E° - R|∆HMe(i,j)| should be positive, because it
represents the activation energy for the given elemen-
tary step. In addition, the heat of formation, ∆HMe(i,j),
contains the protonation enthalpies of the reference
olefins, which have to be estimated also. The reparam-
etrization described in eqs 3-6 was applied to the rate
and equilibrium constants of the eight rival kinetic
models. As an example, the definition of the 33 param-
eters P i of the kinetic model based upon mechanism
a′′ is shown in Table 1.
Physicochemical Constraints
The condition that E° - R|∆HMe(i,j)| should be positive
leads to a nonlinear constraint, resulting from the
According to the differences in stability between
cations established in carbenium ion chemistry, the
protonation enthalpies of the various reference olefins
have to satisfy the following relationship:
∆HPr°(O8r) < ∆HPr°(O7r) < ... < ∆HPr°(O3) <
∆HPr°(O2) (10)
The enthalpy differences in the various protonation
processes are mainly determined by the differences in
the heat of formation of the various carbenium ions,
while the olefins are highly stable species, so that the
contribution of the difference in the heat of formation
for the various olefins is negligible compared with that
of the carbenium ions.
The physicochemical relationship given in eq 10 can
readily be expressed in terms of the parameters defined
in eq 9. For the kinetic model based on mechanism a′′
 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001 4191
t
i.e., k ) CH +k′, the following relationship, obtained by
comparing eq 3 with eq 12, imposes a negative ∆S°q:
t
Pk kBTminCH +
Pj+ - ln <0 (13)
Tm h

If the constraint (13) is satisfied at the minimum

Figure 5. General flow diagram of the application of the hybrid
GA to the constrained parameter estimation.
of part 1, the relationship (10) can be written using the
parameters defined in Table 1 as
P30 < P29 < ... < P25 < P24 (11)
temperature, Tmin, it is also satisfied over the complete
temperature range.
For the parameters involved in the protonation steps,
Boudart’s criteria9 define a rigorous set of constraints
for the standard protonation enthalpy (∆HPr°) and
entropy (∆SPr°)
∆HPr° > 0
0 < -∆SPr° < Sg°
41.8 < -∆SPr° < 51.04 + 1.4 × 10-3(-∆HPr°) (14)

The nature of the elementary step provides an ad-
ditional relationship for the entropy of activation, ∆S°q.
For elementary steps of the type A + B f [A‚‚‚B]qf AB,
∆S°q is negative. From the transition state theory, the
rate coefficient for the elementary step can be written
as
where Sg° is the standard entropy of the molecule in
the gas phase. Combining the second and third inequali-
ties provides the range for the protonation entropy:
-Sg° < ∆SPr° < -41.8 (15)

( ) ( )
With the remaining relationship, i.e., ∆SPr° < 51.04 +
kBT ∆S°q E
k′ ) exp exp - (12) 1.4 × 10-3(-∆HPr°), the area of the parameters that
h R RT satisfy the Boudart criteria can be defined. In the case
of the kinetic model based on the mechanism a′′, for
t
If the total concentration of acid sites, CH +, is incorpo- instance, it can be shown from Boudart’s criteria that
rated into the rate coefficient of the elementary step, the parameters related to the protonation of methanol

Figure 6. Performance of the hybrid GA in the estimation of the parameters of the kinetic model based upon mechanism a′′.
4192 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001

Table 3. List of Final Parameters for Retained Mechanism a′′

Pi lower limita estimate upper limita |t value| parameterb values unit
P1 -4.6433 × 100 -3.9404 × 100 -3.2374 × 100 11.21 ∆SPr°(MeOH) -1.3391 × 102 J‚mol-1‚K-1
P2 -8.5333 × 103 -8.3354 × 103 -8.1375 × 103 84.25 ∆HPr°(MeOH) -6.9305 × 101 kJ‚mol-1
P3 -4.9843 × 100 -4.2179 × 100 -3.4514 × 100 11.01 ∆SHyd°(R+ 1)
-8.5028 × 101 J‚mol-1‚K-1
P4 -4.1758 × 100 -4.1168 × 103 -4.0578 × 103 139.50 ∆HHyd°(R+ 1)
-3.4229 × 101 kJ‚mol-1
P5 3.1244 × 100 3.8080 × 100 4.4916 × 100 11.14 AC′(R+1)
9.3907 × 105 s-1‚bar-1
P6 5.8509 × 103 5.9878 × 103 6.1247 × 103 87.47 EC(R+ 1)
4.9786 × 101 kJ‚mol-1
P7 1.8134 × 101 1.8561 × 101 1.8987 × 101 87.05 AF′(DME) 1.2343 × 109 s-1‚bar-1
P8 7.7518 × 100 8.0004 × 102 8.2492 × 102 64.34 EF(DME) 6.6520 × 100 kJ‚mol-1
P9 -3.8957 × 100 -3.3374 × 100 -2.7792 × 100 11.96 ∆SPr°(DME) -8.6317 × 101 J‚mol-1‚K-1
P 10 -4.9289 × 103 -4.8263 × 103 -4.7237 × 103 94.08 ∆HPr°(DME) -4.0128 × 101 kJ‚mol-1
P 11 2.8721 × 10-1 7.1901 × 10-1 1.1508 × 100 3.33 AF′(CH4) 1.3978 × 1010 s-1‚bar-1
P 12 1.4284 × 104 1.4687 × 104 1.5090 × 104 72.89 EF(CH4) 1.2212 × 102 kJ‚mol-1
P 13 8.3370 × 100 9.0938 × 100 9.8569 × 100 23.83 Asr′(R+1 ;bs)
7.1483 × 1017 s-1
P 14 1.6298 × 104 1.6574 × 104 1.6850 × 104 120.20 Esr(R+1 ;bs)
1.3781 × 102 kJ‚mol-1
P 15 8.2304 × 100 9.0800 × 100 9.9296 × 100 21.38 Asr′(OM;H+) 2.3491 × 1014 s-1
P 16 1.0904 × 104 1.1088 × 104 1.1273 × 104 120.31 Esr(OM;H+) 9.2193 × 101 kJ‚mol-1
P 17 7.9092 × 100 8.3949 × 100 8.8806 × 100 34.57 Asr′(OM;DMO+:R+2)
7.7433 × 108 s-1
P 18 2.8230 × 103 2.9090 × 103 2.9950 × 103 67.64 Esr(OM;DMO+:R+ 2)
2.4187 × 101 kJ‚mol-1
P 19 7.2316 × 100 7.7135 × 100 8.1955 × 100 32.01 Asr′(OM;DMO+:R+3)
9.7050 × 1011 s-1
P 20 8.1202 × 103 8.2635 × 103 8.4068 × 103 115.33 Esr(OM;DMO+:R+ 3)
6.8707 × 101 kJ‚mol-1
P 21 -8.7386 × 100 -8.1645 × 100 -7.5950 × 100 28.45 APr′(O2) 8.5785 × 105 s-1‚bar-1
P 22 1.3916 × 104 1.4129 × 104 1.4342 × 104 132.87 EPr(O2) 1.1748 × 102 kJ‚mol-1
P 23 -8.9252 × 100 -8.4304 × 100 -7.9357 × 100 34.08 ∆S̃Pr -7.0095 × 101 J‚mol-1‚K-1
P 24 -2.3453 × 103 -2.3008 × 103 -2.2563 × 103 103.40 ∆HPr°(O2) -1.9130 × 101 kJ‚mol-1
P 25 -9.4422 × 103 -9.3039 × 103 -9.1656 × 103 134.55 ∆HPr°(O3) -7.7358 × 101 kJ‚mol-1
P 26 -9.9335 × 103 -9.9335 × 103 -9.6959 × 103 81.59 ∆HPr°(O4r) -8.0616 × 101 kJ‚mol-1
P 27 -1.0488 × 104 -1.0488 × 104 -1.0371 × 104 176.73 ∆HPr°(O5r) -8.6230 × 101 kJ‚mol-1
P 28 -1.4485 × 104 -1.4235 × 104 -1.3985 × 104 113.98 ∆HPr°(O6r) -1.1836 × 102 kJ‚mol-1
P 29 -1.4767 × 104 -1.4585 × 104 -1.4404 × 104 160.61 ∆HPr°(O7r) -1.2127 × 102 kJ‚mol-1
P 30 -1.4962 × 104 -1.4626 × 104 -1.4290 × 104 87.06 ∆HPr°(O8r) -1.2161 × 102 kJ‚mol-1
P 31 1.4451 × 101 1.5390 × 101 1.6328 × 101 32.80 Ã′ 1.6111 × 107 s-1‚bar-1
P 32 3.2348 × 10-2 3.4304 × 10-2 3.6259 × 10-2 35.09 R 3.4304 × 10-2 dimensionless
P 33 3.3719 × 105 3.4183 × 105 3.4647 × 105 147.40 E° 9.7496 × 101 kJ‚mol-1
a Approximate 95% confidence limit. b Original parameters included in the reparametrized form.

defined in Table 1 should satisfy the following inequali- should be satisfied:

ties:

-
S°(MeOH)
< P1 +
P2
<-
41.8 Pk -
Pl
T
Pm-(|∆HMe(i,j)|
R
>0 ) (18)
R Tm R
A similar constraint can be written for the activation
-3
1.4 × 10 P2 - P1 + (
P2
Tm
<
51.04
R ) (16)
energy for oligomerization. In the case of β scission, the
relationship (18) is not necessary, because it has been
shown in part 1 that the rate coefficients for the
elementary steps of β scission are not independent: they
The range of ∆SPr° for methanol protonation can be
are calculated from the rate coefficients and the equi-
obtained from eq 16, but generally the range of ∆HPr°
librium constants of protonation. For the kinetic model
is not available. A range extending from 0 to -200 kJ/
based upon mechanism a′′, a total of 311 linear physi-
mol has been selected. The Boudart criteria have been
cochemical constraints, given in Table 2, has been
applied to all of the protonation processes occurring in
implemented.
MTO elementary steps, which include the protonation
of methanol, DME, and various olefins.
The heat effect of the elementary steps of methylation Objective Function
and oligomerization should be negative, and this has
been imposed as another physicochemical constraint. The objective function to be minimized in the estima-
Because the calculation of the heats of formation of tion of the kinetic parameters was based upon the
those elementary steps involves the protonation enthal- difference between experimental and calculated yields
pies of olefins, this constraint leads to of the MTO products:
nrespnresp nexp
∆HMe(i,j,P k) < 0
FM(P j) ) ∑∑ ∑ σhk
(yih - ŷih(P j))(yik - ŷik(P j))
∆HOl(i,j,P k) < 0 (17) h)1 k)1
i)1
(19)
Because of the large number of elementary steps, This is the generalized least-squares criterion, derived
eq 17 generates a large number of constraints. from the maximum likelihood criterion, as reviewed by
The activation energies of each elementary step of Froment and Hosten.10 It is thereby assumed that the
methylation should be positive. Therefore, with the differences between experimental and calculated yields
parameters defined in eq 7, the following inequality are normally distributed with zero mean and that those
 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001 4193

associated with the hth and kth responses are inde-

pendent. The σhk are usually unknown, but they can be
estimated for each response from replicated experi-
ments.3 In the present study, however, the σhk are
considered to be weighting factors which more or less
equilibrate the contributions of the different yields in
the objective function. The weighting factor for the hth
response is defined as

nexp

( ∑
i)1
yih)-$
(σhh)-1 ) (20)
nresp nexp

∑ (∑yik)
k)1 i)1
-$

Figure 7. Experimental (points) and calculated ethylene yields

For $ ) 1, the weighting factors express the relative for mechanisms a′, a′′, and b′ (curves).
importance of the responses, while for $ ) 0, all of the
responses are equally weighted. In the present study,
a value of 0.3 has been used for O7, O8, and methane.
For the rest of the responses, $ has been set to 1. The
predicted responses, ŷi(P j) in eq 19, are calculated from
the continuity equations for the components i in the
integral plug-flow reactor, dFi/dW ) Ri. Because of the
stiff character of the set, resulting from the very fast
rate of formation of DME, Gear’s method11 was used for
the integration of the set.

Constrained Parameter Estimation

To avoid getting trapped in local minima, the param-
eters of the various rival models were estimated in a
first step using the hybrid genetic algorithm (GA)
developed by Park and Froment.12 To increase their
accuracy, the parameter values thus obtained were used
in a second step as initial guesses for the local optimizer.
Because the Levenberg-Marquardt algorithm is an
unconstrained optimization algorithm, a sequential
quadratic program, called FFSQP,13 was used to account
for the constraints listed in Table 2, but the ultimate
parameter estimation was carried out by the Leven-
berg-Marquardt technique.
Figure 5 shows a flow diagram of the complete
estimation procedure. Before the set of parameters
obtained from the GA search is inserted as an initial
guess into the constrained optimizer FFSQP, it is
checked if the parameters satisfy the physicochemical
constraints listed in Table 2. The final estimation is
performed by the Levenberg-Marquardt algorithm,
after which it is checked whether the statistical criteria
(F test on the model and t test on the parameters) and
the physicochemical constraints are still satisfied. If this
is not the case, the procedure returns to the initial
search by the GA.
Figure 6 illustrates the application of the procedure
to the kinetic model derived from mechanism a′′. Three
steps enter in the generation of the initial guess by the Figure 8. Experimental (points) and calculated yields (curves)
GA, as shown in part a of Figure 6, illustrating the for various MTO products vs space time.
evolution of the objective function for the best set of
parameters as a function of the number of GA iterations. lower than 105, is the corresponding set of parameters
In the upper region, the GA is searching for the set of accepted as an initial guess for the local optimization.
parameters satisfying all of the physicochemical con- This is shown in the lower region (part a) of Figure 6.
straints listed in Table 2. Once such a set is found, the In part b of this figure, the performance of the local
GA starts solving the coupled nonlinear differential optimization by the FFSQP and Levenberg-Marquardt
equations (21) to obtain the values of the objective routines is illustrated. Sets of parameters are retained
functions for each set of parameters. Only when the as initial guesses for the local optimizers only when the
value of the objective function is sufficiently low, i.e., current value of the objective function has been suf-
4194 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001
Figure 9. Parity plots for various products for temperatures ranging from 360 to 480 °C, a total pressure of 1.04 bar, and space time
ranging from 0.2 to 2 gcat‚h/mol. Feed: MeOH (+ N2 + H2O).
ficiently improved. The number of iterations performed
by the local optimizers is also listed in Figure 6.
Although the set of parameters estimated from the
initial guess (5) shown in part b was found to satisfy
all of the physicochemical constraints as well as the
statistical tests, the hybrid procedures were continued
until the selected number of GA iterations was com-
pleted. This policy was chosen to confirm that the
parameter estimates derived from the initial guess (5)
truly correspond to the global minimum. More than 100
different initial guesses generated by the GA have been
tried, but none outperformed the initial guess (5). The
bias curve shown in part c of Figure 6 did not reach a
value higher than 0.7 until 120 GA iterations, confirm-
ing that more than half of the sets of parameters in the
group is still distributed over the whole parameter
space. The off-line performance shown in part c of
Figure 6 evolves quite satisfactorily over the GA search,
comprising 120 iterations. The number of parameter
sets used in this run amounted to 1000. The crossover
and mutation probability were 0.10 and 0.005, respec-
tively. Because of the large amount of calculation
required for the evaluation of the objective function, not
all of the 222 data sets were used in the model
discrimination and parameter estimation. A careful
selection reduced this set to 31, thus yielding a degree
of freedom of 246 (31 experiments × 9 responses - 33
parameters).

Results and Discussion
Table 3 shows the set of parameters involved in the
kinetic model based on the mechanism a′′, which is the
retained model. The parameter estimates satisfy all of
the physicochemical constraints listed in Table 2. As
shown in Table 3, the calculated t values confirm that
all of the parameters are statistically significant. The
calculated F value was 1.1 × 106. The absolute values
of the binary correlation coefficients between param-
eters were generally lower than 0.3. The rate of forma-
tion of DME, out of DMO+, itself formed by methylation
of methanol (viz., step i.4 of Table 1 of part 1), is
extremely rapid, even at low temperature (E ) 6652
J/mol). The rate coefficient of R+ 2 formation out of
oxonium ylide, OM, and DMO+ (step iii.a′′.2 in Table 1
of part 1) exceeds that of R+ 3 formation out of the same
reactants (viz., step iii.a′′.4 in Table 1 of part 1) at low
temperatures, but not any more above 485 °C, because
of the higher activation energy of the latter step (68.71
kJ/mol versus 24.19 kJ/mol for the former). The forma-
tion of methane is slow and requires an activation
energy of 122 kJ/mol. The ∆HPr° of the reference olefins
evolves from -19.13 kJ/mol for O2, over -77.3 kJ/mol
for O3, to -121.61 kJ/mol for O8r.
The difference between the rival kinetic models
originates from different pathways for the formation of
the primary products of the MTO process. Ethylene is
the common primary product for all of the kinetic
models, whereas in some models propylene is a second-
ary product only, formed out of ethylene. The evolution
of the experimental yield of ethylene as a function of
space time is S-shaped. Only three kinetic models out
of eight were found to predict ethylene yields that come
close to the experimental value, and these are given in
Figure 7. The kinetic models based on trimethyloxonium
as a central intermediate could not reproduce such a
shape, as exemplified by the kinetic model based upon
mechanism b′. The calculated ethylene yield curves
reflect the experimental trend only when the kinetic
model is based on the oxonium methyl ylide mechanism
[(a-a′-a′′) of part 1]. Among them, the model based on
the mechanism a′′ gave the best fit of the experimental
ethylene yield. Although the kinetic model based upon
mechanism a, which is the original mechanism sug-
gested by Hutchings and Hunter,4 leads to an S-shaped
curve, the predicted values of the ethylene yield were
too low. The kinetic model based upon the mechanism
a′′ with the set of parameters given in Table 3 also
yielded an excellent fit of the complete product spec-
trum, as shown by way of example for the data obtained
at 440 °C in Figures 7 and 8. Figure 9, finally, presents
parity plots of the various MTO products for the
complete range of experimental conditions covered by
the data used for the model discrimination and param-
eter estimation.
Conclusion
A carefully selected set of experiments allowed one
to significantly determine 33 parameters in each of a
number of kinetic models derived from a detailed
mechanistic description of the MTO process. The pa-
rameter estimation involved the minimization of a
multiresponse objective function by nonlinear regres-
sion. This is a substantial effort comprising a combina-
tion of the GA and the Levenberg-Marquardt routine
Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001 4195
but also sequential quadratic programming to account
for the 311 physicochemical constraints. These were
introduced into the optimization proper rather than
verified a posteriori. The procedure led to a clear-cut
discrimination between eight rival models and retained
a model in which the formation of the primary products
ethylene and propylene resulted from a reaction be-
tween oxonium methyl ylide and dimethyloxonium ion.
The production of higher olefins proceeds over elemen-
tary steps of carbenium ion chemistry, and their kinetic
formulation made use of the single-event concept and
the Evans-Polanyi relationship. The model yields an
excellent fit of the experimental data, as evidenced by
the parity plots and the statistical F test. The param-
eters all satisfied the statistical t test.
A tool is now available for an optimal design and
operation of the MTO reactor and for a more oriented
specification of the desired properties of an MTO
catalyst.
Notation
Ai ) preexponential factor of an elementary step i incor-
porating Ctbs and/or CHt
+
Ãi ) single-event preexponential factor of reaction type i
Ctbs ) total concentration of basic sites, mol/gcat
t
CH + ) total concentration of acid sites, mol/gcat
Ea° ) intrinsic activation barrier in the Evans-Polanyi
relation, J/mol
Ei ) activation energy of reaction type i
FM ) multiresponse objective function
h ) Plank constant: 1.841 × 10-37, J‚h
Ki ) equilibrium constant of an elementary step i
kB ) Boltzmann constant: 1.381 × 10-23, J/K
ki′ ) rate coefficient of an elementary step i
kMe(i,j) ) rate coefficient of methylation in category i, and
reaction j, incorporating CHt
+
kMe′(i,j) ) rate coefficient of methylation in category i and
reaction j
ki ) rate coefficient of step i, incorporating CH t t
+ and/or Cbs
k̃ ) single-event rate coefficient
ne ) number of single events
nexp ) number of experiments
nresp ) number of independent responses
nprm ) number of parameters to be estimated
Oij ) olefin with carbon number i (i ) 2, 3, ..., 8) and isomer
index j
P ) parameters to be estimated after reparametrization
of rate and equilibrium constants
R+ ij ) carbenium ion with carbon number i (i ) 1, 2, ..., 8),
and isomer index j
Ri ) net reaction rate for gas-phase species i, mol/gcat‚h
R ) gas constant: 8.314, J/mol‚K
r(i) ) reaction rate for species i, mol/gcat‚h
ri(j) ) reaction rate of type i for species j, mol/gcat‚h
ri(j,k) ) reaction rate of an elementary step of type i at jth
category and
kth reaction, mol/gcat‚h
S°(i) ) standard entropy of component i, J/mol‚K
T ) temperature, K
Tm ) mean temperature, K
Tmin ) minimum temperature, K
W ) amount of catalyst, gcat
yih ) experimental yield of response h for the ith experi-
ment
ŷih ) calculated yield of response h for the ith experiment
4196 Ind. Eng. Chem. Res., Vol. 40, No. 20, 2001

Greek Letters Observation Concerning the Mechanism of Formation of the

Primary Products. Catal. Today 1990, 6, 279.
R ) transfer coefficient in the Evans-Polanyi relation (5) Quann, R. J.; Green, L. A.; Tabak, S. A.; Krambeck, F. J.
∆HPr° ) heat of protonation, J/mol Chemistry of Olefin Oligomerization over ZSM-5 Catalyst. Ind.
σhk ) element of the inverse of nresp × nresp error covariance Eng. Chem. Res. 1988, 27, 565.
matrix (6) Kitrell, J. R. Mathematical Modeling of Chemical Reactions.
∆S°q ) standard entropy of activation, J/mol‚K Adv. Chem. Eng. 1970, 8, 97.
∆S̃Pr ) protonation entropy excluding symmetry contribu- (7) Vynckier, E.; Froment, G. F. Modeling of the Kinetics of
tion, J/mol‚K Complex Processes based upon Elementary Steps. In Kinetic and
wi ) molecular weight of species i, g/mol Thermodynamic Lumping of Multicomponent Mixtures; Astarita,
G., Sandler, S. I., Eds.; Elsevier Science Publishers BV: Amster-
Subscripts dam, The Netherlands, 1984; p 131.
bs ) basic site (8) Press: W. H.; Flannery, B. P.; Teukolsky, S. A.; Vetterling,
g ) gas phase W. T. Numerical Recipes; Cambridge University Press: New York,
1986.
M ) multiresponse
(9) Boudart, M.; Mears, D.; Vannice, M. A. Ind. Chim. Belg.
m ) mean
1967.
Me ) methylation
(10) Froment, G. F.; Hosten, L. H. Catalytic Kinetics: Model-
Ol ) oligomerization ling. In Catalysis Science and Technology; Anderson, J. R.,
Pr ) protonation Boudart, M., Eds.; McGraw-Hill: New York, 1978.
t ) total (11) Gear, G. W. Numerical Initial Value Problems in Ordinary
Superscripts Differential Equations; Prentice-Hall: Englewood Cliffs, NJ, 1971.
(12) Park, T.-Y.; Froment, G. F. A Hybrid Genetic Algorithm
t ) total for the Estimation of the Parameters in Detailed Kinetic Models.
q ) transition state Comput. Chem. Eng. 1998, 22, S103.
(13) Zhou, J. L.; Tits, A. L.; Lawrence, C. T. A Fortran Code
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Aluminosilicate Zeolites. Stud. Surf. Sci. Catal. 1987, 33, 19. Engineering Department, University of Maryland: College Park,
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