Ind. Eng. Chem. Res.

1992,31, 1035-1040 1035

Kautz, K.; Kirsch, H.; Laufhiitte, D. W. Spurenelementgehalte in
Steinkohlen und den daraus entstehenden Reingassauben. VGB
Kraftwerkstech. 1975,55 (lo), 672-6.
Knbzinger, H. Benetzung im festen Zustand-Ein neuer Weg zur
Herstellung uon oxidischen TrEigerkatalysatoren; Dechema:
Frankfurt, June 1,1990.
Linnros, B. The Crystal Structure of LiMo02Asz0,. Acta Chem.
Scand. 1970,24, 3711-22.
Pertlik, F. Structure Refinement of Cubic Asz03(Arsenolithe) with
Single-Crystal Data. Czech. J. Phys. 1978, B B , 170-6.
Rademacher, J.; Borgmann, D.; Hopfengiirtner, D.; Wedler, G.;
Hums, E.; Spitznagel, G. W. X-Ray Photoelectron Spectroscopic
(XPS) Study of DeNO, Catalysts after Exposure to Slag Tap
Furnace Flue Gas. Appl. Catal. 1992, in press.
Russell, A. S.; Stokes, Jr., J. J. Surface Area in Dehydrocyclization
Catalysis. Ind. Eng. Chem. 1946, 38, 1071-4.
Received for review May 13, 1991
Revised manuscript received August 1, 1991
Accepted October 14,1991

Intrinsic and Global Reaction Rate of Methanol Dehydration over

7-A1203Pellets
Gorazd BerEiEt and Janez Levec*J
Department of Catalysis and Chemical Reaction Engineering, Boris KidriE Institute of Chemistry, and
Department of Chemical Engineering, University of Ljubljana, 61 000 Ljubljana, Slovenia, Yugoslavia

Dehydration of methanol on y-Al,O, was studied in a differential fixed-bed reactor at a pressure

of 146 kPa in a temperature range of 290-360 "C. A kinetic equation which describes a Lang-
muir-Hinshelwood surface controlled reaction with dissociative adsorption of methanol was found
to fit the experimental results quite well. Coefficients in the equation follow the Arrhenius and the
van't Hoff relation. The calculated value for the activation energy was found to be 143.7 kJ/mol,
while calculated values for the heat of adsorption of methanol and water were 70.5 and 42.1 kJ/mol,
respectively. The measured global reaction rates for 3-mm catalyst particles were compared to those
calculated by means of intrinsic kinetics and transport processes within the particles. A reasonable
agreement was found when the effective diffusion coefficients for reaction components were calculated
using a parallel-pore model assuming that only Knudsen diffusion is important.

Introduction Table I. Summary of the Published Rate Equations

Catalytic dehydration of methanol over an acidic catalyst ref eauation
(e.g. y-A1203)offers a potential process for dimethyl ether
(DME)production, which is used as an alternative to freon
spray propellants. In the MTG process, as has been de-
scribed by Chang et al. (1978),the first reactor performs
such a reaction. The open literature provides no infor-
mation on kinetic equations which can be used successfully
in designing a commercial reactor. From the patent lit-
erature (Woodhouse, 1935; Brake, 1986) it can be con-
cluded that reaction takes place on pure y-alumina and
on y-alumina slightly modified with phosphates or tita- Kallo and CM1I2
Knozinger, 1967 -rM =k
nates, in a temperature range of 250-400 "C and pressures + k2Cw
up to 1043 kPa. The kinetics of methanol dehydration on
acidic catalysts has been studied extensively resulting in Sinicyna et al., 1986; kKM2CM2
Gates and -rM = (5)'Vb
different kinetic equations. A summary of the published Johanson, 1971 +
(1 + KMCM K w C W ) ~
equations is presented in Table I. Most of the equations, Figueras et al., 1971 kKMCM'I2
i.e. eqs 4-9, have been derived from the experiments -rM =
conducted in conditions not found in an industrial reactor. 1 + KMCM1/' KwCw +
The experiments were mainly performed with mixtures of Than et al., 1972 ~KMCM
methanol, water, and nitrogen at low vapor pressures. -rM = (7)'
(1 + K M C M ) ~
Since water produced during the reaction considerably Schmitz, 1978 -rM kl + kzCM Wb
retards the reaction rate, the derived rate equations have, Rubio et al., 1980 -rM = klCM1lz- kzCwl/z (9Y
more or less, a semiempirical character and are not suitable
for the industrial reactor design, where reaction takes place 'Acidic ion exchange resin as catalyst. bAlumina or silica-alu-
mina as catalyst.
at high conversion levels. The outlet component concen-
trations correspond to the equilibrium values. However, rates in a pilot-plant reactor where 3-mm catalyst particles
the rate equations (1)-(3) in Table I, which were derived were used. In order to calculate the global reaction rate
for an acidic ion exchange resin as a catalyst and are based the effectiveness factor must be known. Since the intrinsic
on the Langmuir-Hinshelwood (L-H) or the Eley-Rideal kinetic equation is highly nonlinear the effectiveness factor
(E-R) mechanism, can be used for design purposes after can be calculated only numerically.
a reversible term is introduced into the driving-force term.
The aim of this work was to determine an intrinsic rate
equation which can be used to model the global reaction Experimental Section
Catalyst. A Bayer SAS 350 -pAl,O, catalyst support
t Boris KidriE Institute of Chemistry. in the form of 3-mm spheres was employed as a catalyst.
* University of Ljubljana. In order to avoid the intraparticle resistances, spheres were
o a a a - ~ a s ~ ~ ~ ~ ~ ~ s ~ ~ -0i 1992
o ~ ~American
$ o ~ . oChemical
o / o Society
1036 Ind. Eng. Chem. Res., Vol. 31, No. 4, 1992
S u p e r f i c i a l velocity, c m / s
50.00 100.00 150.00
3.00 1 ' 1 1 ' 1 1 1 ' 1 1 1 ' 1 1 1 ' 1 ' " ' 1 ' " 1 ' 1 1 1 1 ' 1 " 1 ' 1 1
>
JZ
T=360"C
T=340C, dP=0.87mm
55wCHsOH
< I
LE
0.00
0.1
! 1
I Fo.00
Particle size, mm
Figure 1. Determination of experimental conditions where external
and internal transport resistances could be neglected.
crushed and sieved. Three different particle sizes were
used 0.87,0.37, and 0.17 mm. Experiments showed that
within the particles of 0.17 mm in size the intraparticle
resistances are negligible.
Reactor. The experiments were carried out in a dif-
ferential reactor (8-mm i.d.) in a temperature range of
290-360 "C. The pressure was kept constant at 146 kPa.
The reactor was operated free of interparticle heat and
mass resistances (Figure 1). The inlet concentrations of
reactants were varied between 15 and 90 mol % for
methanol, and from 0 to 50 mol % for water. In this way
we simulated the conditions which are found at high
methanol conversions in a commercial reactor. In fact, the
produced water strongly retarded the reaction rate. As an
inert gas nitrogen was used. The total inlet volumetric flow
rate was kept constant a t 65.3 cm3/s. Methanol or a
methanol-water mixture was fed into the reactor by means
of a Beckman 114M solvent delivery module; nitrogen flow
was controlled by means of an MKS 246 flow controller.
Methanol was evaporated in a specially designed evapo-
rator that consisted of a 5-m long SS coiled tube (1/4-in.
0.d.). The temperatures of the evaporator and reactor oven
were controlled by microprocessor-based controllers and
were kept within *0.3 "C. In order to achieve the desired
conversions, 2-15%, the mass of the catalyst was varied
between 0.2 and 2.4 g. A database of more than 400 points
was obtained.
Analysis. The analysis was performed by means of a
HP 5890 GC connected to the reactor outlet. The GC
conditions were as follows: a 230-cm X l/s-in. column
packed with Porapak T (100/120 mesh). The carrier gas
He (the flow rate through the column was 18 mL/min and
through the reference 25 mL/min). The detector was a
thermal conductivity detector (TCD) set in the low posi-
tion. The oven temperature was 110 "C for the first 17.5
min, increasing at a rate of 40 "C/min until 130 "C was
reached. The duration of the analysis was 25 min. A gas
sample (0.25 mL) was injected into the GC through a
sampling valve which was kept at 110 "C. The reactant
outlet-gas compositions were determined by the calibration
curve for each component.
The reaction rates were calculated on the basis of the
measured conversions, inlet flow rates of methanol, and
the mass of catalyst in the differential reactor. The
estimated error for the rate was within &7% (BerEiE, 1990).
The observed temperature rise, due the reaction progress
in the differential reactor,varied from 0 to 3 "C, dependent
200.00 250.00 on the outlet conversion and inlet concentration of meth-
0.50
anol. The inlet temperature was adjusted 90 that the mean
E
L
\t
temperature in the differential reactor was kept constant
for all experiments. The maximum systematic error
(Massaldi and Maymo, 1969) can be calculated when an
adiabatic operation of the differential reactor is assumed.
At measured conversions, the calculated systematic error
10.30 was about 3%. Since the reactor was not operated adia-
batically, the true error was even smaller.
1 ; 0.20 E
L
Results and Discussion
Intrinsic Rate Equation. The published rate equa-
tions for dehydration of methanol to DME over alumina
and acidic ion exchange resins are listed in Table I. It is
,g
;
0.10
evident that in almost all rate equations for dehydration
8 the reaction rate is proportional to the square root of the
methanol concentration. This indicates that the dehy-
= dration reaction undergoes dissociative adsorption of
methanol on the catalyst surface. In the derivation of rate
equations for the dehydration of methanol, the L-H con-
cept, which has been further developed by Yang and
Hougen (1950), was applied. With the assumption that
the surface reaction is a controlling step and that the
dissociative adsorption of methanol on the surface of y-
A1203is taking place, the L-H model can be represented
in the following form (BerEiE, 1990):
k&M2(CM2 - cWcE/K)
-rM = (10)
+
(1+ 2(KMCM)l/' KWcW)4
The adsorption term for DME in the denominator of eq
10 was neglected since the DME adsorption constant was
too small compared to the adsorption constants of meth-
anol and water (Gates and Johanson, 1971).
Since the rates of dehydration with pure methanol or
methanol-water mixtures were measured in the differential
reactor, the concentrations of produced dimethyl ether
were low. The reversible term in eq 10 has negligible effect
on the value of driving force; therefore this equation can
be compared to those listed in Table I, which all assume
the reaction is irreversible. The reversible term of the
driving-force term (eq 10) consists of three factors: con-
centrations of water and DME, respectively, and the
equilibrium constant which takes values from about 7 to
11 (at conditions employed here). The mole fraction of
water was varied from 0 to 0.5, while the mole fraction of
DME formed during the reaction course was always in the
order of a few hundredths (since methanol conversion is
low). It was estimated that at the experimental conditions
the reversible term might change the value of the driv-
ing-force term not more than 0.5% in a worst case (typi-
cally less than 0.1%). Since the following inequality ap-
plies CM2>> CwCD/K, what is implied is that the driv-
ing-force term is mainly determined by the concentration
of methanol in the feed and does not depend practically
on the methanol conversion. On the other hand, this term
is important when equations are used for the modeling of
an integrally operated industrial or pilot reactor (where
Cw = CDand at the reactor outlet Cw > CM). In that case
the reversible term along the reactor length increases and
consequently reduces the driving-force term.
The following criteria were used to distinguish between
the kinetic equations shown in Table I: the obtained
constants should be positive numbers, the equation gives
the smallest values for least squares residuals, the coef-
ficients in the equation must follow the Arrhenius and
van't Hoff relation, and the equation should be applicable
for predicting behavior of an integral reactor.
 Ind. Eng. Chem. Res., Vol. 31, No. 4,1992 1037

Table 11. Residuals Obtained with Nonlinear Regression of

Dehydration Rate Equations with Our Experimental
Results"
residuals at given T ("C)
eq 360 "C 340 "C 320 O C 290 "C
1 0.909 0.7792 0.407 0.021b
2 0.639 1.307 1.499 0.250b
3 0.380 0.621 0.558 0.026b
4 7.585 6.862 5.179 O.17gb
5 1.452 1.816 1.972 0.004b
6 5.623 5.565 3.670 0.013b
7 0.023* 0.021* 0.037* 0.021* b
8 0.024* 0.019' 0.034* 0.013*
9 0.006* 0.0031 0.015* 0.002*b
10 0.386 0.690 0.567 0.02tjb
"Values marked with an asterisk indicate that only data for an
inlet mixture of MeOH-N2 were used. Experiments were carried
out with mixtures of MeOH-N2 only. L o ~~~~ ' I I I I I V " 3 ~~~*~~ ' 9

1.56E-003 1 .60EL003 1.64EL003 1 .6SEL003

Equations 1-10 were compared to the experimental re- 1 /T
sults for each temperature, applying the Marquardt non- Figure 2. Arrhenius plots for constants obtained by nonlinear re-
linear regression method (Duggleby, 1984). Since, in the gression for rate eqs 1, 3, and 10.
beginning, all nonlinear iteration procedures require ap-
proximate values of parameters, some of the equations concluded that the constants obtained for eqs 3 and 10
have to be transformed into linear forms. With the use agree reasonably well with the Arrhenius and van't Hoff
of a linear and robust linear regression (Rousseeuw and equation and can therefore be considered as the most
Leroy, 1987),we obtained values of parameters which were favorable rate expressions. With respect to the optimi-
subsequently used as starting values of parameters in the zation algorithms, eqs 3 and 10 are nondistinguishable,
Marquardt minimization algorithm. Convergence was fast since they represent the same target function; thus
and independent of starting approximations of parameters
in almost all equations; varying starting values of param- m X I 2 -X2X,/K)
Y= (11)
eters for a few orders of magnitude have not influenced
the results. Reaction rates were calculated with the mean
(1 + 2 ( B x 1 ) ' / 2 + DX&4
concentrations of components in the differential reactor. In the case of eq 3, coefficient A is equal to the product
Proportional weights were used. The equations which do of coefficients A and B obtained for eq 10. Coefficients
not include the term of water concentration were tested B and D have the same values as is evident from Table III.
only with the data obtained by the methanol-nitrogen inlet Small differences are obtained by neglecting the reversible
mixture. Results are summarized in Table 11. From this term in the case of eq 3. On the basis of statistical criteria
table it is evident that eqs 1,3, and 10 have the smallest alone, we cannot distinguish between the L-H mechanism
and almost equal sums of least squares. Therefore, an and the E-R mechanism for dehydration of methanol on
additional test was necessary. From Figure 2 it can be yA1203.Furthermore, when calculated values of the ac-
Table 111. Optimum Parameter Set for Tested Equations Obtained with Nonlinear Regression (NLR) and Starting Values of
Parameters Obtained with Linear (LR) and Robust Regressions (RR)
k, kmol(kg/h) KM,m3/kmol Kw,ma/kmol
T,"C eq NLR LR RR NLR LR RR NLR LR RR
320 1 5.4 6.0 4.6 52.6 34.2 54.0 453.9 384.2 386.9
3 12 167 11957 13415 1000.4 1077.2 1333.6 455.4 447.6 479.0
10 11.7 11.1 10.1 884.6 1086.2 1346.0 418.4 449.1 480.1
340 1 13.1 25.1 15.8 50.4 10.5 25.3 463.1 286.4 360.4
3 23 186 14 468 13371 722.2 425.4 359.2 414.1 305.8 298.9 .
10 31.9 33.9 37.1 551.3 429.9 362.7 355.4 307.0 299.9
360 1 33.6 61.7 30.1 25.3 7.5 25.5 301.6 224.6 283.0
3 31 753 23 193 23 263 422.9 290.3 290.5 269.4 220.2 221.5
10 73.5 79.6 78.3 358.3 293.7 305.5 243.2 221.0 226.0

Table IV. Summary of Published Values for Activation Energy and Heat of Adsorption for Methanol and Water on Various
Catalysts
E,, kJ/mol HM,kJ/mol Hw,kJ/mol T, "C catalyst ref
108.3" 160-195 alumina Kallo and Knininger, 1967
66.6" 289-418 silica-alumina Schmitz, 1978
120.P 300-350 alumina Rubio et al., 1980
138.9* 125.5 20.9 150-225 silica-alumina Bakshi and Gavalas, 1975
114.2b 127.6 111-150 ion exchange resin Than et al., 1972
123.0 Than et al., 1972
This Work
117.2c 290-360 alumina Figure 3
143.7b 70.5 41.1 320-360 alumina eq 10
75.1b 67.0 40.7 320-360 alumina eq 3
a Value obtained by linear regression of initial rate data. Value obtained by nonlinear regression for selected equation. Value obtained
from slope In (-rM) v8 1/T.
1038 Ind. Eng. Chem. Res., Vol. 31, No. 4,1992

Concentration of Table V. Sensitivity of Numerically Calculated

&
CHIOH In Inlet Effectiveness Factor on Parameter Variation
mixture CHIOH-N2
(volr) variation of produced change
+ 0 1% CHIOH parameter parameter, % in calculated 7, %
0
( u L u 3 M CHIOH
6 Onnno 45% CHIOH Ae +goo, -90 -0.1; +1.5
\ 'I UIW 60% CHIOH De f20 f8
r &&Ab75% CHIOH
f10 F8
\ A\\ -90% CHIOH d,
f10 =i4
I -rM
0 , - PP *lo 74
-Iu
Table VI. Physical Properties of Catalyst Particles (3-mm
Granules of Bayer SAS 350 yA1208)
n surface area (BET) 247 m2/g
L
I surface area (a > 100 8, Hg porosimetry) 2.24 m2/g
I bulk density (Hg porosimetry) 1.2846 g/cm3
W particle density (He picnometer) 3.268 g/cm3
10 - I -
particle porosity 0.607
k
+m ' ' ' ' ' ' 8 ' I I I ' ' 1 I ''' '' I 8 ' I 8 r ' ' 1 '7' I I I I ferential equations describing mass and heat transfer
1 S7E-003 1.65E-003 1.72E-003 1.80E-003
1/T ,1/K within a catalyst particle must be solved. Mass and heat
Figure 3. Determination of apparent activation energy from initial transport within a spherical particle are governed by
rate measurements.
d2C; 2 dCi
dr2 + -r -
dr ] = ppyirv (14)

with boundary conditions

L atr=O
c
.- C
0.1 : atr=R T = Ts; Ci = Cis (17)
U
Q)
+ A n analytical solution of the above system is possible only
-0J when iosthermal conditions within a particle are main-
tained. For the power-law rate expressions, analytical
-0u solutions are given in terms of the Thiele modules (Fro-
0 0.01 4% I
0.01
/

0.1
I I
Measured r a t e
Figure 4. Comparison between experimentally measured and cal-
culated intrinsic reaction rates with eq 10.
tivation energies are compared to the data found in the
literature (Table IV) and to the results of the initial rate
measurements (Figure 3), eq 10 seems to give more realistic
predictions than eq 3. The comparison between the ex-
perimentally determined reaction rates and those calcu-
lated for the same reaction conditions by eq 10 is illus-
trated in Figure 4.
Global Reaction Rate. The catalyst particles which
are used in commerical fixed-bed reactors are usually
greater than those used in the kinetic rate equation de-
termining experiments. These particles are less reactive,
as can be seen from Figure 1, because they exhibit intra-
particle mass- and heat-transfer resistances. The reaction
rate measured for such particles is called the global reac-
tion rate. The global reaction rate is calculated from the
intrinsic rate equation and effectiveness factor by the
following equation
-RM = q(-rM) (12)
where the effectiveness factor is defined as
(l/WJ(-rd
7 =
(-rM) IS
In fact, to calculate the effectiveness factor a set of dif-
1
ment and Bischoff, 1979). For more complex rate equa-
tions, a generalized approach or a numerical computation
can be applied. In the case of the nonisothermal conditions
within a catalyst particle, the effectiveness factor must be
calculated numerically.
To solve the set of eqs 14-17, the algorithm proposed
by Riggs (1988) was used. The approach taken in that
algorithm converts a boundary value problem with ordi-
nary differential equations (ODES)into an initial value
problem with partial differential equations (PDEs) by
adding an appropriate transient term to the differential
equations describing the material and energy balances.
The obtained set of PDEs is then integrated, according to
initial conditions, using a mathematical package LSODE
(Hindmarsh, 1986), to the steady state. The solution ob-
tained at that point is also a solution to the original
problem.
In eqs 14 and 15, two parameters appear which describe
the transport of heat (Aeff) and mass (Deffi) for a particular
component in a catalyst particle. From the results of the
sensitivity analysis presented in Table V, it is obvious that
the effective diffusion coefficients for components should
be predicted more accurately than the coefficient of ef-
fective heat conductivity. A value of the effective thermal
conductivity coefficient was predicted on the basis of lit-
erature data and correlations and was found to be 2.7 X
kJ/(s m K). From Table VI, where some data of the
measured physical properties of the catalyst particles are
dV summarized, it can be concluded that the majority of the
(13) total surface arises from the pores with a diameter under
100 A. Thus, it an be assumed that for the reaction under
the investigated conditions the Knudsen diffusion prevails
 Ind. Eng. Chem. Res., Vol. 31, No. 4,1992 1039

Table VII. Comparison between the Experimentally Determined and Numerically Calculated Effectiveness Factors
inlet composition" conversion VulC

mol % CH30H mol % H20 T,"C dp = 0.17 mm dp = 3 mm qexptb eq 1 eq 3 eq 10

45 10 320 7.2 12.1 0.370 0.413 0.394 0.394
45 10 340 9.9 11.8 0.294 0.292 0.275 0.275
45 10 360 10.6 10.1 0.236 0.206 0.196 0.194
45 0 340 7.9 6.8 0.217 0.205 0.216 0.218
45 20 340 6.5 9.1 0.349 0.356 0.327 0.323
45 30 340 4.3 7.1 0.415 0.415 0.379 0.372
45 40 340 3.2 5.7 0.449 0.469 0.430 0.421
15 10 340 15.0 14.2 0.243 0.256 0.236 0.229
30 10 340 11.0 12.8 0.277 0.277 0.258 0.255
60 10 340 4.8 10.6 0.282 0.303 0.290 0.290
75 10 340 4.5 9.6 0.268 0.312 0.302 0.304
"Mole percent of CH30H and H20 in N2.bqexpt= [-R,(3 mm)/-r~(0.17mm)llT,~l.

T = 360'C 690
T = 340'C
T = 3200C Y 665-
T = 290'C
OPERATING

c
5 640:
CONDITIONS
TI = 551.15 K
- P = 2.1 bar
/ E : 0" = 5.32 kg/h
dl = 0.078 rn

;:
Q) 615-

2 590-
565 -

$ -.__
5401, , I , I , , I , I I I , , I I , I I I I I , , I , , , I I , I I , I , I F 0.00
0.00 0.10 0.20 0.30 0.40

4 1 1 1 1 1 1 I I
0.01 0.1
Measured rate
Figure 5. Comparison between experimentally measured global
reaction rates for 3-mm catalyst particles and those calculated nu-
merically.
in the catalyst particles. For materials like yAl,O, ef-
fective diffusivity can be estimated using a parallel pre
model:
Deffi= dit/^ (18)
According to Satterfield (1970), effective diffusivity, within
a factor of 2, can be predicted if it is assumed that a
parallel pore model with an experimentally measured po-
rosity and a value of 4 for the tortuosity factor is used.
Assuming different values of this factor, calculations on
a trial and error basis were performed until the value which
provided a good agreement between the measured and
calculated reaction rates for 3-mm catalyst particles was
obtained. When a value of 3 was taken for the tortuosity
factor in calculating the effective Knudsen diffusion
coefficient and the numerical procedure for calculating the
effectiveness factor, the agreement between the measured
and calculated reaction rates was fairly good. A compar-
ison of the calculated and experimental measured global
rates in a differential reactor is shown in Figure 5. In
Table VI1 some values are given for the calculated end
experimentally determined effectiveness factor at different
temperatures and compositions of reaction mixtures en-
tering the differential reactor. As one can conclude from
the results in Table W, either one of eq 1,3, or 10 predicts
the effectiveness factor quite reasonable.
In Figure 6, comparison between experimentally mea-
sured temperature and concentration profiles in an integral
adiabatic fixed-bed pilot reactor is shown (BerEiE, 1990).
For operating conditions as specified in Figure 6, it was
shown (BerEiE and Levec, 1991) that a one-dimensional
Axial coordinate, m
Figure 6. Comparison between experimentally measured tempera-
ture and concentration profiles in an adiabatic pilot reactor and
those predicted by a pseudohomogeneous model.
pseudohomogeneous model can be successfully used for
modeling of an industrial reactor. From that figure it is
obvious that neglecting the reversible term in a rate
equation leads to the wrong predictions, as demonstrated
by the use of eq 1 or 3.
Conclusions
From the results discussed above it is obvious that there
exist no significant differences among eqs 1,3, and 10 when
they are used for interpretation of the results obtained in
a differential reactor. Equations 3 and 10 provide the
temperature dependency of the activation energy and heat
of adsorption according to the Arrhenius and van't Hoff
relation. On the basis of the criteria applied, it is further
concluded that eq 10 represents the kinetic behavior of the
dehydration reaction more realistically and is appropriate
for modeling purposes. It is also evident that the global
reaction rate can be successfully predicted with the pro-
posed intrinsic rate equation and the numerical procedure
for the effectiveness factor calculation. The effective
diffusivities for components can be effectively predicted
using a parallel pore model and assuming the Knudsen
diffusion mechanism.
Acknowledgment
We acknowledge support from the Research Council of
Slovenia under Grant No. C2-0541-104 and Nafta Lendava
for making it possible to run a pilot reactor at their fa-
cilities for more than 2 months.
Nomenclature
c i = pore diameter, 1\
1040 Ind. Eng. Chem. Res. 1992,31, 1040-1045
A , B, D = constants in eq 11, dimensionless BerEiE, G. Dehydration of Methanol over yA1208.Kinetics of Re-
c = specific heat of component i, kJ/(mol K) action and Mathematical Model of an Industrial Reactor. Ph.D.
4 = concentration of component i, kmol/m3 Dissertation, The University of Ljubljana, 1990.
BerEiE, G.; Levec, J. Reactor Model for the Catalytic Gas-Phase
dp = particle diameter, m Dehydration of Methanol to Dimethyl Ether (DME). Vestn. Slou.
dT = reactor diameter (Figure 6), m Kem. Drus. 1991,38,253-270.
Di = diffusivity of component i, m2/s Brake, L. D. U.S. Patent 4,595,785,1986.
Deff = effective diffusivity of component i, mz/s Chang, C. D.; Kuo, J. C. W.; Lang, W. H.; Jacob, S. M. Process
E, = activation energy, kJ/mol Studies on the Conversion of Methanol to Gasoline. Ind. Eng.
AH = reaction enthalpy, kJ/mol Chem. Process Des. Deu. 1978,17,255-260.
ks = rate constant of surface reaction, mol/(g,,,/h) Duggleby, R. G. Regression Analysis of Nonlinear Arrhenius Plots:
K = equilibrium constant, dimensionless An Empirical Model and a Computer Program. Comput. Biol.
Ki = adsorption constant of component i, m3/kmol Med. 1984,14,447-455.
P = pressure, bar Figueras, F.; Nohl, A.; Mourgues, L.; Trambouze, Y. Dehydration of
Methanol and tert-Butyl Alcohol on Silica-Alumina. Trans.
r = radial coordinate, m Faraday SOC.1971,67,1155-1163.
R = particle radius, m Froment, G. F.; Bischoff, K. B. Chemical Reactor Analysis and
-rM = reaction rate, mol/(g,,/h) Design; John Wiley & Sons: New York, 1979;p 185.
-RM = global reaction rate, mol/(g,./h) Gates, B. C.; Johanson, L. N. Lungmuir-Hinshelwood Kinetics of the
Hi= heat of adsorption of component i , kJ/mol Dehydration of Methanol Catalyzed by Cation Exchange Resin.
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Kinetics of the Catalytic Hydrochlorination of Methanol to Methyl

Chloride
Albert0 M. Becerra, Adolfo E. Castro Luna, Daniel E. Ardissone, and Marta I. Ponzi*
Facultad de Ingenieria y Administracion, Uniuersidad Nacional de San Luis, INTEQUI-CONICET, Au. 25 de
Mayo 384, 5730 Villa Mercedes, San Luis, Argentina

The intrinsic kinetics of the catalytic hydrochlorination of methanol to methyl chloride on yAl,O,
was determined from experiments in a tubular reactor in the temperature range of 513-593 K and
at atmospheric pressure, after a catalyst screening and a study of operative conditions. A large number
of detailed reaction mechanisms was considered. A strategy of model discrimination and parameter
estimation led to a Hougen-Watson type model with statistically significant and thermodynamically
consistent parameters.
The two main technologies used commercially for ob- and chlorination of methane. Methyl chloride is used as
taining methyl chloride are hydrochlorination of methanol an intermediate in the obtainment of chlorinated bypro-
0888-5885/92/2631-1040$03.00/00 1992 American Chemical Society