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Art 2
Kautz, K.; Kirsch, H.; Laufhütte, D. W. Spurenelementgehalte in Rademacher, J.; Borgmann, D.; Hopfengártner, D.; Wedler, G.;
Steinkohlen und den daraus entstehenden Reingasstáuben. VGB Hums, E.; Spitznagel, G. W. X-Ray Photoelectron Spectroscopic
Kraftwerkstech. 1975, 55 (10), 672-6. (XPS) Study of DeNOj Catalysts after Exposure to Slag Tap
Knózinger, H. Benetzung im festen Zustand—Ein neuer Weg zur Furnace Flue Gas. Appl. Catal. 1992, in press.
Herstellung von oxidischen Trágerkatalysatoren; Dechema: Russell, A. S.; Stokes, Jr., J. J. Surface Area in Dehydrocyclization
Frankfurt, June 1,1990. Catalysis. Ind. Eng. Chem. 1946, 38, 1071-4.
Linnros, B. The Crystal Structure of LiMo02As204. Acta Chem.
Scand. 1970, 24, 3711-22. Received for review May 13, 1991
Pertlik, F. Structure Refinement of Cubic As203 (Arsenolithe) with Revised manuscript received August 1, 1991
Single-Crystal Data. Czech. J. Phys. 1978, B28, 170-6. Accepted October 14,1991
(7 )“
methanol, water, and nitrogen at low vapor pressures. (1 + KMCM)2
Since water produced during the reaction considerably Schmitz, 1978 + k2Cu
-rM =
fej (8)6
retards the reaction rate, the derived rate equations have, Rubio et al., 1980 _rM =
*1CM1/2
-
W/2 (9)6
more or less, a semiempirical character and are not suitable
“Acidic ion exchange resin as catalyst. 6Alumina or silica-alu-
for the industrial reactor design, where reaction takes place 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 - 1203 catalyst support
f Boris Kidric Institute of Chemistry. in the form of 3-mm spheres was employed as a catalyst.
1
University of Ljubljana. In order to avoid the intraparticle resistances, spheres were
Superficial velocity, cm/s in the differential reactor, varied from 0 to 3 °C, dependent
50.00 100.00 150.00 200.00 250.00 on the outlet conversion and inlet concentration of meth-
3.00 anol. The inlet temperature was adjusted so that the mean
<XXWX> T=340°C, dp=0.87mm
i 55*CH’0H
;
temperature in the differential reactor was kept constant
T=360°C for all experiments. The maximum systematic error
> 2·50 3
X
A
A
A
A 0 u
O
:0.40 (Massaldi and Maymo, 1969) can be calculated when an
adiabatic operation of the differential reactor is assumed.
o
x 2.00 j 0 At measured conversions, the calculated systematic error
_u was about 3%. Since the reactor was not operated adia-
:0.30 o
É E batically, the true error was even smaller.
1.50 -
: T=340°C
Results and Discussion
:0.20
©
O'
methanol concentration. This indicates that the dehy-
0.00 +
0.1
dration reaction undergoes dissociative adsorption of
Particle size, mm methanol on the catalyst surface. In the derivation of rate
Figure Determination of experimental conditions where external
1. equations for the dehydration of methanol, the L-H con-
and internal transport resistances could be neglected. cept, which has been further developed by Yang and
Hougen (1950), was applied. With the assumption that
crushed and sieved. Three different particle sizes were the surface reaction is a controlling step and that the
used: 0.87,0.37, and 0.17 mm. Experiments showed that dissociative adsorption of methanol on the surface of y-
within the particles of 0.17 mm in size the intraparticle A1203 is taking place, the L-H model can be represented
resistances are negligible. in the following form (Bercic, 1990):
Reactor. The experiments were carried out in a dif-
ferential reactor (8-mm i.d.) in a temperature range of ksKMHCM2
-
CyCz/K)
µ =
~
·2. / )
eters for a few orders of magnitude have not influenced y ~
(11)
(1 + 2(Bx1)1/2 + Dx2)4
the results. Reaction rates were calculated with the mean
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 HI.
only with the data obtained by the methanol-nitrogen inlet Small differences are obtained by neglecting the reversible
mixture. Results are summarized in Table II. 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 - 1203. Furthermore, when calculated values of the ac-
Table III. 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 Jfw, m3/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 12167 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 23186 14468 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 31753 23193 23263 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 ííw, kJ/mol O catalyst ref
108.3° 160-195 alumina Hallo and Knózinger, 1967
66.6° 289-418 silica-alumina Schmitz, 1978
120.0" 300-350 alumina Rubio et al., 1980
138.96 125.5 20.9 150-225 silica-alumina Bakshi and Gavalas, 1975
114.26 127.6 111-150 ion exchange resin Than et al., 1972
123.0 Than et al., 1972
This Work
117.2" 290-360 alumina Figure 3
143.76 70.5 41.1 320-360 alumina eq 10
75.16 67.0 40.7 320-360 alumina eq 3
"Value obtained by linear regression of initial rate data. 6
Value obtained by nonlinear regression for selected equation. "Value obtained
from slope In (-rM) vs 1/T.
1038 Ind. Eng. Chem. Res., Vol. 31, No. 4, 1992
d2T 2 dT
|
PprV(-AH(T)) (15)
dr2 r dr
with boundary conditions
at r = 0
q-LS
II
f-0 (16)
at r = R 6^ C¡ = Qs
8-h II (17)
An analytical solution of the above system is possible only
when iosthermal conditions within a particle are main-
tained. For the power-law rate expressions, analytical
solutions are given in terms of the Thiele modules (Fro-
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
Measured rate within a catalyst particle, the effectiveness factor must be
Figure 4. Comparison between experimentally measured and cal- calculated numerically.
culated intrinsic reaction rates with eq 10. To solve the set of eqs 14-17, the algorithm proposed
by Riggs (1988) was used. The approach taken in that
tivation energies are compared to the data found in the algorithm converts a boundary value problem with ordi-
literature (Table IV) and to the results of the initial rate nary differential equations (ODEs) into an initial value
measurements (Figure 3), eq 10 seems to give more realistic problem with partial differential equations (PDEs) by
predictions than eq 3. The comparison between the ex- adding an appropriate transient term to the differential
perimentally determined reaction rates and those calcu- equations describing the material and energy balances.
lated for the same reaction conditions by eq 10 is illus- The obtained set of PDEs is then integrated, according to
trated in Figure 4. initial conditions, using a mathematical package lsode
Global Reaction Rate. The catalyst particles which (Hindmarsh, 1986), to the steady state. The solution ob-
are used in commerical fixed-bed reactors are usually tained at that point is also a solution to the original
greater than those used in the kinetic rate equation de- problem.
termining experiments. These particles are less reactive, In eqs 14 and 15, two parameters appear which describe
as can be seen from Figure 1, because they exhibit intra- the transport of heat (Xeff) and mass (Deffl) for a particular
particle mass- and heat-transfer resistances. The reaction component in a catalyst particle. From the results of the
rate measured for such particles is called the global reac- sensitivity analysis presented in Table V, it is obvious that
tion rate. The global reaction rate is calculated from the the effective diffusion coefficients for components should
intrinsic rate equation and effectiveness factor by the be predicted more accurately than the coefficient of ef-
following equation fective heat conductivity. A value of the effective thermal
=
v(~r m) (12) conductivity coefficient was predicted on the basis of lit-
erature data and correlations and was found to be 2.7 X
where the effectiveness factor is defined as 10~4 kJ/(s m K). From Table VI, where some data of the
measured physical properties of the catalyst particles are
(1/V) J(-rM) dV summarized, it can be concluded that the majority of the
V (13) total surface arises from the pores with a diameter under
(~rM)|s
100 Á. Thus, it an be assumed that for the reaction under
In fact, to calculate the effectiveness factor a set of dif- 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 composition0 conversion *7calc
JZ
o
o
5
Affi =
A6/T (18)
Conclusions
According to Satterfield (1970), effective diffusivity, within From the results discussed above it is obvious that there
a factor of 2, can be predicted if it is assumed that a exist no significant differences among eqs 1,3, and 10 when
parallel pore model with an experimentally measured po- they are used for interpretation of the results obtained in
rosity and a value of 4 for the tortuosity factor is used. a differential reactor. Equations 3 and 10 provide the
Assuming different values of this factor, calculations on temperature dependency of the activation energy and heat
a trial and error basis were performed until the value which of adsorption according to the Arrhenius and van’t Hoff
provided a good agreement between the measured and relation. On the basis of the criteria applied, it is further
calculated reaction rates for 3-mm catalyst particles was concluded that eq 10 represents the kinetic behavior of the
obtained. When a value of 3 was taken for the tortuosity dehydration reaction more realistically and is appropriate
factor in calculating the effective Knudsen diffusion for modeling purposes. It is also evident that the global
coefficient and the numerical procedure for calculating the reaction rate can be successfully predicted with the pro-
effectiveness factor, the agreement between the measured posed intrinsic rate equation and the numerical procedure
and calculated reaction rates was fairly good. A compar- for the effectiveness factor calculation. The effective
ison of the calculated and experimental measured global diffusivities for components can be effectively predicted
rates in a differential reactor is shown in Figure 5. In using a parallel pore model and assuming the Knudsen
Table VII some values are given for the calculated end diffusion mechanism.
experimentally determined effectiveness factor at different
temperatures and compositions of reaction mixtures en- Acknowledgment
tering the differential reactor. As one can conclude from
the results in Table VII, either one of eq 1,3, or 10 predicts We acknowledge support from the Research Council of
the effectiveness factor quite reasonable. Slovenia under Grant No. C2-0541-104 and Nafta Lendava
In Figure 6, comparison between experimentally mea- for making it possible to run a pilot reactor at their fa-
sured temperature and concentration profiles in an integral cilities for more than 2 months.
adiabatic fixed-bed pilot reactor is shown (Bercic, 1990).
For operating conditions as specified in Figure 6, it was Nomenclature
shown (Bercic and Levee, 1991) that a one-dimensional a =
pore diameter, Á
1040 Ind. Eng. Chem. Res. 1992, 31, 1040-1045
A,B,D = constants in eq 11, dimensionless Ber6i6, G. Dehydration of Methanol over 7-Al203. Kinetics of Re-
action and Mathematical Model of an Industrial Reactor. Ph.D.
Cpj specific heat of component i, kJ/(mol K)
=
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/ig^t/h) Design; John Wiley & Sons: New York, 1979; p 185.
-Rm = global reaction rate, mol/(gegt./h) Gates, B. C.; Johanson, L. N. Langmuir-Hinshelwood Kinetics of the
H¡ = heat of adsorption of component i, kJ/mol Dehydration of Methanol Catalyzed by Cation Exchange Resin.
T = temperature, K AIChE J. 1971, 17, 981-983.
Ti = reactor inlet temperature (Figure 6), K Hindmarsh, A. C. Solving Ordinary Differential Equations on an
V = particle volume, m3 IBM-PC Using LSODE. LLNL Tentacle Magazine; LLNL:
Livermore, CA, April 1986; Vol. 6, No. 4.
x¡ = mole fraction of component i
X = conversion, dimensionless Kallo, D.; Knozinger, H. Zur Dehydratisierung von Alkoholen an
Aliminiumoksid. Chem.-Ing.-Tech. 1967, 39, 676-680.
Greek Letters Klusacek, K.; Schneider, P. Stationary Catalytic Kinetics via Surface
Concentrations from Transient Data. Methanol Dehydration.
< = catalyst particle porosity, dimensionless Chem. Eng. Sci. 1982, 37, 1523-1528.
eB
=
catalyst bed porosity (Figure 6), dimensionless Massaldi, H. A.; Maymo, J. A. Error in Handling Finite Conversion
= effectiveness factor, dimensionless Reactor Data by the Differential Method. J. Catal. 1969, 14,
Xeff
= effective heat
conductivity of catalyst particle, kJ/(s 61-68.
m K) Riggs, J. M. An Introduction to Numerical Methods for Chemical
Vi
~
stoichiometric coefficient of component i, dimensionless Engineers; Texas Tech University Press: Lubbock, TX, 1988; p
406.
pP
=
particle density, g/cm3
r = tortuosity, dimensionless Rousseeuw, P. J.; Leroy, A. M. Robust Regression and Outlier De-
= methanol mass flow rate (Figure 6), kg/h tection; John Wiley & Sons: New York, 1987.
Rubio, F. C.; Diaz, S. D.; Castillo, D. D.; Trujillo, J. D.; Alvarez, R.
A. Deshidratacion Catalítica de Metanol en Fase Vapor. Ing.
Subscripts
Quim. (Madrid) 1980,12, 113-119.
D = dimethyl ether Satterfield, C. N. Mass Transfer in Heterogeneous Catalysis; M.I.T.
i = component i (H20, (CH3)20, CH3OH, N2) Press: Cambridge, MA, 1970; p 42.
= methanol
Schmitz, G. Deshydration du Methanol Sur Sílice-Alumine. Chim.
S = conditions at catalysts surface Phys. 1978, 75, 650-655.
v = per volume Sinicyna, O. A.; Cumakova, V. N.; Moskovskaja, I. F. Kinetika De-
W = water gidratacii Metanola do Dimetilovogo Efira na SVK Ceolite. Ki-
0 = initial conditions net. Ratal. 1986, 27, 1160-1162.
Than, L. N.; Setinek, K.; Beranek, L. Kinetics and Adsorption on
Registry No. MeOH, 67-56-1; 7-Al203, 1344-28-1; DME, Acid Catalysts. IV. Kinetics of Gas-Phase Dehydration of
115-10-6. Methanol on a Sulphonated Ion Exchanger. Collect. Czech.
Commun. 1972, 37, 3878-3884.
Woodhouse, J. C. U.S. Patent 2,014,408, 1935.
Literature Cited Yang, K. H.; Hougen, O. H. Determination of Mechanism of Cata-
lyzed Gaseous Reactions. Chem. Eng. Prog. 1950, 46, 146-157.
Bakshi, K. R.; Gavalas, G. R. Effects of Nonseparable Kinetics in
Alcohol Dehydration over Poisoned Silica-Alumina. AIChE J. Received for review May 7,1991
1975, 21, 494-500. Accepted November 1, 1991
The intrinsic kinetics of the catalytic hydrochlorination of methanol to methyl chloride on 7-Al203
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
tabling methyl chloride are hydrochlorination of methanol an intermediate in the obtainment of chlorinated bypro-