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JOURN.4L OF CAT.

4LYSIS 13, 20%214 (1969)

Kinetics of Dehydrogenation of Isopropyl Alcohol


over a Zinc Oxide Catalyst
Consistency with the Adsorption Function of Isopropyl
Alcohol on Zinc Oxide

STEIN KOLBOE
From the Central Institute for Industrial Research, Oslo 3, Norway

Received June 18, 1968; revised September 30, 1968

The rate of dehydrogenation of isopropyl alcohol over a zinc oxide catalyst has been
measured at 15%195”C, at, an isopropyl alcohol pressure range of 0.03-100 torr.
The rate measurements have been tested for consistency with a previously determined
adsorption function of isopropyl alcohol on zinc oxide. The adsorption function assumes
Langmuir adsorption on a heterogeneous surface with five sets of adsorbing sites.
The corresponding kinetic equation could be well fitted to the experimental rates using
a suitable set of rate constants and activation energies, but using the previously deter-
mined adsorption function directly. In the experimental sange which covered a factor of
more than 3000 in isopropyl alcohol pressure and a factor in reaction rates of 170 the mean
deviation between observed and calculated rates was less than 6yo. The results are there-
fore an indication that a previously proposed model, assuming that a heterogeneously
catalyzed reaction may take place on more than one set of active centers on the catalyst,
is correct.

On the basis of a recently advanced


theory that there may be more than one
The two preceding papers (I, 5’) present
set of active centers on a catalyst (S), it was
a mathematical description of the adsorption
found to be of much interest to see if the
function for isopropyl alcohol on a zinc
adsorption function of isopropyl alcohol on
oxide catalyst.
zinc oxide is consistent with rate data for
It was found that on fresh (nonaged)
the dehydrogenation reaction of the alcohol
samples of zinc oxide made by heating zinc
on the cataIyst. The system isopropyl
earbonate to 350°C in air for 24 hr the ad-
alcohol/zinc oxide was chosen because
sorption function could be described by the
previous work (4) had shown that rate
following equation
measurements in this system could not be
5 fitted to the kinetic equations of Hougen
W=
WOiaipA and Watson (5).
0)
c 1 + aip.4 At this point it may be mentioned that
i=l
Schrage and Burwell (6) have recently given
with ai = eXp(AXi/R -AHi/RT) evidence that isotopic exchange between
Equation (1) corresponds to the assump- cyclopentane and deuterium on palladium-
tion that the adsorption is a Langmuir on-alumina catalysts takes place on more
adsorption on a heterogeneous surface than one set of catalytically active centers.
where there are five distinct sets of adsorp-
tion sites. The values of the 15 parameters NOMENCLATURE
of Eq. (1) have been determined (,2). They ai Adsorption equilibrium constant
are given in Table 1 of the preceding paper for isopropyl alcohol over active
(-8. center Ci
DEHYDROGENATION OF ISOPROPANOL ON ZIlO 209

Active center type i tion, and temperature. All measurements


Activation energy over center Ci were carried out at a total pressure in the
Adsorption enthalpy over center Ci reactor between 1.0 and 1.2 kP/cm2. The
Rate constant over Ci pressure drop from inside the reactor to the
Pre-exponential factor of rate cou- outside took place mainly in the sintered
stant over center C, glass disc which supported the catalyst.
Partial pressure of isopropyl alcohol Most of the isopropyl alcohol partial
Rate pressures were measured directly in the tail
Rate at conversion 77 gas, but at the highest partial pressures
Rate at zero conversion saturation effects in t’he det,ector of the gas
General gas constant chromatograph occurred. A relation is,
Standard deviat,ion estimate however, easily established between the
Adsorption entropy over center Ci isopropyl alcohol partial pressure in the
Absolute temperature sampling valve, and the part’ial pressure in
Adsorbed qua&t> the gas leaving the saturator, or in the
Adsorbed quantity at saturation over reactor, so the isopropyl alcohol pressures
center Ci were known within a few percent in all
Conversion of isopropyl alcohol to experiments. In order to minimize possible
acetone time effects as far as possible the measure-
Natural logarithm of the pre-expo- ments were carried out in partly random
nential factor for the rate constant order at each temperat,ure.
over Ci
RESCLTS AND DISCUSSION
EXPEHIMESTAL
Apparatus. A flow system of essen- The reaction rates which have been ob-
t’ially the same construction as previously tained are given in Table 1 together with the
described was employed (1). The following isopropyl alcohol partial pressures and
important features were not mentioned conversions. It is seen that the majority of
previously: The apparatus was equipped the rates have been obtained at very low
wit’h an additional inlet for carrier gas conversions. Separate experiments have
between the saturator and the reactor. shown that in the t,emperature and pressure
Bot’h branches were equipped with a needle range where these measurements have been
valve and flow met’er, so that t’he flow in carried out, the following relation is ap-
each branch could be varied at will, thus proximately fulfilled at, conversions up to
allowing a wide range of isopropyl alcohol a few percent
partial pressures in the reactor. The whole 1’$dl
apparatus (from the saturator on) was - = 1 + 0.005,)pA (2)
r,
heated to 70” to 80°C so that condensation of
isopropyl alcohol at. high partial pressures where q is in percent and pA in torr.
was avoided. It is obvious from Eq. (2) that when it
Materials. The catalyst was not aged applies, all the rates given in Table 1 are
ZnO (from ZnC03) previously described (1). essentially independent of conversion. The
Isopropyl alcohol and carrier gas were also assumption is therefore made in the fol-
as previously described (1). lowing that the measured rates represent
Procedure. The reaction rates were true differential rate data (probably not
found by multiplying the acetone concen- strictly correct for the rates at the two
trat,ions in the effluent gas from the reactor highest conversions).
by t,he flow rat’e through the sampling The adsorption fun&ion previously re-
device. This flow rate was not measured ported (1, 9) was measured on a nonaged
directly, but was calculated from the mea- catalyst sample, consequently the rate
sured carrier gas flows, correcting for effects measurements reported here have been
from pressure, isopropyl alcohol concemra- obtained from nonaged catalyst samples t’oo.
210 STEIN KOLBOE

TABLE 1
ISOPROPYL ALCOHOL PARTIAL PRESBURES,
CONVERSIONS, AND
DEHYDROQENATION RATES with n 2 2 can be consistent with the ‘mea-
surements. If the adsorption function [Eq.
(l)] is to be consistent with the rate mea-
surements reported here it must be possible
168°C to fit the following equation to the data:
105.9 0.004 0.1562
f6
105.9 0.003 0.1381
wdwspA
4.824 0.037 0.6300 T=
2.235 0.10 0.7424 c (1 + aipA)*
i=l
1.165 0.24 0.9143
2.259 0.13 0.6890 where
0.706 0.52 0.8660
ki = eXp[Ki - (EJRT)]
0.229 1.14 0.9780
= lci0 exp( -Ei/RT) (4)
178°C
62.94 0.072 1.249 and
31.77 0.089 1.907 ai = exp(A&/R - AHi/RT)
20.71 0.11 2.355
11.88 0.20 2.934 where K~ and Ei are unknown parameters
7.012 0.35 3.331 and Woi, AS,, and AHi are the previously
3.765 0.59 4.047 determined adsorption parameters (2) given
3.035 0.64 4.996 in Table 1 of the preceding paper (2).
2.153 0.88 5.709 Equation (4) has been fitted to the data
0.346 5.0 6.328
10.2 6.864
by the standard least-squares technique,
0.134
0.065 16.4 6.138 making the sum of squared percentage
0.036 21.1 4.822 deviations become a minimum [see ref. (S)]
15.53 0.15 2.704 for three values of n, viz. n = 2, 3, and 4. A
10.18 0.15 2.952 digital computer was used to carry out the
6.118 0.1.5 3.685 computations. Due to the fact that the
3.229 0.30 4.555 adsorption constants were given (thus fixed)
1.076 0.27 6.466 there was littlec oupling between the param-
0.771 0.40 6.892 eters and the iterative procedure necessary
0.624 0.67 7.292 to find the parameter set leading to the
0.371 1.05 6.860
0.19 5.412
smallest possible sum of squared residuals
2.153
converged rapidly. The parameter estimates
195°C and standard deviation estimates of the
2.188 0.78 22.01 rate measurements for n = 2, 3, and 4 are
3.035 0.62 18.79 given in Table 2. Calculated and observed
20.82 0.31 10.87 values are shown in Figs. 1, 2, and 3. It is
1.118 1.03 25.68 seen that Eq. (4) can be fitted to the ex-
0.682 1.78 26.26 perimental points with fair accuracy with
0.371 3.18 25.44
4.30 24.74
n having any of the values 2, 3, and 4. It is,
0.271
8.824 0.71 13.12 however, doubtful that n = 2 is really
9.882 0.67 13.00 consistent with the measurements. The
11.82 0.63 12.92 standard deviation estimate for the experi-
14.65 0.55 11.56 mental points is higher than the correspond-
117.6 0.14 4.920 ing estimate when n = 4, although the
significance is weak. It is also apparent
The rate measurements obtained are from Fig. 1 that Eq. (4) with n = 2 cannot
shown in Fig. 1. From this figure it is clear be fitted to the experimental points at the
that only rate expressions of the type two lowest isopropyl alcohol pressures,
DEHYDROGENATION OF ISOPROPANOL ON &lo 211

TABLE 2
ESTIMATED VALUES OF PIUS-EXPONENTIAL FACTORS (NATURAL LOGARITHM) AND ACTIVATION
ENERGIES OF EQ. (4) FOR n = 2, 3, AND 4, AND RATE CONSTANTS AT 178°C
n=2 n=3 n=4
Ed ES Ei
i fc* (Cal/mole) k? xi (Cal/mole) kia I< (osl/mole) ki.

1 33.319 30000b 0.854 36.180 32OOP 1.608 36.742 32OOP 2.433


2 Does not contribute 37.382 31820 6.535 36.616 30480 13.91
3 30.850 26610 3.185 29.208 24510 6.421 32.307 26760 11.48
4 33.979 28270 11.42 39.651 32260 38.68 40.977 32970 65.83
5 40.080 33780 10.90 39.006 32430 16.78 40.814 33870 21.18
Estimated standard deviation Estimated standard deviat,ion Estimated standard deviation
from this model, s = 11.0% from this model, s = 9.06% from this model, s = 8.85%
Mean deviation between cal- Mean deviation between cal- Mean deviation between cal-
culated and observed culated and obsemed culated and observed
values, 7.27% values, 6.34% values, 5.95 y0

0 Rate constant at 178°C.


b Not estimated from the least-squares procedure because the lack of experimental points at high pressure
makes this impossible. The value was chosen to be similar to the other activation energies.

where the calculated rates are much smaller taken into account that the rates vary by
than the observed ones (which should a factor of 170 and the isopropyl alcohol
perhaps be even higher at zero conversion). pressures vary by a factor of more than
The values of n, n = 3, or n = 4 in Eq. 3000. It is also a satisfactory result that,
(4) are seen to lead to calculated rate curves when n = 3 or n = 4 in Eq. (4), all adsorp-
which are fully consistent with the rate tion sites are found to contribute to the
points, and it must be considered very dehydrogenation rate, as is seen from the
satisfactory that n = 4 leads to a mean rate constants at 178°C which are given in
percentage deviation between observed and Table 2.
calculaOed rates of only 5.95% when it is It would have been desirable to extend

0.01 01 1 10 100 TOW


ISOPROPYL ALCOHOL PRESSURE
LOGARITHMIC SCALE

FIG. 1. Observed and calculated rates at 158”, 178”, and 195°C. The calculated rates have been obtained
from Eq. (4) with n = 2, using the parameter values given in Table 1 of ref. (a) and Table 2 of this paper.
212 STEIN KOLBOE

1 10
ISOPROPYL ALCOHOL PRESSURE
LOGARITHMIC SCALE

FIG. 2. Observed and calculated rates at 158”, 178”, and 195°C. The calculated rates have been obtained
from Eq. (4) with n = 3, using the parameter values given in Tables 1 [ref. (S)] and 2.

the pressure range by another factor of 10 to catalyst, because fresh catalyst samples
100 upwards, as this increase of isopropyl exhibit a rapid decline in activity at higher
alcohol pressure is necessary in order to get temperatures (7).
full information about the weakest adsorbing It was pointed out above that the mean
site. A pressure apparatus making this percentage deviation between observed and
possible is under construction. Also the calculated values was 5.95ojn (s = 8.85%).
temperature range could profitably have The true standard deviation of the rate mea-
been extended upwards, but this was not surements at constant catalyst activity is not
possible when working with a nonaged accurately known (it will depend upon the

0.1’
0.01 0.1 1 10 ml TORR
ISOPROPYL ALCOHOL PRESSURE
LOGARITHMIC SCALE

FIG. 3. Observed and calculated rates at 158’, 17P, and 195°C. The calculated rates have been obtained
from Eq. (4) with n = 4, using the parameter values given in Tables 1 [ref. (@I and 2.
DEHYDROGENATION OF ISOPROPANOL ON ZIlO 213

particular conditions necessary to obtain spectroscopy to be closely centered around


a given rate) but it is believed to be some- 1.0 X 1014 se+. When an agreement be-
-what less than 3%, except when measuring tween the adsorption function of a system
rates at 158’C at low isopropyl alcohol and the reaction rates in the same system is
pressures, when 5% standard deviation is sought for, it is implicitly assumed that the
probably a better estimate. In the present catalytic reaction is not confined to a very
case the overall standard deviation will be few active centers on the catalyst. Rather it
higher, however, because there was un- is assumed that over large areas of the cata-
doubtedly some activity decrease of the lyst an adsorbing site is also a catalytically
catalyst due to aging taking place when the active site. The agreement found here be-
measurements were carried out. It is be- tween the pre-exponential factor (frequency
lieved that this catalyst aging will increase factor) and the vibrational frequencies of
the standard deviation to about f&70/,. The hydrogen atoms is therefore highly
standard deviation estimate (s = 8.85%) satisfactory.
from the fitting of Eq. (4) is still higher than
t,he expected standard deviation of the rate CONCLUSIOn-

measurements. But all errors in the adsorp- It is apparent from the preceding dis-
t ion parameters in Table 1 of ref. (1) (which cussion that a model assuming that the
have not been varied) will increase the dehydrogenation reaction of isopropyl al-
st’andard deviation estimate from Eq. (4) of cohol on zinc oxide is taking place simul-
t.he experimental rates above the true least- taneously on several (five) sets of active
squares minimum. The two standard de- centers is in complete agreement with the
viation estimates, s = 6-7%, and s = experimental results. The reaction is de-
8.850j0, can therefore be considered to be scribed mathematically by Eq. (4) with
in full agreement. n = 3 or 4 (n = 2 cannot be rigorously
If the experimental rates are expressed as excluded but seems unlikely). According to
molecules transformed per second and gram the model the rate-determining step is a sur-
catalyst, and the values of Woi are expressed face reaction, and in the rate-determining
as sites per gram catalyst, the ~Q’Sand thus step an adsorbed isopropyl alcohol molecule
also the kio’s are seen from Eq. (4) to have reacts simultaneously with two or three
the dimension molecules site -l se+. So far neighboring free active centers (5). Detailed
t’he following units have been used: T, reaction mechanisms in agreement with such
nanomole see-’ rnm2; Woi, mg isopropyl a model can be proposed, but at the present
alcohol adsorbed per gram catalyst. The state of knowledge this is hardly warranted.
rate T is expressed as desired after mul- It is of interest to compare the results
t,iplying by N X S X 10Pg where N is obtained here with results previously ob-
Avogadro’s number and S is the surface tained for the dehydrogenation reaction of
area of the catalyst, which is 52 m2/g (1). set-butyl alcohol over a brass catalyst (3,8).
llYoi is converted to sites g-l by multiplying The brass catalyst had been oxidized in air
by 1.0 X lo-l9 (i.e., molecules isopropyl at 430°C and was then reduced in hydrogen
alcohol per mg). The conversion factor for at the same temperature. It is thus inferred
expressing ki (and k,) in units molecules that the brass was covered by zinc oxide
&e-l se& is thus N X 8 X low9 X lo-l9 = (possibly mixed with copper oxide) and
3.13 X 10P3. The values of the lci<s have copper. The presence of zinc oxide makes
been calculated in these units and they were a similarity with a pure zinc oxide catalyst
found to be of the order of magnitude 1014 likely. It is therefore to be expected that the
molecules/site sec. [The mean value (geo- reaction mechanism of dehydrogenation of
metric) of the five sites was found to be 0.5 X see-butyl alcohol over a brass catalyst will
1014molecules site-’ se+ when n = 4.1 This be similar to the reaction mechanism of
is the same order of magnitude as the vi- dehydrogenation of isopropyl alcohol over
brational frequencies of hydrogen atoms in a zinc oxide catalyst. This expectation is in
molecules, which are known from infrared fact in agreement with the results obtained
214 STEIN KOLBOE

so far. The results on dehydrogenation of adsorption function may be rather different.


set-butyl alcohol were consistent with The measurements were also carried out
a model assuming the same mechanisms over a much smaller pressure range rat
as proposed above (3). Also in that case no considerably higher pressures. R’o detailed
clear choice between mechanisms assuming correspondence can therefore be expected.
simultaneous reaction between an adsorbed
alcohol molecule and two or three free active
centers could be made. But a model assum-
ing reaction between an adsorbed alcohol 1. KOLB~E,S., J. Calalysis 13, 193 (this issue).
molecule and one free active center was on the 8. KOLBOE, S., J. Cakzlyti 13, 199 (preceding
whole not satisfact,ory. When the dehydro- paper).
genation of set-butyl alcohol was investigated 3. KOLBOE, S., Ind. Eng. Chem. Fundamentals 6,
a model assuming only two sets of active 169 (1967).
centers was satisfactory, whereasthe analysis 4. KOLBOE, S., unpublished.
5. HOUOEN, 0. A., AND WATSON, K. M. “Chem-
carried out here is based on the assumption ical Process Principles,” Part 3, Wiley, New
that there are five sets of active centers. York, 1952; or YANO, K. H., AND HOUOEN,
This difference does not imply that there 0. A., Chem. Eng. Progr. 46, 146 (1950).
is a discrepancy between the two investi- 6. SCHRAOE, K., AND BURWELL, JR., R. L., J. Am.
gations, however. The results concerning Chem. SOC. 88, 4549 (1966).
dehydrogenation of set-butyl alcohol were 7. KOLBOE, S., unpublished.
obtained on a different catalyst which had 8. THALLER, L. H., AND THOD~S, G., A1.Ch.E. J.
been given a different pretreatment, so the 6, 369 (1960).