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CINETICADELADESHIDRATACIONCATALITICA2PROPANOL
CINETICADELADESHIDRATACIONCATALITICA2PROPANOL
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CATALYTIC DEHYDRATION a For each series a new blank run is made with
silica-alumina Ketjen (13%).
This section is divided into two parts:
A, the evaluation of the activity of dif- The initial rates show a large difference,
ferent catalysts; and B, the investigation which cannot be explained by the surface
of the reaction itself, and particularly the area (last column). From these values the
influence of water. catalysts can be classified in three cate-
gories : silica, alumina and thoria, silica-
A. Activity of Different Catalysts
alumina. This last one is much more active
This section includes at first a compari- than the other catalysts. It is well known
son of different oxides, then a study of the that silica-alumina is active in cracking,
evolution of the activity of a silica- isomerization, and polymerization, but
alumina catalyst as a function of various practically no paper mentions its high
treatments. activity in dehydration, where alumina
and thoria are generally regarded as the
1. Cla.&$cation of Oxides best catalysts.
The materials which appear in the Table Among these oxides, silica-alumina is
1 are described here. The silica was pre- known to reveal acid properties which are
pared in the Institute of Catalysis by considered as responsible for the cracking
120 DE MOURGUES, PEYRON, TRAMBOUZE, AND PRFXTRE
activity. It does seem that acid properties Two points must retain our attention:
take some part in dehydration, but yet we (1) The alcohol dehydration rate is more
may think that the sites are not the same, drastically reduced than the cumene crack-
because silica-alumina 25% is much less ing activity. These results confirm the
act,ive than silica-alumina 13% though experiments of Boreskov concerning the
their activity in cracking is equal (12). influence of sodium hydroxide on alumina
This is confirmed by the experiments on the rate of dehydration of ethanol into
described next. ethylene at 420°C (If).
(2) With catalysts treated by NaCl
2. Modijkution of a Silica-Slurnina solutions, the variations of the dehydration
Catalyst rate is small. This may explain why
The very high level of the activity of Topchieva (6) and co-workers concluded
the silica-alumina (13%) catalyst led us that sodium does not change the catalytic
to search for the nature of the sites work- activity of silica-alumina in the dehydra-
ing in dehydration. Three treatmen& were tion of ethanol.
investigated. c. Removal of aluminum with acetyl-
a. Preheating at different temperatures. acetone, Aluminum can be removed from
The catalysts are heated 16 hr in an air the catalysts by treatment with HCl or
flow then brought back to 130°C and the with acetylacetone solutions. This last
activity is measured. The results are given method seems better, because no chlorine
in Table 2. Only a small increase of the is involved and chlorine itself could bring
TABLE 2
COMPARISON OF THE ACTIVITIES AND ‘I’HE ACIDITIES OF A KETJEN (130/, ALUMINA) AT
DIFFERENT TEMPERATURES OF TREATMENT
n Reference (10).
activity is observed and Barthomeuf had some modifications. The activity variations
noticed a similar effect for the Bronsted due to the removal of aluminum are shown
activity (10). in Table 4.
h. Exchange with sodium salt solutions. As in the previous paragraph it seems
In Table 3 are given the results of our difficult to draw a conclusion from the
experiments and data from the thesis of activation energy, but the initial rate of
Barthomeuf (10). The amount of ex- dehydration is multiplied by a factor of
changed sodium depends on the basicity of 9 at the maximum.
the solution. It is interesting to compare the results
TABLE 3
VARIATIONS OF DIFFERENT PROPERTIES AS A FUNCTION OF THE BASICITY OF THE
EXCHANGING SOLUTION
Catalytic
activity in,
VW Bronsted acidity Exchanged Na cum~3~5$kmg 0
Catalyst (mole/kaec g) (kca$n:mole) 0-w H+/g) b-l/d
if water is continuously evacuated during in the work of Vasserberg (4), who char-
the experiment; (c) the reaction is zero acterizes different catalysts by the half-de-
order at 120°C with respect to initial composition time, which is correct only if
pressure. the reaction has been proved to be first
The data of Dohse (3) must be ex- order; but this does not seem to be the
amined with respect to the two previously case for temperatures and catalysts
mentioned aspects of the problem. studied.
Order as a function of initial pressure: Our first work consisted in determining
At any temperature the reaction is not first the influence of the initial pressure of 2-
order [Dohse, (S), p. 1361 characterized propanol.
by a half-reaction time independent of the The preliminary experiments were made
initial pressure, but close to a zero order; with Ketjen 137% alumina; the conditions
indeed the ratio half-reaction time/initial and the results are collected in Table 5.
pressure is practically constant. These results are transformed into
Order as a function of the pressure vary- logarithmic form and the curves log v0 =
ing in the time: In this case the first order f (log pO) are represented in Fig. 3. They
rate of the reaction is fairly well verified clearly prove that the reaction is zero order
with an equation of the form log a/ (a-x) at a temperature lower than 165°C. Above
II let [Dohse, (S), p. 1351 but it is difficult 165°C the order becomes fractional and
to understand a first order reaction with tends to one but does not reach it yet at
2-propanol, and it is more likely that the 220°C.
inhibition by water causes an apparent After these experiments the temperature
first order with respect to 2-propanol. was fixed below 160°C and for practical
Indeed, when water is removed the reaction reasons two pressures, 8.6 mm Hg cor-
is zero order. responding to 0°C and 23 mm Hg cor-
The same confusion seems to be present responding to 15”C, were used. Under these
2.1
12
165’
0
2.1 0
I II
1 t5 log Pmm Hg
Vx107 mole/rw 9
‘0 .
f
2-Pmpand p (Hgmm>425
11.25
155°C
FIG. 4. Influence of water on the dehydration rate. (Curves are exactly the same with the 11~0
pressures of Zpropanol.)
values is explained by Dohse by the de- catalysts. Acid sites are surely involved in
sorption heat of water, which is 13 kcal/ dehydration as it is proved by sodium
mole. action, but they seem to be helped by
The value of 16 kcal/mole obtained at other sites. Aluminum removal experiments,
350°C might be explained in a similar way. and the influence of water led us to assume
At 350°C the rate of decomposition should the existence of two types of active centers.
normally be first order with respect to This is expressed by an equation with two
propanol, and the apparent activation values for the numbers and for the cover-
energy would be the difference between ages of these sites.
the true activation energy (25 kcal) and
the heat of adsorption of 2-propanol. A REFERENCES
good approximation of the heat of physical 1. (a) WINFIELD, M. E., in “Catalysis” (P. H.
adsorption is given by the 2-propanol heat Emmett, ed.), Vol. 7, p. 93. Reinhold, New
of liquefaction, which is 10 kcal/mole. York, 1960; (b) ibid., p. 131; (c) p. 116;
Our results concerning activation energy (d) p. 173; (e) p. 134; (f) p. 157.
are given in Tables 1, 3, and 4. Except for 2. PEYRON, F., Thesis, Lyon, 1964.
silica (43.5 kcal/mole, Table 1) the values 3. DOHSE, H., AND KALBERER, W. Z., 2. Physik.
for the other catalysts do not allow any Chem. B5, 131 (1924).
conclusion to be drawn. As far as silica is 4. VASSEEBERQ, V. E., Intern. Congr. Catalysis,
3rd, Amsterdam, 1.964,Preprint 1.~
concerned it seems that the active sites, or
5. BORK, A. K., AND TOLSPOPYATOWA, A. A. Acta
the steps of the reaction are different, Physicochim.URSS8, 603 (1938).
which may explain the gap of about 14 6. TOPCHIEVA, K. V., YUN PIN, K., SMIRNOVA,
kcal/mole with the other catalysts. It I. V. Advan. Catalysis, 9, p. 799 (1957).
should be mentioned that in all the meas- 7. RALEK, M., AND GRUBNER, O., Proc. Intern.
urements the reaction is zero order. Congr. Catalysis, Srd, Amsterdam, 1964
2, 1303 (1965).
CONCLUSION 8. DZISKO, V. A., BORISOVA, M. S., KOTSARENKO,
2-Propanol dehydration certainly is an N. S., AND KUSNATSOVA, E. V. Kinetics
interesting activity test for the oxide Catalysis (USSR) (Engl. Transl.) 3, 633
catalysts. The catalysts do not age, the (1962).
temperatures of reaction are low, and zero 9. MISONO, M., AND SAITO, Y., Proc. Intern.
Congr. Cata&&, Srd, Amsterdam, 1964 L,
order is easy to reach. Moreover the 408 (1965).
techniques used are simple and rapidly 10. BARTHOMEUF, D., Thesis,Lyon, 1963.
supply initial rate, kinetic order, and 11. BARTHOMEUF, D., Compt. Rend. 25g, 3520
activation energy. (1564).
It has been shown that the dehydration 12. DE MOURGUES, L., FICHET,M., AND CHASSAING,
rate is the highest with silica-alumina G. Bull. Sot. Chim. France, p, 1918(1962).