Chemical Engineering Science, 1964, Vol. 19, pp. 371-378. Pergamon Press Ltd., Oxford. Printed in Great Britain.

The kinetics of the brass-catalysed dehydrogenation of set-butyl alcohol

F. E. FORD and D. D. PERLMUTTER

University of Illinois, Urbana, Illinois

(Received 3 1 January 1963 ; in revised form 10 June 1963)

Abstract-The dehydrogenation of set-butyl alcohol over a brass catalyst has been investigated in
a stirred vessel reactor over the temperature range of 572 to 842F at atmospheric pressure. The
temperature range of this study extends the range of previous investigations which suggested that
a dual mechanism model best characterizes the dehydrogenation from 550 to 700F at 1 atm. It was
found in the present study that a dual mechanism does appear to operate within this temperature
range, and moreover that a second transition takes place at about 800F to what is most probably
the original low-temperature mechanism. Several advantages of the stirred vessel reactor are
discussed.

INTRODUCTION by increase in agitation at a given flow rate, whereas

AMONG the surface-catalysed vapour-phase reac-
tions the dehydrogenation of set-butyl alcohol to
methyl ethyl ketone is of special interest in part
because of its commercial use, but in particular
also because of peculiarities in the mechanism of
reaction reported by THALLER and THODOS [l].
These workers concluded that there is a definite
change in the mechanism by which the reaction oc-
curs on a brass catalyst as temperature is increased
in the range from 550 to 700F. Earlier work [2]
over a narrower range of temperature had not
shown this behaviour. In both studies data were
obtained in a differential tubular flow reactor.
In this study the range of temperatures investiga-
ted has been enlarged through the use of a stirred
vessel reactor which achieves pseudo-differential
conditions with finite relatively large conversions.
The use of mechanical stirring eliminates the need
for very small conversions and consequently enables
the investigator to use higher temperatures. Since
feed rate is not the agitation controlling parameter
in the system, feed rates may be made very small
to achieve measurable conversions at low tempera-
tures, thereby making possible investigation over
a greater temperature range.
A further benefit of independent agitation control
is the relative ease with which the effects of mass
transfer may be evaluated. In the stirred reactor
mass transfer effects may be effectively eliminated
in the tubular flow reactor the same objective
requires a series of runs at different mass velocities,
but equal space velocity [3].
APPARATUS
The reactor used in this study is made of type 416
stainless steel. As shown in Fig. 1, it contains a
cylindrical vapour space (33 in. in diameter by 3 in.
in height) agitated by a two-bladed propeller enter-
ing through the top. The inlet to the reactor is at
the bottom near the wall; the outlet is 180 from
the inlet, in the top section. To prevent vertical
temperature gradients which might result from the
use of a hot reaction zone between cooler ends,
the reactor is wound with three separate resistance
heating elements: one over the reaction zone, and
one each over either end of the cylinder. Thermo-
couples are buried in the stainless steel wall l/16 in.
from the inner surface. The temperatures are
measured at three points equally spaced vertically
along the reaction zone. These are automatically
controlled to within f2F over-all range by two-
position controllers.
The catalyst is a thin-walled brass cylinder which
fits into the reaction chamber. Because brass has
a greater thermal coefficient of expansion than steel,
the apparatus could only be assembled or taken
apart when relatively cool. On the other hand,
this same circumstance assured a snug fit at the

371
 F. E. FORDand D. D.
FIG. 1. Reactor.
reaction temperatures. The catalyst cylinder was
machined from commercially obtained 6@-40 brass
tubing to a wall thickness of l/l6 in.
The feed system consists of a constant head
gravity tank for liquid feed, and compressed gas
tanks connected through a manifold system for
gas components. Rotameters are connected in
each feed line to meter the various reactants. These
lines join at a vaporizer consisting of a short vertical
length of glass tubing packed with 3 mm glass beads.
Coming out of the vaporizer, the stream is passed
through a heated horizontal glass coil which brings
the feed stream to the reaction tem~rat~e, The
analysis of the exit stream is by a gas chromato~aph
that includes a thermal conductivity detector.
Methyl ethyl ketone concentrations from 1 to
75 per cent were found in the product gases during
various runs. Conversions to alcohol during parti-
cular runs were on occasion as high as 38 per cent.
372
PERLMIJTER
CATALYST PREPARATION
To be useful as a catalyst, the brass surface had
to be activated initially and then regenerated after
each run. This treatment was based upon earlier
work with brass catalysts extended by experience
gained during this investigation: the catalyst was
air-oxidized at 750F for 5 hr, and reduced under
hydrogen at 842F for 14 hr. When prepared in
this manner, the activity of the fresh catalyst surface
was found to decrease slowly over a lo-hr period.
After this time the activity became constant.
Fig. 2 is a graph of results from a typical 14-hr
run. Only the final 4 hr of the run (47 points) were
used for kinetic data. During this period the aver-
age composition of product was 9.91 per cent with
a standard deviation of 0.17 per cent. Comparison
of this figure with results from several other runs
made under identical conditions over a two week
period shows that rates can be reproduced with a
deviation of less than &It_ per cent between runs.
This figure represents the combined errors in tem-
perature, feed rate and feed composition, as well
as analytical error. If the reactor is run at a lower
temperature at which measurable reaction cannot
occur, the reproducibility should be representative
of analytical error only. Results for such tests
indicate that the anaIytica1 scatter accounts for
more than half the variance found under reaction
conditions.
Time, hr
FIG. 2. Results for a typical run.
 The kinetics of the brass-catalysed dehydrogenation of see-butyl alcohol

I /*--- - - 642F ditions on the catalyst surface can be justified by

SOi-- f operating under conditions within the hor~ont~
I d
portion of this graph.
G 752F
RESULTSAND KINETIC ANALYSIS
Because component concentrations are uniform
over the entire catalyst surface for a stirred vessel
reactor, rates were calculated from the simple
662-F
defining equation
FAX
r=- (1)
I
1000 20bo A
mixhg
region
Agitation variable, rev/minThe kinetic analysis used these rates together
with the corresponding component concentrations.
FIG. 3. Mass transfer effect. A wide range of reactant and product partial
pressures were covered by using various feed com-
binations supplemented by as much helium as
MASS TRANSFER was needed to keep the total pressure at one
A series of preliminary runs were made at differ- atmosphere.
ent agitator speeds. These runs were part of a The rates obtained from this apparatus were
mass transfer experiment designed to assess the about an order of magnitude smaller than those
effect of concentration gradients in the stirred reported by PERONAand THODOS[2] for the same
reactor. Fig. 3 summarizes the results of these tests. chemical system at comparable temperatures. The
On the co-ordinates shown a horizontal line indi- great variability in activity between catalysts pre-
cates that concentration gradients within the reactor pared by different workers is not surprising. The
are negligible. At 662F the experimental results smaller rates found in this work suggest that the
were the same at all stirrer speeds from zero to stirred reactor is especially useful for studies of
2100 rev/min. Evidentally, the jet mixing due to relatively low-activity catalyst.
feed injection was sufficient to match the chemical The experimental results of this study were used
reaction rate at this temperature. The rate would to test ten possible rate equations. These equations
be expected to fall to zero if mixing ceased entirely. (Table 1) correspond to all the apparently logical
This has been indicated in Fig. 3 by the dotted line mechanisms suggested by the well-known analysis
which extends into the Flow Mixing Region. for heterogeneous catalytic reactions that is based
At the two higher temperatures a decrease in on various combinations of adsorption, desorption,
conversion was noted at zero rev/min, indicating and surface reaction rates (see, for example, Ref. 4).
that the increased catalyst activity at these tem- The possibility of a homogeneous mechanism was
peratures resulted in concentration gradients which discarded on the basis of studies made with no
required agitator action for their dispersion. In catalyst in which conversions less than 1 per cent
both cases it is safe to operate in the region beyond of the catalytic conversions were recorded.
824 rev/min, where the curve again becomes flat. To compare the experimental data with each of
At 842F conversion at zero rev/min was not dupli- the postulated mechanisms, the constants of each
cated in two seemingly identical tests. The observed model (as many as four in some of the models used
effect is most likely related to the position that the here) were computed by means of a least squares
idle agitator blades happened to take when stop- analysis of the data, done on a standard 32K
ped. It may then be attributed to a slight change IBM 7090 digital computer. The numerical results
in the flow mixing characteristics. Accordingly, of this study are shown in Table 2. The various
one point has been placed in the Flow Mixing constants listed correspond to those shown in the
Region. The assumption regarding constant con- rate equations of Table 1. The last column is an

373
 F. E. FORD and D. D. PERLMUTTER

index of the goodness to fit as computed from
the deviations between experimental and computed
rates. In interpreting these results, any mechanism
that yielded one or more negative constants was
rejected, since equilibrium and rate constants have
no meaning as minus numbers. In any case in
which there was more than one possible mechanism
(based on positive constants) the one was selected
which minimized the sum of the squared deviations.
If the least-squares fit to any one mechanism is
sufficiently close, while others fit poorly, a case may
arise such that only one mechanism is found with
positive constants. An examination of Table 2
shows that (of those postulated) there was only
one possible mechanism at the two intermediate
temperatures studied, 662 and 752F. The conclu-
sion is that at these temperatures, the mechanism
most applicable is that in which the adsorption of
alcohol is the controlling step, while the surface
reaction occurs by means of a single site mechanism

Table 1. Postulated ~e~~~nisms and rate equations

A. Dual site surface reaction controlling.

c[PA- (PKPH/KE)l

= (~+KAPA+KKPKSKHPH)

B. Single site surface reaction ~ntrolling, ketone adsorbed.

C[PA - (PKPHIKEII
r = (1 +KAPA+KKP~

C. Single site surface reaction controlling, hydrogen adsorbed.

C[PA-(PxPHIKEII
r = (I+KAPA+KKPK)

D. Adsorption of alcohol controlling, dual site.

C[PA - @KPHIKE)I
= (~+KKHPKPH+KxPK+KHPH)
E. Adsorption of alcohol control&g, single site, ketone adsorbed.
C[PA-(PKP~KEII
r=
(1 + KYKPK)

F. Adsorption of alcohol controlling, single site, hydrogen adsorbed.

c[PA- (PxPxiIKdl
r=
(I +KHPH)

C. Desorption of ketone controlling, dual site.

C[PA- (PKPHIKEN
= PH[~+KAPA+KAH(PA/PH)-~KEIPH]

H. Desorption of ketone controlling, single site.

C[PA- (PKPH/KE)~

= p~[l+ PAPA+ KAH(PA/PHII

-1. Desorption of hydrogen controlling, dual site.

C(PA - (PxPEIKEI

J. Desorption of hydrogen controlling, single Site.

C[PA - (PKPHIKEII
r = PK[I + KAPAS- KAK(PA/PK)I

374
 The kinetics of the brass-catalysed dehydrogenation of xc-butyl alcohol

forming adsorbed ketone. The expression for this sion given in Table 1 for this mechanism, but differs
reaction rate (mechanism E) is: by the absence of the term in the numerator con-
taining the equilibrium constant for this reaction.
CPA
(2) Because of very large equilibrium conversions in
r =lmKKpK
the temperature range of interest, the term contain-
It may be noted that this is not exactly the expres- ing the equilibrium constant is negligible.

Table 2. Summary of kinetic constants

Number of Sum of
negative squared
Mechalrism C x lo3 KA KK KH KKH KAH KAK constants deviations

At a temperature of 572F
A 0.640 1.04 0.221 0.076 None 2.12 x 10-g
B 0.620 2.72 0.324 None 2.11 x 10-9
C 0.570 2.41 0.158 None 2.08 x 1O-g
D -0.110 -4.43 -3.83 13.2 3 8.05 x lo-lo
E 0.310 -0.263 1 2.38 x 1O-9
F 0.390 0.585 None 2.26 x lo-
G - 0.700 34.3 18.3 -12.7 2 2.78 x 1O-9
H 0.160 -4.66 2.10 1 3.84 x 1O-9
I -1.51 83.7 - 39.7 -28.0 3 6.04 x lo-lo
J 0.140 -500 1.92 1 1.79 x 10-9

At a temperature of 662F
A 2.71 -0.966 1.88 0.034 1 1.12 x 10-a
B 2.76 - 0.263 5.01 1 1.66 x 10-E
C 1.32 -0.757 0.030 1 9.20 x 10-a
D 5.65 9.21 -0.137 o.OOO+ 1 1.97 x 10-a
E 5.87 9.59 None 1.97 x 10-a
F 1.60 -0.021 1 9.32 x 10-s
G 0.280 -2.14 0.45 1 1 9.25 x 10-E
H 0.360 -340 0.749 1 9.92 x 10-s
I 0400 -3.03 0.878 0448 1 2.08 x lo-*
J 0.320 -1.96 0.241 1 1.71 x 10-s

At a temperature of 752F
A 5.64 - 0.962 0.211 -0.108 2 9.24 x 10-s
B 5.94 - 1.83 0.359 1 1.31 x 10-7
C 5.18 - 1.46 -0.169 2 1.54 x 10-7
D 0.370 - 2.92 -3.01 9.18 2 5.57 x 10-T
E 7.97 0.128 None 4.28 x 1O-7
F 6.59 -0444 1 3.85 x 1O-7
G 1.54 -4.94 -0.216 1.10 2 5.51 x 10-7
H 1.65 - 5.54 1.24 1 6.24 x 1O-7
I 1.12 - 1.69 - 0.954 0.181 2 4.62 x 18-*
J 1.61 -411 0.755 1 3.10 x 10-7

At a temperature of 842F
A 31.8 1.48 -0.335 0.373 1 1.25 x 1O-6
B 28.9 4.19 - 0.526 1 1.35 x 10-C
C 39.3 4.37 0.712 None 1.48 x 10-e
D -40.1 -6.17 -8.61 19.3 3 1.70 x 10-G
E 21.3 -0.133 1 2.06 x lO-j
F 34.5 1.49 None 1.88 x 10-G
G 4.86 2.24 - 1.57 0.222 2 1.70 x 10-a
H 9.41 -6.14 2.82 1 1.65 x 1O-6
I 3.65 2.96 -1.93 0.474 1 2.58 x 1O-6
J 9.91 - 6.08 3.04 1 2.05 x lO-6

315
 F. E. FORDand D. D.
At the highest temperature studied, and at the
lowest temperature, the rate data calculations gave
positive constants for more than one mechanism.
However, both temperatures (572 and 842F) yield
the same result when the sums of squared devia-
tions are compared; the best fit occurs for the
mechanism of single site surface reaction control-
ling, the adsorbed species being hydrogen. This
rate relation (mechanism C) is
DISCUSSION
It is not particularly surprising to fmd a transi-
tion from one controlling mechanism to another
as temperature is varied, since the earlier studies
mentioned showed similar behaviour. It is especially
interesting, however, to find that at a still higher
temperature there is a second transition to what is
most probably the original mechanism. The data
at 572 and 842F do admit the possibility of inter-
pretation based on mechanisms other than C, leav-
ing the decision to be made on a best-fit basis.
As a result there is a greater degree of uncertainty
on this point, than on the applicability of mecha-
nism E at the intermediate temperatures. On the
other hand, the results are unambiguous in demand-
ing an interpretation which includes two changes
in mechanism: E must be discarded at 572 and
842F because of large negative constants. Clearly
the data do not fit the same mechanism at all tem-
peratures.
The work of THODOSand THALLERon the same
chemical system in a tubular reactor showed that
at a constant pressure of 1 atm a transition between
mechanisms would be expected at about 600F;
thus these workers agree that the mechanism would
not be the same at 572F as at 662F. Unfortun-
ately, no data were taken above 750F in the
earlier study. At this temperature they indicate the
mechanism would be the same as that at 662F.
An analysis of their data and explanation suggest
nevertheless that it would indeed be possible for
the mechanism to revert to the original low-
temperature mechanism at sufficiently high tem-
peratures. In THALLER and THODOSFig. 4 the
PERLMUTIER
envelope of the region of the intermediate
mechanism appears to shift to higher pressures at
high temperatures, and would perhaps recross the
I-atm line at some point.
The mechanisms offered by THODOS and co-
workers are not the same as those found in this
study. It may be well to note differences in the
investigations which might give rise to this dis-
crepancy. In the work of THODOSthe brass catalyst
was 65-35x copper and zinc; in this study 60-40
brass was used. The prior work did not use an
inert diluent to obtain independent variation of
all three active-component partial pressures. As
noted above, the earlier work used a considerably
more active catalyst. It is possible that an alter-
native mechanism favoured by the more active brass
overpowered those found in this investigation.
The constants for the two applicable mechanism
equations (2) and (3) are plotted against reciprocal
temperature in Fig. 4. It is interesting to note that
both positive and negative slopes appear (depend-
ing on the mechanism). It has generally been
o-
.O-
IO-
Solid lines: mkchanism C
Dashed lines: mechanism E
)I -
)I -
O.OC
Reciprocal temp., OR-
FIG.4. Temperature dependence of rate and equilibrium
constants.
376
 The kinetics of the brasscatalysed dehydrogenationof set-butyl alcohol

assumed in the literature that adsorption constants region, a path is traced which evidently represents
must have negative temperature coefficients, and the mechanism shift as found in this study. At the
the majority of experimental evidence supports intermediate temperatures of 662 and 752F the
this view. There have, however, been several higher curve is the alcohol adsorption curve, while
studies [l, 2, 51 that report positive coefficients at the extreme temperatures the surface reaction
such as reported here for the adsorption equilibrium
constants involved in the single site surface reaction
controlling mechanism. It should be noted that
two of these studies are those of THODOSfor this
same chemical system.
Thermodynamic considerations lead to the con-
clusion that the adsorption equilibrium constant
should decrease as temperature increases. The
increased thermal energy associated with the ad-
sorbed species at higher temperatures would lead
to a higher probability of finding a molecule in the
gas phase. The desorption rate is thus increased,
and the equilibrium constant, here defined as the
forward (adsorption) rate divided by the reverse
rate, would decrease. There appears to be no
reasonable alternative to this reasoning at the
present time. However, in dealing with the entire
catalyst, there is present the possibility that at
higher temperatures more adsorption sites are
activated; thus while the distribution at a single
site favours the gas phase, the adsorption summed
over all sites could be increased by an increase in Temperature, F

temperature. FIG. 5. Temperature dependenceof reaction rate.

Since two distinct mechanisms apply to this
system there are only two temperature points for
each mechanism. It is felt that these data are in-
sufficient to justify a computation of activation
energies and heats of adsorption. In order that
qualitative comparisons may be made, however,
the over-all apparent activation energy of the reac-
tion (the slope from the Arrhenius plot of the con-
stants C) is useful. These figures are 18.5 kcal/g mol
for the mechanism in which the controlling step
is the adsorption of alcohol, and 100 kcal/g mol
for the surface reacting mechanism.
The mechanism shift found in this study may
also be illustrated by showing the relationships
between reaction rate and temperature for the two.
This is done in Fig. 5, where calculated curves are
superimposed (for both cases, the partial pressure
of each active component was taken as O-25). These
curves cross at about 630 and 790F. By following
the higher of the two curves across the temperature
mechanism results in a higher reaction rate. An
increase in temperature beyond 572F increases
the rate governed by the single site surface control-
ling mechanism, but also increases the rate at
which alcohol is being adsorbed. This increase is
reflected in an increase in the primary rate con-
stant Cin the alcohol adsorption mechanism (Fig. 4).
The surface rate, originally much slower than the
alcohol adsorption rate, increases with temperature
at a greater rate than does the adsorption step, and
thus gives way to the slower rate of adsorption as
the controlling step.
The rate expressions also show why the curves
cross a second time at higher temperatures. The
temperature dependence of the adsorption mecha-
nism constants is negative, while the adsorption
equilibrium constant in the surface mechanism
exhibits a positive temperature dependence. As a
result, the temperature derivatives of the two rate

377
 F. E. FORD and D. D. PERLMUIVR

mechanisms will have opposite signs, indicating
that an intersection will occur. In general an inter-
section of the temperature dependence curves of
the various rate constants might be expected. The
fact that dual mechanisms are not commonly
reported is probably to be attributed to the rela-
tively restricted temperature range of most
investigations.
CONCLUSIONS
the results of this study indicate that a reverse
transition to the original low-temperature mecha-
nism occurs at about 800F.
Under the conditions used in this study, it may
be concluded that the experimental data best fit
the m~hanism models in which the adsorption of
alcohol is the controlling mechanism at tempera-
tures between 662 and 752F, and the single site
surface reaction is the controlling mechanism at
temperatures outside this range.

This study represents the first application .of a Acknowledgement-This work wassupportedby a grant from
the Petroleum Research Fund. The authors wish to acknow-
stirred vessel reactor to the study of a surface- ledge with thanks the support of the fund donors.
catalysed gas-phase reaction mechanism. The sec-
butyl alcohol dehydrogenation reaction was chosen
for this investigation because it had previously NOTATION
been reported to show mechanism peculiarities in A Surface area of catalyst ft
other reactor geometries. Comparisons show that F Feed rate of reactants lb mols/hr
K Adsorption equilibrium constant atm-l
there are many areas of qualitative agreement Over-all equilibrium constant atm-l
KE
between the work done in tubular flow systems P Partial pressure in the gas phase atm
and the stirred reactor work reported here. c Primary kinetic constant lb mols/hr ft2 atm
Reaction rate lb mols/hr ft2
The results of this inv~tigation indicate that if Fractional conversion
A;
the now-classical approach [4] is at all applicable,
there is a definite shift in the mechanism of the Subscripts
reaction as temperature is varied. While the pre- A Alcohol
vious studies cited agree that there is a change in H Hydrogen
K Ketone
the reaction mechanism at about 600F at 1 atm,

REFERENCES

111 THALLERL. H. and THODOSG., Amer. Inst. Chem, Engrs. J. 1960 6 369.
PERONAJ. J. and Tnonos G., Amer. Insf. Chem. Engrs. J. 1957 3 230.
;; HOELSCHERH. E., Amer. Inst. Chem. Engrs. J. 1957 3 144.
[41 HOUGAN 0. A. and WATXIN K. M., Chemical Process Principles Vol. Hf. John Wiley, New York 1947.
PI SUSSMANM. V. and POTTERC., Zndustr. Engng. Chem. 1954 46 457.

R&m&--On a etudie la cinetique de la d&hydrogenation de lalcool butylique secondaire a des

temperatures allant de 572 a 842F sur un catalyseur de bronze et dans un reacteur agite.
Des etudes anterieures ont rev& qua des temperatures allant de 550 a 700F et I atm la
deshvdrodnation
_ _ aurait bien selon un mecanisme dual-site. Les r&hats present&s ici semblent
confirmer ce mecanisme.
Une seconde transition semble avoir lieu aux environs de 8OOF, temperature a laquelle le
mecanisme predominant a basse temperature semble reprendre le dessus.
On discute encore les avantages du reacteur agite.

Zusammeufassung-Es wurde die Dehydrierung von set-Butylalkohoi an einem Messing-Katalysator

bei Temperaturen von 300 - 450C unter Atmospharendruck in einem Rtibrkesselreaktor untersucht.
Der untersuchte Temperaturbereich iiberschreitet denjenigen friiherer Untersuchungen, die gefunden
hatten, dass sich im Bereich von 290- 370C der Reaktionsmechanismus Pndert. Es konnte daher
nachgewiesen werden, dass oberhalb 425C die Reaktion nach einem dritten Mechanismus ablauft.
Verschiedene Vorteile des Rtihrkesselreaktors werden diskutiert.

378