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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.
371
F. E. FORDand D. D. PERLMIJTER
CATALYST PREPARATION
372
The kinetics of the brass-catalysed dehydrogenation of see-butyl alcohol
373
F. E. FORD and D. D. PERLMUTTER
index of the goodness to fit as computed from sufficiently close, while others fit poorly, a case may
the deviations between experimental and computed arise such that only one mechanism is found with
rates. In interpreting these results, any mechanism positive constants. An examination of Table 2
that yielded one or more negative constants was shows that (of those postulated) there was only
rejected, since equilibrium and rate constants have one possible mechanism at the two intermediate
no meaning as minus numbers. In any case in temperatures studied, 662 and 752F. The conclu-
which there was more than one possible mechanism sion is that at these temperatures, the mechanism
(based on positive constants) the one was selected most applicable is that in which the adsorption of
which minimized the sum of the squared deviations. alcohol is the controlling step, while the surface
If the least-squares fit to any one mechanism is reaction occurs by means of a single site mechanism
c[PA- (PKPH/KE)l
= (~+KAPA+KKPKSKHPH)
C[PA- (PKPHIKEN
= PH[~+KAPA+KAH(PA/PH)-~KEIPH]
C(PA - (PxPEIKEI
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.
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. PERLMUTIER
At the highest temperature studied, and at the envelope of the region of the intermediate
lowest temperature, the rate data calculations gave mechanism appears to shift to higher pressures at
positive constants for more than one mechanism. high temperatures, and would perhaps recross the
However, both temperatures (572 and 842F) yield I-atm line at some point.
the same result when the sums of squared devia- The mechanisms offered by THODOS and co-
tions are compared; the best fit occurs for the workers are not the same as those found in this
mechanism of single site surface reaction control- study. It may be well to note differences in the
ling, the adsorbed species being hydrogen. This investigations which might give rise to this dis-
rate relation (mechanism C) is 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
DISCUSSION
more active catalyst. It is possible that an alter-
It is not particularly surprising to fmd a transi- native mechanism favoured by the more active brass
tion from one controlling mechanism to another overpowered those found in this investigation.
as temperature is varied, since the earlier studies The constants for the two applicable mechanism
mentioned showed similar behaviour. It is especially equations (2) and (3) are plotted against reciprocal
interesting, however, to find that at a still higher temperature in Fig. 4. It is interesting to note that
temperature there is a second transition to what is both positive and negative slopes appear (depend-
most probably the original mechanism. The data ing on the mechanism). It has generally been
at 572 and 842F do admit the possibility of inter-
pretation based on mechanisms other than C, leav- o-
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
.O-
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-
IO-
peratures. Solid lines: mkchanism C
The work of THODOSand THALLERon the same Dashed lines: mechanism E
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;
)I -
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. )I -
An analysis of their data and explanation suggest
nevertheless that it would indeed be possible for O.OC
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
377
F. E. FORD and D. D. PERLMUIVR
mechanisms will have opposite signs, indicating the results of this study indicate that a reverse
that an intersection will occur. In general an inter- transition to the original low-temperature mecha-
section of the temperature dependence curves of nism occurs at about 800F.
the various rate constants might be expected. The Under the conditions used in this study, it may
fact that dual mechanisms are not commonly be concluded that the experimental data best fit
reported is probably to be attributed to the rela- the m~hanism models in which the adsorption of
tively restricted temperature range of most alcohol is the controlling mechanism at tempera-
investigations. tures between 662 and 752F, and the single site
surface reaction is the controlling mechanism at
temperatures outside this range.
CONCLUSIONS
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.
378