Chemical Engineering Science, 1964, Vol. 19, pp. 807-818. Pergamon Press Ltd., Oxford. Printed in Great Britain.

Kinetic study of the dehydrogenation of ethanol

J. FRANCKAERTS and G. F. FROMENT

Laboratorium voor Organische Technische Chemie, Rijksuniversiteit Gent, Belgium

(Received 5 May 1964)

Abstract-The catalytic dehydrogenation of ethanol into acetaldehyde was studied in a flow apparatus
in the temperature range 225285°C at pressures varying between 1 and 10 atm and W/FAO values
ranging from 0.2 to 1.6 g.hr/mole. By the method of initial rates the rate-controlling mechanism was
found to be the surface reaction on dual sites, without dissociation. The adsorption- and kinetic
coefficients were determined by the method of least squares applied to the reaction rate equation.
Statistical tests were performed on these coefficients and the closeness of fit of the multiple regression
was also calculated. The temnerature denendencv of the rate- and adsorption coefficients was formu-
lated according to Arrhenius:

I. INTRODUCTION of ethanol and water will be referred to as “pure”

feed, the mixture of ethanol, water and acetaldehyde
THE HOUGEN and WATSON type of rate equations as “mixed” feed.
for reactions catalysed by solids are widely known
and used. Yet, the number of kinetic studies com- 2. Catalyst
prising sufficient experimental data to justify an
approach along the HOUGEN and WATSON lines [7] The catalyst was prepared according to the recipe
is deceivingly small and the physical meaning of the of CHURCH and JOSHI [l] and contained in the un-
values found in most cases appears to be extremely reduced state CuO with 5 % Co0 and 1% Cr,O,,
doubtful. In this respect it seems meaningful that precipitated on asbestos.
to-day, 17 years after the publication by HOUGEN
and his collaborators of their now famous study of 3. Apparatus
the hydrogenation of iso-octenes [6], investigators
advocating mathematically more sophisticated A flow diagram of the apparatus is given in Fig. 1,
methods of approach still have to go back to this which is self explanatory, save perhaps for a few
so-called “codimer’‘-example for their data [8, lo]. special features of the reactor.
This work reports on an extensive kinetic study The reactor was constructed from Cr-steel, free
of a potential industrial process, namely the pro- of Ni, had an inside diameter of 3.3 cm and a length
duction of acetaldehyde by ethanol dehydrogenation. of 110 cm. It consisted of two sections, a preheat
It is presented here mainly as an illustration of the and a reaction section with independent wiring. The
present-day status of the methods for establishing heat flux in these sections was adjusted by variable
the rate equations of reactions catalysed by solids. transformers. The temperature in the reaction sec-
tion was measured by three Ni-Ni-Cr-thermo-
couples, inserted in a central tube of O-6 cm o.d. and
II. APPARATUS AND EXPERIMENTAL PROCEDURE recorded on a Hartmann-Braun mV-recorder. The
catalyst was placed in the lower section of the ver-
1. Feed stock
tical tube and was mixed with inert material, por-
In most experiments the ethanol fed was the celain, in order to realize isothermal conditions.
binary azeotrope containing 135 mole % water. The preheat section and a short section at the bot-
In a number of experiments the reaction product, tom of the tube were packed with porcelain only.
acetaldehyde, was added to the ethanol. The feed The pressure in the reactor was regulated by means

807
 and G. F. FROMENT
J. FRANCKAERT~

FIG. 1.
m
! 21

I I
2

Apparatus: 1,2, feed burettes; 3, metering pump; 4, thermocouples; 5, ice-bath; 6, mV-recorder; 7, reactor;
8, reactor-mantle; 9,10, variable transformers; 11,13, manometers; 12, pressure regulating device; 14, cooler; 15, cooling
unit; 16, circulating pump; 17, sampling flask; 18, liquid air trap; 19, saturator, eventually also absorber in periods
between sampling; 20, wet test meter; 21, flowmeters for air and nitrogen.

of a special membrane-device, located at the reactor III. EXPER~MJSNTAL

PROGRAMME
AND RESULTS
outlet.
1. Side reactions
4. Experimental procedure and analysis Analysis of the liquid samples indicated that
ethylacetate was formed in small amounts, probably
Depending upon the experimental conditions a
according to the reaction:
stabilizing period of about l-1-5 hr was observed
at the start of each run, due in part to temperature 2 CH&HO + CH,COOC,H, (1)
effects associated with the reduction of the catalyst.
Because of the low conversions to ethylacetate and
After stabilization liquid samples were taken in a
the scatter of the data no attempt was made to
flask cooled by liquid air. The samples were
establish a rate equation for this reaction, but the
weighed and analysed by gas-chromatography on
following linear relationship was found to hold
a Carbowax 1500 Chromosorb-column at a tem-
over the whole temperature range investigated:
perature of 100°C and with He as carrier-gas.
From time to time gas-samples were taken and xE
_ = @0363x,._
analysed with an Orsat-apparatus. After each run
The analyses of the exit-gas led to the following
nitrogen was sent through the reactor in order to
observations :
remove the remaining gases and adsorbed reaction
partners. After flushing for about 2 hr the carbon- 1. Below 300°C the gases contained l-2 mole %
aceous deposit was burnt off with air at a tempera- of CO and CH,, probably resulting from acetal-
ture of 400°C and the catalyst was reoxidized. dehyde decomposition.

808
 Kinetic study of the dehydrogenation of ethanol
2. No ethylene was found below 300°C so that no
dehydration of ethanol took place.
3. In all cases the effluent hydrogen had a purity of
96-99 %.
The ethanol conversion based on the analysis of
the liquid sample equaled that based on the hydro-
gen production.
Hence ethanol was converted only by a single
reaction, namely:
CH,CH,OH * CH,CHO + H,
2. Equilibrium constant
As reaction (2) does not go to completion in the
temperature range 225-285”C, it was found neces-
sary to determine the values of the equilibrium con-
stant experimentally at those temperatures. Fig. 2
shows the results.
3. Infuence of the resistance qf the external$lm
Preliminary calculations, using the method of
YANG and HOUGEN [2], indicated that mass-transfer
effects were negligible at the space velocities used.
A set of experimental data, obtained by varying
the mass velocity of the feed, while maintaining
W/F*, constant, confirmed these calculations.
-a-
, 80
FIG. 2. Equilibrium constant as a function of l/T.
4. Influence of the resistance to internal transport
Semi-quantitative calculations, based upon the
method of CHOU and HOUGEN [3], showed that the
influence of the resistance to internal diffusion was
negligible.
5. Thermal cracking
In the temperature range 225-285°C no thermal
cracking was found to occur in a series of blank
runs.
(2)
6. Fouling
The activity of the catalyst was found to decrease
with process time. The deactivation was probably
due to a gradual polymerization of the reaction prod-
uct acetaldehyde on the catalyst surface [4]. By re-
generation of the catalyst the carbonaceous material
was oxidized to CO and CO,. The CO was con-
verted on CuO into COZ, which was absorbed in
KOH and ascarite. The amount of COZ is a
measure of the amount of carbon deposited on the
catalyst. A discussion of the formation of carbon-
aceous deposit and a graph showing the effect of
fouling upon the catalyst activity is given in [5].
It was shown that for the short process times dealt
with in this work the fouling-effect was negligible.
190 2;oo
809
 J. FRANCKAERTS
and G. F. FROMENT
I. Conversion vs. W/F,,-diagrams
In this section a brief survey is given of the ex-
perimental programme designed for the elucidation
of the reaction mechanism and the determination
of the unknown coefficients of the rate equation.
In order to sweep a wide range of space velocities
three different weights of catalyst were used resp.
3; 6 and 10 g so that it became possible to obtain
data at W/FA, values of 0.2; 0.4; 0.6; 0.88 and
1.6 g.hr/mole.
With “pure” feed x, vs. W/F*,-curves were estab-
lished at total pressures resp. 1,3,4,7 and 10 atm;
with “mixed” feed at 1 and 3 atm.
“Mixed” feeds of the following compositions were
used :
67.2 mole % ethanol, 18.3 mole % acetaldehyde
and 14.5 mole % water;
75.0 mole % ethanol, 11.9 mole % acetaldehyde
and 13.0 mole y0 water ;
FIG. 3. Conversion XAas a function of
73.2 mole % ethanol, 9-l mole % acetaldehyde
and 16.7 mole % water;
79.6 mole % ethanol, 4-O mole % acetaldehyde
and 158 mole ‘A water.
The temperatures investigated were 225,235,250,
265,275 and 285°C.
Complete tabular material may be found in [5].
By way of example the data obtained at 1 atm with
“pure” feed are represented in Fig. 3 in the form
of x,- W]FAO-curves.
IV. ELUCIDA~ON OF THE RATE-CONTROLLING
STEP
The elucidation of the rate-controlling step was
based on the differential method.
From the conversion x,, the partial pressures of
ethanol, acetaldehyde, hydrogen and water were
easily calculated, e.g. in the case of “pure” feed
W/FAo forpl = 1 atm and “pure” feed.
 Kinetic study of the dehydrogenation of ethanol

FIG. 4. TAOas a function of pa0 for pure feed.

according to : The initial rate is then given by:

1- XA XA
‘=APAo
PA = 1.155 + XAk’t; PR = PS = 1.155 + xA Pt rAo= [l + ~,pA,lz

and which means that straight lines should be obtained

0.155 when J(PAo/rAo) is plotted as a function of pAo.
(3) This is shown to be true in Fig. 5.
pw = 1.155 + XAPt
In fact, the denominator in (4) should also reflect
The reaction rates, rA, were found by numerical the possibility that water may be adsorbed on the
differentiation of the xA-W/FA,, curves. The initial catalyst and therefore contain a term K,,,p,,. The
rates or rates at zero conversion, rA,, were deter- straight line observed in the diagram J(PAo/rA,,)
mined by calculating the slopes of the conversion vs. PA, may be explained either by the absence of
curves in the origin. any effect of water or by the linear relationship
The kinetic mechanism .for the dehydrogenation existing between PA, and pw, in the experiments
of ethanol was selected according to the method with “pure” feed, namely pw, = O-155pa,.
outlined by YANG and HOUGEN[2] and which in- Consequently the complete rate equation for the
volves consideration of the effect of the total pres- reaction has the form:
sure, pt, on the initial rates, obtained with “pure”
feeds. The shape of the curves r,,, or groups con- kK,[&, - y]
taining rA,, vs. pt reveals unambiguously the rate-
(5)
controlling step. rA = c1 + KApA + KRpR + &PS + k&i,2

In Fig. 4 the data are plotted as suggested by

YANG and HOUGEN. It follows from the shape of In this equation an adsorption term for water has
the curves that the reaction is controlled by the been accounted for but the term for ethylacetate
surface reaction on dual sites. has been neglected.

811
 J. FRANCKAERTSand G. F. FROMENT

25

FIG. 5.

V. EVALUATION OF THE RATE- AND ADSORPTION linear regression. From (7) the values of the rate-
COEFFICIENTS and adsorption coefficients may be calculated for
each temperature investigated.
The numerical values of the rate and adsorption
According to HOUGEN and WATSON a proposed
coefficients are evaluated simultaneously by means
rate-equation is consistent and acceptable only
of the method of least squares.
when positive values are found for each of the re-
For this purpose equation (5) is transformed into
gression coefficients. However, if a mechanism is
an expression linear in the unknown coefficients,
to be rejected on the basis of a negative regression
which are combinations of the rate- and adsorption
coefficient, it is necessary that this coefficient be
coefficients :
significantly different from zero [8]. The required
y= a+bp,+Cp,+dp,+ep, (6) information about the significance of the regression
where coefficients may be obtained by some supplementary
PRPS statistical calculations.
PA-7 .
9 To establish whether a regression coefficient bj
Y= is significantly different from zero, use is made of
J( f-A 1
the t-test
b=-&+ c=&; t=bi-O
a=&; (8)
s(bJ
&3- and e= (7) From a r-distribution table [9] the probability
&=_-i) Jo P, corresponding to the calculated t value with
As the partial pressures, the reaction rate and the (n - g - 1) degrees of freedom may be found.
equilibrium-constant are known, the most probable When this probability is larger than a predetermined
values of the regression coefficients a, b, c, d and e value, the result of the test is non-significant, when
in equation (6) may be determined by multiple smaller, significant. In this work a regression co-

812
 Kinetic study of the dehydrogenation of ethanol

efficient is considered to be significant if its P value Table 1. Number of experimental points n = 5

is 5 ‘Aor less and as highly significant if its P value is (p, = 1,3,4, I and 10 atm) Confidence limits: 95 %
1% or less; any regression-coefficient, whose P
value is larger than 5 ‘A is nonsignificant. Further- Temp. (“c) k III to.o5s(k) Ka zb to.oss(KA)
more, if a regression coefficient bj is found to be non-
225 1.07 * 0.49 0.74 f 0.34
significantly different from zero, the corresponding 235 1.30 f 0.32 0.62 f 0.15
variable may be deleted. 250 l-71 f 0.36 0.46 f O-11
In addition, the adequacy or significance of the 265 2.96 f 1.29 O-37 z 0.16
275 4.03 + 0.22 0.40 f 0.02
multiple regression may be checked by means of 285 5.58 f 1.25 0.44 f 0.10
the F-test:
c c2
F= (9) If the logarithms of the values of k and & from
s2(E>.s
Table 1 are plotted as a function of l/T, the activa-
In the preceding section it was shown by the use tion energies and frequency factors can be calcu-
of the method of initial rates that the rate-controlling lated, also by means of the method of least squares.
mechanism is the surface reaction on dual sites. The Arrhenius equations are:
In this section this conclusion will be tested by
15300
applying linear regression together with statistical In k = - RT f 15.32; ln K, = 5560 - 5.97
tests to the complete rate equation (5). These tests RT
will be carried out on a number of different com- (b) Data at all values of WIF,,
binations of the experimental data built up, e.g. Consideration of the data at WJF;,, # 0 in addi-
by the data obtained with “pure” feed only or by tion to those at WIF,, = 0 permits the sum
the data obtained with both “pure” and “mixed” KR + KS to be calculated and the values of k and
feed. In this way the possibilities and limitations of KA to be checked.
each set of data will be demonstrated and it will Omitting in equation (5) the term ep, for reasons
become clear what type of experiments are needed which will be justified further and noting that
for kinetic studies of this kind. pR = pn the following expression is obtained:
1. Using “pure” feed only y” = a + bp, + C’p, (12)
(a) Data at W/F*, = 0 where
From (5) it follows that at W/F,, = 0

Y’ = a + bp,,, + epwo (10) and c’ = Kg

where A

The results of the regression are given in Table 2.

The values of Table 2 are in fair agreement with
From equation (10) the coefficients a, b and e those of Table 1, which indicates that the proposed
cannot be determined simultaneously because of the complete rate equation is consistent over the whole
fixed ratio between PA,, and pw, (p,, = 0’155p&), range of W/FA, values and temperatures. From
which leads to a zero determinant for the system plots of In k and In KA vs. l/T the following
of normal equations. Arrhenius equations are found :
Omitting p,,,, (10) reduces to :
15860 5830
y’ = a + bpAO
Ink= - - RT + 15.85; In KA = - - 6.33
(11) RT

When y’ is plotted as a function of PA,, straight It is obvious that, in order to determine the
lines are obtained whose slope is b and intercept a numerical values of KR and KS separately, results
(see Fig. 5). of experiments with “mixed” feeds, containing either
The results of the regression are given in Table 1. acetaldehyde or hydrogen, must be available.

813
 J. FRANCKAERTS and G.F. FROMENT

Table 2. Confidence limits: 95%

Temp. (“C) n k i to.oss(k) KA i ~O.OSS(KA) (KR f KS) f to.osS(KR + KS)

225 22 0.99 & 0.29 0.69 & 0.19 6.20 f 2.23

235 24 1.26 & 064 0.55 f 0.28 4.85 + 2.87
250 27 1.70 f 0.56 0.43 * 0.14 2.80 f 1.06
265 27 3.00 * 0.65 0.36 & 0.08 2.94 f 0.63
275 28 4.23 4 0.73 0.37 * 0.06 2.70 f 0.43
285 27 5.37 & 1.21 0.37 & 0.08 2.12 f 0.45

2. Using both “pure” and “mixed”.fl?eds In this case the regression coefficient e can be deter-
(a) Data at WII;,, = 0 mined because the water contents of the feeds used
For “mixed” feeds, containing ethanol, water and differ slightly from one series to another. The co-
acetaldehyde, equa+;^* /a Lannm~n*
Cl”U\J/ “Cb”IIIGJ. efflcients of (13) are determined at each temperature
by multiple regression using the data at W/F,, =0
y”I = a + bpAo+ epwo and “pure” and “mixed” feeds. The values of the
cpRo + (13)
regression coefficients together with those of t and
where F at 225, 250 and 275°C are given in Table 3.
Table 3 indicates that the adequacy of equation
(13) is excellent although the regression coefficient
e is not significant. Even the consideration of the

Table 3. Number of experimental points n = 10. Conjidence limits: 9.5 %

Temp. (“C) af to.oss(a) b & to.oss(b) c f to.oss(c) e f to.oss(e)

225 1.29 & 0.40 1.24 f 1.18 6.43 f 417 -2.81 f 7.59
235 1.16 f 0.21 0.90 f 0.62 4.14 f 2.20 -1.38 f 3.99
2.50 1.04 * 0.20 0.62 & 0.58 2.95 & 2.06 -0.53 f 3.75
265 0.93 f 0.17 0.54 f 0.50 2.09 i 1.78 -1.16 k 3.24
275 0.76 k 0.09 0.50 f 0.25 1.82 i 0.89 -1.19 & 1.62
285 0.61 f 0.16 0.26 & 0.86 1.34 f 1.75 0.17 f 5.58

Temp.(“C) Valuesoft Valuesof F

a 7.94 (HA)
225 b 260 (S.) 1.126 (H.S.)
c 3.81 (H.S.)
e 0.92 (N.S.)

a 11.62 (H.S.)
250 b 2.70 (S.) 2.247 (H.S.)
c 3.54 (S.)
e o-34 (N.S.)

a 21.90 (H.S.)
275 b 4.94 (H.S.) 4.840 (H.S.)
c 5.05 (H.S.)
e 1.81 (N.S.)

H.S. = highly significant

S. = significant
N.S. = nonsignificant

814
 Kinetic study of the dehydrogenation of ethanol

results of additional experiments in which the water
content of the so-called “pure” feed was extended
to 22.8 mole % water did not lead to significant
values for e. The reason for this may be of physico-
chemical nature or simply because the water con-
tent of the feed was still not varied over a sufficient
range.
Now, if a nonsignificant regression coefficient is
found, the corresponding variable may be deleted.
This is the reason why the term ep, was omitted
in equation (12).
By deleting the term ep,, equation (13) is simpli-
fied to:
J”” = U + bp,, + Cp& (14)
The results of the regression are given in Table 4.
(b) Data at all values of W/F,,
If experiments are carried out at different values
of W/F*, with “mixed” feeds, whereby pR # ps,
it is possible to calculate simultaneously k, KA, KR
and KS. Deleting again for statistical reasons the
term ep,, equation (5) is reduced to:
y = U + bp, + cp, + dJ’, (15)
Taking into account all data, obtained at different
W/FAo values and with “pure” and “mixed” feeds,
the following values are found (see Table 5).
It can be seen that the four coefficients are posi-
tive for all temperatures investigated. The t test
has shown, however, that only three of them are
significant and that the fourth, namely KS, is not.
In this case, however, the term Ksps is kept in

Table 4. Number of experimental points n= 10. Confidence limits: 95 %

Temp. (“C) k i fo.o&) K, & to.oos&) K, f to.oss(K&

225 O-98 f 0.33 0.63 f 0.21 4.31 f 298

235 1.26 f 0.24 0.59 f 0.11 3.17 i l-62
250 1.79 & 0.42 o-49 + 0.12 1.92 f 1.84
265 3.04 f 064 0.39 f 0.08 1.83 f 1.65
275 4.16 f 0.62 0.42 f 0.06 1.88 f 1.14
285 5-55 f 1.10 0.46 f 0.09 2.49 f 1.60

The t test shows that all coefficients of Table 4 are
significant positive. The values for k and KA are
in agreement with those of Tables 1 and 2, obtained
with “pure” feed and resp. W/FAo = 0 and all data.
From a plot In k, In KA and In KR as a function
of l/T the following Arrhenius equations are
derived :
the rate-equation because it concerns a reaction
partner.
In Fig. 6 the values of In k, In KA, In KR and In KS
from Table 5, based on all the data, are plotted as
a function of l/T. The values of the constants in
the Arrhenius-equations are calculated by means of
the method of least squares:

ln k = - g + 16.14; ln K, =g - 4.20; ln k = - g + 16.25; ln KA = g _ 6.40

11070 6850
In K, = ‘g - 4.13 InK,== - 9.40; In K, = RT - 7.18 (16)

Table 5. Confidence limits: 95%

tP.3 n k f to.oss(k) K, f to.o&K) K, f to.oss(K& K, f to.oss(Ks)

225 48 l+m f 0.50 0.73 f 0.36 7.28 h 5.17 0.76 f 4.19

235 48 l-20 + 0.35 0.50 f 0.15 4.47 + 245 0.66 f 2.21
250 52 1.66 i 0.35 040 & 0.08 2-23 & 1.55 0.49 f 144
265 52 3.02 f 0.45 0.35 f 0.05 2.48 * 1.05 0.41 f 0.97
275 53 4.30 f 0.57 0.36 f 0.05 2.35 3 0.98 0.39 + o-91
285 33 5.39 f 1.05 0.37 f 0.07 1.76 f 2.19 0.37 f 212

815
 J. FRANCKAERTSand G. F. FROMENT

IO-

__--
--
o.o-

1 r KS:

___---
ES’ -s..dso
__II-
___--- -@--

1;
__ --
q e
___---
__--
6D KA E*z. s.sso
-I
_---
U___----T-- e
+.d

FIG. 6. In k, Ka, KR, KS as a function of l/T (data of Table 5).

3 2:o

FIG. 7. Comparison of calculated curves with experimental data.

t = 250°C
Experimental points at it = 1 atm
g Experimental points at it = 4 atm
I3 Experimental points at it = 10 atm
- Calculated curve at it = 1 atm
_--- Calculated curve at it = 4 atm
. .. .. . .. . Calculated curve at it = 10 atm

816
 Kinetic study of the dehydrogenation of ethanol

Although plausible the value of Es is subject ates the test of a great number of possible mechan-
to caution as it is derived from nonsignificant isms whereby the coefficients of the corresponding
&-values. rate equations are first calculated by the method
The closeness of fit of the derived kinetic equation of least squares and the selection of the proper
to the data may be examined by different methods, mechanism is based on the often unsufficient con-
one of which, the F test, has already been men- dition that all coefficients should be positive. In
tioned in Table 3. Other methods are: contrast to this the initial rate criterion used in
this paper leads unambiguously to the form of the
Comparison between experimental and calculated rate equation and the method of least squares is
rates used only once, namely to determine the numerical
When K,,,pw is omitted in equation (5) and the values of the unknown coefficients of the retained
values of k, KA, KR and KS calculated from the rate equation. In this way it was shown that the
Arrhenius equations (16) are substituted in this surface reaction on dual sites, without dissociation,
equation the following deviations between experi- is the rate controlling step in the dehydrogenation
mental and calculated r,-values are found (Table 6). of ethanol. Significantly positive values were found
for k, KA and KR, whatever the way the experimental
Table 6 data were combined. The positive values of KS
were shown to be nonsignificant. Negative values
Temp. (“C) Initial rate data (%) AN rate data (%) were found for K,,,. This was considered not to
225 25.1 26.8 affect the validity of the above conclusions as these
235 17.9 23.3 negative values were nonsignificant. Therefore the
250 5.6 17.3 adsorption term for water, which is not a reaction
265 15.3 16.2
215 15.4 18.7 partner, was deleted from the rate-equation (5).
285 14.9 29-l Codification of the experimental data, primarily
designed, however, in view of the initial rate ap-
mean: 15.8 21.8
proach, has shown that the effectiveness of the data
points forp, andp, is small, in spite of their number.
By way of comparison it may be noted that the
In other words : mathematically speaking, enough
mean deviation between experimental and calculated
information was available to determine KS and K,
r,-values for the codimer hydrogenation amounts
but the insufficient distribution of the ps- and
to 19.4% [6; 81, for the synthesis of ethylchloride,
p,,,-values may be responsible for the nonsignificance
investigated by THODOSand STUTZMAN,to 31.4 %
of the corresponding regression coefficients.
v11. Finally, it should be mentioned that high-speed
Comparison between experimental and calculated computers enable the application of non-linear
x,-W/F,, values regression to the problem under consideration [lo].
When the values of k, KA, and KR + KS from The experimental data obtained at the different
Table 2 are substituted into the integrated rate temperatures are then treated simultaneously and
equation and K, is again deleted, the x_.,-W/FA, the coefficients appear in (5) with their temperature
curves may be calculated. Figure 7 comprises experi- dependency. The first approximation of the co-
mental points and xA--W/FAO curves, calculated efficients fed to the computer are the values obtained
for 250°C and total pressures of 1.4 and 10 atm. by linear regression.
The same satisfactory fit is obtained at the other
temperatures investigated.
Acknowledgment-J. FRANCKAERTS is very grateful to the
VI. DISCUSSION “Nationaal Fonds Voor Wetenschappelijk Onderzoek” for
a grant of “Aspirant navorser”.
The present work clearly demonstrates the value The calculations were performed in the Digital Computing
of the initial rate approach. This approach elimin- Centre of the Rijksuniversiteit Gent.

817
 J. FRANCKAERTSand G. F. FROMENT

NOTATION Pt total pressure atm

rA reaction rate mole/hr.g.cat

bz
z regression coefficient = l/z/(kKa)
regression coefficient = K.&(kKA)
any regression coefficient
rAo, r’Ao

s(a, b, k, KA. .)
initial rates with resu.
feeds
_ “mire”
_ and “mixed”
mole/hr.g.cat
standard deviation of the coefficients a, 6,
c, c’ regression coefficients resp. Kn/d(kKa) k,KA..
and (KR f K.s)l/(kKa) s2 w variance of estimate
XC2 sum of squares of deviation removed by t temperature “C
regression Student’s “t’‘-distribution
d regression coefficient = Ks/d(kK_.t) i temperature “K
regression coefficient = K&(kKA) W weight of catalyst, unreduced g
; activation energy Cal/mole XA conversion of ethanol
F ratio of Fisher moles ethanol converted
zz
FAO feed rate of ethanol at the reactor inlet moles ethanol fed
mole/hr XE conversion of ethanol to ethylacetate
number of independent variables moles ethylacetate formed
i reaction rate coefficient mole/hr.g.cat =
moles ethanol fed
K equilibrium constant atm
KA, KR, . adsorption coefficients atm -l
n number of experimental points Subscripts:
P partial pressures atm A, R, S, W refer to ethanol, acetaldehyde hydrogen and
PO partial pressure at the reactor inlet atm water respectively.

REFERENCES

HI CHURCHJ. M. and JOSHIH. K., Industr. Engng. Chem. 1951 43 1804.

PI YANG K. H. and HOUGEN0. A., Chem. Engng. Progr. 1950 46 146.
[31 CHIEHCHOUand HOUGEN0. A., Chem. Engng. Sci. 1962 17 167.
[41 STEGNERG., BALANDINA. A. and RIJDENKO P., Izv. Akad. Nauk SSR-Otdel. Khim. Nauk 1959 1896.
PI FRANCKAERTS J., Kinetische Studie van de katalytische Dehydrogenatie van Ethanol to Acetaldehyde. Ph. D. thesis,
Labor. voor Oraanische Technische Chemie (Riiksuniversiteit Gent. Belgium1 1963.
161 TSCHERNITZ J., &RNS~VN S., BECKMANN R. h. &d HOUGEN0. A.,.TraG. Amer. Inst. Chem. Engrs 1946 42 883.
171 HOUGEN0. A. and WATSONK. M., ChemicalProcess Principles, Vol. III, Kinetics and Catalysis. Wiley, New York 1947.
PI CHAN-HUI CHOU, Zndustr. Engng. Chem. 1958 50 797.
[91 VOLK W., Applied Statistics for Engineers p. 99. McGraw-Hill, New York 1958.
BLAKEMORE J. W. and HOERLA. E., Chem. Engng. Progr. Symposium series. 1963 No. 42,59 14.
t::; THODOSG. and STUTZMANL. F., Industr. Engng. Chem. 1958 SO 413.

R&urn&-La d&hydrogenation de l’ethanol en acetaldehyde a Cte btudiee dans un appareillage a

ecoulement continu aux temperatures allant de 225 a 285”, aux pressions variant de 1 a 10 atm et aux
valeurs de W’/FA~allant de 0,2 a 1,6 g.hr/mole.
L’utilisation de la methode des vitesses initiales a permis de conclure que la vitesse de la reaction est
contrUe par la reaction a la surface sur deux sites adjacents et sans dissociation. Les coefficients de
vitesse et d’adsorption ont et& determines par la methode des moindres car&, appliquke aux tqua-
tions cinetiques. Ces coefficients ont Bte soumis B des tests statistiques. La variation des coefficients
de vitesse et d’adsorption avec la temperature a et& exprimee selon Arrhenius.

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