Kinetics of the Dehydrogenation of Ethanol to
Acetaldehyde on Unsupported Catalysts
A kinetic study of the dehydrogenation of ethanol to acetal-
dehyde on an unsupported catalyst of base composition CuO-
CqO, was carried out in an isothermal reactor fed with
A . PELOSO, M . M O R E S P , C. MUSTACHI* B . SORACCO
Istituto di Scienze e Tecnologie Dell’lngegneria Chimica,
Facolta di Ingegneria dell‘ Universita’ di Genova, Genova, Italy
ethanol 95% vol. in the temperature range 225-285°C
with space velocities 1.5 -7.5 LHSV at atmospheric pres-
sure.
The mechanism which was found suitable to describe the
reaction was that of surface adsorption on dual sites.
Taking into account interphase and intraphase diffusion,
the observed conversions of ethanol were reconstructed with
a standard error below l o % , thus confirming the validity of
the physical assumptions.
T
zyxwvutsrqp
he large scale diffusion of the industrial pro-
duction of acetaldehyde through ethanol dehy-
drogenation has been, so f a r , hindered by the poor
performance of the available catalysts, which gen-
erally exhibit a low activity and selectivity (con-
version less than 50% per pass and yields lower than
92 % ) . Further, they require frequent regeneration
cycles - a s much a s daily - to retain a sufficient
perf o~-rnance“*~’.
Adopting more active and specific catalysts may
therefore lead to a commercially convenient exploita-
tion, since present conversions a r e f a r removed from
the equilibrium onesc4’.
The behavior of a few unsupported commercial
catalysts of composition CuO-Crz03 and CuO-BaO-
Cr203 in a fixed bed reactor was formerly investi-
gatedI4’ to get higher yields than those mentioned
above, with no major loss of activity f o r a t least
150 h of operation.
The present paper reports on a successful attempt
t o identify the controlling kinetic mechanism of the
reaction carried out with the unsupported catalyst
which provided the best performance.
A number of runs were made a t atmospheric pres-
sure in a fixed bed reactor fed with ethanol 955%
vol., varying the potentially more significant factors
(space velocity and reaction temperature) within
ranges of practical interest.
Analysis of the observations were carried out by
means of a sequential methodology. A t first, various
possible reaction mechanisms were examined under
the assumption of isothermal conditions, plug-flow
and no transfer resistance between the fluid and
the solid.
The only mechanism which was found acceptable
was that of a dual-site surface reaction of the ad-
sorbed ethanol. However, though this mechanism al-
lowed a rather satisfactory reconstruction of the
observed conversions of ethanol, an attempt was made
t o improve it. So the model was perturbed by taking
into account the diffusion phenomena. Using a non-
’Iatituto di Chimica Applicata e Industriale, Facolta di Ingegneria
dell’universita’ di Roma, Roma. Italy.
The Canadian Journal of Chemical Engineering, Vol. 57, April, 1979
z
zyxwv
zyxw
zyx
zyxwv
On a fait une 6tude cinktique de la transformation de
l‘alcool kthylique en acktaldehyde SUI un catalyseur non s u p
port6 dont la composition de base h i t CuO-CrzOs; on a
7.5 LHSV, zyx
employ6 a cette fin un rCacteur isotherme aliment6 avec de
l’alcool 6thylique a 95% en volume, sur une gamme de
tempkrature comprise entre 225°C et 285°C; ainsi que des
vitesses spatiales (inverse du temps de passage) de 1.5 B
pression atmosphkrique.
On a trouvC que le mkcanisme appropriC pour d6crire la
rtaction Ctait l’adsorption superficielle sur un double site.
En tenant compte des diffusions interne et externe, on a
pu reproduire les conversions de l’alcool kthylique observhes,
avec une erreur standard infkrieure i l o % , ce qui confirme
la validit6 des hypoth6ses physiques.
linear regression t o f i t the observations, the kinetic
parameters of the second model were determined, al-
lowing a f a i r reconstruction of the observed results
with a standard error below 10%) thus confirming
the validity of the physical assumptions.
Apparatus and experimental procedure
1. Catalyst
A commercial Harshaw copper chromite catalyst
was used after activation with hydrogenc5’.
The main characteristics of this catalyst were :
- composition: CuO 41.2%, Cr20333.4%) SiOz 9.376,
Na10 3.3%, binder 12.8%;
- shape : cylindrical pellets, height and diameter
3.5 m m ;
-
-
B E T surface:
solid density:
19.85 m2/g
4.30 g /cm’;
- apparent density: 2.15 g /cm3;
- porosity: 50% ;
- total pore volume: 0.2325 cm3/g;
- mean pore radius: 56.7 nm
2. Apparatus
The experimental set-up is shown in Figure 1 ; it
consists of a metering block for the feed, a n evapora-
tor, a pre-heater, the reactor and, finally, equipment
for condensing and separating the products.
The evaporator and the pre-heater a s well a s the
reactor a r e made of stainless steel (AISI 304). They
a r e heated by means of independent electrical heaters
which a r e adjusted on the basis of wall-temperatures
indicated by a set thermocouples of series K . Down-
stream from the pre-heater a thermocouple monitors
the inlet temperature t o the reactor. The latter is of
the tubular fixed-bed type, with an active length of
600 mm and a n inside diameter of 12 mm. It is
subdivided into 4 sections - each 150 mm long -
containing the catalyst diluted with a n inert material
(a! alumina). Each section is electrically heated by
a n independent resistor coil controlled by the tem-
perature sensors.
159
 Figure 1 -Apparatus: 1- Feed tank; 2-
Feed pump; 3- Evaporator; 4- Preheater;
5- Reactor; 6- Water cooler; 7- Brine
condenser; 8,9- Dry ice condensers.

zyxwvut
zyxwvutsr
This arrangement and the dilution of the catalyst
allow isothermal operating conditions, as confirmed
by the thermocouples inserted between the various
layers of the catalyst bed.
I
t *
Condensed
rbaae

because in this range side reactions are negligible

as compared with the formation of acetaldehyde by
dehydrogenation of ethanol.
Space velocity was varied in the range 1.5 to 7.5 h-'

zyxwvu
(LHSV). To vary stepwise the space velocity, i.e.
3. Product analysis

zyxwv
1.5; 2.5; 3.5; 4.5; 5.5 and 7.5 h-', the catalyst weight

zyxwvuts
After 1.5-2 h from the beginning of each cycle, i.e.
when the system attained a steady-state, the con-
densate fraction was weighed and analysed through
a gas chromatograph C. ERBA mod. C type C, using
a Carbowax 1500 Chromosorb-column 2 m long and
with an internal diameter 0 = 4 mm (operating
condition : temperature 130°C.; helium flowrate
8 t/h).
As reported in'4), the catalyst exhibited a much
higher selectivity than those of the supported type.
In accordance with that and also because of the low
ethanol conversions in the reactor (due to the fact
that the ratio catalyst/inert in the filling was only
around 1/30), the by-products present in the con-
was kept constant and the flow rate of the feed was
varied.
The mass of catalyst used in the runs was 4.55 g
with a bulk density of 0.067 g/cm' and a volume flow
rate of feed - in vapor phase - between 40 and
220 1 (NTP) /h.
5. Results
Table 1 shows for the various series of runs the molar
flow rate of feed. Table 2 shows, beside the set of tempe-
ratures established as working basis (Ti), the average gas
temperature at the reactor inlet ( T I ) ,the internal tem-
peratures ( T 2 , T 3 , T4, T5),the wall temperatures (I,, t,,,
t i / , , Ilv) for each reactor section indicated in Figure 1 and

zyxwvu
densate (ethyl acetate and acetic acid) never ex-
ceeded 0.3% by weight even a t the maximum operat- the observed conversions of ethanol.
ing temperature. Kinetic model
Analysis carried out on the uncondensed fraction,
on the other hand, indicated results essentially i n The choice of an appropriate kinetic model for the
line with those obtained by J. Franckaerts and G . F. dehydrogenation reaction
Froment with catalysts supported on asbestod6'. +

zyxwvutsrqponmlkjih
CH3CHzOH F? H2 CH3CHO
4. Experimental runs AF?R+S ..........
Operating pressure (1 atmosphere) and the feed- was carried out as suggested by Hougen and Watson'".
stock composition (ethanol 95% vol.) were selected The homogeneous model :
on the basis of current industrial routine. The other
significant parameters, i.e. the temperature and the R, = k, . (PA - P R . ps/K,). . . . . . . . . . . . . . . . . . . . . . . . (2)
space velocity, were varied within suitable ranges"'. was found to be unacceptable notwithstanding S. Yada
The range of temperatures investigated was 255 - and Y. Mihara's results''), since i t led to deviations
285"C, in order to establish comparisons with the up to 50% a s compared with experimental observa-
results of J. Franckaerts and G. F. Froment and tions.
A heterogeneous mechanism was then tried, with
TABLE1 selection of the controlling step among the following:
MOLARFEED RATES A + CL + CA.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (3)

SPACE VELOCITY
LHSV, h-1
1.5
2.5
3.5
4.5
5.5
I N O

(mol/h)
1.94
3.23
4.53
5.82
7.11
CA

CA2
+

CR -+ C L
CL

CR +
+R
CAz..

CS.,

cs zyxwvu
.................................
..................................
4 CL

The corresponding expressions for the rate of

reaction a r e :
+ S . .. . . . . . . . . . . . . . . . . . . . .
. , (4)
, (5)
(6)

7.5 9.70 k . (PA - PR . Ps/KJ

RA = ( 1 + KR . PR + Ks . P s + KRS. PR . P Y ) . . . . . . (7)
I60 The Canadian Journal of Chemical Engineering, Vol. 57, April, 1979
-
Ti
-

-
225
240
255
270
285
Ti
225.5
240.0
256.0
270.5
286.0
zy
zyxwvuts
WORKING BASIS TEMPERATURES,

zyxwv
T2 T3 T4

225.0
241.0
254.5
269.0
285.0
TABLE

AND PERCENTAGE ETHANOL CONVERSIONS.

2
INLET TEMPERATURES AND THERMAL PROFILES OF GAS

262.0
276.0
295.0
304.0
320.0
~
MIXTURE,

284.0
278.0
292.0
302.0
316.0
WALL TEMPERATURES

trv
295.0
302.0
320.0
335.0
354.0
EA

6.64
9.17
11.18
15.36
18.53
sv

1.5

225 225.5 225.0 265.0 256.0 252.0 275.0 4.27

240 240.5 240.0 285.0 278.0 265.0 295.0 6.16
255 255.0 255.0 302.0 285.0 285.0 312.0 8.82 2.5
270 270.5 269.0 325.0 303.0 300.0 328.0 11.09
285 285.5 285.5 340.0 320.0 315.0 350.0 15.56
- ~

225 224.5 225.0 264.0 251.0 246.0 278.0 2.61

240 240.5 239.0 282.0 270.0 262.0 291.0 4.50
255 255.5 255.0 299.0 280.0 279.0 312.0 6.83 3.5
270 270.0 271.5 322.0 302.0 294.0 337.0 9.71
285 285.5 286.0 330.0 314.9 307.0 345.0 11.80
225 225.5 226.0 226.0 225.0 262.0 256.0 I 249.0 271.0 2.31
240 239.5 240.0 240.5 240.0 280.0 267.0 262.0 287.0 3.39
255 255.0 255.5 255.0 255.5 295.0 281.0 279.0 302.0 5.45 4.5
270 270.0 269.5 270.0 269.0 313.0 296.0 294.0 320.0 7.90
285 285.5 285.0 284.5 283.5 331.0 312.0 307.0 332.0 10.09
225 226.5 225.0 225.5 225.0 224.5 262.0 251.0 I 246.0 267.0 2.18
240 240.5 240.0 239.5 240.5 240.0 276.0 262.0 261.0 277.0 2.94
255 256.5 255.5 256.5 255.5 255.0 296.0 279.0 278.0 298.0 4.42 5.5
270 270.5 270.0 270.0 270.0 270.5 312.0 295.0 293.0 314.0 7.10

zyxw
285 285.0 285.0 285.5 285.0 285.0 325.0 314.0 302.0 325.0 9.10
225 226.0 224.0 225.0 225.0 225.5 256.0 246.0 I 244.0 258.0 1.84
240 241.5 241.0 241.5 241.5 240.0 277.0 271.0 261.0 274.0 2.12
255 254.5 255.0 254.5 255.0 254.5 291.0 277.0 273.0 290.0 3.11 7.5
270 270.5 270.5 270.0 270.0 270.0 307.0 293.0 290.0 307.0 4.43
285 285.5 285.0 285.0 284.5 284.5 324.0 305.0 303.0 322.0 5.88
-
__

RA = (1

zyx
zyxwvuts
k . (PA - P R Ps/KJ
+ KA . P A + K R * PR
'

. ( P A - P R Ps/KJ
k
+ KS * P s ) ~ .......(8)

...(9)
ferential balance

. . . . . . . . .(10)

zyxwvu
'

RA = (ps + K A S P A + K A . P A . P S + K S PU
' * is integrated with initial condition
which imply, as controlling step, respectively, t h e t0 = for z = 0..
........................... .(11)
adsorption of A , the dual-site reaction and the de- The overall mass balance and those f o r each com-
sorption of S.
The second mechanism was found t o be t h e most
appropriate of t h e three, in accordance with the con-
clusions drawn by J. Franckaerts and G. F. Froment'6'
on supported catalysts.
Actually, minimizing t h e deviation between t h e
observed and calculated conversions leads t o unaccept-
A , R and S :

PA = ___
- zyx
ponent yield expressions f o r the partial pressures of

v + 4
.P PR
Combining Equations (8) and (10) ;
= ps = .v-
t . p
v=W/ni and

able values f o r t h e physical parameters, which appear dE - PB ' s

in the f i r s t and third model. For instance, one o r dz nA"
more of the adsorption constants increase with tem-
perature.
Therefore, t h e dual-site mechanism was adopted
in the subsequent data analysis.
Interpretation of results
Two different models were used to f i t t h e observa- which integrates to
tions. I n both cases the same step (dual-site reac-
tion) was assumed to be t h e chemical controlling
step. However, i n model A, t h e diffusion phenomena
were ignored whereas in model B due account was
made of their effect on t h e reaction rate.
Model A
The reactor i s assumed to be essentially isothermal
and operating under plugflow conditions. The dif-
+ = 0. . . . . . . . . . .

The Canadiun Journal of Chemical Engineering, Vol. 57, April, 1979

where
1.70

cx =
zyxwvutsrqpon
zyxwvuts
zyxwvu 1.82 1.86 1.90

Figure 2 - Kinetic parameters versus 1 /TK.

zyxwvuts
1 - K A. P +
1.94

KRS. P... . . . . . . . . . . . . . . . . . . .
1.98 zyxwvutsrqpo
zyxwvutsrqpon
2.02

.(14)
Figure 3
0

be expressed as:
a1o

calculated

A).
0.15

conversion. 5.
020

- Experimental versus calculated conversions (Model

025

@ = v +
K.4 . P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .(15) In k = 17.900 - 5810.5/Tk ;
correlation coefficient: 0.99. . . (20)

f1,z =
2 ( 1+- -g, +
In KRs = 1.057 690.2/Tk;
+
In K A = - 1.175 1166.6/Tk :
correlation coefficient: 0.86. . . (21)

correlation coefficient: 0.77. . . (22)

Constant K R Srelates to the combined effect of ad-
sorption of hydrogen and acetaldehyde. The separate
contribution of these two actions was deliberately not
ai = - @'/fz.. ................................. .(17) investigated since the physical separation (fractiona-
tion) of the reaction products from the unreacted
............... ethanol is a relatively simple and inexpensive indus-
trial operation. Even in the case of a recycle process,
Experimental values for the equilibrium constant virtually pure ethanol would still constitute the re-
K , were reported earlier"0~11~12'
with discrepant results. actor feedstock. The ratio aldehyde/hydrogen would
We therefore used the data of J. W. Anderson et a1"O) therefore always be unit. On the other hand, the
'to construct the following expression : Arrhenius plot of expression (Equation (22) does
not show an appreciable deviation from a single ac-
In K , = 11.82 - 6189.1/Tk.. . . . . . . . . . . . . . . . . . . (19) tivation energy. This allows dumping the effect of
To determine the unknown parameter k , Ka and the absorption of both components into a single con-
K R S in the kinetic expression (Equation (8)), the stant.
standard error between observations & and computed Using correlations (Equations (19-22) ) and Equa-
results & was minimized by an indirect search tions (13-181, conversions were calculated and com-
method"". pared to observations in Figure 3.
Table 3 summarizes the best fits to constants k , The assumed theoretical model overestimates con-
K , and KR,y;the logarithms of the values of k , K n versions by an amount up to ZO:T, ; only for a few
and K R Sare plotted as a function of l / T k in Figure 2. instances a t space velocity 1.5 this deviation attained
According to Arrhenius the same coefficients may 30%.

~~~
TABLE4
SOME VALUES OF MOLECULAR DIFFUSIVITIES, KNUDSENDIFFUSI-

zyxwvutsrqpo
zyxwvutsrqponm
TABLE3
VITIES AND OF EFFECTIVE DIFFUSION COEFFICIENTS FOR ETHANOL
KINETICPARAMETERS FROM MODEL"A" FIT. IN THE RANGE FROM 225 TO 285 "c.
.
-

k
T K ,K kmol/(kg.h.atm) K A ,atm-l K H Satm-1
, "C
498.15
513.15
528.15
0.478
0.685
0.987
3.167
2.993
2.975
I 11.177
11.274
11.137
225
240
255
0.2988
0.3168
0.3354
0.8110
0.1837
0.1864
0.0188
0.0194
0.0200
1.651
1.725
1.8CO
543.15 1.367 2.754 10.387 270 0.3544 0.1890 0.0205 1.875
568.15 1.624 2.399 9.628 285 0.3739 0.1916 0.0211 1.951

162 The Canadian Journal of Chemical Engineering, Vol. 5 7 , April, 1979

 zyx zyxwvu
zyxwv
ho = Jh r..
. G
.c, .............................. (26)

Function j, and j h depend on the Reynolds number

Re = G.dp/p as follows:
R~ 5 350 j~ = 1.82 * Re-0.51
3h = 1.95 . Re-0.6'. . . . . . . . . . . . . . . . . . . . .
. (27)
,
R~ 350 j~ = 0.99
Re-0.41
3 h = 1.06 . Re-0.41. . . . . . . . . . . . .
The determination of psi and T , implies iterating
from a starting point p.j = pj and T , = T . These itera-

. zyxwvutsrq
11.1.1
tions must be repeated f o r each simulated test and
for every integration step of Equation (10).
The effectiveness factor was estimated by means
A
1

zyxwvutsrqponmlkjihgfed
IY'i5.5
SY-L5
I Y ia.5
SY sL1
of the Satterfield relation"" :

(29)

zyxwvutsrqponmlkjih
S Y -1.1

calculated zyxwvutsrqponml
c o n v e r s i o n , L.

Figure 4 - Experimental versus calculated conversions (Model

B).
t__
where the pellet is assumed to be isothermal and the
reaction of a pseudo-first order.
The effective diffusion coefficient of reactants and
products was obtained by combining the effect of
ordinary bulk diffusion and Knudsen diffusion with a
tortuosity r = 3, as indicated in"" :

D i.e - 1
In order to improve the fitting of the experimental 1
data, a second model suitable to account f o r the dif-
fusion phenomena was then introduced.
where D M and
~ DKj a r e function of TK. Table 4 shows
Model B the molecular and Knudsen diffusivities of ethanol
The reaction rate Ra expressed by (Equation ( 8 ) ) with temperatures varying from 225 to 285°C.
is evaluated a t the temperature and compositions of Using the same kinetic expression as in model A
the pellet surface, that is, corrected with an effective- and fitting the observations, parameters k, K n and
ness factor: K R swere obtained in the form of activation functions :
R A ,=~ 11 * R A , ~ In k = 13.65 - 7086.2/T~
In K A = 0.251 + 636.9/T~

zyxwvutsrqpo
-
when q is related to external conditions and intrapore

zyxwvuts
diffusion. In KRS= 1.260 + 592.7/T~
Partial pressures of reactants and products to- Figure 4 shows computed versus observed data;
gether with the surface temperature of the pellet are 70% of the data fall within a 10% deviation band.
evaluated by means of the relations : Model B thus demonstrates a much better capability
R A-, ~...........................
of correlating observations if one accounts for the
Paj = Pi +6 j -
Koj a
. (23) diffusion phenomena.
A further reason for the introduction of model B
arises from the observations of Table 5, which enables
one to compare the effectiveness factor rigorously
calculated / 16/ with that evaluated after Satterfield(")
where the mass transfer coefficient of each component when varying both the temperature of reaction (range
K,J and the heat transfer coefficient k c between gas 225-285°C) and the degree of conversion (range 0-
and pallet are estimated as proposed by Smith"4': 60).
The percentage deviation between the rigorous
effectiveness factor q ( l f i )and that estimated after
Satterfield 77'15) never exceeds 5% within the range

TABLE
5
COMPARISON
BETWEEN THE RIGOROUS EFFECTIVENESS FACTOR 18 AND THAT EVALUATED AFTER SATTERFIELD'~
AT DIFFERENT TEMPERATURES AND DEGREES OF CONVERSIONS.

270

0.74125 0.73996 0.67710 I 0.66923

0.15
0.30
0.45
0.60
1I 0.91789
0.92092
0.92471
- I
1 0.93320
0.05263
0.97206
- I
1 0.88378
0.89157
0.89832
- I
I 0.89739
0.92284
0.94663
- I
1 0.83934
0.86058
0.87625
- I
I 0.85058
0.90245
0.96978
-
0.79310
0.83015
0.82062
0.83239
0.79358
0.83192
0.86486
0.90233
0.72314
0.74927
0.76950
0.79867
0.72899
0.77231
0.80884
0.93927

The Canadian Journal of Chemical Engineering, Vol. 57, April, 1979 163
 zyxwv
zyxwvut
zyxwvutsrq
of experimental conversions measured for the ethanol.
Therefore it follows t h a t the f i r s t approximation
procedure used for the development of model B is
zyxwvuts
sound. On the other hand, by correlating a t every
temperature the effectiveness factor q“” with the
degree of conversion [ and introducing these relation-
ships to evaluate the effective reaction rate of ethanol,
no significant improvement was obtained in recons-
tructing the observed data, even after iteration on
zy
convergence on the value of 7.
Conclusions
From the experimental data analysis it follows that
the controlling mechanism of the dehydrogenation of
ethanol on unsupported copper chromite catalysts is
also that of a dual-site surface reaction of adsorbed
ethanol, as proposed by J. Franckaerts and G. F.
Froment“’ for supported catalysts.
Further, it is shown t h a t in the range of operating
parameters chosen, diffusion phenomena cannot be
ignored since they greatly affect the kinetic behavior
of the system.
specific outside surface area of single catalyst
particle, (mZ/kg)
active site on the surface of the catalyst
specific heat of the gas mixture, (J/kg. “Cj
diameter of sphere equivalent to cylindrical
pellet, (mj
effective diffusion coefficient for each compo-
nent, (m2)/h)
Knudsen diffusion coefficient, (m2/h)
ordinary bulk diffusion coefficient, (m2/h)
mass velocity of gas, (kg/m2 . h)
.
gas-pellet heat transfer coefficient, (J/m2 h.”C)
component index
Colburn factor for mass transfer, dimensionless
Colburn factor for heat transfer, dimensionless
heterogeneous reaction rate constant, (mol/h.
zyxwvutsrq
kg. cat. atm.)
homogeneous reaction rate constant, (mol/s
kg. cat. atm.)
effective thermal conductivity of pellet, (J/m.
h.”C)
adsorr,tion coefficient, (atm.) -l
equilibrium constant, atm.
mass transfer coefficient for each component,
(mol/m2 atm. h)
initial molar feed rate for each component,
(?OW)
initial molar feed rate, (mol/h)
partial pressure, (atrn.j
gas constant, (J/mol. K j
zyxwvuts
reaction rate of ethanol, (mol/kg.cat.h)
homogeneous mechanism reaction rate expres-
sion, (mol/kg.cat.hj
zyxwvuts
cross section of reactor, (m2)
wall temperature, (“C)
temperature (“C and K)
average gas temperature at the reactor inlet,
(“C)
volume of reactor. (mSj
axial abscissa of reactor (m).
164 The Canadian Journal of Chemical Engineering, Vol. 5 7 , April, 1979
Greek letters
6 j = stoichiometric coefficients for each component
(- A H ) R = heat of reaction, (J/mol)
porosity of catalyst
€ =
17 = effectiveness factor
A = THIELE modulus, (d,/2).
d p p ’ R A , s . R.T,/(DA,; Paps))
= viscosity, (Pas)
= ratio N ” / n j
= ethanol conversion, (moles ethanol convextedj
moles ethanol fed)
= particle density, (kg/m3j
= bulk density of catalyst bed, (kg/m“)
= tortuosity factor
Subscriets
A, R, 8 = ethanol, hydrogen and acetaldehyde
c = calculated
0 = effective
L = free active site on the surface catalyst
s = referred to pellet surface
References
(1) Miller, S. A., Chem. Process Eng. 49, 75 (1968).
( 2 ) Faith, W. L., Keyes, D. B. and Clark, R. L., “In-
dustrial chemicals”, 3rd Edn., Wiley, New York
(1965).
( 3 ) Shenvood, P. W., Ind. Eng. Chem. Int. Edn., 55, 37
(1963).
(4) Peloso, A., Soracco, B., Busacca, G. and Ferraiolo,
G., Chim. Ind. Ital. 58, 10 (1976).
(5) Thomas, C. T., “Catalytic Process and Proven
Catalysts”, Academic Press, New York (1970), p. 51.
(6) Franckaerts, J. and Froment, G. F., Chem. Eng.
Sci. 19, 807 (1964).
(7) Thomas, C. T., reference 5, p. 50.
(8) Hougen, 0. A. and Watson, K. M., “Chemical process
principles”, 3rd Vol., “Kinetics and Catalysis”,
Wiley, New York (1947).
(9) Yada, S. and Mihara, Y., Kagaku Kogaku 25, 518
(1961).
(10) Anderson, J. W., Beyer, G. H., Watson, K. M., Nat.
Pet. News 36, R476 (1944).
(11) Parks, G. S. and Huffman, H. M., “Free energies of
some organic compounds”, Reinhold New York
(1932).
(12) Rideal, E. K., Proc. Roy. SOC. (London) 99A, 153
(1921).
(13) Fletcher, R. and Powell, M. J. D., Computer J. 5,
147 (1962).
(14) Smith, J. M., “Chemical Engineering Kinetics”, 2nd
Ed., McGraw-Hill, New York (1971).
(15) Satterfield, C. N., “Mass transfer in heterogeneous
catalysis”, M.I.T. Press, Cambridge, Mass. (1970).
(16) Moresi, M., Ing. Chim. Ital. 13, 45 (1977).
Manuscript received November 28, 1977; accepted for
publication November 22, 1978.
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