Académique Documents
Professionnel Documents
Culture Documents
A kinetic study of the dehydrogenation of ethanol to acetal- On a fait une 6tude cinktique de la transformation de
dehyde on an unsupported catalyst of base composition CuO- lalcool kthylique en acktaldehyde SUI un catalyseur non s u p
CqO, was carried out in an isothermal reactor fed with port6 dont la composition de base h i t CuO-CrzOs; on a
ethanol 95% vol. in the temperature range 225-285C employ6 a cette fin un rCacteur isotherme aliment6 avec de
with space velocities 1.5 -7.5 LHSV at atmospheric pres- lalcool 6thylique a 95% en volume, sur une gamme de
sure. tempkrature comprise entre 225C et 285C; ainsi que des
The mechanism which was found suitable to describe the vitesses spatiales (inverse du temps de passage) de 1.5 B
reaction was that of surface adsorption on dual sites. 7.5 LHSV, pression atmosphkrique.
Taking into account interphase and intraphase diffusion, On a trouvC que le mkcanisme appropriC pour d6crire la
the observed conversions of ethanol were reconstructed with rtaction Ctait ladsorption superficielle sur un double site.
a standard error below l o % , thus confirming the validity of En tenant compte des diffusions interne et externe, on a
the physical assumptions. pu reproduire les conversions de lalcool kthylique observhes,
avec une erreur standard infkrieure i l o % , ce qui confirme
la validit6 des hypoth6ses physiques.
The Canadian Journal of Chemical Engineering, Vol. 57, April, 1979 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.
t *
Condensed
rbaae
This arrangement and the dilution of the catalyst I because in this range side reactions are negligible
allow isothermal operating conditions, as confirmed as compared with the formation of acetaldehyde by
by the thermocouples inserted between the various dehydrogenation of ethanol.
layers of the catalyst bed. Space velocity was varied in the range 1.5 to 7.5 h-'
(LHSV). To vary stepwise the space velocity, i.e.
3. Product analysis 1.5; 2.5; 3.5; 4.5; 5.5 and 7.5 h-', the catalyst weight
After 1.5-2 h from the beginning of each cycle, i.e. was kept constant and the flow rate of the feed was
when the system attained a steady-state, the con- varied.
densate fraction was weighed and analysed through The mass of catalyst used in the runs was 4.55 g
a gas chromatograph C. ERBA mod. C type C, using with a bulk density of 0.067 g/cm' and a volume flow
a Carbowax 1500 Chromosorb-column 2 m long and rate of feed - in vapor phase - between 40 and
with an internal diameter 0 = 4 mm (operating 220 1 (NTP) /h.
condition : temperature 130C.; helium flowrate
8 t/h). 5. Results
As reported in'4), the catalyst exhibited a much
higher selectivity than those of the supported type. Table 1 shows for the various series of runs the molar
In accordance with that and also because of the low flow rate of feed. Table 2 shows, beside the set of tempe-
ethanol conversions in the reactor (due to the fact ratures established as working basis (Ti), the average gas
tha t the ratio catalyst/inert in the filling was only temperature at the reactor inlet ( T I ) ,the internal tem-
around 1/30), the by-products present in the con- peratures ( T 2 , T 3 , T4, T5),the wall temperatures (I,, t,,,
t i / , , Ilv) for each reactor section indicated in Figure 1 and
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'. 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)
CA + CL CAz.. ................................. . , (4)
SPACE VELOCITY
LHSV, h-1
1.5
I N O
(mol/h)
1.94
CA2
CR -+ C L
CR +
+R
CS., ..................................
cs 4 CL + S . .. . . . . . . . . . . . . . . . . . . . .
, (5)
(6)
2.5 3.23 The corresponding expressions for the rate of
3.5 4.53
4.5 5.82 reaction a r e :
5.5 7.11
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
TABLE
2
WORKING BASIS TEMPERATURES,
INLET TEMPERATURES AND THERMAL PROFILES OF GAS MIXTURE,
WALL TEMPERATURES
AND PERCENTAGE ETHANOL CONVERSIONS.
-
Ti
- Ti T2 T3 T4 trv EA sv
225 225.5 225.0 262.0 284.0 295.0 6.64
240 240.0 241.0 276.0 278.0 302.0 9.17
255 256.0 254.5 295.0 292.0 320.0 11.18 1.5
270 270.5 269.0 304.0 302.0 335.0 15.36
285 286.0 285.0 320.0 316.0 354.0 18.53
- ~
k . (PA - P R Ps/KJ
' ferential balance
RA = (1 + KA . P A + K R * PR + KS * P s ) ~ .......(8)
. . . . . . . . .(10)
. ( P A - P R Ps/KJ
k '
...(9)
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. ponent yield expressions f o r the partial pressures of
The second mechanism was found t o be t h e most A , R and S :
appropriate of t h e three, in accordance with the con-
clusions drawn by J. Franckaerts and G. F. Froment'6'
on supported catalysts.
PA = ___
-
v + 4
.P PR = ps = .v-
t . p
v=W/ni and
Actually, minimizing t h e deviation between t h e Combining Equations (8) and (10) ;
observed and calculated conversions leads t o unaccept-
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. . . . . . . . . . .
calculated conversion. 5.
Figure 2 - Kinetic parameters versus 1 /TK.
Figure 3 - Experimental versus calculated conversions (Model
where A).
cx = 1 - K A. P +
KRS. P... . . . . . . . . . . . . . . . . . . . .(14) be expressed as:
@ = 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)
~~~
TABLE4
TABLE3 SOME VALUES OF MOLECULAR DIFFUSIVITIES, KNUDSENDIFFUSI-
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
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 285C.
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~
TABLE
5
COMPARISON
BETWEEN THE RIGOROUS EFFECTIVENESS FACTOR 18 AND THAT EVALUATED AFTER SATTERFIELD'~
AT DIFFERENT TEMPERATURES AND DEGREES OF CONVERSIONS.
270
The Canadian Journal of Chemical Engineering, Vol. 57, April, 1979 163
of experimental conversions measured for the ethanol. Greek letters
Therefore it follows t h a t the f i r s t approximation 6 j = stoichiometric coefficients for each component
procedure used for the development of model B is (- A H ) R = heat of reaction, (J/mol)
sound. On the other hand, by correlating a t every = porosity of catalyst
temperature the effectiveness factor q with the 17 = effectiveness factor
A = THIELE modulus, (d,/2).
degree of conversion [ and introducing these relation-
d p p R A , s . R.T,/(DA,; Paps))
ships to evaluate the effective reaction rate of ethanol, = viscosity, (Pas)
no significant improvement was obtained in recons- = ratio N / n j
tructing the observed data, even after iteration on = ethanol conversion, (moles ethanol convextedj
convergence on the value of 7. moles ethanol fed)
= particle density, (kg/m3j
= bulk density of catalyst bed, (kg/m)
Conclusions = tortuosity factor
From the experimental data analysis it follows that Subscriets
the controlling mechanism of the dehydrogenation of
ethanol on unsupported copper chromite catalysts is A, R, 8 = ethanol, hydrogen and acetaldehyde
c = calculated
also that of a dual-site surface reaction of adsorbed 0 = effective
ethanol, as proposed by J. Franckaerts and G. F. L = free active site on the surface catalyst
Froment for supported catalysts. s = referred to pellet surface
Further, it is shown t h a t in the range of operating References
parameters chosen, diffusion phenomena cannot be
ignored since they greatly affect the kinetic behavior (1) Miller, S. A., Chem. Process Eng. 49, 75 (1968).
of the system. ( 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
specific outside surface area of single catalyst (1963).
particle, (mZ/kg) (4) Peloso, A., Soracco, B., Busacca, G. and Ferraiolo,
active site on the surface of the catalyst G., Chim. Ind. Ital. 58, 10 (1976).
specific heat of the gas mixture, (J/kg. Cj (5) Thomas, C. T., Catalytic Process and Proven
diameter of sphere equivalent to cylindrical Catalysts, Academic Press, New York (1970), p. 51.
pellet, (mj
effective diffusion coefficient for each compo- (6) Franckaerts, J. and Froment, G. F., Chem. Eng.
nent, (m2)/h) Sci. 19, 807 (1964).
Knudsen diffusion coefficient, (m2/h) (7) Thomas, C. T., reference 5, p. 50.
ordinary bulk diffusion coefficient, (m2/h) (8) Hougen, 0. A. and Watson, K. M., Chemical process
mass velocity of gas, (kg/m2 . h) principles, 3rd Vol., Kinetics and Catalysis,
.
gas-pellet heat transfer coefficient, (J/m2 h.C) Wiley, New York (1947).
component index (9) Yada, S. and Mihara, Y., Kagaku Kogaku 25, 518
Colburn factor for mass transfer, dimensionless
Colburn factor for heat transfer, dimensionless (1961).
heterogeneous reaction rate constant, (mol/h. (10) Anderson, J. W., Beyer, G. H., Watson, K. M., Nat.
kg. cat. atm.) Pet. News 36, R476 (1944).
homogeneous reaction rate constant, (mol/s (11) Parks, G. S. and Huffman, H. M., Free energies of
kg. cat. atm.) some organic compounds, Reinhold New York
effective thermal conductivity of pellet, (J/m. (1932).
h.C)
adsorr,tion coefficient, (atm.) -l (12) Rideal, E. K., Proc. Roy. SOC. (London) 99A, 153
equilibrium constant, atm. (1921).
mass transfer coefficient for each component, (13) Fletcher, R. and Powell, M. J. D., Computer J. 5,
(mol/m2 atm. h) 147 (1962).
initial molar feed rate for each component, (14) Smith, J. M., Chemical Engineering Kinetics, 2nd
(?OW) Ed., McGraw-Hill, New York (1971).
initial molar feed rate, (mol/h)
partial pressure, (atrn.j (15) Satterfield, C. N., Mass transfer in heterogeneous
gas constant, (J/mol. K j catalysis, M.I.T. Press, Cambridge, Mass. (1970).
reaction rate of ethanol, (mol/kg.cat.h) (16) Moresi, M., Ing. Chim. Ital. 13, 45 (1977).
homogeneous mechanism reaction rate expres-
sion, (mol/kg.cat.hj
cross section of reactor, (m2)
wall temperature, (C) Manuscript received November 28, 1977; accepted for
temperature (C and K) publication November 22, 1978.
average gas temperature at the reactor inlet,
(C)
volume of reactor. (mSj
axial abscissa of reactor (m). * * *