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Catalytic Dehydrogenation
of C4 Hydrocarbons Over
Chromia-Alumina
a b
S. Carrà & L. Forni
a
Istituto di Chimica Fisica Università di ,
Bologna
b
Istituto di Chimica Fisica Università di , Milano
Published online: 19 Dec 2006.
To cite this article: S. Carrà & L. Forni (1972) Catalytic Dehydrogenation of C4

Hydrocarbons Over Chromia-Alumina, Catalysis Reviews: Science and Engineering,
5:1, 159-198, DOI: 10.1080/01614947208076867
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Catalytic Dehydrogenation of
C4 Hydrocarbons Over Chromia-Alumina
s. CAR&
Istituto d i Chimica Fisica
Universit& di Bologna
and
L. FORNI
Istituto di Chimica Fisica
Universit; di Milano
I. THERMODYNAMICS AND KINETIC ASPECTS . . . . . . . . 160

11. CATALYST FOULING ........................ 175
111. PHYSICAL CHEMICAL P R O P E R T I E S O F T H E
CATALYST ............................... 179
IV. HYPOTHESES ON T H E REACTION MECHANISM. ...... 186
V. TECHNOLOGICAL ASPECTS. . . . . . . . . . . . . . . . . . . . 190
List of Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Reactions involving hydrogenation and dehydrogenation are em-

ployed particularly in the petrochemical industry. Among these the
dehydrogenation of butane over chromia-alumina catalysts plays an
important role, because it represents the most important process
for obtaining butenes and butadiene. Due to their practical interest,
such processes have been the object of extensive investigations. The
aim of these researches on dehydrogenation reactions is not con-
fined t o the solution of technological problems, however, and the re-
sults have allowed important contributions to some aspects of the
theory of heterogeneous catalysis to be obtained.
159
Copyright 0 1971 by Marcel Dekker, Inc.
160 s. CAR& AND L. FORNI
Some review articles [l-31 are available in which the early de-
velopment of the dehydrogenation of hydrocarbons over transition
metal oxides i s reported. The present review will give a general
survey of some newer results which have been obtained recently,
particularly concerning the kinetics of the dehydroisomerization re-
action of C, hydrocarbons and of coke deposition reactions. In addi-
tion, interesting papers a r e reviewed in which the physical chemical
properties of the catalyst have been deeply investigated. Such re-
sults allow some reasonable hypotheses about the reaction mechanism
t o be proposed.
I. THERMODYNAMICS AND KINETIC ASPECTS
The catalytic dehydrogenation of n-butane occurs through a com-

plex reaction pattern in which dehydrogenation and isomerization re-
actions take place. It can be described with the scheme given in
Fig. 1. Many cracking side reactions also take place, with the forma-
tion of coke, which lead t o a deactivation of the catalyst. Such reac-
tions cannot be described by a single stoichiometric equation. Actu-
ally cracking reactions take place with formation of light hydrocar-
bons (CH,, CH,-CH,, CH2=CH2), dehydrogenations, aromatizations,
and formation of condensed ring aromatic structures.
B n-butane
2Ac cis-2-butene
2At trans-2-butene
!A I-butene
2Ac 2At D bu tad i en e
D
FIG. 1. Reaction network.
DEHYDROGENATION OF C, HYDROCARBONS 161
The equilibrium constant for the chemical reactions of Fig. 1 can

be evaluated from the familiar equation:
AG; = -RT In Kp (1)

and at any temperature and pressure the equilibrium system compo-
sition can be easily obtained. A collection of reliable values of AG;
as a function of T is given in Table 1.
TABLE 1
Values of AGO. kcal/mole, a s a Function of T, "K [4,5]
ReactioniT 400 500 600 700 800 900
---
B- l A 18.14 15.01 11.79 8.54 5.24 1.91
B 2Ac 16.83 13.88 10.87 7.87 4.87 1.85
B 2At 16.22 13.29 10.28 7.26 4.23 1.19
lA
lA - 2Ac
2At
2Ac - 2 A t
1.17
1.66
-0.51
0.87
1.35
-0.46
0.57
1.04
-0.44
0.27
0.74
-0.44
-0.03
0.43
-0.46
-0.33
0.13
-0.50
la -D 16.23 13.50 10.71 7.87 5.03 2.15
2At -
2Ac- D
D
17.54
18.15
14.63
15.22
11.63
12.22
8.54
9.15
5.40
6.04
2.21
2.87
The study of the reaction rates occurring in the dehydrogenation

of C, hydrocarbons involves many difficulties, associated with the
complexity of the system and with the non-steady nature of the pro-
c e s s , due to the change in activity of the catalyst. On the basis of
the scheme of Fig. 1 we can build the stoichiometric matrix shown
in Table 2 , in which aij indicates the stoichiometric coefficients of
component i in reaction j .
A s a first subject the reaction:
n-C,H,, = n-C,H, + H,
can be analyzed.
Balandin and coworkers [S] , on the basis of the multiplet theory
of catalysis, developed a general simplified mechanism of organic
compounds dehydrogenation. For reaction (2) the following rate ex-
pression can be obtained:
PB
r = k (3)
P, + ZiPi
in which P, is the partial pressure of n-butane, Pi the partial pres-
TABLE 2
Stoichiometric Matrix of Reaction
Scheme of Figure 1
j\i B 1A 2AC 2At D H,
1 -1 0 1 0 0 1
2 -1 1 0 0 0 1
3 -1 0 0 1 0 1
4 0 0 1 -1 0 0
5 0 -1 1 0 0 0
6 0 -1 0 1 0 0
7 0 -1 0 0 1 1
8 0 0 0 -1 1 1
9 0 0 -1 0 1 1
sure of compound i , and Z i the relative adsorption coefficient of com-

pound i with respect to n-butane. Equation (3) has been derived tak-
ing into account the non-uniformity of the catalytic surface, and the
rate constant i s given by k = [&/(h - l/RT)] exp (h - l / k T ) E , E being
the observed activation energy, k, a constant, and (Y and h the co-
efficients of the function expressing the distribution of the active
centers of the catalyst with respect t o activation energies: @(E) =
cy exp (hE). Over chromia-alumina the application of Eq. (3) revealed
that the adsorption coefficients of butenes, butadiene and hydrogen at
560°C are in the ratios 1:9.5:0.82. Thus the presence of butadiene
in the reaction mixture has a significant effect on the dehydrogena-
tion rate.
Lyubarskii and coworkers [7,8] studied the n-butane dehydrogen-
ation on a chromia-alumina catalyst (6% of chromium) at 460- 500" C
and at partial pressures of reactant ranging from 0.1 to 1 atm. The
kinetics of the reaction has been empirically described by means of
a power-law rate equation that, with allowance for the reversibility
of the reaction, gave the following results:
In order to broaden the form of the rate equation it is important

to determine the nature of the rate-controlling step in the catalytic
process. Actually the dehydrogenation reaction occurs through a
close sequence of elementary steps and an important problem is to
rule out some of them as possible rate-limiting steps. If in a given
set of conditions it is possible to recognize a rate-determining step,
the other steps will be in quasi-equilibrium. In this case the number
DEHYDROGENATION O F C, HYDROCARBONS 163
of times the limiting step occurs during one occurrence of the main
reaction is called stoichiometric number Y.
Thus, if in a complex set of mechanistic equations the slow step
is given for instance by the simple reversible equation:
kl
A - B (5)
k- 1
the general net rate r of the process is given by:
r = rf - r r
rf and rr being the r a t e s of the forward and reverse reactions re-

spectively. For reaction (5) the rate can be written as follows:
K = kl/k-, being the equilibrium constant and C, and C, the reactant

concentrations.
The Gibbs free energy of reaction (5) is given by:
AG = - RT In K + RT In (CB/C,) (8)
that, substituted in Eq. (7), gives:
r = rfll - exp (AG,/RT)] (9)
Since all the reaction steps can be considered at the equilibrium ex-
cept the rate-limiting one, the free energy of the overall process
can be written as AG = YAG, and Eq. (9) becomes:
r = rf[l- exp (AG/vRT)] (10)
Remembering Eq. (6) the following expression for the stoichiometric

number can be derived:
It follows that for determining experimentally the stoichiometric

number it is necessary t o evaluate, in the same conditions of tem-
perature, pressure, and concentration, the forward and the reverse
r a t e s of the reaction. Both the reaction r a t e s were determined in the
same experiment by feeding a differential flow reactor with a mixture
164 s. C A R R ~AND L. FORNI
of n-butane, 1-butene, and hydrogen in which one of the hydrocarbons
was radioactively tagged [9]. The overall rate of reaction was ob-
tained from the mole change of n-butane and the unidirectional rates
were determined on the basis of radioactive gain by non-tagged hy-
drocarbon. The Gibbs free energy was evaluated from the average
reaction conditions.
The experimentally obtained results a r e graphically summarized
in Fig. 2, in which a plot of the In (rf/rr) versus - AG/RT i s shown.
n b
h-4
-
Y
2
-3 -
-2 -
-’‘
0p
0 -1 -2 -3 -4
In f /rr
T In Y/T,.
FIG. 2. Reaction free energy for n-butane dehydrogenation vs. l n ( r r / r r )

[9];t r a c e r s (a) CI4 butene-1, (b) C,, butane.
On the figure the values of the stoichiometric numbers, that a r e the
slopes of the lines passing through the origins, a r e also given. Such
numbers are found t o be very close to unity. This fact rules out the
chemisorption or desorption of hydrogen as being the rate-control-
ling step. In fact, in this case, the recombination of hydrogen atoms
t o give hydrogen molecules should occur very slowly, due t o the hy-
drogen atoms migration on the surface [9]. Since the Gibbs free
energy of reaction (2) is given by:
%*PA
AG = -RT In K + RT In ___
PB
Taking into account that the stoichiometric number of the reaction is

equal to one, Eq. (13) becomes:
Dodd and Watson [lo] applied the Langmuir-Hinshelwood scheme

for determining the expression of rf and OD the basis of a set of in-
tegral reactor data they proposed a rate law corresponding to a dual-
site mechanism. Recently [ll]the differential reactor technique has
been employed for studying the kinetics of the dehydrogenation reac-
tion by feeding a flow reactor with a mixture of n-butane and nitro-

gen a s a diluent, in order to analyze the influence of n-butane par-
tial pressure.* The trend of experimental data, reported in Fig. 3,
seems to confirm that the rate-determining step is the surface reac-
?-.lo2
1.4
1.0 -
0.6 -
0.2 -
0 .2 .4 .6
FIG. 3. Reaction r a t e s (moles/h g.cat) vs. n-butane partial pressure

(atm): 3 , 5 5 0 " C ; 0 ,530°C; 0 , 510°C. Solid lines calculated from eq. ( 1 6 )
(11I.
*It was verified that neither external nor internal diffusion affected the
obtained kinetic data.
166 s. CARF~AAND L. FORNI
tion, which involves two adjacent active centers. The rate equation
corresponding to this mechanism is
b,, b,, b,, and b, being the adsorption equilibrium constants. For
feeding mixtures constituted only of n-butane and nitrogen, as a con-
sequence of the small conversion degrees attained in the differential
reactor, the chemisorption of the reaction products can be neglected.
In this case Eq. (15) can be ,written:
that is a linear relationship between (PB/r)lD and PB. Such a plot is

given in Fig. 4. From the parameters of the best straight lines,
evaluated by the least-squares method, the values of kr and b, col-
lected in Table 3 were obtained.
p 14 -
10
6,
FIG. 4. (PB/r)1/2a s a function of n-butane p a r t i al pressure 0,550°C;

0,530°C; 0,510°C 1111.
TABLE 3
Reaction Rate and Adsorption Equilibrium Constants
k, x lo2,
T, "C moles/ h g cat b g , atm-' bA, atm-l bH, atm-*
510 2.44 19.50 57.605 52.436

530 3.11 8.00 22.10 21.80
550 5.05 3.63 9.61 11.00
For feeding mixtures of n-butane, nitrogen, and a component i

(butene o r hydrogen) and working at constant partial p r e s s u r e of n-
butane the dehydrogenation rate law can be written:
Ri being the mole ratio of the i component over n-butane. The pre-
vious equation can be rearranged as follows:
that is a linear relationship between the left-side member and the

ratio Ri. Such plots are given in Figs. 5 and 6 for runs correspond-
ing t o mixtures of n-butane and 1-butene and of n-butane and hydro-
gen respectively. F r o m the p a r a m e t e r s of the straight lines of
Figs. 5 and 6 and from the values of kr and b,, given in Table 3, the
adsorption equilibrium constants bA and b,, reported in the same
table, were obtained. It is interesting t o observe that the values of
the ratios bH/bA a r e close t o the value 0.82 obtained by Balandin
11,121.
In Fig. 7 the plots of log k,, bB, b,, b, versus 103/T a r e given;
f o r kr the following equation was derived:
log kr = 4.850 - 23,223/2.303 RT (19)
F r o m the slopes and the intercepts of these lines, the standard heats
and entropies of adsorption were evaluated through the equation:
b = exp[- (AHo/RT) + (ASo/R)] (20)
and the obtained values a r e given in Table 4.

168 s. C A R R AND
~ L. FORNI
15 L
V r
10
I-
5 -
- 0
0 .1 .2 3
.4 RA
FIG. 5. (’ B-PHPA/K)1/2a s a function of RA (1-butene/n-butane) molar
ratio in the feeding mixtures [ll].
FIG. 6. (pB-p~pA/K)”z
a s a function of RH (hydrogenh-butane) molar
ratio in the feeding mixtures [HI.
I
1.2 1.25 1.3
-
103
T
FIG. 7. Log k,, b g , bA, bH a s a function of 103/T (data of Table 3) [ll].
TABLE 4
Adsorption P a r a m e t e r s
Compound -AH", Kcal/mole -ASo, cal /moleOK
n- butane 53.90 (i0.55) 62.94 (* 0.72)

n-butene 57.43 (* 0.84) 65.30 (*1.05)
hydrogen 50.11 (* 1.78) 56.17 (i2.24)
It is important to emphasize that Eq. (15) has been derived only

from the analysis of a s e t of reaction rate data far from equilibrium
conditions, and this fact s e e m s t o limit i t s application when the re-
action is performed in conditions close to the equilibrium. For this
reason a different approach to the formulation of a kinetic model for
the butane-butene system h a s been developed by Happel and col-
leagues [13-171, in which both the dehydrogenation and hydrogenation
rate data are taken into account. The approach is largely semiem-
pirical and does not require any assumption as to the nature of the
170 S. C A R d AND L. FORNI
sit e s for adsorption and interaction among adsorbed species. The

following expression for the forward rate expression was obtained:
The parameters of the previous equation, obtained by applying a non-

linear least- squares analysis a r e collected in Table 5.
TABLE 5
Constants of Equation (21)
k if 2.70 X lo-’* 1.51 X lo-’

kzf 2.75 x *3.11 x 1 0 - ~
bB 3.44 f 6.12
bA 13.29 f 20.11
bH 4.56 * 11.52
n 1.31 + 0.21
The kinetic study of the dehydroisomerization reactions of butenes

is largely complicated by the intervention of ,the cracking side reac-
tions that bring about a consequent progressive deactivation of the
catalyst and a r e more notable with an olefinic than with a paraffinic
feed. The influence of such cracking reactions on the dehydrogena-
tion reactions may be evaluated [18] by means of a material balance
on a small catalyst volume element dV, of c r o s s section A and thick-
n e s s dz. This leads t o the following equation:
F ax - ax
-- - a!-+ rs
A az atc
F being the 1-butene feeding flow-rate (moles/hr); x the 1-butene
molar fraction referred to 1 mole of fed olefin; (Y the ratio: moles
of 1-butene/total volume at the inlet; rs the rate of coke formation
(hydrocarbon cracked moles/hr per catalyst volume); tc the time
(hr) that 1-butene molecules a r e in contact with the catalyst.
The first t e r m of the right member of Eq. (22) gives the disap-
pearance of 1-butene, in the volume element dV,, due t o all reac-
tions, except coke formation reactions. If it i s possible to perform
kinetic runs in such conditions that rs is negligible with respect to
(Y ax/%,, it is possible to write:
t tvAz V a a
7
-
c- F F Pcat
r = W/F being the time factor of the olefin, where W is the catalyst
weight (g), F the 1-butene feeding rate (moles/hr), V, the catalyst
volume (cm3), and peat. the catalyst density (g/cm3). Such an equa-
tion gives a relationship between the time tc and the time factor 7.
Some kinetic runs were made in a temperature range between
510 and 550°C and with 1-butene partial pressure at the inlet rang-
ing from 0.071 and 0.250 atm. During such runs the amount of the
cracking reactions has been evaluated by weighing the deposited
coke, employing a Cahn microbalance. It was thus possible to choose
a time factor corresponding t o a very low time tc, in which the re-
sulting coke deposition was negligible. This procedure allowed the

performance of a kinetic analysis in which both the 1-butene iso-
merization and dehydrogenation reactions were taken into account.
Following the scheme of Fig. 1 the reaction kinetics can be ex-
pressed by the following equations:
---
dxu -
dr
r, + r, + rl
-
d x ~
= rl + r8 + r9
dr
where xi a r e the molar fractions, referred t o the fed olefin, of the

substances and rj a r e rates of the j-th reactions. Following the
Langmuir-Hinshelwood model, it was assumed that the rate-deter-
mining steps a r e the surface reactions, with a dual-site mechanism
for the dehydrogenation and a single-site mechanism for the iso-
merization. According t o the scheme of Fig. 1 it can be derived that
the reaction rates for dehydrogenation can be expressed as follows:
and for isomerization:

172 s. CARFAAND L. FORNI
If the total p r e s s u r e is equal t o 1 atm, Eq. (24) can be written in

simplified form as:
where:
A = 1/(1 + xD + c)
and
B = b,(x,A + X& + XzAt) f (b, + b&D
b, being the adsorption equilibrium constant of butenes (atm-I) as-

sumed to be the same for the three isomers; bD and b, the adsorp-
tion equiliorium constants (atm-l) of butadiene and hydrogen; c the
molar ratio between inert gas (nitrogen) and 1-butene at the feed;
k. the reaction rate constants. From the reaction paths on triangular
1
diagrams (Fig. 8) one can see that experimental data lie always on
the line representing the equilibrium composition of the cis/trans-
2-butene system independently of the time factor and 1-butene par-
tial pressure. So the integration of Eqs. (27) has been carried out
assuming that during the whole reaction time the cis/trans- 2-butene
system was at equilibrium. After integration the following function:
has been minimized with respect to the parameters kj and bi by apply-

ing the steepest-descent method. In Eq. (28) Cn,m represents the cal-
culated value of conversion a t the mth run, performed at l-butene
partial pressure at the inlet characterized by the subscript n, and
s ~represents
, ~ the corresponding experimental value; N i s the total
number of runs. Since the minimization turned out t o be quite insen-
sitive t o the difference between the dehydrogenation reaction rate
DEHYDROGENATIONOFC,HYDROCARBONS 173
CZA
FIG. 8. Reaction paths of 1-butene dehydroisomerization reactions at

510"C, referred to the sum of three butenes only: 0 ,0.071 atm; 0,0.111 atm;
0 , 0.181 atm; 0, 0.250 atm; (- ) the equilibrium composition of cis-trans-2-
butene system [18].
constants at the three butenes, the same value has been attributed to
such constants.
The results of the calculations a r e collected in Table 6 . The
agreement between calculated curves and experimental data is shown
in Fig. 9, while in Fig. 10 the plots of log b,, log 10OO(k, = k,= kg),
log (10 k5), log (100 &) versus 103/T a r e reported.
TABLE 6
Reaction Rate and Adsorption Equilibrium Constants
T, "C 510 530 550
bAb, atm-' 40.0 18.0 10.1

b, + b,, atm-' 142.92 120.85 100.1
k, = k, = k,, moles/ h g cat 0.0068 0.0151 0.0171
k,, moles/ h g c a t 0.1096 0.1232 0.131
k6, moles/ h g c a t 0.0918 0.1086 0.11
In Table 7 the values of the apparent activation energies of l-bu-

tene isomerization and dehydrogenation reactions and of standard
enthalpies and entropies of n-butene adsorption, calculated from the
slopes and intercepts of straight lines of Fig. 10 are reported.
174 s. CAR^ AND L. FORNI
xi I. Xi I.
.5 .5
0 ltf2zLL
0 5 10
0 k f z i
0 5
2- z
FIG, 9. Reaction of 1-butene a t 530°C: (left), PA = 0.071 atm; ( r i g h t ) ,
PA = 0.111 atm; 0 , 1-butene; 0, cis-2-butene; 0 ,trans-Z-butene;.O, buta-
diene; solid lines calculated f r o m eq. ( 2 7 ) [18].
t
I
0
1.20 1.24 1.28
-
lo3
T
FIG. 10. Arrhenius plots of dehydroisomerization reactions: 0,log b A ;
0 ,log [1000(k, = k , = ks)]; 0 , log (10.ks); 0 ,log (100.ks) [18].
TABLE 7
Activation Energies of Reactions and
Adsorption P a r a m e t e r s
A E =~A E ~ =AE$ 29.8 kc a1/mole

AE 5' 5.7 kcal/mole
A E ~ 5.8 kc a1/mole
AH& -44.5 kcal/mole
AsA -49.5 cal/mole"K
11. CATALYST FOULING

We have already pointed out that in the dehydrogenation of butane
and butenes important reactions a r e those leading to the formation
of carbonaceous deposits that foul the catalyst. It seems likely that
such deposits could be compared with the coke deposition that occurs
in the cracking on silica-alumina [19]. In such cases the formation
of condensed ring aromatic structures resulted. An infrared spec-
troscopic analysis revealed a low hydrogen content, corresponding
t o a high degree of condensation towards a pseudographitic structure.
The cracking reactions can be both catalytic and thermal. The
catalytic process is l e s s pronounced with a paraffin, that i s with n-
butane. For such a compound the thermal decomposition has been
described [20] through a first-order kinetic equation, in which the
rate constant is given by the following equation:
log k = - (73,900/4.575 T) + 17.05 (29)
The rate of butane cracking in its catalytic dehydrogenation has been
examined too, and it was found [21,22] that it can again be described
by a pseudo-first-order rate equation with a rate constant given by:
log k = - (60,000/4.575T) + 15.2734 (30)
The comparison of the thermal and catalytic cracking rate constants
applying the previously mentioned equations shows that the process
is slightly faster in the presence of the dehydrogenation catalyst.
For the olefins there a r e grounds [23,24] for assuming that the coke
deposition on the catalyst occurs according t o the scheme:
2C,Hn - vinylcyclohexene + %nH,
- polycondensation, dehydrogenation, cracking
- polycyclic hydrocarbons - coke
176 s. CARRA AND L. FORNI
The kinetics of the butene cracking has been extensively examined

[18] in a temperature range between 510 and 550°C and butene par-
tial pressures at the inlet ranging from 0.071 and 0.250 atm. The
analysis has been performed by studying the change in 1-butene con-
version due t o the catalyst fouling as a function of time. A typical
result is graphically shown in Fig. 11, in which a plot of the ratio
Xt/X, versus time is reported, Xt being the conversion that the
fouled catalyst gives at time t and X, the conversion that the fresh
catalyst gives at t = 0.
X
t
xo
0 2 4 6
t
FIG. 11. Change in 1-butene conversion vs. reaction time ( h ) ; T = 550°C;
0 , 0.071 atm; 0 ,0.250 atm; solid lines calculated from eq. ( 3 9 ) [ l a ] .
At the same time a run was made in which the reacting gases
flowed on the pan of a Cahn microbalance, on which a catalyst sam-
ple was placed. In such a run it was possible to measure the in-
crease of the catalyst weight, due t o coke formation, with the time.
The kinetics of the deactivation reactions was described by applying
the following scheme:
B + u = Ba (31)
Bu - Ya + LG (32)
where B indicates the reacting substance and u an active site. The
first reaction represents the adsorption and the second one the de-
activation, which takes place with formation of a deactivated site
(Yo) and light gaseous products (LG). The rate of the catalytic re-
action may be expressed as follows:
r = L,@(P~,T) (33)
Lo being the number of active sites per unit mass of fresh catalyst
and @ a function of reacting gases partial pressures (Pi) and of
temperature (T). If the catalyst deactivates, Eq. (33) becomes:
Lt being the number of active sites present at time t. In a first ap-

proximation, a s proposed by Pozzi and Rase [25], we can write:
%/Lo = xt/xo (35)

Let 9, be the fraction of active sites covered by the reagent B; 3,

the fraction of vacant sites at the time t ; and 3t = ,YV + 3 , = Lt/L,
the fraction of nondeactivated sites at the time t and 3 the fraction
of deactivated sites. The rate of the surface reaction ($2) will be ex-
pressed by:
-
d3y = ky8,
dt
ky being the reaction rate constant. Assuming that the adsorption

process of Eq. (31) is at equilibrium, we have:
~ B / P A=~b,V (37)
b, being the adsorption equilibrium constant.
From these assumptions we can write:
where
By integrating Eq. (38) we have:
In applying Eq. (39) (which gives the catalyst deactivation a s a func-

tion of reaction time t ) to the adsorption equilibrium constant b,,
appearing in the parameter p , the values of Table 6, corresponding
t o the adsorption equilibrium values of n-butenes, were given. In
such an approach the same adsorption equilibrium constant has been
attributed also t o butadiene, since its concentration was always very

low with respect to that of butenes.
The increase in catalyst weight due to coke formation can be ex-
pressed by
Ap = a a Y
a being the coke weight (mg) deposited at complete deactivation of

active sites. The integration of Eq. (38) with such assumptions gives:
log- a - P ,
--
a - Ap 2.303
Equation (40) was employed t o interpret the increase in weight of the

catalyst with time. In Table 8 the values of the constant ky as a func-
tion of temperature are reported, while in Fig. 12 the Arrhenius plot
f o r ky is shown. The value of constant a indicates that the increase
of catalyst weight tends to a limiting value of 170 mg of deposited coke
per gram of catalyst, corresponding to a value of the order of
7.10'5 mg/cm2 of catalyst surface. It is likely that the first step of
olefin isomerization over alumina is the adsorption on sites on which
there i s at least a vacancy of a pair of oxide ions [26]. In such sites
a couple of exposed aluminium ions are present, one of them acting
as a weak Lewis acid center for the olefin adsorption, and the other
one helping the migration of a proton, that occurs during the isomer-
ization reaction. A reasonable model of the hydrated y-alumina SUF-
face [27] indicates the presence of one pair vacancy per about 200 A2
of surface. A s previously seen, the coke deposition occurs through
the formation of a pseudographitic structure: In an ideal graphitic
monolayer there is one carbon atom per 2.8A2 [281. If the alumina
surface would be covered by a uniform graphitic monolayer, 7.2 X
mg of C per cm2 would be present. This value is quite close to
the limiting value obtained from the runs performed with the Cahn
TABLE 8
Deactivation Reaction
Rate Constants
T, "C
510 0.187
530 0.59
550 1.13
01
1.20 1.24 1.28 .."
T
FIG. 12. Arrhenius plot of coke formation reaction [18].
microbalance. Actually the coverage of the real alumina surface with

coke should occur through the formation of different zones of multi-
layer graphitic a r e a s and the poisoning of the catalyst seems to indi-
cate that the formation of such a r e a s preferentially takes place in
the vicinity of active centers.
As t o the decomposition of butadiene, both the thermal transfor-
mation and catalytic cracking a r e involved. The main reaction of
thermal transformation at temperatures higher than 400"C and at-
mospheric pressure is the polymerization, that follows a second-
order kinetic equation [29]. At low pressures the polymerization
ends with the dimer formation. The catalytic cracking follows a dual-
site mechanism [30].
ID. PHYSICAL CHEMICAL PROPERTIES O F THE CATALYST
Chromia-alumina i s an extensively employed catalyst, which is

active in a large set of reactions, such a s dehydrogenation, dehydro-
isomerization, dehydropolymerization of paraffins and olefins, olefin
polymerization and hydrogen-deuterium exchange. It can be con-
sidered as a dual-functional catalyst, in which an acidic function,
associated with the alumina phase, and a dehydrogenation function,
associated with the chromia phase, a r e present. Actually, chromia-
alumina is a complicated and subtle system and the oversimplified
description as a dual-functional catalyst represents only a useful
model for describing its catalytic behavior.
Chromia-alumina is a typical catalyst formed by a transition
metal oxide and a c a r r i e r (alumina). In it the c a r r i e r does not only
affect the mechanical and physical properties of the catalyst, for in-
stance by increasing the specific surface area or by preventing the
sinterization of the solid, but it also operates on the catalytic prop-
erties, such as activity and selectivity. In fact the presence of a
c a r r i e r stabilizes particular electronic states of the chromium. This
fact plays an important role in its catalytic behavior.
Chromia-alumina catalysts can be prepared in three ways: (1) im-
pregnation of preformed alumina with a chromium trioxide solution,
followed by drying and calcination in a reducing atmosphere (e.g., hy-
drogen); (2) coprecipitation of the aluminium and chromium hydrox-
ides from a solution containing A13' and Cr3+ by means of an alkaline

solution, followed by a calcination of such hydroxides; and (3) pre-
cipitation of chromium hydroxide onto the surface of preformed
alumina. By x-ray investigations [31-341 of chromia-alumina sam-
ples, heated at temperatures not higher than 1000"C, it has been
shown that such catalysts are formed of a mixture of y-alumina,
9-alumina, a-chromia and two solid solutions, called a- and
y-phases. It has been claimed [31] that precipitated catalysts con-
tain chromia crystallites of all sizes, from almost single chromium
ions to crystallites large enough to give x-ray diffraction patterns,
impregnated catalysts contain chromia crystallites of roughly equal
size for each chromium concentration, and coprecipitated catalysts
show no chromia diffraction lines even at 50 wt % chromium.
A more extensive study of coprecipitated chromia-alumina cata-
lysts was made by Davis et al. [34].They concluded that such ma-
terials a r e inhomogeneous in composition due to the presence of
different phases of the pure oxides. Otherwise the effectiveness of
alumina as a support or promoter for chromia is the result of its
being a high-area oxide, which i s isomorphous with y-chromia and
thus capable of stabilizing catalytically active y-oxide-phase solid
solutions.
From the magnetic susceptibility measurements, made by Ei-
schens and Selwood [31], important conclusions have been drawn,
concerning the valence state of chromium in chromia-alumina cata-
lysts, and the manner in which the chromium was combined with the
diamagnetic alumina. These authors obtained a series of so-called
susceptibility-composition isotherms of the type shown in Fig. 13
for a series of catalysts. It is well known that the magnetic suscep-
tibility of a paramagnetic material can be expressed as follows:
C
x=T+a
C being a constant (Curie constant) and A the Weiss constant, that is
I0 20 30
% Cr
FIG. 13. Magnetic susceptibility of chromia-impregnated on bohemite
( O ) , y-alumina (0)and a-alumina (0) [31].
related to the properties of the material by the following formula:
A -
2JzS(S + 1)
3k
where S i s the electronic spin, k the Boltzmann constant, and z the

number of nearest neighbor metal ions. J i s a quantum-mechanical
t e r m called exchange integral, describing the electronic exchange
interaction between the ions. The decrease of y, shown in Fig. 13 is
due to the increase of A , which, according to the argument given by
Eischens and Selwood, i s not due to a variation of J, but rather to a
change in the average number of C r - C r nearest neighbors, by in-
creasing the amount of chromia in the samples. Therefore it appears
that, for an impregnated chromia-alumina catalyst, as the chromium
content i s increased, small crystallites o r clumps of chromia a r e
present on the surface of alumina. At higher chromium concentra-
tion these crystallites tend t o become thicker and thicker, rather
than t o spread out over the surface of the alumina. On the other hand,
for a catalyst obtained by coprecipitation, the magnetic susceptibility'
measurements revealed much greater dispersion of the chromium.
This fact has been attributed to the presence of a three-dimensional
dispersion of the chromium, as compared to a two-dimensional dis-
persion in the case of the impregnated catalysts.
In some cases the activity and selectivity of a chromia-alumina
catalyst can be changed by the addition of promoters, the most com-
mon of which is an alkali metal o r alkaline earth salt [11,35-371. It
has been seen [38] that an alkali metal has a deep influence on the
182 s. CARRAAND L. FORNI
chromia. For instance, the presence of potassium in the catalyst at

concentrations higher than 0.2 wt % increases the degree to which
the chromia can be oxidized, but does not stabilize the chromia
against subsequent reduction; small amounts of potassium (< 0.2 wt %)
are not associated with the chromia, but rather with the alumina on
the surface. It is well known that even such small quantities of
potassium generally increase the dehydrogenation reaction rate. It
was found [39] that the addition of 0.5 wt % of K,O to a 10% chromia
on alumina catalyst led t o a value of n-butane dehydrogenation reac-
tion rate of almost twice the value of nonpromoted catalyst.
Of particular interest is the ESR investigation of chromia-alumina

catalysts [40,41], by which the presence of isolated Cr3+ ions (6-
phase), of clusters of Cr3+ ions (P-phase) and of Cr5+ ions has been
shown. The P-phase must be formed by coupled Cr3+ions, because
it appears when the concentration of Cr3+ ions is high. The presence
of C r 5 + ions is particularly important because it demonstrates that
the c a r r i e r can stabilize particular electronic states of the transi-
tion metal. In fact it was postulated that these ions occupy the octa-
hedral vacancies formed by oxygen ions in the cubic lattice of y -
alumina. Following Van Reijen and Cossee [42,43] they exist as
cromyl (CI-=O)~+ions, as one metal-oxygen bond i s shorter than the
other two. In fact on the surface they possess a square pyramidal
coordination. These ions seem to play an important role in the olefin
polymerization on chromia- alumina catalysts.
Chromia-alumina samples also have been studied optically 144-461.
A s e t of optical reflectance spectra, recorded for a set of catalysts
containing different amounts of chromia and at different temperatures,
reveals the presence of two absorption maxima around 17,000 and
23,000 cm-' [44]. Such maxima correspond to the electronic transi-
tion of the Cr3+ ion in a n octahedral site, in which the energy levels
a r i s e from the splitting of the energy levels of the free ion due to the
effect of a strong octahedral crystal field. The chromic ion Cr3+ has
three electrons in the 3d shell. When Cr3+ is placed in an octahedral
crystal field this energy level splits into a lower orbital singlet and
- 4TT, -
two higher energy triplets (Fig. 14). The described optical transition
corresponds to the 4A, and 4A, 4T, transitions called h and
Tf respectively. If the Cr3+ substitutes an A13+ in an a-alumina
lattice, it is surrounded by a distorted octahedral of nearest-neighbor
oxygen ions. In this case the chromium ions a r e placed in sites of
trigonal symmetry and the upper energy levels split a s shown on the
right side of Fig. 14. Actually such splitting cannot be resolved in
powder samples of chromia-alumina.
The increasing of the amount of chromia in the samples leads to
a gradual shifting of the absorption maxima, due to the lattice ex-
I I
I
4.
I*
rr I .--
,<---
free strong strong

aon octahedral octahedral
p l u s weak
t .1gonal
FIG. 14. Energy level d ia g r a m of Cr3+ in octahedral and in an octahedral

plus a trigonal c r y s t a l field environment [44].
pansion that results when chromia i s added to the aluminajattice. In

fact the closest metal-oxygen distances a r e 1.89 and 1.93 A in the
@-alumina and 1.97 and 2.01 A in the chromia lattice [44].
In the oxidized chromia-alumina a strong absorption band i s ob-
served between 305 and 450 mp, which is due to the presence of
Cr6+ ions. This band disappears when the sample is heated in hy-
drogen flow, corresponding to a conversion to lower valence states,
mostly C r 3 + , of chromium.
An interesting point is the one related to the formation of stabilized
C r 2 +ions during the reduction of the catalyst sample:
Cr3+On+ H, Cr2+On-l + H,O (43)
Van Reijen et al. [47] on the basis of ESR and magnetic suscepti-
bility measurements, suggest the existence of this ion but the actual
evidence is still controversial. This point is particularly interesting
because Burwell and coworkers [48] had already proposed the exist-
ence of these ions as active centers of dehydrogenation. Shvets and
Kazanskii [49], however, have analyzed the reverse of the reaction
(43) by adsorbing water on the reduced catalyst; they found that the
amount of released hydrogen i s very small. This result seems to
call in question the existence of stabilized Cr2+ ions. Since a strong
poisoning effect of water on the dehydrogenation reaction catalyzed
by chromia-alumina i s well known, the authors mentioned attribute
184 s. CARF& AND L. FORNI
this effect to the adsorption of water on surface Cr3+ ions as follows:
This hypothesis is supported by optical data on dehydrated samples,

where the electronic transition of the Cr3+ ion in a square pyramidal
ligand field (C4v symmetry) was observed.
The electrical conductivity of chromia-alumina has been exten-

sively studied. The electrical properties of a chromia-alumina cata-
lyst are much more influenced by the chromia content, than they a r e
by the alumina carrier. Fischer and Lorenz [50,51] attributed the
intrinsic conductivity of chromia above 1250"C to the reaction:
2cr3* f Cr2+ -+ Cr4+
whereby a pair of chromium ions form an electron donor and an

electron acceptor, and the resultant conductivity arising from elec-
tron exchange is independent on the oxygen pressure. This shows
that the equilibrium between the bulk and the surface lattice struc-
ture is not an important contributor to the electrical conductivity,
because the number of Cr3+ pairs which can form Cr2++ Cr4+ ions
far exceeds the number of excess oxygen ions. Since the transport
in chromia takes place by electron transfer, chromia does not ex-
hibit the Hall effect, photoconductivity, or carrier injection. In fact
the energy distribution curve of the photoelectrons emitted by chromia
shows a spreading of many electron volts [52], as is typical for in-
sulators.
Chapman et al. [53] studied the dependence of the electrical con-
ductivity, activation energy and thermoelectric potential on the chro-
mium concentration in a series of chromia-alumina catalysts, pre-
heated at 500"C . The dependence of electrical conductivity on chromia
content in the catalysts is shown in Fig. 15, while the dependence of
the thermoelectric potential on chromia percentage is shown in
Fig. 16. One can see that the thermoelectric potential is positive
for the samples with 43% or more chromia, and negative for the
samples with 29% o r lower chromia content. This corresponds to
a change from n-type to p-type conductivity at the lower chromia
concentrations, where the electrical conductivity is essentially that
of pure alumina. The conductivity measurements in vacuo also indi-
cate the same electrical behavior as the measurements in hydrogen.
Chapman et al. attributed the conductivity of these high surface area
'E
%
b
1 1 I I I I
0 20 40 60 80 100
FIG. 15. Dependence of electrical conductivity on the chromium content

for a set of chromia-alumina catalysts [ 5 3 ] .
1 I 1 I
0 20 40 60 80 100
FIG. 16. Dependence of thermoelectric potential on the chromium concen-

tration for a s e r i e s of chromia-alumina catalysts [ 5 3 ] .
catalysts mainly to the presence of surface impurity levels. In an

oxygen atmosphere the surface incorporates 0'- ions, and the chro-
mium valence increases, leading to a change from n-type to p-type
conduction. In an hydrogen atmosphere the excess oxygen is removed,
the average surface chromium valence is decreased, and n-type con-
duction is observed.
Large changes in electrical conductivity occur in chromia-alumina
during catalytic reactions. Bremer and Stach [54], for instance, found
a linear relationship between the logarithm of the specific electrical

conductivity and the activity for the dehydrogenation of isopropyl
alcohol.
IV. HYPOTHESES ON THE REACTION MECHANISM
Two mechanisms can be devised for the hydrocarbons dehydro-

genation over chromia-alumina [55]. In both cases the active centers
are surface chromium ions coordinatively unsaturated and the chem-
isorption of the reactant occurs through the fulfillment of their octa-

hedral coordination. The chemisorption is associated with a cleavage
of the C-H bond and the alkyl group is bound to a chromium atom
giving an organometallic s u r f w e compound. In the first mechanism
one can assume that the breaking of the C-H bond is an heterolytic
process which generates two ions acting as donor and acceptor and
that are simultaneously chemisorbed. The hydrogen ion is bound to
an oxygen atom near to the chromium ion. The process can be visual-
ized as shown in Fig. 17. In this process the charge transfer is
localized in the valence shell of the cation and it follows that no re-
lationship should exist between the chemisorption and the electrical
properties of the solid. It i s interesting to point out that the reverse
of this process is similar to the one proposed by Halpern et al. [56]
for the homogeneous hydrogenation of olefins with RuC1, complexes,
in which the formation of the alkyl-metallic compound proceeds a s
shown in Fig. 18.
FIG. 17. C-H bond breaking in the heterolytic chemisorption of a paraffin

on chromia.
In the second mechanism the spin free cations, which a r e the

charge c a r r i e r s in electrical phenomena, that is Cra+ and C r 4 + ,a r e
involved (Fig. 10). The Cr2+centers act as electron donors to the
hydrocarbon radical fragments, while hydrogens shift to the nearest
Cr4+centers. In this case the breaking of the C-H bond occurs
through an homolytic process and the bonding between the obtained
N+
FIG. 18. Reaction mechanism in homogeneous hydrogenation of olefins
with RuCI, complexes [ 5 6 ] .
I? H
FIG. 19. Mechanism for paraffins dehydrogenation on chromia [55].
radicals and the metal ions will be rather covalent. It is worthwhile

remembering that for this case we also can find a similarity in homo-
geneous catalysis in the reaction of hydrogen with the previously men-
tioned RuC1, complexes in dimethylacetoamide solvent. In this case
the reaction probably occurs through the homolytic breaking of the
H - H bond:
According to the fact that chromia-alumina behaves a s a semicon-

ductor and since in a semiconductor lattice the d electron shifting is
easy, it follows that the second mechanism can be interpreted at the
light of the electronic theory of catalysis. If ni indicates the surface
concentration of the i-th species, 0 and 0 indicate the electrons and
the holes on the catalyst surface, neglecting the adsorption of reac-
tion products and denoting by B, n-butane; A, R-CH2-CHz-, R,

R-CH'-CH2-; E , R-CH=CH,, for low coverage, that is for
n o >> n A , we obtain, referring to Fig. 19:
3
dt
= klP, - k-,nAn,+ - k,nAnO (44)
-
d n =~ b n A n g - (45)
dt
where ki a r e the reaction rate constants. At the equilibrium:
k,PB = k-,nAnH+ + k,nAnO (46)

k,n, = k,n,ng =rE (47)
r E being the desorption rate of n-butane, that is the rate of the over-
all process. If
k,nAng << k-lnAnH+ (48)

as it is justified by the fact that the rate-determining step is the sur-
face reaction, from Eq. (46) it follows that:
n A = klPB/k-In,t
and therefore Eq. (47) becomes:
rE = kl&PBng/k-,n,+ = bBkzPBnH+ (49)
For small coverages the reaction rate equation
becomes
A comparison with Eq. (49) gives:
kr = k,ng/nHt (52)
This equation allows the evaluation of the effect of the free-electron

concentration on the kinetics of the reaction and then to relate the
catalytic activity to the semiconductivity of the solid. It is important,

however, to emphasize that C r2+concentration could be considered
instead of the electron concentration n o , the difference consisting
only of the localization of the nucleophilic center to a well-defined
metal cation.
The previous analysis can be used for the interpretation of the
influence of the added impurities (e.g., Na, Li) to the catalyst. From
the values of ionic radii [28] of N a + , Li', Cr3+,and A13+ it follows
that Li' ions can substitute both Gr3+ and A13+ ions in the crystalline
lattice much better than Na' ions, which tend to remain in larger
amounts of interstitial positions at the surface of the catalyst. A

monovalent alkali atom, present in a reticular position, acts as an
electron acceptor, because it provides to the system only one elec-
tron, while the communal sharing system demands three [57]. The
indispensible two electrons will be extracted from the normal elec-
tronic distribution of the crystal, leaving on it two partially free
positive holes able to wander in the neighborhood of the defect. On
the other hand a monovalent largely electropositive atom in an inter-
stitial position a c t s as an electron donor, giving to the system one
electron. As to test such interpretation, the activity of a set of cata-
lysts, containing small percentages of Na,O and Li,O was measured
for the dehydrogenation reaction of n-butane [ll]. The results a r e
shown in Fig. 20, where the activity in the dehydrogenation reaction
has been plotted versus the percentages of Na,O or LbO in the cata-
lysts. It can be seen that the addition of lithium, which acts as an
electron acceptor, gives at every concentration a decrease in cata-
lyst activity; while the addition of sodium gives a decrease in activity
at small percentages, when it can be accomodated mainly in the crys-
tal lattice, followed by an increase of the activity at higher percent-
ages, when it is present mainly in interstitial positions where it acts
as an electron donor. Summarizing, it is possible to say that prob-
ably in the dehydrogenation over chromia-alumina both homolytic
and hetherolytic fissions can take place, depending on many factors,
such as catalyst preparation technique and pretreatment and working
conditions,
The formation of dienes from olefins probably involves the forma-
tion of a n-allyl-surface complex:
0-M-0 ---c 0-M-0

P
O'L A'O
a lo4
4 550°C
0 540°C
530°C
0 520'C
A 510°C
L I
% Na20 2. 1. .5 0 .5
.5 1.
1. 2.
FIG. 20. Activity of a set of chromia-alumina catalysts with alkaline

modifiers. The activity i s given a s initial dehydrogenation rate. All the values
corresponding to samples containing alkaline oxides have been corrected
taking into account the surface a r e a change due to doping process. Surface
a r e a s determined by B.E.T. technique.
Dienes a r e formed through the subsequent elimination of hydrogen

atoms from the -CH, group near t o the ally1 system. This mecha-
nism implies that the dehydrogenation occurs through a stepwise
path. This hypothesis is confirmed by very recent results 1581 show-
ing that over a chromia-alumina catalyst cyclohexene and cyclohexa-
diene are formed during the dehydrogenation of cyclohexane to ben-
zene.
V. TECHNOLOGICAL ASPECTS
The catalytic dehydrogenation of n-C, hydrocarbons is usually

performed in tubular flow reactors with total recycle of the unre-
acted products, as shown in the scheme of Fig. 21. The operation of
such heterogeneous catalytic reactors gives rise to many optimiza-
tion problems, as a consequence of catalyst deactivation. Such prob-
recycle
-
broduc ts
FI 21. Scheme of a dehydrogenation unit wil total recycle of unreacted
substance 159 1.
l e m s a r e essentially connected to the following two points:

1. Operational time and conditions
2 . Catalyst regeneration time.
The first problem is the more complex one from the mathematical
point of view, because the operational conditions vary with time. The
solution of this problem i s obviously connected to a sound knowledge
of the kinetics of the reaction and of the catalyst deactivation. The
optimization policy for the reactor involves the knowledge of the
following informat ion:
1. The maximum profit, corresponding t o the maximum output
of product per unit time
2. The temperature-flow- rate-time function
3 . The catalyst regeneration policy [59].
Let q(t,Ti,qs) be the amount of product formed per unit time and
t the catalyst regeneration time, assumed fixed, T i being the input
temperature of the mixture fed t o the reactor and qs the heat ex-
changed per unit time and per unit reactor volume. The production
per unit time is obviously given by the following expression:
where (t + t R ) . i s the total length of an operation-regeneration cycle.

Within any single operation- regeneration cycle it i s possible t o define
a yield objective function:
192 s. CARF& AND L.FORNI
‘pobeing the value of ‘p at zero deactivation.

The optimization problem implies the determination of the optimum
values for Ti and qs and for operation time t. Such optimization may
be expressed in the following form:
2 = .,M{[Max
a ~ ( t , t R )vo(Ti,qs)}
] (55)
i?\
5 being the maximum profit corresponding t o the maximum output.

The previous Eqs. (53) (54) (55) may be applied as follows: once
given some arbitrary starting values for T i and qs, the yield 17 is
maximized with respect to the operational time t. On the basis of
such a time, the optimal Ti and qs a r e computed using a gradient
method technique and the former maximization is then repeated and
s o on, until the optimum value of CP is found. Such a method is visu-
alized in Fig. 22, in which, for generality’s sake, the operational
variables X i a r e more than two.
For the set of dehydrogenation reactions given in Fig. 1’ it is use-
ful to develop a generalized system of representation that can con-
veniently be adopted for computer programming logic. Let Ai denote
a total of N chemical species of components, which are taking part
in a system of M chemical reactions. The stoichiometry balance
can be written as follows:
N
C cr..A.
4 1= 0 j = -
1,2; . M (56)
i =1
where crij is the stoichiometric coefficient for the component Ai in

the j-th reaction, taken positive for reaction products and negative
for reactants.
In a non-stationary flow-type tubular reactor the mass balance
system of equations can be formulated as follows: neglecting radial
and axial diffusion and the radial gradient of velocity, the mass
balance for the component Ai in a volume element of differential
length dz gives:
In Eq. (57) G is the molal flow rate per unit cross-section area of
the reactor, pm the molal density, X j a factor which converts cata-
lyst weight t o the system volume and rj is the rate of the j-th reac-
tion.
DEHYDROGENATION OF C LYHYDROCARBONS 193
check
output
FIG. 22. Block logic diagram of the described optimization procedure [59]
The non- stationary energy balance over a differential reactor

volume element of length dz leads to:
where Hf i s the enthalpy of formation of species i taken negative

for exothermic reactions and g, the exchanged heat per unit time and
194 S. CAR- AND L. FORNI
reactor volume element. The solution of the previous differential

equations system gives the dynamic behavior of the reactor. The
integration of such equations cannot be obtained analytically, but a
finite-difference procedure must be applied. For such an aim
Eqs. (57) and (58) must be rewritten in a finite-difference way as
follows:
t being a small time interval and the subscripts n and n-1 denoting
two successive operation times. The initial conditions are:
X,(Z,O) = 1
T(z,O) = Ti
Xi(O,t) = 0
x1(0,O) = 1
i denoting the reaction products, xl(r) the 1-butene in the recycle

flow, and %(e>the butadiene at the exit.
Equations (59) and (60) can be solved using the Runge and Kutta
method. Such a procedure allows one t o obtain the fluid temperature
and conversion profiles along the reactor axis for any operation
time. From the variation with time of the conversion to butadiene
it is possible t o evaluate the function 71 defined by Eq. (54).
Afterwards the calculation procedure described by the block
logic diagram of Fig, 22 according t o Eq. (55) can be applied.
It is noteworthy that the application of this procedure by employ-
ing the s et of previously mentioned Eqs. (14), (15), (27), and (34)
allows one t o obtain optimum policy variables (operation time, Ti
and qs) that correspond fairly well t o the industrial operational
conditions of a dehydrogenation unit, as obtained from practical
management experience.
DEHYDROGENATION OF C, HYDROCARBONS
.-
195
Acknowledgments
This work has been done with the financial support of the Italian
Consiglio Nazionale delle Ricerche.
List of Symbols
A reactor tube c ross section
bi adsorption equilibrium constant of substance i
B n-butane
Ci concentration of substance i
D butadiene
AE * activation energy of reaction
F olefin feed rate
G molal flow rate per unit cross-section area
AGo, standard free energy change
Hf ,i enthalpy of formation of species i
AHo standard enthalpy change
k reaction rate constant
KP equilibrium con stant
number of active sites per unit mass of fresh catalyst
2
ni
number of active sites per unit ma ss of fouled catalyst
surface concentration of species i
N total number of runs
Pi partial pressure of substance i
AP change in catalyst weight due to coke formation
qs exchanged heat
r reaction rate
Ri mole ratio of component i over n-butane
ASo standard entropy change
tC time that olefin molecules a r e in contact with the catalyst
tR catalyst regeneration time
T absolute temperature
VR catalyst volume
W catalyst weight
xi molar fraction of substance i referred to 1 mole of fed olefin
xo conversion given by fresh catalyst at time zero
xt conversion given by fouled catalyst at time t
2 reactor tube length
Greek Letters
a! moles of 1-butene/total volume at the inlet
@ij stoichiometric coefficient of substance i in reaction j
lA 1-butene
2Ac cis- 2- butene
2At trans- 2-butene
77 yield objective function
9 coverage of active sites
Xj
factor converting catalyst weight to the system volume
v stoichiometric number
t operative time
peat catalyst density
pm molal density
T time factor
q function denoting the amount of formed product
2 maximum profit
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Catalysis Reviews: Science

To cite this article: S. Carrà & L. Forni (1972) Catalytic Dehydrogenation of C4

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I. THERMODYNAMICS AND KINETIC ASPECTS . . . . . . . . 160

Reactions involving hydrogenation and dehydrogenation are em-

I. THERMODYNAMICS AND KINETIC ASPECTS

The catalytic dehydrogenation of n-butane occurs through a com-

The equilibrium constant for the chemical reactions of Fig. 1 can

AG; = -RT In Kp (1)

Values of AGO. kcal/mole, a s a Function of T, "K [4,5]

ReactioniT 400 500 600 700 800 900

The study of the reaction rates occurring in the dehydrogenation

j\i B 1A 2AC 2At D H,

sure of compound i , and Z i the relative adsorption coefficient of com-

In order to broaden the form of the rate equation it is important

rf and rr being the r a t e s of the forward and reverse reactions re-

K = kl/k-, being the equilibrium constant and C, and C, the reactant

r = rfll - exp (AG,/RT)] (9)

r = rf[l- exp (AG/vRT)] (10)

Remembering Eq. (6) the following expression for the stoichiometric

It follows that for determining experimentally the stoichiometric

FIG. 2. Reaction free energy for n-butane dehydrogenation vs. l n ( r r / r r )

Taking into account that the stoichiometric number of the reaction is

Dodd and Watson [lo] applied the Langmuir-Hinshelwood scheme

tion by feeding a flow reactor with a mixture of n-butane and nitro-

FIG. 3. Reaction r a t e s (moles/h g.cat) vs. n-butane partial pressure

In this case Eq. (15) can be ,written:

that is a linear relationship between (PB/r)lD and PB. Such a plot is

FIG. 4. (PB/r)1/2a s a function of n-butane p a r t i al pressure 0,550°C;

510 2.44 19.50 57.605 52.436

For feeding mixtures of n-butane, nitrogen, and a component i

that is a linear relationship between the left-side member and the

log kr = 4.850 - 23,223/2.303 RT (19)

b = exp[- (AHo/RT) + (ASo/R)] (20)

and the obtained values a r e given in Table 4.

1.2 1.25 1.3

Compound -AH", Kcal/mole -ASo, cal /moleOK

n- butane 53.90 (i0.55) 62.94 (* 0.72)

It is important to emphasize that Eq. (15) has been derived only

sit e s for adsorption and interaction among adsorbed species. The

The parameters of the previous equation, obtained by applying a non-

Constants of Equation (21)

k if 2.70 X lo-’* 1.51 X lo-’

The kinetic study of the dehydroisomerization reactions of butenes

sulting coke deposition was negligible. This procedure allowed the

where xi a r e the molar fractions, referred t o the fed olefin, of the

and for isomerization:

If the total p r e s s u r e is equal t o 1 atm, Eq. (24) can be written in

b, being the adsorption equilibrium constant of butenes (atm-I) as-

has been minimized with respect to the parameters kj and bi by apply-

FIG. 8. Reaction paths of 1-butene dehydroisomerization reactions at

T, "C 510 530 550

bAb, atm-' 40.0 18.0 10.1

In Table 7 the values of the apparent activation energies of l-bu-

A E =~A E ~ =AE$ 29.8 kc a1/mole

11. CATALYST FOULING

The kinetics of the butene cracking has been extensively examined

Lt being the number of active sites present at time t. In a first ap-

%/Lo = xt/xo (35)

Let 9, be the fraction of active sites covered by the reagent B; 3,