.I. appl. Chem. Biotechnol.

1914, 24, 759-168

Hydrogenation of Cyclopentadiene on a Nickel Catalyst

H. Sakamoto, K. Takasaki, Y. Ha ra no and T. Imoto
Department of Applied Chemistry, Faculty of Engineering, Osaka City University,
Sugimoto-cho, Sumiyoshi-ku, Osaka, Japan
(Paper received 1 April 1974, amended paper accepted 30 July 1974)

The hydrogenation of cyclopentadiene on Ni catalyst was carried out with a

fixed bed reactor.
The initial reaction rates were expressed by the following equations.
ro = k U P C 0 ~ 4 5 P H 0 ~ 9 3
kKcKij PJ'H
ro =
(1 + KcPc + KHPII)*
The activation energies of overall- and surface-reaction rates were, respectively,
1.9 and 6.5 kcal/mol and the heats of adsorption of hydrogen and cyclopentadiene
were, respectively, 5.6 and 1.6 kcal/mol.
The hydrogenation of cyclopentadiene on Ni catalyst is a consecutive reaction
passing through cyclopentene, where the activation energy of the 1st stage is higher
than that of the 2nd one, namely, E l > E 2 . At the lower ratio of PHIPc,cyclo-
pentene is produced with 100% selectivity, whereas, increasing Pli/Pc or W/Fo,
the selectivity decreases. At the intermediate reaction temperature, there appears
the minimum selectivity. This phenomenon is considered to be due to El > E2.

1. Introduction
Recently, usages of the fraction of C,-hydrocarbons in the petrochemical industry,
in particular, of cyclopentadiene have received much attention.
The catalytic hydrogenation of benzene is a well known reaction and, for exampIe,
that on nickel catalyst'-3 has been studied by many investigators, giving the kinetic
informations in detail. On the contrary, concerning to cyclopentadiene, only a few
papers have been given, where Ni-AI,O, (40-140 "C,under high p r e ~ s u r e ) Ni-ZnO,s
,~
borides of platinum group6 and Ni (10 wt.- %)-sepidite [H,MgSi ,,(OH), 0 6 H 2 0 ,
25-155 "C, 100 lb/in2J7were used as catalysts and detailed kinetic data have not been
reported.
In this work, from the above point of view, an attempt has been made to study on
the kinetics of the hydrogenation of cyclopentadiene on Ni catalyst and on the effects
of the operational conditions on the selectivity of cyclopentene.

2. Experimental
2.1. Materials and catalyst
The materials used in this work were prepared in the following manner: cyclopentadiene
was prepared**9by decomposition of dicyclopentadiene obtained by distillation of
759
760 H. Sakamoto ef al.

commercial grade under about 16 mmHg of nitrogen (b.p. 43-44 "C),and was stored
in a vessel immersed in dry ice-methanol bath, because of its rapid redimerisation at
room temperature. Commercial grade hydrogen and nitrogen were purified by passing
through a oxygen-eliminator column packed with reduced copper and then a silicagel
tower. Commercial sulphur-stable nickel catalyst (N-1 1 I, supplied by Nikki Chemicals
Co. Ltd., Ni 4547, Cr 2-3, Cu 2-3, kieselguhr 27-29 wt.- %, 5 mm x 4 mm; surface
area 150-170 m2/g) was ground to powder and its three fractions of 40-60,6040 and
100-150 mesh size in this work.
Before every reaction run, the catalysts were pretreated as following, in order that
they have the constant stable activity under the reference conditions. The catalysts
were heated up to 100 "C in a stream of nitrogen and then reduced with a flowing
hydrogen at the same tcmperature for 1 h and at 180 "C for 3 h. The replacement of
nitrogen by hydrogen stream at 100 "C should be done gradually. The activity of the
catalyst pretreated as mentioned above settled to the constant level after a 1 h reaction
run. When a soap film flowmeter was used, the catalyst activity dropped rapidly.
Hence, two tubes packed with, respectively, calcium chloride and silica gel were
placed between the flowmeter and the reactor, then the activity recovered completely.
This may be due to the effect of water, in analogy with the case of the hydrogenation
of benzene over a nickel catalyst. O

2.2. Apparatus and procedure

The main part of the apparatus is shown in Figure 1. The reactor (K) is a quartz
tube of 13 rnm i.d. and 850 mm long. Catalyst was contained in the reactor, diluted
four times with catalytically inert glass particle. The furnace (I) was heated electrically

A I

Figure 1 . Experimental apparatus. A, Needle valve; B, oxygen eliminator; C, silica gel bed; D, orifice
meter; E, cock; F, manometer; G , evaporator; H, sampler; I, furnace; J. alumel~hromelthermo-
couple; K. reactor; L, catalyst bed; M, sampling hole; N, trap.
 Hydrogenation of cyclopentadiene on a nickel catalyst 761

with two nichrome wires, the electrical resistance of which are different. The bed
temperature was controlled with the lower resistance wire. There existed a longitudinal
distribution of the temperatures, where the maximum difference among them was
1.6 "C at steady state and under the experimental conditions. Then the average value
was taken as the reaction temperature. The feed gas composition was controlled by the
flow rates of gases and the temperature of the cyclopentadiene evaporator (G,
- lo-+20 "C).
Hydrocarbons were analysed by a gas chromatography, using Squalane 3 m and
Silicon DC-550 3 m at 70 "C as the packing materials, 100 "C as a cell temperature
and hydrogen as a carrier gas at the flow rate of 45 ml/min. No dicyclopentadiene was
detected in the gases at inlet and outlet of the reactor.
The experimental conditions were as follows: reaction temperature 65-120 "C,
partial pressure of cyclopentadiene 0.04-0.2 atm, of hydrogen 0.04-0.6 atm (total
pressure 1 atm, using nitrogen as a diluent), catalyst 0.1-0.5 g, the ratio of the catalyst
mass to the feed rates, W/Fo,0.58-7.4 g-cat. min/mol.

3. Results and Consideration

The reaction products were cyclopentene and cyclopentane. The film diffusion resist-
ance was confirmed to be negligibly small in the experimental conditions and at smaller
W/Fo than 3 g-cat. min/mol, varying the flow rate at constant W/Fo(W = 0.1,
0.15 and 0.2 g). Table 1" shows the results obtained with various sizes of catalysts,
at the highest reaction temperature.b Table 1 indicates that, with the catalyst of larger
size than 0.2 mm, the intraparticle diffusion affects the reaction rate. Therefore, the
catalyst of 100-150 mesh (0.13 mm) was used in the subsequent experiments.
1. Effect of catalyst size on reaction performance and selectivity of cyclopentene
TABLE
Catalyst size
Conversion of Selectivity of
(mesh) mm (average) cyclopentadiene ( %) cyclopentene
40-60 0.2334.205 (0.219) 56.4 16.4
80-100 0.1774.149 (0.163) 61.7 26.5
100-150 0.1494.105 (0.127) 62.6 29.6

Figure 2 illustrates the relation between the cyclopentadiene conversion and W/Fo
and Figure 3 does the effects of partial pressures of cyclopentadiene (Pc)and of
hydrogen (PH)on the initial rates (ro), which was obtained from the slopes of the
tangents to the curves at W/Fo = 0 in Figure 2. As the results, the initial rate was
expressed by
r o = kap,o.45pHo.93 (1)
Experimental conditions; PH = 0.6 atm, Pc = 0.06 atrn, reaction temperature = 120 "C, W/Fo =
0.15 g-cat.min/mol.
Since the hydrogenation of cyclopentadiene is a exothermic reaction with high calories," it is
difficult to control the temperature of reactor. Hence, at high temperature, high PH/Pc,and high

7
Q +H1
+H2
-.0
catalyst mass, the errors of kinetic data went up to over 5%.

- , A H = -23.9 kcaliniol (25 " C )

, A H = -27.0 kcal/mol(25 "C).
762 H. Sakamoto et al.

under conditions: Pc = 0.04-0.2 atm, PH = 0.04-0.6 atm and reaction temperature

= 65-120 "C.The apparent activation energy was 1.9 kcal/mol.
Since equation (1) indicates that the initial reaction rate is proportional to PIi0."
and Pc0.45, the rate determining step of the reaction is presumed not to be the
adsorption process. Hougen-Watson type rate expressions based o n the surface
reaction controlling mechanisms shown in equation (2) were tested. In equation (2),

I
WIF, (g-cat.min/rnol)

Figure 2. Conversion of cyclopentadienc 1'5. W'IF,. catalyst 0.15 g. Solid lines: at 65 "C,PI,, (0.6 aim).
Pv (atm): 0 , 0.1, 0,0.06, x , 0.04. Dotted lines: a1 I Z O T , P 0.2 (atm). P H I(atrn): 0 , 0.06,
0 , O . l ; x,O.15; D,O.2. v
however, the mechanism, in which two molecules of hydrogen (in molecular or
dissociative state) react with one molecule of cyclopentadiene at the same time to
produce cyclopentane, was excluded, because cyclopentene was obtained as inter-
mediate.
r = kecPIi (a) = keHPc (b)
= kWrr (c) = keCe'zH (d)
= kiYZCBH (e) = ,tke'2ce'2i1 (f) (2 1
= kef2CPIr (g) = k8''fiPc (h)
= kO"c8"iI (i),

where suffix C and H mean, respectively, cyclopentadiene and hydrogen, and 0 and
8' are the coverages of the competitive adsorption, respectively, on single and dual
 Hydrogenation of cyclopentadiene on a nickel catalyst 763

site (in the case of hydrogen, dissociative adsorption) and 8” is that of the non-
competitive adsorption on single site.
From equation (l), the mechanism (b) and (h) in equation (2) need not to be taken
into account. Testing the fitness of data obtained for ro, it was found that the hydro-
genation of cyclopentadiene proceeds according to mechanism (c), namely that both
cyclopentadiene and hydrogen adsorb on single sites of the catalyst, respectively, and
the reaction takes place between them, and that overall reaction rate is determined
by the latter process, according to the following equation.

where k and K are, respectively, the surface reaction rate constant and the adsorption
equilibrium constant.

0.01 0.1 1.0

PH2(atrn)or P’(atm)

Figure 3. Apparent order of reaction with respect to partial pressure of and H2,at 0.15 g of
catalyst. 0 , 65 “ C ; 0,120 “C: (I) r o us. Pep at PHI = 0.6 a t m ; (11) r o cs. PHIus. at P v = 0.2 atm.

The desorption control mechanism also should be tested. The rate expressions in
this case, however, give the same type of testing equations as those derived from
mechanism (a) or (b) in equation (2), to which the data did not fit as mentioned above
(the plots of PHPc/ro us. PH at constant Pc or Pc at constant PH are not linear but
curved).
Figure 4 illustrates the relation between (P,IPc/ro)”2and PH (straight lines I, at
Pc = constant) or Pc (straight lines IT, at P,, = constant). From slopes and intercepts
I64 H. Sakamoto er al.

of these straight lines, k, K's in equation (3) are obtained. At 120 "C, for example,
k , KH and Kc were, respectively, 2.66 (mol/g-cat.min), 0.257 (I/atm) and 7.21 (I/atm).
From the data obtained at every temperature, the activation energy of the surface
reaction rate and heats of adsorption of hydrogen and cyclopentadiene were estimated
to be, respectively, 6.5, 5.6 and 1.6 (kcal/mol). The average deviation of the calculated
ro [using the kinetic parameters obtained above and equation (3)] from the observed
ones was 8.8 %.
PH (atrn)
0 0.1 0.2 0.3
1.5 ~ - " 1 " ' ' 1 ' ' '
I

0 0.05 0.10 0.15

Pc (at rn)

Figure 4. Plot according to eqiiation (4). (I) at Pv = 0.2 atm; (11) at PI,, = 0.6 a m ; 0 , 65 " C ;
b, 120°C.

There have been many reports of the benzene hydrogenation on a nickel catalyst.
According to some of them,' the hydrogenation proceeds via the reaction of three
molecules of adsorbed hydrogen in molecular or dissociative state simultaneously with
one molecule of adsorbed benzene. Recently, however, Kehoe and Butt3 have studied
the reaction at low temperature and confirmed the results to be consistent with a
Rideal mechanism for the hydrogenation, proceeding via consecutive molecular
addition of gaseous hydrogen to the adsorbed benzene. In the case of cyclopentadiene,
the addition of two molecules of adsorbed hydrogen takes place not at the same time,
but stepwise, producing the intermediate, that is, this reaction is a consecutive one.
Figures 5 and 6 show the effects of W/Fo,the partial pressure of hydrogen and the
reaction temperature on the selectivity of cyclopentene and cyclopentane, where
selectivity is defined as the percentage of the consumed cyclopentadiene which goes to
cyclopentene or cyclopentane, respectively. From Figure 5, it was found that the
selectivity of cyclopentene increases as W/Foand PH decrease and that cyclopentene
is able to be obtained with 100 % selectivity,depending upon the operational conditions.
These results are considered to arise from the nature of the consecutive reaction.
Figure 6 indicates that the selectivity of cyclopentene has the minimum value at the
intermediate temperature (about 80 "C). This phenomenon may be understood
qualitatively in the following way.
Hydrogenation of cyclopentadiene on a nickel catalyst 765

Figure 7 shows the plots of the dimensionless concentrations of each component

in effluent obtained at 65 and 120 "C against the conversion of cyclopentadiene.
Comparing the yields of cyclopentene at two temperatures with each other, it can be
seen that kl/k,[see equation (4)] increases with increase in the reaction temperature,
hence that the activation energy of the first step, El, is larger than that of the second,
E2.
Assuming the reaction (4) to be a first order consecutive one,

- I
- I

01 I I I
0 2 4 6
W/F,(g-cat.min/rnol)

Figure 5 . Effect of hydrogen pressure on selectivity at 120 ' C , P = 0.2 atni and 0.15 g of catalyst.
W
P,, (atm): 0,0.06; 3, 0.1; @, 0.15; 0 , 0.2

01 1
0.5 1.0 1.5 2.0
W/F, (9-cat. rnin/rnol)

Figure 6. Effect of reaction temperature on selectivity. Catalyst 0.15 g, P,, = 0.6 atm, Pv = 0.06
atm.
766 H. Sakamoto et ul.

- C A ) where
the selectivity of B, SB [ = CB/(CA, , C, is the concentration of component
i and suffix 0 means the initial one], is given by equation ( 5 ) .

where
1 - X , = XA = exp [-(W/F,3)k1],
k, = A l exp(-E,/RT),
k2 A2
u=y-l =--I = -exp[-El(6-1)/RT]-1,
kl A1

where x,, X A and A are, respectively, the conversion and the unreacted fraction of
reactant A and the frequency factor. The relation between S , and x A are shown in
Figure 8. Increasing the reaction temperature, T, from equations (5) and (6), x A
increases and hence X A decreases at constant W/Fo,and, at the same time, y decreases
at 6 < 1 or increases at 6 > 1. Therefore, SB is a function of T and its derivative as
to T is given by equations (7)-( 1 1 ).

From equations (7)-(ll), it can be proved that when 6 < I , there may exist the
condition, under which dS,/dT = 0, namely that when El > E2,SB has the possi-
bility to have a minimum value at the intermediate reaction temperature. The same
discussion holds also for the relation between S , and X A or xA, as illustrated by a
dotted line in Figure 8.
From above consideration, it may be due to El (for cyclopentadiene to cyclo-
pentene) > E2 (for cyclopentene to cyclopentane) that the selectivity of cyclopentene
Hydrogenation of cyclopentadiene on a nickel catalyst 767

has the minimum at the intermediate reaction temperature. For quantitative discussion,
however, further experiments should be done to determine the overall reaction rate
and its kinetic parameters.

$-V”--*U
A B C

GlZ 0.5--

0 0.5 1.0

Figure 7. Dimensionlcs; concentrations of reaction components. 0 , 65 ’C; u,120 T;

catalyst 0.15 g ;
P,,, = 0.6 atm, P Q = 0.06 atm.

xA -- 1 - L A

-
cAO

ki ki
Figure 8. Selectivity of B, SBos. x A . A B --f C; consecutive 1st order reaction; y = kJk,. The
dotted line indicates SBus. x A at constant W/Foand El > E2,changing with the reaction temperature.

References
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