Hydrogenation of Dicyclopentadiene in the Presence of a Nickel Catalyst Supported onto a Cation Exchanger in a Flow-Type Reactor

Article abstract of DOI:10.1134/S0023158418040109

The process of dicyclopentadiene hydrogenation in the gas–liquid–solid catalyst system with a catalyst of nickel nanoparticles supported onto a Purolite CT-175 cation exchange resin was studied. The surface structure of the catalyst and the kinetics of the dicyclopentadiene hydrogenation process were examined. Optimum conditions were found for the production of endo-tetrahydrodicyclopentadiene and the simultaneous production of endo-tetrahydrodicyclopentadiene and 5,6-dihydrodicyclopentadiene at atmospheric pressure.

Full text of DOI:10.1134/S0023158418040109

ISSN 0023-1584, Kinetics and Catalysis, 2018, Vol. 59, No. 4, pp. 444–449. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © Yu.V. Popov, V.M. Mokhov, D.N. Nebykov, S.E. Latyshova, K.V. Shcherbakova, A.O. Panov, 2018, published in Kinetika i Kataliz, 2018, Vol. 59, No. 4,
pp. 435–440.
Hydrogenation of Dicyclopentadiene in the Presence of a Nickel
Catalyst Supported onto a Cation Exchanger in a Flow-Type Reactor
a,
a
a
a
Yu. V. Popov *, V. M. Mokhov , D. N. Nebykov , S. E. Latyshova ,
a
a
K. V. Shcherbakova , and A. O. Panov
a
Volgograd State Technical University, Volgograd, 400131 Russia
e-mail: tons@vstu.ru
Received April 6, 2017
*
Abstract—The process of dicyclopentadiene hydrogenation in the gas–liquid–solid catalyst system with a
catalyst of nickel nanoparticles supported onto a Purolite CT-175 cation exchange resin was studied. The sur-
face structure of the catalyst and the kinetics of the dicyclopentadiene hydrogenation process were examined.
Optimum conditions were found for the production of endo-tetrahydrodicyclopentadiene and the simultane-
ous production of endo-tetrahydrodicyclopentadiene and 5,6-dihydrodicyclopentadiene at atmospheric
pressure.
Keywords: hydrogenation, dicyclopentadiene, nanosized nickel catalyst
DOI: 10.1134/S0023158418040109
INTRODUCTION
possible to considerably intensify the chemical pro-
cesses that occur in their presence and to increase their
energy efficiency. In particular, it was found that the
hydrogenation of dicyclopentadiene on the nanoparti-
cles of palladium can be performed in a stirred batch
reactor at 60°C and a hydrogen pressure of 5 atm for
Dicyclopentadiene as a by-product in the manu-
facture of ethylene and propylene by the high-tem-
perature pyrolysis of petroleum fractions is an import-
ant intermediate in industrial chemical synthesis. It is
used for the production of adamantane and its deriva-
tives and in the manufacture of pesticides, ternary eth-
ylene–propylene rubbers, hydraulic fluids, rubber
antioxidants, and the components of perfume compo-
sitions [1]. An important line in the application of dicy-
clopentadiene is the production of high-energy rocket
propellants based on the exo isomer of tetrahydrodicyclo-
pentadiene. This isomer is obtained by the hydrogena-
tion of dicyclopentadiene to endo-tetrahydrodicyclopen-
tadiene with the subsequent isomerization [2].
2
h with a yield of ~50% at a catalyst load of about
.31 mg per 0.028 mol of dicyclopentadiene [4]. The
0
catalysts based on the nanoparticles of noble metals—
platinum, palladium, ruthenium, and rhodium—are
most commonly used for the heterogeneous catalytic
processes of the hydrogenation of unsaturated hydrocar-
bons [5–8]. For increasing the stability of the nanoparti-
cles, they are supported onto different carriers, in partic-
ular, aluminum oxide, silicon oxide, activated carbon,
barium sulfate, and calcium carbonate [9–13].
However, the process of dicyclopentadiene hydro-
genation requires either severe process conditions with
the use of available nickel catalysts or the use of highly
active and selective catalysts based on expensive met-
als (platinum, palladium, iridium, and rhodium). For
example, the hydrogenation of dicyclopentadiene on a
Pd/Al O catalyst is conducted at a temperature to
We developed a method for the hydrogenation of
alkenes, cycloalkenes, and unsaturated aromatic
hydrocarbons in a gas phase in a continuous flow reac-
tor with the fixed bed of a nanocatalyst of nickel
nanoparticles supported on zeolite A. Thus, for
instance, endo-tetrahydrodicyclopentadiene was
obtained with a yield of 98% (180°C; a fivefold or six-
2
3
1
65°C and a pressure to 30 atm in a stirred batch reac-
fold excess of H at atmospheric pressure) [14].
tor for 40–60 min with a product yield to 90% with a
catalyst load about 0.6 g per 0.27 mol of dicyclopenta-
diene [3].
2
Within the framework of this study, we were the
first to use the submicro- and nanoparticles of nickel
The application of nanosized catalysts is a method stabilized on the surface of a Purolite CT-175 cation
for improving dicyclopentadiene hydrogenation tech- exchange resin (CER) carrier as a catalyst for the
nologies. The catalysts of this kind, which possess hydrogenation of dicyclopentadiene [15]. In compari-
quantitatively and qualitatively new properties, make it son with other carriers (zeolites, silica gel, aluminum
444

HYDROGENATION OF DICYCLOPENTADIENE
445
oxide, and activated carbon), ion-exchange resins as C=C bonds in dicyclopentadiene, the process was car-
the carriers of nanoparticles have a number of advan- ried out at temperatures of 80–120°C.
tages: the possibility of nanoparticle stabilization due
to charged functional groups and porosity, commer-
cial availability, satisfactory chemical, mechanical,
and thermal stability, and convenient transportation
and regeneration [16].
The influence of hydrogen absorption by liquid
reaction mass on the overall rate of the process was
judged from the effect of changes in the conditional
residence time of a gas phase in the catalyst bed (τH2
was varied from 5.4 to 36 s kg /mol) on changes in
Cat
the mole fraction of dicyclopentadiene and its hydro-
genation products at constant temperature (80, 90,
EXPERIMENTAL
1
00, 110, or 120°C) and dicyclopentadiene feed rate to
The catalyst was obtained by the impregnation of a
cation exchange resin (Purolite CT-175, mCER = 0.5 g)
with an aqueous solution of nickel(II) chloride hexa-
hydrate (mNiCl2 ⋅ 6H2O = 0.3 g, 2.5 mL of water) for 24 h
with the subsequent filtration and washing with dis-
tilled water. Then, adsorbed nickel was reduced by
the reactor (0.0504 mmol/s).
The influence of external diffusion on the apparent
rate of the process of dicyclopentadiene hydrogena-
tion was evaluated based on the effect of the flow rate
of dicyclopentadiene on changes in the mole fractions
of dicyclopentadiene and its hydrogenation products
sodium tetrahydroborate (mNaBH4 = 0.1 g) in 2.5 mL of at a constant conditional residence time of reactants in
water at 20–25°C for 30 min.
the catalyst bed and the ratio dicyclopentadiene : H =
2
1
1
: 4. The catalyst weight was varied in a range of 0.3–
The mass concentration of nickel was determined
by photocolorimetry on a Shimadzu UV-1800 spec-
trophotometer (Shimadzu, Japan). It was found that
g, and the feed rate of a liquid phase was changed
within the limits of 0.0011–0.0036 mmol/s.
0
Test samples for analysis were taken directly at the
reactor outlet 0.5 h after the beginning of filling a col-
lector for the products of catalysis and placed in indi-
vidual vessels with the subsequent dissolution in n-
hexane for analysis by gas–liquid chromatography
the Ni /CER catalyst contained 6.7 wt % nickel.
A FEI Versa 3D DualBeam instrument (FEI, the
United States) was used for scanning electron micros-
copy (SEM). The working distance was 10 mm; ETD
and CBS detectors were used for secondary and back-
scattered electrons, respectively; elemental analysis
was performed by EDS.
(
GLC). In the parallel testing of reproducibility, the
deviation from mean was no higher than 3%.
The quantitative GLC analysis of the reaction mass
was carried out on a Kristallyuks-4000M chromato-
graph (OOO NPF Meta-khrom, Russia) equipped
with an HP-5 polar column (0.52 μm × 50 m; active
0
The Ni /CER catalyst in a wet form was loaded in
a flow reactor and dried to remove water in a flow of
H at a temperature of 120°C for 0.5 h. The catalyst in
2
the reactor was placed between the layers of quartz phase, (5% phenyl)-methylpolysiloxane) and a flame-
glass as an inert packing material. Hydrogen was dried ionization detector (FID). Nitrogen was used as a car-
in a BiGasCleaner laboratory system for gas cleaning rier gas. Cyclohexylamine served as an internal stan-
and drying, which consisted of two tandem columns dard. Conditions for the analysis: T = 100–210°C,
i
packed with silica gel and activated carbon. After dry-
Tinj = 250°C, and TFID = 250°C.
ing in the flow of H , dicyclopentadiene and hydrogen
2
The material balance was calculated based on the
total products of catalysis collected for 1 h of the con-
tinuous operation of the setup with consideration for
chromatographic data. The calculated balance on car-
bon showed that the losses of hydrocarbons did not
exceed 2 mol %.
were continuously supplied to the catalyst in a direct
flow from top to bottom at a specified temperature and
atmospheric pressure. The temperature in the reaction
zone was no higher than 130°C because of the upper
limit of the operating temperature of the Purolite CT-
1
75 cation exchange resin [15] and no lower than 80°C
for preventing the crystallization of endo-tetrahydrod-
icyclopentadiene.
RESULTS AND DISCUSSION
The conditional residence time of dicyclopentadi-
According to the data of scanning electron micros-
ene in the catalyst bed (τ) was varied in a range from 18 copy (SEM), the size of nickel particles, which form
to 108 s kg /mol (where Cat is the catalyst), and the aggregates on the surface of the cation exchange resin,
Cat
conditional residence time of H in the catalyst bed varied from 70 to 150 nm (Fig. 1).
2
0
(
τH2 ) was changed in a range from 5.4 to 36 s
The Ni /CER catalyst exhibited high activity in the
kg /mol. The molar ratio dicyclopentadiene : H was reaction of dicyclopentadiene hydrogenation. Thus,
Cat
2
varied from 1 : 1 to 1 : 8. For studying the effect of tem- the almost complete conversion (97%) was achieved at
perature on the reaction rate of the hydrogenation of the molar ratio dicyclopentadiene : H
= 1 : 2 and a
2
KINETICS AND CATALYSIS Vol. 59 No. 4 2018

4
46
POPOV et al.
а)
(
500 nm
(b)
500 nm
0
Fig. 1. SEM images of (a) the support surface and (b) the surface of the Ni /CER catalyst with specified sizes of separate nickel
particles.
temperature of 80°C. The catalyst retained its activity
—the diffusion of dissolved hydrogen through a
in an excess of hydrogen with respect to dicyclopenta- laminar liquid film to the external surface of the
0
diene of 3 : 1 (a 1.5-fold excess) for 15 h; thereafter, Ni /CER catalyst;
purging with hydrogen for 0.5 h was required for
—
the adsorption of dicyclopentadiene (A) and dis-
regenerating the catalyst activity.
solved hydrogen on the catalyst surface;
The hydrogenation of dicyclopentadiene by molec-
ular hydrogen under the process conditions occurs in
—
the reaction of dicyclopentadiene (A) hydroge-
nation with hydrogen on the catalyst surface with the
formation of 5,6-dihydrodicyclopentadiene (B);
the three-phase gas (H )–liquid (dicyclopentadi-
2
0
ene)–solid (Ni /CER catalyst) system. This process
can be represented in more detail as the following sev-
eral stages:
—
the reaction of 5,6-dihydrodicyclopentadiene
B) hydrogenation with hydrogen on the catalyst sur-
face with the formation of endo-tetrahydrodicyclo-
(
—
the absorption of gaseous hydrogen by liquid pentadiene (C) or the desorption of 5,6-dihydrodicy-
reaction mass;
clopentadiene into the liquid phase;
KINETICS AND CATALYSIS
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HYDROGENATION OF DICYCLOPENTADIENE
447
Table 1. Apparent reaction kinetic parameters of the hydrogenation of dicyclopentadiene
Apparent rate constant kapp, × 10–3 L s–1 kg–1
Cat
Reaction order
with respect
to reactants
Apparent
activation energy
Reaction
temperature, °С
Eа, kJ/mol
8
0
90
100
110
120
1
. A + H → B
1
1
2.43 ± 0.06 3.61 ± 0.07 4.44 ± 0.12 4.93 ± 0.11 5.52 ± 0.12
9.30 ± 0.18 10.31 ± 0.25 11.08 ± 0.26 11.77 ± 0.34 11.83 ± 0.14
22.82 ± 0.99
7.18 ± 0.20
2
2. B + H → C
2
—
the desorption of endo-tetrahydrodicyclopenta- the basis of the experimental results, we can hypothe-
diene (C) from the catalyst surface.
size the absence of the effect of external diffusion in a
temperature range of 80–120°C on the apparent rate
of the process at both the first and the second stages of
The processes occurring on the catalyst surface can
be represented as the following simplified reaction
scheme:
0
the hydrogenation of compound A on the Ni /CER
catalyst.
B
C
Based on the data obtained and the reaction
scheme proposed, we can consider that the consecu-
tive process of the hydrogenation of A to intermediate
product B and than to product C on the surface of the
LP
LP
0
Ni /CER catalyst can be described by the following
system of differential equations:
(2)
(4)
n
r = dC dτ = −k C ,
(1)
(2)
(3)
1
A
app1 A
+
H2
+H2
(3)
n
A
m
B
r = dC dτ = k C − k C ,
2
B
app1
app2
(1)
Ads.
А
Ads.
B
Ads.
C
m
B
r = dC dτ = k C ,
3
C
app2
where Ads. and LP refer to adsorption and liquid where r is the rate of consumption of substance A; r
1 2
phase, respectively.
is the rate of change in the concentration of interme-
diate product B; r is the rate of formation of end prod-
3
Because it is difficult to construct a complete
uct C; k
and k
are the apparent rate constants of
kinetic model with consideration for not only the
app1
app2
adsorption coefficients of substances A, B, and C but the first and second stages of the process, respectively,
also the absorption of gaseous H by liquid reaction which include the concentration of hydrogen on the
2
−
Cat
1
mass and the diffusion of reactants to the catalyst sur-
catalyst surface (L s–1 kg ); C , C , and C are the
A B C
face at the nearly zero solubility of H in the liquid
2
concentration of reactants A, B, and C in the liquid
phase, respectively (mol/L); τ is the conditional resi-
dence time of reactant A in the catalyst bed
phase, the aim of this work was to find the apparent
(
effective) rate constants of formation of compounds
B and C.
(
s kg /mol); and n and m are the orders of reaction
Cat
On the determination of the influence of the
with respect to reactants in the kinetic equation.
absorption of H by the liquid reaction mass on the
2
In order to confirm this mathematical model, we
overall rate of the process, we found that the mole
experimentally studied the functions C = f(τ), C =
fractions of reactants A, B, and C in the reaction sys-
A
B
f(τ), and C = f(τ) at temperatures of 80, 90, 100, 110,
tem remained constant at τH2 = 5.4–36 s kg /mol.
C
Cat
and 120°C. The conditional residence time of A (τ)
This was, apparently, caused by the fact that a constant
value of the concentration of H dissolved in the liquid was varied within a range of 18–108 s kg /mol, other
2
Cat
film was reached for each particular temperature (80, conditions being the same (A : H = 1 : 4, atmospheric
2
9
0, 100, 110, or 120°C) with the continuous supply of
2
pressure).
H into the reactor at τ ≥ 5.4 s kg /mol. Thus, the
H2
Cat
The processing of the kinetic curves of C = f(τ),
A
apparent rate of the process depends only on changes
in the concentrations of substances A, B, and C on the
catalyst surface.
C = f(τ), and C = f(τ) with the aid of the Comsol
B
C
Reaction Engineering Lab 1.5 [17] and Frund [18]
software showed that, at 80–120°C, the experimental
data were adequately (error of no higher than 3%)
described by equations (1)–(3) with the apparent rate
As the flow rate of compound A was changed from
0
.0011 to 0.0036 mmol/s at τ = const, the degrees of
conversion of compound A at 80, 90, 100, 110, and
1
20°C had constant values for each temperature. On constants of kapp1 and kapp2 summarized in Table 1.
KINETICS AND CATALYSIS Vol. 59 No. 4 2018

4
48
POPOV et al.
C, mol/L
C, mol/L
(а)
(b)
8
8
7
6
5
4
3
2
1
7
6
5
4
3
2
1
3
1
1
3
2
2
0
20 40 60 80 100 120 140 0
20 40 60 80 100 120 140
τ, s kgCat/mol
τ, s kgCat/mol
C, mol/L
(c)
C, mol/L
(d)
8
8
3
3
7
6
5
4
3
2
1
7
6
5
4
3
2
1
1
1
2
2
0
20 40 60 80 100 120 140 0
20 40 60 80 100 120 140
τ, s kgCat/mol
τ, s kgCat/mol
C, mol/L
(e)
8
3
7
6
5
4
3
2
1
1
2
0
20 40 60 80 100 120 140
τ, s kgCat/mol
Fig. 2. Concentrations of substances (1) A, (2) B, and (3) C as functions of the conditional residence time of liquid phase in the
catalyst bed at temperatures of (a) 80, (b) 90, (c) 100, (d) 110, and (e) 120°C. Curves and points refer to the calculated and exper-
imental data, respectively.
Figure 2 compares the experimental data and the
The effective values of activation energy for the sec-
kinetic curves constructed according to the mathe- ond stage were found lower than those for the first
matical model proposed. Based on the found values of stage. Analogous regularity was described by Skála and
the apparent reaction rate constants, we determined Hanika [19], who studied the hydrogenation of dicy-
the apparent activation energies for the reactions A + clopentadiene on a Pd/C catalyst. Consequently, a
H → B and B + H → C from the graph of the func- more detailed study is required for explaining the
2
2
tion ln k = f(1/T), which is shown in Fig. 3. Table 1 smaller value of activation energy for the second stage
also summarizes the data obtained.
with respect to the first stage.
KINETICS AND CATALYSIS
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HYDROGENATION OF DICYCLOPENTADIENE
REFERENCES
449
–
3
–1
1
/Т ×10 , К
1
. Claus, M., Claus, E., Claus, P., Hönicke, D., Födisch, R.,
2
.50 2.55 2.60 2.65 2.70 2.75 2.80 2.85
and Olson, M., Ullmann’s Encyclopedia of Industrial
0
Chemistry,
Wiley,
2016,
p.
1.
doi
10.1002/14356007.a08_227.pub2

0.5
2
. Hao, M., Yang, B., Wang, H., Liu, G., Qi, S., Yang, J.,
Li, Ch., and Lv, J., J. Phys. Chem. A, 2010, vol. 114,
p. 3811.

1.0
1.5

3. Liu, G., Mi, Z., Wang, L., and Zhang, X., Ind. Eng.
Chem. Res., 2005, vol. 44, p. 3846.






2.0
2.5
3.0
3.5
4.0
4.5
4. Behr, A., Manz, V., Lux, A., and Ernst, A., Catal. Lett.,
2013, vol. 143, p. 241.
2
1
5. Jacinto, M.J., Landers, R., and Rossi, L.M., Catal.
Commun., 2009, vol. 10, p. 1971.
. Ren, Zh., Wang, H.-L., Cai, Y.-Q., Chen, M., and
Qian, D.-J., Mater. Chem. Phys., 2011, vol. 127, p. 310.
6
7. Chen, J., Liu, X., and Zhang, F., Chem. Eng. J., 2015,
vol. 259, p. 43.
8
. Abu-Reziq, R., Shenglof, M., Penn, L., Cohen, T., and
Blum, J., J. Mol. Catal. A. Chem., 2008, vol. 290,
nos. 1–2, p. 30.
lnk[L s–1 kgcat–1]
9. Canning, A.S., Jackson, S.D., Monaghan, A., and
Wright, T., Catal. Today, 2006, vol. 116, p. 22.
1
0. Marín-Astorga, N., Pecchi, G., Fierro, J.L.G., and
Reyes, P., J. Mol. Catal. A. Chem., 2005, vol. 231,
nos. 1–2, p. 67.
Fig. 3. Graph of the function ln k = f(1/T) for calculating
the activation energies of different stages of the processes
(
1) A + H → B and (2) B + H → C.
2 2
1
1. Du, W.Q., Rong, Z.M., Liang, Y., Wang, Y., Lu, X.Y.,
Wang, Y.F., and Lu, L.H., Chin. Chem. Lett., 2012,
vol. 23, no. 7, p. 773.
0
Thus, we were the first to develop a Ni /CER cat-
12. Cram, D.J. and Allinger, N.L., J. Am. Chem. Soc.,
alyst and to study the reaction kinetics of dicyclopen-
1956, vol. 78, no. 11, p. 2518.
0
tadiene hydrogenation on the Ni /CER heteroge- 13. Chandrasekhar, S., Narsihmulu, Ch., Chandrashekar, G.,
and Shyamsunder, T., Tetrahedron Lett., 2004, vol. 45,
p. 2421.
neous catalyst at atmospheric pressure in a tempera-
ture range of 80–120°C. Comparison with published
14. Popov, Yu.V., Mokhov, V.M., Nebykov, D.N.,
analogs makes it possible to judge prospects for the
further study of the catalyst proposed. Thus, for
instance, Liu et al. [20] performed the hydrogenation of
dicyclopentadiene on Pd/Al O in a flow reactor at
Latyshova, S.E., Panov, A.O., Dontsova, A.A.,
Shirkhanyan, P.M., and Shcherbakova, K.V., Russ. J.
Gen. Chem., 2016, vol. 86, no. 12, p. 273.
1
5. Product data sheet Purolite® CT175, 2017.
http://www.purolite.com/product-pdf/ct175?product-
Type=regular.
2
3
1
20°C and 20 atm with a 98% yield of endo-tetrahydrod-
icyclopentadiene and a productivity of about 0.38 kgprod 16. Liguori, F., Moreno-Marrodan, C., and Barbaro, P.,
Chin. J. Catal., 2015, vol. 36, p. 1157.
−
Cat
1
–1
h kg , whereas the same yield of the product can be
17. Comsol Inc., 2017. http://www.comsol.ru/chemical-
0
reached on the Ni /CER catalyst at 120°C and 1 atm
with a productivity of 4.40 kgprod h–1 kg−
reaction-engineering-module.
1
1
8. Frund, Frund, 2015. http://frund.vstu.ru.
1
.
Cat
9. Skála, D. and Hanika, J., Pet. Coal, 2003, vol. 45,
nos. 3–4, p. 105.
The reaction rate equations obtained adequately
describe the test process, and they can be used for fur-
ther study and optimization of the process of dicyclo-
pentadiene hydrogenation.
2
0. Liu, G., Mi, Z., Wang, L., Zhang, X., and Zhang, S.,
Ind. Eng. Chem. Res., 2006, vol. 45, p. 8807.
Translated by V. Makhlyarchuk
KINETICS AND CATALYSIS Vol. 59 No. 4 2018