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KALENCHUK et al.
A high yield of DHA was achieved on a modified autoclave in an inert atmosphere (N2) and hydroge-
Cu–Cr2O3 catalyst under milder conditions (Т =
nated at 215, 245, and 280°C and pressures of 40 and
100°C, Р = 95 atm). However, conversion to THA 90 atm, respectively. For each discrete point, the reac-
(1,2,3,4-tetrahydroanthracene, С14Н12) occurred at tion was conducted for 8 h until a completely hydroge-
nated product was obtained (sample No. 2). It was
then analyzed. In addition, a completely hydrogenated
product was obtained via the hydrogenation of another
240–260°C. On Ni/kieselguhr catalyst [8], all inter-
mediates were obtained at 180–220°C and 98 atm,
though a fresh portion of the catalyst was required for
the end product (perhydroanthracene (PHA, С14Н24)) anthracene sample (No. 3: 100 cm3, ρ = 1.25 g/cm3)
under steady-state conditions at 280°C and 90 atm
(sample No. 4). In both cases, a Pt/C catalyst (3 wt %
Pt, Aldrich) based on nanoscale carbon was used.
The completely hydrogenated product (sample
No. 2) was dehydrogenated in the autoclave using a
Pt/C catalyst (3 wt % Pt, Aldrich). The reaction was
conducted in a continuous regime in the temperature
range of 260–325°C at a pressure of 1 atm. For analy-
sis, the resulting liquid and gaseous reaction products
were released and sampled via the outlet valve.
Sample No. 4 was dehydrogenated in a high-flow
catalytic converter using a Pt/C catalyst (3 wt % Pt,
Sibunit) prepared by impregnating a carrier with an
aqueous solution of [H2PtCl6] (ωPt = 36.3%) [18]. The
reaction was conducted in a continuous mode in the
temperature range of 300–360°C at a substrate feed
rate about 1 h−1 (linear rate, 6 mL/h; catalyst volume,
12 cm3; catalyst bulk density, 0.67 g/cm3). The catalyst
was preliminarily activated for 2 h in a flow of hydro-
gen (30 mL/min) at 320°C.
The products of hydrogenation and dehydrogena-
tion were analyzed using a KrystaLux-4000M chro-
matograph (Russia) equipped with a ZB-5 capillary
column (Zebron, United States), a flame ionization
detector, and a FOCUS DSQ II GC-MS (Thermo
Fisher Scientific, United States) equipped with a TR-
5MS capillary column (Thermo, United States).
to be formed. In [9], the formation of PHA with a
selectivity greater than 25% was observed upon the
hydrogenation of anthracene on a Pd/C catalyst at
300°C and 30 atm.
In a supercritical CO2 medium (69 atm), complete
conversion in anthracene hydrogenation on a Ni-con-
taining zeolite catalyst was observed at 100°C, with a
mixture of intermediates (DHA, THA and sym-OHA
(1,2,3,4,5,6,7,8-octahydroanthracene, С14Н18)) being
formed [10]. The conversion of anthracene to sym-
OHA on Pd and Rh-containing catalysts (i.e., metal
nanoparticles embedded in a silicate sol–gel matrix)
was described in [11]. Selectivity greater than 60% was
achieved at 80°C and a hydrogen pressure of 28 atm.
The conversion of anthracene to DHA on nanoparti-
cles of Rh and Ir embedded in aluminum oxyhydrox-
ide nanofibers under ambient conditions was reported
in [12]. However, more harsh reaction conditions and
an increased concentration of the active component
are required for other reaction products to be
obtained. Catalytically active carbon was used in [13,
14]. Molecular hydrogen was dissociated into hydro-
gen atoms on the catalyst’s surface, followed by the
transfer of hydrogen to the aromatic ring of anthra-
cene. When using similar nonmetal catalysts, a high
yield in conversion of anthracene to DHA and THA
was observed at 300°C.
In addition to decalin, a great many studies have been
devoted to the dehydrogenation of perhydroethylcarba-
zole [15], its hydrogen capacity being 5.7 wt %. In [16,
17], the dehydrogenation of perhydro-m-terphenyl, a
compound with three relatively independent benzene
rings and a hydrogen capacity of more than 7 wt %,
was conducted on a Pt/C catalyst.
In this work, we studied the patterns of anthracene
hydrogenation up to complete saturation with hydro-
gen, and the reverse dehydrogenation of the resulting
perhydroanthracene on Pt/C catalysts.
Conversion (X) and selectivity (S) of the reaction
products were calculated according to the formulas
Х = (c0 – c)/c0 × 100%; S = ∑c(i)/∑c(k) × 100%,
where c0 and с are the initial and final concentrations
of the initial substrate, and ∑с(i) and ∑c(k) are the
sums of the concentrations of the individual and com-
bined reaction products, respectively.
RESULTS AND DISCUSSION
The data show that the complete saturation of
anthracene with hydrogen proceeded through several
stages, the conditions for the formation of each inter-
mediate being different. To determine the optimum
conditions providing the highest end product (perhy-
droanthracene) yield, anthracene was hydrogenated
EXPERIMENTAL
The hydrogenation of anthracene (97%, Aldrich;
Tm.p = 218°C, Tb.p = 340°C) was conducted in a
PARR-5500 high pressure autoclave (United States) (sample No. 1) at different temperatures and pres-
with an internal volume of 600 mL at stirring speed of sures.
600 rpm. The autoclave was charged with a catalyst
(10 cm3, ρ = 0.32 g/cm3) and activated for 2 h in a flow
of hydrogen (30 mL/min) at 305°C. Upon cooling to
room temperature, the initial anthracene sample
The hydrogenation of anthracene was conducted at
215, 245, and 280°C and pressures of 40 and 90 atm.
The temperature dependencies of anthracene conver-
sion and the yield of completely hydrogenated product
(No. 1: 100 cm3, ρ = 1.25 g/cm3) was charged into the are shown in Fig. 1. The experimental data were com-
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 92
No. 4
2018