Hydro-Oxygenation of Furfural in the Presence of Ruthenium Catalysts Based on Al-HMS Mesoporous Support

Article abstract of DOI:10.1134/S1070427219090167

Ru-containing catalyst based on an Al-HMS mesoporous aluminosilicate was synthesized. The mesoporous support and the catalyst on its basis were characterized by the methods of low-temperature desorption/adsorption of nitrogen, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray photoelectron microscopy, and energy-dispersive X-ray fluorescence analysis. The synthesized catalyst was investigated in the hydrodeoxygenation of the model compound of bio-oil, furfural, in the presence of H₂O. The reaction was carried out at initial hydrogen pressures of 1–7 MPa at 200°C–300°C temperature range. The results revealed that the synthesized catalyst displayed a high activity in the hydrotransformation of furfural. The conversion was 100% in 1 hr at a 5 MPa hydrogen pressure and 200°C.

Full text of DOI:10.1134/S1070427219090167

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2019, Vol. 92, No. 9, pp. 1306−1315. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Prikladnoi Khimii, 2019, Vol. 92, No. 9, pp. 1214−1224.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Hydro-Oxygenation of Furfural in the Presence
of Ruthenium Catalysts Based on Al-HMS
Mesoporous Support
a,
a
a,b
E. A. Roldugina *, N. N. Shayakhmetov , A. L. Maksimov ,
a
and E. A. Karakhanov
a
Moscow Lomonosov State University, Moscow, 119991 Russia
b
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
*
e-mail: rolduginakate@mail.ru
Received May 25, 2019; revised June 17, 2019; accepted June 17, 2019
Abstract—Ruthenium-containing catalyst based on anAl-HMS mesoporous aluminosilicate was synthesized, The
mesoporous support and the catalyst on its basis were characterized by the methods of low-temperature desorp-
tion/adsorption of nitrogen, temperature-programmed desorption of ammonia, transmission electron microscopy,
X-ray photoelectron microscopy, and energy-dispersive X-ray fluorescence analysis. The catalyst obtained was
examined in the reaction of hydrodeoxygenation of the model compound of bio-oil, furfural, in the presence of
water. The reaction was performed at initial hydrogen pressures of 1–7 MPa in the temperature range 200–300°C.
It was shown that the catalyst under study exhibits a high activity in the hydrotransformation of furfural: the
conversion was 100% in 1 h at a hydrogen pressure of 5 MPa and temperature of 200°C.
Keywords: hydrodeoxygenation, furfural, mesoporous material, nanoparticles, ruthenium
DOI: 10.1134/S1070427219090167
An increased interest is presently observed in the phenols, and syringoles of varied structure [3]. The
processing of renewable phytogenic raw materials for distribution of components in bio-oil directly depends
obtaining biofuel and valuable chemical products. One on the type of a biomass and on the conditions of fast
of promising sources of biofuel is the lignin-cellulose pyrolysis.
biomass formed as wood wastes of nonfood industries
1]. The technology of fast pyrolysis makes it possible
from this biomass the product named bio-oil [2]. Bio-oil
The complex chemical composition, high content
of oxygen and water formed in the pyrolysis of the
biomass provide a high polarity and acidity of bio-oil, its
[
contains hundreds of organic products formed in thermal thermal instability and immiscibility with hydrocarbons.
decomposition of the polymers in the biomass: cellulose To improve the quality of bio-oil and enable its joint
(
(
30–40 wt %, hemicellulose (20–30 wt %, and lignin processing with hydrocarbon oil products on the
20–25 wt %), which belong to different classes: low- conventional oil-processing equipment, an additional
molecular alcohols, acids, esters, aldehydes, ketones, stage of bio-oil upgrading is necessary. The main
furans, and also phenols of varied structure [1]. The methods for bio-oil upgrading are the esterification [4],
main compounds formed in the pyrolysis of cellulose catalytic cracking [5], and catalytic hydrodeoxygenation
are levoglucosan, hydroxyacetaldehyde, hydroxyacetone, (HDO) [6]. A disadvantage of bio-oil upgrading is the
furfural, and 5-hydroxymethylfurfural. Pyrolysis of insufficiently effective removal of oxygen from bio-oil,
hemicellulose yields acetic acid, glycol aldehyde, furfural, which may lead to its repolymerization [7]. The catalytic
and anhydro sugars, and that of lignin gives guaiacols, cracking is characterized by a fast deactivation of a
1306

HYDRO-OXYGENATION OF FURFURAL
1307
catalyst, which results from its coking, and by the low
yield of the liquid product, caused by the loss of carbon
due to the reactions of decarbonylation/decarboxylation
The goal of our study was to examine the activity of
the Ru-containing catalysts synthesized in the study on the
basis of theAl-HMS mesoporous material in the reaction
of hydroxydeoxygenation of the model compound of bio-
oil, furfural, in the presence of water.
[8]. Furthermore, one or several stages of hydroprocessing
are commonly performed prior to the cracking in order
to stabilize and deoxygenate bio-oil [9]. Therefore, a
promising technology for upgrading of bio raw materials
is HDO, during which oxygen is removed from bio-oil
in the form of water, and the coking level is substantially
lower than that in the catalytic cracking [10].
EXPERIMENTAL
Synthesis of Al-HMS mesoporous material. The Al-
HMS mesoporous material (Si/Al = 10) was synthesized
by the procedure similar to that reported in [30]. As
Development of HDO catalysts exhibiting activity in
the processing of such a specific bio raw material as bio-
oil is a topical task of petrochemistry. There exist a wide
variety of HDO catalysts: conventional NiMoS/Al O
reagents served hexadecylamine (C H N, Sigma-
16 35
Aldrich, 98%), aluminum sec-butoxide (Sigma-Aldrich,
9
7%), tetraethoxysilane (Sigma-Aldrich, 99.99%),
2
3
isopropanol (IPA, IREA 200, analytically pure), and
distilled water. The gel containing the Al-HMS template
had the following molar composition: 20SiO : Al O :
and CoMoS/Al O [11], catalysts based on transition (Ni
2
3
[12], Cu [13], Mo [14], W [15], Fe [16]) or noble (Rh,
Ru, Pt, Pd [17]) metals and mixtures of these [18–20].
Of interest are catalysts based on noble metals and, in
particular, Ru-containing catalysts because in the case
of their application there is no need to introduce sulfur
compounds into the reaction system. These catalysts are
active and stable in processes occurring in the presence of
water formed in substantial amounts in the HDO reactions
with bio-oil and can provide an effective hydrogenation/
deoxygenation even under mild process conditions [21].
The activity of HDO catalysts and the distribution of
reaction products are strongly affected by the nature of
a support. In the presence of water, the classical γ-Al O
2
2
3
5
C1 H N : 166IPA : 888H O.
6 35 2
Synthesis of the Ru/Al-HMS catalyst. The typical
procedure for synthesis of the Ru/Al-HMS catalyst
includes impregnation of the support material with a
solution of a ruthenium salt in methanol (Sigma-Aldrich,
99.8%), followed by removal of the excess of the solvent
on a rotor evaporator. For this purpose a calculated amount
of the support was added at 25°C to a solution of the metal
salt in 30 mL of methanol. The mixture was agitated for
12 h. Then, a sample was dried in an air flow at 60°C for
6 h and then at 100 and 250°C for 3 h at each temperature.
The resulting sample was suspended in 15 mLof methanol
and 15 mL of water. Then 15 mL of a cooled aqueous
2
3
is transformed into boehmite AlO(OH),which blocks
and deactivates the active centers of the catalyst [22]. As
alternative to γ-Al O can serve the following: zeolites
solution of NaBH (Sigma-Aldrich, ≥98.0%) was added
2
3
4
[
23]; oxides ZrO , SiO , TiO , CeO , and mixtures of
portionwise to the suspension (NaBH4/Ru molar ratio
10). The reduction was performed in the course of 12 H.
To remove sodium borate formed as a by-product, the
resulting mixture was three times washed with water and
then three times with methanol. The catalyst produced
after the reduction was dried in air and then at 60, 100,
and 250°C for 3 h at each temperature. Ruthenium(III)
chloride (Aurat, mass fraction of ruthenium ≥46.5%).
When the metal salt solution was prepared, the amount
2
2
2
2
these [19, 24]; and carbon supports [25]. A disadvantage
of the latter is their difficult regeneration under industrial
conditions [1]. Of particular interest is the HDO with
mesoporous supports. It has been noted in studies
concerned with the HDO of model compounds of bio-
oil in the presence of catalysts based on oxides Al O ,
2
3
ZrO , TiO , SiO and their mesoporous analogs that these
2
2
2
latter exhibit a higher catalytic activity, manifested in the
larger degrees of deoxygenation and conversion of the
substrate [26–30].
of RuCl was calculated so that the theoretical content
3
of ruthenium in the catalyst was 2 wt % (according to
the results of an energy-dispersive X-ray fluorescence
analysis the content of Ru was 1.79 wt %).
Furfural is frequently used as a model compound
in studies of the bio-oil HDO mechanisms because of
being one of the main products formed in the pyrolysis
of the cellulose/hemicellulose part of the biomass and
containing the furan and carbonyl groups characteristic
of the bio-oil composition.
Instruments and methods. The nitrogen adsorption/
desorption isotherms were recorded at a temperature
of 77 K on a Gemini VII 2390 instrument. Prior to
measurements, the samples were degassed at 350°C for
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ROLDUGINA et al.
6
h. The specific surface area was determined by the
X-rays from the aluminum anode (AlK = 1486.6 eV. The
α
BET method with the use of adsorption data at relative
pressures (p/p0) in the range 0.04–0.20. The pore volume
and the pore size distribution were determined from the
adsorption branch of the isotherms by using the Barrett–
Joyner–Halenda model. The specific pore volume was
determined from the amount of nitrogen adsorbed at a
photoelectron peaks were calibrated against the carbon
line C1s with binding energy of 284.4 eV. The pass energy
of the energy analyzer was 160 eV (survey spectrum) and
40 eV (separate lines).
Catalytic experiments. The catalytic experiments
on HDO of furfural were performed at an increased
hydrogen pressure an vigorous agitation in a 45-mL
steel autoclave equipped with a magnetic rabble and
glass insert-tube in which a calculated amount of the
catalyst (0.1 g) and a model mixture containing 0.25 g
of furfural (Sigma-Aldrich, 99%) and 1 g of water were
placed. The autoclave was hermetically sealed and filled
with hydrogen to a pressure of 1–7 MPa. The reaction
was performed in the temperature range 200–300°C in
the course of 0.5–4 h, with the temperature monitored
with a thermocouple. After the reaction was complete,
the autoclave was cooled to below room temperature. The
catalyst was separated from the solution by centrifugation.
To provide a full dissolution of organic compounds and
homogenization of the reaction mixture, isopropanol was
added to a sample before a chromatographic analysis. The
hydrogenation products were analyzed on a Kristallyuks
relative pressure p/p = 0.99.
0
The acidity of a catalyst sample was determined by
the method of temperature programmed desorption of
ammonia (TPD–NH ) on a Micromeritics Auto Chem
3
HP Chemisorption Analyzer instrument. A sample under
study was crushed; the 1–2-mm fraction was selected,
placed in a reactor and kept in a flow of helium at 400°C
for 30 min. Then, the temperature was lowered to 100°C
and the sample was saturated with ammonia for 30 min.
The physically adsorbed ammonia was blown away in
a flow of helium until the zero line ceased to drifty. Then
the reactor temperature was raised to 750°C at a rate of
–1
2
0 deg min . The amount of ammonia desorbed in the
course of the TPD was calculated with Auto Chem HP
V2.04 software.
The catalyst was examined by transmission electron
microscopy (TEM) on a Jeol JEM-2100 microscope at
magnifications of 50 to 1 500 000 at image resolution of
4
000 M chromatograph equipped with a PID and a
Petrocol® DH 50.2 column with polydimethylsiloxane as
fixed liquid phase (50 m × 0.25 mm, carrier-gas helium,
flow division 1 : 90). Additionally, liquid products were
analyzed by chromato-mass spectrometry on Finnigan
MAT 95 XL instrument equipped with a chromatograph
with Varian VF-5MS capillary column (30 m × 0.25 mm ×
0
.19 nm at 200 kV.
The content of ruthenium was determined by energy-
dispersive X-ray fluorescence analysis (EDXFA) on a
Thermo Fisher Scientific ARL Quant’X analyzer in a
vacuum. The results obtained were processed by using the
no-standard UniQuant method. Samples were prepared as
follows: powdered samples were compacted into pellets
on a boric-acid substrate and covered with a Lavsan film
pressed with an annular holder to a cuvette.
3
–1
0
.25 mm), carrier-gas helium (1.5 cm min ).
RESULTS AND DISCUSSION
The procedure used to synthesize the Al-HMS
Measurements by the method of X-ray photoelectron
spectroscopy (XPS) were made on a Kratos Axis Ultra
DLD instrument. Photoelectrons were excited by the
support and its characteristics were described in more
detail earlier in [30]. The main physicochemical
characteristics of the Al-HMS mesoporous support are
Support
Surface area according to the
Pore diameter,
Å
Pore volume,
Total number of acid centers,
μmol g–1 NH3
2
–1
3
–1
BET model, m g
cm g
Al-HMSa
935
35
1.04
286
a
SiAl molar ratio in the Al-HMS sample is 10.
presented below:
data according to which the sample is characterized by
a type-IV isotherm with a hysteresis loop. According to
TheAl-HMS sample has a high specific surface area of
2
–1
9
35 m g and mesoporous structure, which is confirmed
TPD-NH , the total number of acid centers in theAl-HMS
3
–
1
by the low-temperature nitrogen adsorption/desorption
support (Si/Al = 10) is 286 μmol g NH . The material
3
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HYDRO-OXYGENATION OF FURFURAL
1309
(a)
(b)
1
0 nm
Particle diameter, nm
Fig. 1. (a) TEM micrograph of Ru/Al-HMS and (b) ruthenium particle size distribution.
mostly contains medium-strength acid centers (Tmax
≈
3
00–500°C) and a minor amount of strong acid centers
(Tmax > 500°C) [29].
After the metal was deposited, the Ru/Al-HMS
catalyst was characterized by the methods of TEM and
XPS. According to TEM, Ru/Al-HMS has an ordered
structure with ruthenium particles uniformly distributed
over the surface of the support. Distinct channels and
hexagonally ordered mesopores with sizes of 30–40 Å
can be distinguished in TEM micrographs (Fig. 1a).
The average size of ruthenium particles is 1.4–1.8 nm
(Fig. 1b).
Figure 2 shows a high-resolution part Ru3d of the
XPS spectrum for a Ru/Al-HMS sample. Because of
the superposition of lines C1s (285 eV) Ru3d3/2 only
the component Ru3d5/2 (280.1 eV) can be reliably
identified. However, the deconvolution of the spectrum
demonstrated the presence of two ruthenium states with
Bond energy, eV
Fig. 2. XPS Ru3d spectrum of a Ru/Al-HMS sample.
binding energies of 280.0 and 283.9 eV for Ru3d5/2
temperature on the conversion and composition of
products formed in HDO of furfural in the presence of Ru/
Al-HMS (Fig. 3). In the temperature range 200–300°C,
the conversion of furfural was 100% (2 h, 5 MPa H2).
and Ru3d , which corresponds to metallic ruthenium
3/2
[30, 31]. The spectrum also shows peaks at energies of
2
81.0, 282.2, 285.2, and 287.9 eV, which correspond to
ruthenium in the oxidized state [31] According to XPS
data, about 69% of ruthenium is in the metallic state.
At 200°C, the main products formed in the HDO of
furfural were tetrahydrofurfuryl alcohol (THFA, 35%) and
cyclopentanol (47%). The reaction mixture also contained
methyltetrahydrofuran/tetrahydrofuran (MeTHF + THF,
The catalytic activity of the Ru/Al−HMS sample
obtained was evaluated in the reaction of hydrodeoxygen-
ation of the model compound of bio-oil (furfural) in the
presence of water for three varied reaction parameters:
temperature, initial hydrogen pressure, and reaction
duration.
2
%, in aggregate) and mono- and diatomic C –C alcohols
4 5
of varied structure (1,2-pentanediol, 1,5-pentanediol, 2-
pentanol, n-pentanol, and n-butanol, 9%, in aggregate).
It should be noted that the reaction mixture can contain,
in addition to alcohols, the corresponding ketones and
We examined the influence exerted by the reaction
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ROLDUGINA et al.
Pentanols + butanol
MeTHF + THF
Cyclopentanol
THFA
Pentanediols
Condensation products
Temperature, °C
Fig. 3. Distribution of products formed in the HDO of furfural (2 h, 5 MPa, G2) at various reaction temperatures in the presence of
Ru/Al-HMS catalyst.
aldehydes (cyclopentanone, 2-pentanone, butanal,
etc.). However, their total content does not exceed
conditions into C10+ alkanes, which can serve as
components of the propellant and diesel fuel [37]. Thus,
the HDO of furfural in the presence of Ru/Al-HMS in the
temperature range 200–300°C yielded a multicomponent
mixture of products (C –C alcohols, tetrahydrofurans,
2
%, which is probably due to the large number of
acid centers in Ru/Al-HMS, the presence of which is
responsible for the predominant formation of alcohols.
Presumably, C=O groups are firmly fixed on acid centers
of the support, which makes slower the desorption of
aldehydes/ketones from the catalyst surface and favors
their further conversion into the corresponding alcohols
4
5
cyclopentanol, THFA and condensation products). An
increase in temperature leads to active formation of
C –C alcohols of varied structure, products of opening
4
5
of a furan ring, and tetrahydrofurans produced via the
hydrogenation of the ring and deoxygenation of the
terminal OH group of furfural [13, 38]. Raising the
reaction temperature also leads to an increase in the
share of condensation products.
[32]. Compounds obtained as a result of condensation
between furfural and(or) half-products formed in the
course of HDO (dimers of varied structure, 7%, in
aggregate). As the HDO temperature is raised to 250°C,
the shares of THFA and cyclopentanol decreased to
It was shown that the initial hydrogen pressure strongly
affects the conversion of furfural and the distribution of
HDO products (Fig, 4).At a hydrogen pressure of 1 MPa,
the conversion of furfural was 29%, with furfuryl alcohol
being the main reaction product with a selectivity of 93%.
Raising the hydrogen pressure to 3 MPa resulted in that
the conversion sharply increased to 95%, with furfuryl
alcohol also remaining the main reaction product, but its
selectivity decreased to 83%. Other furfural HDO products
were detected in minor amounts: THFA, cyclopentanol,
2
7 and 43%, respectively, with the selectivity with
respect to tetrahydrofurans and C –C alcohols slightly
4
5
increasing to 6 and 10%, respectively. The content of
condensation products in the reaction mixture increased
to 16%. Performing the reaction at 300°C resulted in a
sharp increase in the share of tetrahydrofurans to 17%
and in that of C –C monoatomic alcohols to 36%. The
4
5
selectivity with respect to pentanols decreased to 2%,
which is indicative of a partial deoxygenation of OH
groups at 300°C. The selectivities with respect to THFA pentanediols, MeTHF/THF, and condensation products.
and cyclopentanol decreased to 7 and 14%, respectively.
The share of the condensation products increased to
If the HDO is performed at a hydrogen pressure of 5
MPa, the conversion of furfural reached a value of 100%,
with the reaction mixture mostly containing THFA(35%)
and cyclopentanol (47%). The HDO of furfural at a high
hydrogen pressure (7 MPa) resulted in a more selective
formation of THFA (79%) with the conversion also
being 100%. Hence a conclusion can be made that the
HDO in the presence of Ru/Al-HMS at a low hydrogen
2
3%. On the one hand, the formation of heavy oxygen-
containing condensation products is an undesirable side
process because these compounds can be adsorbed on
the active centers of the catalyst and thereby decrease
its activity [35, 36]. On the other hand, the condensed
furan derivatives can be transformed under the HDO
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HYDRO-OXYGENATION OF FURFURAL
1311
(a)
(a)
6
0
6
0
Pressure, MPa
(b)
Pressure, MPa
b)
(
Reaction time, h
Pressure, MPa
Pentanols + butanol
MeTHF +THF
Furfuryl alcohol
Pentanediols
Pentanols + butanol
Cyclopentanol
THFA
MeTHF +THF
Furfuryl alcohol
Pentanediols
Cyclopentanol
THFA
Condensation products
Condensation products
Fig. 4. (a) Conversion of furfural and (b) distribution of products
formed in the HDO of furfural (2 h, 200°C) at various initial
hydrogen pressures in the presence of Ru/Al-HMS catalyst.
Fig. 5. (a) Conversion of furfural and (b) distribution of products
formed in the HDO of furfural (2 h, 200°C) at various reaction
durations in the presence of Ru/Al-HMS catalyst.
pressure (<3 MPa) leads to a poor conversion of furfural,
with furfuryl alcohol selectively formed. As the pressure
of industrial installation and requires a gross expenditure
of materials and energy [1].
is raised to 5 MPa H , a full conversion of furfural is
2
Figure 5 shows the results of the HDO of furfural at
various reaction durations. After 0.5 h of the reaction the
conversion of furfural was 35%, with furfuryl alcohol
being the main product (94%). Tetrahydrofurfuryl
alcohol (THFA, 4%) and condensation products (2%)
were detected in trace amounts. After 1 h of the HDO,
the conversion of furfural was 90%, with the selectivity
with respect to furfuryl alcohol decreasing to 54% and
that with respect to THFA increasing to 34%. Also,
tetrahydrofurans ( MeTHF + THF, 2%, in aggregate) and
cyclopentanol (1%) were detected in the reaction mixture
reached. However, the reaction occurs simultaneously
by several pathways, which is evidenced by te complex
composition OF the reaction mixture after the HDO.
At high hydrogen pressure (>5 MPa) is predominantly
converted in the presence of Ru/Al-HMS to THFA, in
agreement with published data on the HDO of furfural
in the presence of catalysts based on noble metals [39,
4
0]. It should be noted, however, that, as regards the
industrial applicability, performing the processes at a
high hydrogen pressure makes more intricate the design
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ROLDUGINA et al.
Scheme. Possible pathways of furfural HDO in the presence of Ru/Al-HMS catalyst.
Furfuryl alcohol
THFA
THF
MTHF
Penta-2,4-dien-1,4-diol
Pentanediols
C –C Alcohols (butanol,
4
5
pentanol)
Cyclopentanol
with low selectivities.AS the reaction duration increased
to 2 h, the conversion of furfural reached 100%, furfuryl
alcohol was not found in the reaction mixture, and the
amount of THFA remained at the same level (35%). The
selectivity with respect to cyclopentanol substantially
increased, to 47%. The products formed in the opening
of the furan ring were found in the reaction mixture
for the first time: pentanediols (2%, in aggregate) and
aggregate) and alcohols (C –C alcohols 7%, pentanediols
4 5
9%). As the reaction duration increased from 0.5 to 1 h,
the content of the condensation products increased to 7%,
as the reaction duration was raised further, it remained
constant, 6–8%.
Based on the results obtained, we can conclude that
the Ru/Al-HMS catalyst we synthesized exhibits a high
activity in the HDO of furfural (5 MPa H , 200°C: in
2
monoatomic C –C alcohols (pentanols and butanol, 7%,
4
5
1 h, the conversion of the substrate reaches a value
of 90%. In the conditions under study, a double-stage
hydrogenation of furfural occurs at short reaction duration
to give furfuryl alcohol in the first stage with its further
conversion to THFA. At long reaction duration, the
conversion of furfural may occur by several pathways
in aggregate). As the reaction duration increased further,
to 4 h, the selectivity with respect to THFA decreased to
1
2%, and that with respect to cyclopentanol increased
to 62%. In this case, a gradual increase in the selectivity
with respect to tetrahydrofurans (MeHTF + THF, 4%, in
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HYDRO-OXYGENATION OF FURFURAL
1313
(
see the scheme). The presence of a small amount of
that the reaction may occur by several pathways:
hydrogenation by the scheme furfural → furfuryl
alcohol → tetrahydrofurfuryl alcohol with the subsequent
deoxygenation of the OH group to give tetrahydrofurans;
hydrogenation with opening of the furan ring to give linear,
branched, and cyclic C –C alcohols of varied structure.
tetrahydrofurans in the reaction mixture suggests that
a dehydroxylation/decarbonylation of the THFA being
formed can occur on the acid centers of the catalyst to
MeTHF and THF, respectively (see Scheme, I) [41].Also
possible is the further opening of the tetrahydrofuran ring,
accompanied by the formation of pentanols and butanol;
the latter was found in the reaction mixture in amounts
4
5
The influence exerted by temperature on the course of the
hydrodeoxygenation was examined: in the temperature
not exceeding 1–2%. However, the conversion of THFA range 200–300°C, the conversion of furfural is 100%,and
the reaction mixture contains tetrahydrofurfuryl alcohol,
C –C alcohols, and tetrahydrofurans. It was shown
by this pathway is a side process, which is evidenced
by the low selectivities with respect to tetrahydrofurans
and butanol.
4
5
that the initial pressure of hydrogen strongly affects the
conversion of furfural. Raising the initial pressure of
hydrogen within the range 1–7 MPa leads to an increase
in the conversion of furfural, with its full conversion
reached at 5 MPa.
In the HDO of furfural in the presence of water on
Ru-containing catalysts, alcohols can be formed by
another mechanism (see Scheme, II) [42, 43] Originally,
pentanediols are formed via opening of the furan ring
at C –O or C –O bonds, followed by the hydrogenation
2
5
CONFLICT OF INTEREST
of the resulting intermediate to pentanediols with linear
or branched chain. Under the HDO conditions, the
pentanediols can undergo further stepped deoxygenation
to give pentanols and butanols and then also the
A co-author, A. L. Maksimov, is the Editor in Chief of
Zhurnal Prikladnoi Khimii, the rest of the co-authors state that
they have no conflict of interest to be disclosed in the present
communication.
corresponding C –C alkanes.
4
5
The opening of the furan ring in the presence of a
catalyst having acid centers may also yield cyclopentanol
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1
,4-diol. The terminal OH group of the diol is subjected
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