Hydrodeoxygenation of glycerol into propanols over a Ni/WO3–TiO2 catalyst

Article abstract of DOI:10.1016/j.mencom.2020.01.040

Hydrodeoxygenation of glycerol in a flow reactor over a bifunctional Ni/WO₃–TiO₂ catalyst at 240–255 °C and hydrogen pressure of 3 MPa affords propan-1-ol and propan-2-ol in total yield of 94%.

Full text of DOI:10.1016/j.mencom.2020.01.040

Mendeleev
Communications
Mendeleev Commun., 2020, 30, 119–120
Hydrodeoxygenation of glycerol into propanols over a Ni/WO3–TiO2 catalyst
Alexander A. Greish,*a Elena D. Finashina,a Olga P. Tkachenko,a Pavel A. Nikul’shin,b
Mikhail A. Ershovb and Leonid M. Kustova,c
a N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow,
Russian Federation. Fax: +7 499 137 2935; e-mail: greish@ioc.ac.ru
b All-Russian Research Institute of Oil Refining, 111116 Moscow, Russian Federation.
Fax: +7 495 787 4887
c Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation
DOI: 10.1016/j.mencom.2020.01.040
Hydrodeoxygenation of glycerol in a flow reactor over a
bifunctional Ni/WO3–TiO2 catalyst at 240–255 °C and
hydrogen pressure of 3 MPa affords propan-1-ol and
propan-2-ol in total yield of 94%.
Keywords: bifunctional catalysis, hydrogenolysis, glycerol, propanols, titania, tungsten oxide.
Propan-1-ol (1-Pr) and propan-2-ol (2-Pr) are the products that
can be produced by hydrodeoxygenation of glycerol.1–4 The
values for the Gibbs free energy ∆G° for the glycerol conversion
into 1-Pr and 2-Pr are significantly negative (–206 and
–166 kJ mol–1, respectively),5 so the reactions can proceed
irreversibly. Obviously, the process comprises consecutive
dehydration and hydrogenation steps. Dehydration requires
strong Brønsted acid centers on the catalyst surface, whereas
hydrogenation needs metal centers.6,7
important because nickel is significantly cheaper than any of
noble metals.
The 20%WO3–80%TiO2 carrier was prepared by co-
precipitation with an ammonia solution of titanium and tungsten
hydroxides from an aqueous solution containing ammonium
tungstate (NH4)10[H2W12O41] and titanium tetrachloride TiCl4.
The resulting precipitate was washed with distilled water to a
neutral reaction, dried in air at 150 °C for 2 h and calcined in an
air flow at 520 °C for 3 h. The 16%Ni/WO3–TiO2 catalyst was
prepared by impregnating the 20%WO3–80%TiO2 carrier with an
aqueous solution of nickel nitrate Ni(NO3)2·6H2O, followed by
drying the catalyst at 120 °C for 2 h and calcination at 350 °C for
2 h. Before the catalytic tests, the catalyst loaded into the reactor
was reduced in a hydrogen flow at 350 °C for 3.5 h. The phase
and elemental compositions of the catalyst were characterized by
XRD and EDX data (see Online Supplementary Materials).
Experiments on glycerol hydrogenolysis (Scheme 1) were
carried out in a stainless steel flow reactor with an inner diameter
of 7 mm. The catalyst (2 g) with a particle size of 0.25–0.5 mm
was loaded into the central part of the reactor. The free volume
of the reactor was filled with ground quartz with particle size of
0.5–1.0 mm. A 30% aqueous solution of glycerol was fed to the
reactor by a syringe pump, the LHSV of the glycerol solution
was varied in the range of 0.46–1.66 h–1. The process was
carried out at 240–270 °C. The hydrogen pressure was varied
in the range of 2.0–3.6 MPa. The feed rate of hydrogen was 40
cm3 min–1. Liquid samples for the GC analysis were taken
every 30 min.
The yield of intermediate propane-1,3-diol correlated with
the concentration of the acidic Brønsted centers.1,8–14 Some
active catalysts for glycerol hydrogenolysis contain tungsten
12
15
oxides,8,5–17 in particular Pt/WO3/TiO2 or 4%Pt/WO3–ZrO2
(the yields of 1-Pr and 2-Pr were 56.2 and 5.3%, respectively,
and the glycerol conversion was 84.5% at 130 °C and 4 MPa of
H2). The 1-Pr formation in yields up to 24% was observed18,19 on
the Ir/SiO2 catalyst modified with Re and small additive of
sulfuric acid at 120 °C and 8 MPa of hydrogen. A 33% yield of
1-Pr was obtained in the glycerol hydrogenolysis over the Pt–
HSiW/SiO2 catalyst with a heteropolyacid at 200 °C and 5 MPa
of hydrogen.8 Bimetallic Pd–Fe nanoparticles provided a high
yield of alcohols.20
Nickel catalysts are rarely employed in glycerol conversion,
because the yield of alcohols remains low even under severe
conditions. Nickel nanoparticles on oxide carriers (Ni/SiO2 or
Ni/Al2O3) with a Ni content of 45–55 wt%
catalyze
hydrogenation of glycerol into alcohols at 230–320 °C, a
hydrogen pressure of 40–75 atm and liquid hourly space velocity
(LHSV) of 3 h–1, the selectivity to 1-Pr at 275 °C and 60 atm on
Ni/SiO2 was close to 14%.4
It should be noted that the yield and selectivity to propanols
are affected not only by the composition and properties of the
The present work was focused on the development of an
active catalyst for glycerol hydrogenolysis into propanols, as
well as the search for the appropriate conditions in order to
improve the selectivity towards propanols. Thus, a bifunctional
catalyst based on a co-precipitated mixture of WO3 with TiO2
with a molar WO3/TiO2 ratio of 1:4 exhibiting strong Brønsted
acidity was used as a carrier.21,22 Metallic nickel (16 wt%)
served as a hydrogenating component of the catalyst, which is
cat. ꢅꢆꢇNiꢈꢉ20ꢇꢊOꢄꢋꢌ0ꢇꢍiO2ꢎ
Oꢀ Oꢀ Oꢀ
Cꢀ2 Cꢀ Cꢀ2
2ꢁ0 ꢂCꢃ ꢄ MPa of ꢀ2
Oꢀ
MeCꢀ2Cꢀ2Oꢀ
ꢏ MeCꢀMe
Scheme 1
© 2020 Mendeleev Communications. Published by ELSEVIER B.V.
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
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Mendeleev Commun., 2020, 30, 119–120
In summary, the present study demonstrates that the catalyst
ꢉ00
ꢊ0
ꢋ0
ꢌ0
ꢈ0
16%Ni/20%WO3–80%TiO2 is capable of providing the total
yield of propanols as high as 94%. Such an extraordinary result
can be explained by the optimal ratio of the two different
functions in the catalyst prepared using co-precipitated oxides
WO3–TiO2. On the one hand, the catalyst possesses a rather
strong Brønsted acidity, providing high dehydration activity, and
on the other hand, the presence of a large amount of Ni
nanoparticles supported on the catalyst surface creates the
conditions favorable for efficient hydrogenation.
2ꢆ0
2ꢆꢇ
2ꢇ0
TꢀꢁC
2ꢇꢇ
2ꢈ0
Figure 1 The dependence of the yields of propanols on the reaction
This work was supported by the Ministry of High Education
and Science of the Russian Federation (project
RFMEFI57617X0089).
temperature (Vcat. = 2 ml, 30% glycerol solution, PH = 3.0 MPa, LHSV =
2
–
–
= 0.46 h 1, UH = 15 ml min 1).
2
catalyst, but also by the conditions of the process, in particular,
such parameters as the concentration of glycerol in the initial
solution, the reaction temperature, pressure, the volume rate of
hydrogen supply and the contact time. The optimal conditions
for glycerol hydrogenolysis imply higher yield of propanols with
minimized yield of by-products, including propanediols. It was
necessary to carry out the reaction under conditions ensuring
glycerol being in a liquid state. Indeed, in this case highly viscous
glycerol does not penetrate into the pores of the catalyst, and the
reaction occurs exclusively on its outer surface. Then the main
factor affecting the reaction rate is the value of the external
catalyst surface, which directly depends on the size of the
catalyst granules. In our experiments, the catalysts with grain
sizes of 0.25–0.50 mm were used.
According to experimental data obtained, the specified
conditions have a complex effect on the reaction outcome. In
particular, propanols have a lower boiling point than glycerol, as
a result they can be removed from the catalyst by a hydrogen
flow. At the same time, the increase in the hydrogen pressure in
the reactor not only enhances the rate of hydrogenation of
unsaturated bonds, but simultaneously reduces evaporation of
intermediate propanediols, thereby ensuring their conversion
into propanols. It must be noted that the reaction temperature
and the LHSV value (or contact time) have a crucial impact on
the yield of propanols.
Figures 1 and 2 show the dependence of the yields of
propanols on these parameters in the reaction catalyzed by
16%Ni/WO3–TiO2. According to these data, the optimum
temperature is 250 °C and the LHSV parameter should be not
higher than 0.46 h–1. Noteworthy, only a certain combination of
the reaction parameters provides rather high yield of propanols
with the conversion of glycerol close to 100%. In our case, the
maximum yield of propanols reaches 94.1%. Importantly, the
higher total propanol yield, the higher the 1-Pr/2-Pr ratio, e.g.,
when the total propanol yield grows from 80 to 94%, the 1-Pr/2-Pr
ratio increases from 9 to 14. This means that the selectivity
towards 1-Pr increases approaching 93% in the mixture of 1-Pr
and 2-Pr. Thus, the catalyst 16%Ni/WO3–TiO2 is characterized
by a high selectivity towards primary propan-1-ol.
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2020.01.040.
References
1 S. Zhu, Y. Zhu, S. Hao, H. Zheng, T. Mo and Y. Li, Green Chem., 2012,
14, 2607.
2 M. Wang, H. Yang, Y. Xie, X. Wu, C. Chen, W. Ma, Q. Dong and
Z. Hou, RSC Adv., 2016, 6, 29769.
3 X. Lin, Y. Lv, Y. Xi, Y. Qu, D. L. Phillips and C. Liu, Energy Fuels,
2014, 28, 3345.
4 E. van. Ryneveld, A. S. Mahomed, P. S. van Heerden, M. J. Green and
H. B. Friedrich, Green Chem., 2011, 13, 1819.
5 NIST Chemistry WebBook SRD 69, 2017.
6 Y. Nakagawa, M. Tamura and K. Tomishige, J. Mater. Chem. A, 2014,
2, 6688.
7 T. Miyazawa, Y. Kusunoki, K. Kunimori and K. Tomishige, J. Catal.,
2006, 240, 213.
8 S. Zhu, Y. Zhu, S. Hao, L. Chen, B. Zhang and Y. Li, Catal. Lett., 2012,
142, 267.
9 S. Zhu, Y. Qiu, Y. Zhu, S. Hao, H. Zheng and Y. Li, Catal. Today, 2013,
212, 120.
10 F. Cavani, S. Guidetti, L. Marinelli, M. Piccinini, E. Ghedini and
M. Signoretto, Appl. Catal., B, 2010, 100, 197.
11 A. Alhanash, E. F. Kozhevnikova and I. V. Kozhevnikov, Catal. Lett.,
2008, 120, 307.
12 L. Gong, Y. Lu, Y. Ding, R. Lin, J. Li, W. Dong, T. Wang and W. Chen,
Appl. Catal., A, 2010, 390, 119.
13 Y. Zhang, X.-C. Zhao, Y. Wang, L. Zhou, J. Zhang, J. Wang, A. Wang
and T. Zhang, J. Mater. Chem. A, 2013, 1, 3724.
14 K. Kongpatpanich, T. Nanok, B. Boekfa, M. Probst anf J. Limtrakul,
Phys. Chem. Chem. Phys., 2011, 13, 6462.
15 L.-Z. Qin, M.-J. Song and C.-L. Chen, Green Chem., 2010, 12, 1466.
16 J. Chaminand, L. Djakovitch, P. Gallezot, P. Marion, C. Pinel and
C. Rosier, Green Chem., 2004, 6, 359.
17 T. Kurosaka, H. Maruyama, I. Naribayashi and Y. Sasaki, Catal.
Commun., 2008, 9, 1360.
18 Y. Amada, Y. Shinmi, S. Koso, T. Kubota, Y. Nakagawa and
K. Tomishige, Appl. Catal., B, 2011, 105, 117.
19 Y. Nakagawa, Y. Shinmi, S. Koso and K. Tomishige, J. Catal., 2010,
272, 191.
20 F. Mauriello, A. Vinci, C. Espro, B. Gumina, M. G. Musolinoa and
R. Pietropaolo, Catal. Sci. Technol., 2015, 5, 4466.
21 A.A.Greish,S.S.DemyginandL.M.Kustov,KatalizvPromyshlennosti,
2002, no. 4, 4 (in Russian).
ꢂ00
ꢊ0
ꢉ0
ꢋ0
ꢈ0
22 V. P. Ananikov, D. B. Eremin, S. A. Yakukhnov, A. D. Dilman, V. V.
Levin, M. P. Egorov, S. S. Karlov, L. M. Kustov, A. L. Tarasov, A. A.
Greish, A. A. Shesterkina, A. M. Sakharov, Z. N. Nysenko, A. B.
Sheremetev, A. Yu. Stakheev, I. S. Mashkovsky, A. Yu. Sukhorukov, S. L.
Ioffe, A. O. Terent’ev, V. A. Vil’, Yu. V. Tomilov, R. A. Novikov, S. G.
Zlotin, A. S. Kucherenko, N. E. Ustyuzhanina, V. B. Krylov, Yu. E.
Tsvetkov, M. L. Gening and N. E. Nifantiev, Mendeleev Commun., 2017,
27, 425.
0.20
0.ꢇ0
0.ꢈ0
LꢀSV/hꢁꢂ
0.ꢉ0
ꢂ.00
Figure 2 The dependence of the yield of propanols on LHSV (Vcat. = 2 ml,
–
30% glycerol solution, T = 250 °C, PH = 3.0 MPa, UH = 15 ml min 1).
Received: 17th July 2019; Com. 19/5988
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