Selectively Chemocatalytic Conversion of Fructose to 1,2-Propylene Glycol over Ru-WOx/Hydroxyapatite Catalyst?

Article abstract of DOI:10.1002/cjoc.201900431

The conversion of fructose to 1,2-propylene glycol (PG) is an important process from cellulosic biomass to high-value added chemicals. Herein, Ru-WO_x/hydroxyapatite (HAP) catalyst was employed for this reaction and reached up to 91.3% yield of PG at 180 °C, 1 MPa initial hydrogen for 8 h in water. On this catalyst, Ru and WO_x were highly dispersed on HAP support and they interacted with each other to form a special catalytic center. The lack of isolated Ru or RuW alloy site led to a moderate activity for hydrogenolysis and hindered the further conversion of PG to propanol. The weak basic HAP support efficiently prevented the humin formation. This precisely controlled catalyst has potential in green PG production.

Full text of DOI:10.1002/cjoc.201900431

Chinese Journal
of Chemistry
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Accepted Article
Title: Selectively chemocatalytic conversion of fructose to 1,2-propylene glycol over
Ru-WOx/HAP catalyst
Authors: Chuang Li, Guangyue Xu, Xiang Zhang and Yao Fu*
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This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.201900431.
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Selectively chemocatalytic conversion of fructose to 1,2-propylene glycol
over Ru-WOx/HAP catalyst
Chuang Li,a# Guangyue Xu,a# Xiang Zhang a and Yao Fu*,a
a Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of
Biomass Clean Energy, iChEM, University of Science and Technology of China, Hefei, Anhui 230026, China.
# These authors, C. Li and G. Xu, contributes equally to this work.
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion The conversion of fructose to 1,2-propylene glycol (PG) is an important process from cellulosic biomass to
high-value added chemicals. Herein, Ru-WOx/HAP catalyst was employed for this reaction and reached up to 91.3% yield of PG at 180 °C, 1 MPa initial
hydrogen for 8 h in water. On this catalyst, Ru and WOx were highly dispersed on HAP support and they interacted with each other to form a special catalytic
center. The lack of isolated Ru or RuW alloy site led to a moderate activity for hydrogenolysis and hindered the further conversion of PG to propanol. The
weak basic HAP support efficiently prevented the humin formation. This precisely controlled catalyst has potential in green PG production.
However, acidic sites may lead to the dehydration of fructose to 5-
hydroxymetylfurfural and then to humins via resinification; while
Background and Originality Content
The utilization of renewable biomass resources for the
metallic sites might over hydrogenate fructose to hexitols, or PG to
production of high value added chemicals has attracted increasing
propanol. Therefore, a delicate balance among various catalytic
attention due to the urgent demand of green chemistry. Short
sites is the key issue for catalyst design.
carbon polyol, such as 1,2-propylene glycol (PG), is one of the most
In our previous work, Ru-WOx/HZSM-5 was employed for the
important chemicals for the production of pharmaceutical,
[4b]
hydrogenolysis of cellulose to ethylene glycol.
When fructose
polyester resins, paints, cosmetics, antifreeze, etc.[1] Instead of
petroleum-based ethylene or propylene oxide route, PG can also
be directly produced from sustainable cellulosic biomass feedstock
via one-pot chemocatalytic process.
was used as feedstock in this system, the major product was PG
but the carbon balance was low due to the dehydration reaction
over acidic HZSM-5 support. We also employed weak basic catalyst
Co/CeOx to increase the carbon balance in another work but the
selectivity to PG was not high. [4a] Hydroxyapatite (HAP) was proved
to be a weak basic support appropriate for hydrogenation
reactions in our previous works [5]. HAP is a naturally existing
calcium orthophosphate and has high biocompatibility, which was
suitable for biomass conversion. Therefore, we want to design a
multifunctional catalyst for the conversion of fructose to PG, taking
advantages of the above works.
In this paper, a series of bifunctional Ru-WOx/HAP catalysts
were designed for the selectively chemocatalytic conversion of
fructose to 1,2-propylene glycol. The catalysts were characterized
by various techniques including XRD, Raman spectroscopy, H2-TPR,
HAADF-STEM, TEM, and XPS to explore the surface structure of the
catalysts. Then the catalysts were tested in fructose conversion
and revealed outstanding performance.
Fructose is the second most abundant sugar on the earth, and
widely exists in waste molasses, main by-product of sugar
refineries. With a carbonyl group at C2 location, fructose can be
directly converted to C3 chemicals via retro-aldol reaction.[2] These
C3 chemicals, including glycerosone and glyceraldehyde, can be
further hydrogenated to PG.[2] Therefore, compared with other
sugar-derived feedstocks [3], fructose is more likely to produce PG.
For instance, in 2012, Liu et al. used Ru/C and WO3 to catalyze
fructose conversion and got 47.9% yield of PG [2a]; in 2014, Wang
et al. employed Ru/NbOPO4 and reached 18.6% yield of PG from
fructose [2b]; in 2015, Zhu et al. reported on the fructose
hydrogenolysis over Pd−WOx/Al2O3 catalyst and the yield of PG was
up to 62.2% [2c]; our group has recently employed Co/CeOx catalyst
to reach 50.8% PG yield from fructose [4a]
.
These previous studies revealed a complex process from
fructose to PG that required precise control in catalyst design.
Acidic or basic sites were necessary for the retro-aldol reaction of
fructose to C3 intermediates; while acidic and metallic sites were
necessary for the next step hydrolysis of C3 intermediates to PG.
Results and Discussion
A series of Ru-WOx/HAP catalysts with different W content as
well as mono-metallic Ru/HAP and WOx/HAP was prepared and
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characterized. In XRD patterns in Figure 1, all the diffraction peaks
were assigned to HAP support. In our previous study on Ru-
WOx/HZSM-5 catalyst, we find out the formation of Ru3W17 alloy
which revealed outstanding hydrogenation activity. However, no
peaks of Ru, WOx or RuW alloy were observed in Ru-WOx/HAP
catalyst. It could be due to the interaction between highly
dispersed WOx and HAP support. From XRD patterns of catalysts
with various W content, it revealed that the increasing content of
W loading will decrease and broaden the diffraction peaks of HAP,
which was well fitted with BET surface area data (see Table S2). For
monometallic WOx/HAP, the peaks of HAP was the weakest. It
suggested that W species had a special interaction with HAP.
Figure 2. Raman spectroscopy of 5%Ru/HAP, 5%Ru-5%WOx/HAP, 5%Ru-
15%WOx/HAP, 5%Ru-25%WOx/HAP, and 5%Ru-35%WOx/HAP.
The H2 temperature-programmed reduction (H2-TPR) profiles
of the as-calcined Ru-WOx/HAP samples were shown in Figure 3.
Ru was very likely to be reduced. The weak peak before 200 °C was
assigned to Ru reduction. For the as-calcined 25%WOx/HAP
catalyst, a broad and weak reduction peak was observed in the TPR
profile at approximately 765 °C and it was assigned to the
reduction of W species. When Ru was introduced into the catalyst,
the reduction peak of W species shifted to lower temperature. It
indicated that Ru could promote the formation of low-valent W
species. Therefore, we named the supported W species as WOx,
while the subscript x means the W species was not coordination
saturated WO3.
Figure 1. XRD patterns of pure HAP, 25%WOx/HAP, 5%Ru/HAP, 5%Ru-
5%WOx/HAP, 5%Ru-15%WOx/HAP, 5%Ru-25%WOx/HAP, and 5%Ru-
35%WOx/HAP.
Raman spectroscopy was then employed to determine the
molecular structure of the catalyst, as shown in Figure 2. The
Raman band of the dehydrated surface WOx species (~1010 cm-1)
and crystalline WO3 NPs (~800 cm-1) were neither present in the
spectroscopy. [6] The new peaks at 908 cm-1 and 485 cm-1 were
ascribed to the Ca(WO4,PO4)n and (Ca,W)mPO4 species, respectively.
It revealed that W species and HAP support reacted with each
other and formed surface WOx-HAP species.
Figure 3. H2-TPR curves of 25%WOx/HAP, 5%Ru/HAP, 5%Ru-5%WOx/HAP,
5%Ru-15%WOx/HAP, 5%Ru-25%WOx/HAP, and 5%Ru-35%WOx/HAP.
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Running title
Chin. J. Chem.
HAADF-STEM image as well as EDS Mapping images were
shown in Figure 4. The Ru and W species were highly dispersed on
HAP surface, which was in accordance with the above results. No
isolated Ru or W blocks were observed in either HAADF-STEM
image or TEM images (Figure S1).
Figure 4. HAADF-STEM images of 5%Ru-25%WOx/HAP and EDS mapping of
various elements. The scale bar is 50 nm.
X-ray photoelectron spectroscopy (XPS) was carried out to
obtain the chemical environment of Ru and W species, as shown in
Figure 5. It demonstrated Ru4+ and Ru0 both existed on the surface
of Ru-WOx/HAP catalysts, and the metallic Ru0 was the main
component. Both W6+ and W5+ were observed, further proved the
WOx component. As the W content various, the binding energies
of W 4f and Ru 3p both shifted. It revealed that the WOx and Ru
species interacted with each other. Although no crystalline Ru-W
alloy was formed, the interacted Ru and W affected each other and
could exhibit special activity in the conversion of fructose to PG.
Figure 5. XPS spectra of Ru 3p (top) and W 4f (bottom) in (a) 5%Ru-
5%WOx/HAP, (b) 5%Ru-15%WOx/HAP, (c) 5%Ru-25%WOx/HAP and (d)
5%Ru-35%WOx/HAP.
The as-reduced catalysts were then tested in fructose
conversion, as shown in Table 1. Monometallic Ru/HAP revealed
very low yield of PG, while the main product was hexitols. The
reaction over WOx/HAP led to unknown products without any PG
detected. With physically mixed Ru/HAP and WOx/HAP, the yield
of PG was a little bit higher than that over Ru/HAP. It revealed that
any isolated Ru or W sites were not the key catalytic center in this
reaction. The bimetallic Ru-WOx/HAP catalysts with various W
content all revealed good selectivity to PG. Among which, 5%Ru-
25%WOx/HAP gave the highest PG yield up to 91.3%. Glucose was
also tested in this system but no PG was detected. It indicated that
this catalyst has no activity for the aldose-ketose isomerization
reaction. It also explained that why no C2 or C4 products were
detected in fructose conversion. The basic HAP support will hinder
the dehydration side reaction. Therefore, the total carbon yield
kept high in all tests. Moreover, different from our previous
reported Ru-WOx/HZSM-5, no RuW alloy was formed in this
catalyst, so that the PG will hardly be further hydrogenolyzed to
propanol. As shown in Figures 7-9, higher reaction temperature,
higher initial hydrogen pressure as well as extending reaction time
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
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will lead to a slight over-hydrogenolysis of PG to propanol. The
optimized PG yield is 91.3% at 180 °C, 1 MPa for 8 h reaction. Worth
mentioning that the reaction can occur under as low as 0.1 bar
initial hydrogen pressure, indicating that the catalyst was very
active at low hydrogen atmosphere.
Table 1 The catalytic performance of various catalysts in the conversion
of fructose to PG.a
Carbon Yield/%
Entry
Catalyst
Conv./%
PG
5.0
0
propanol
1.2
0
1
2
5Ru/HAP
25WOx/HAP
100
100
100
83.7
91.6
100
100
100
Figure 8. The effect of initial hydrogen pressure. Reaction conditions: 100
mg of fructose, 65 mg of 5%Ru-25%WOx/HAP catalyst, 10 mL water as the
solvent, 180 °C, 8 h, 800 rpm.
3
5Ru/HAP+25WOx/HAP
5Ru-5WOx/HAP
5Ru-15WOx/HAP
5Ru-25WOx/HAP
5Ru-35WOx/HAP
5Ru-25WOx/HAP
8.5
69.4
80.4
91.3
87.1
0
0.7
1.5
1.9
2.3
2.0
0
4
5
6
7
8b
a The reaction conditions: 100 mg of fructose, 65 mg of catalyst, 10 mL
water as the solvent, 180 °C, 1 MPa initial hydrogen pressure, 8 h, 800 rpm.
b The feedstock is replaced by glucose.
Figure 9. The distribution of fructose conversion products as a function of
time. Reaction conditions: 100 mg of fructose, 65 mg of 5%Ru-
25%WOx/HAP catalyst, 10 mL water as the solvent, 180 °C, 1 MPa initial
hydrogen pressure, 800 rpm.
Based on the characterizations and reaction tests, the reaction
route was shown in Scheme 1. In the catalyst surface, Ru, WOx and
HAP formed a special species via strong interactions. This catalytic
site can catalyze both the retro-aldol reaction of fructose to C3
intermediates and the hydrogenolysis of C3 intermediates to PG.
This catalytic site had weaker activity for hydrogenation than Ru or
RuW alloy, and will hardly lead to over reaction of fructose to
hexitols or PG to propanol. The HAP support was weak basic and
prevented the formation of humins to increase the total carbon
balance.
Figure 7. The effect of reaction temperature. Reaction conditions: 100 mg
of fructose, 65 mg of 5%Ru-25%WOx/HAP catalyst, 10 mL water as the
solvent, 1 MPa initial hydrogen pressure, 8 h, 800 rpm.
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Running title
Chin. J. Chem.
Scheme 1 The reaction pathway of fructose to PG.
The temperature-programmed reduction (H2-TPR) was carried
out in a home-built reactor system coupled to a gas chromatograph.
Before TPR tests, the samples were pretreated in Ar flow at 200 °C
for 1 h. The TPR was carried out in a 5% H2/Ar mixture gas flow
from 40 °C to 800 °C with a heating rate of 10 °C/min. The liquid
nitrogen/ethanol cooling bath was used to remove the moisture
from the effluent stream before the stream entered a thermal
conductivity detector (TCD).
The temperature-programmed desorption was carried out in a
home-built reactor system coupled to a gas chromatograph. All the
gas flow was set to 40 mLmin-1. Temperature-programmed
desorption of ammonia (NH3-TPD) was employed to determine the
total acidity of the catalysts. Prior to absorption of ammonia, 100
mg of catalyst sample was heated at 500 °C for 1 h under Ar flow
and then cooled to 80 °C followed by saturating with pure NH3 for
1 h. After flushing with Ar for 1h, the NH3-TPD was performed from
80 °C to 800 °C with a heating rate of 10 °Cmin-1. The desorbed
ammonia was monitored by an on-line gas chromatograph
equipped with a thermal conductivity detector (TCD).
The transmission electron microscopy (TEM) image and fast
fourier transform (FFT) diffraction of the HRTEM image were taken
with a JEOL n JEM 2010 apparatus operating at 200 kV voltages.
Before being transferred into the TEM chamber, the samples
dispersed with ethanol for 30 min were deposited onto a carbon-
coated copper grid and then quickly moved into the vacuum
evaporator.
The powder X-ray diffraction (XRD) patterns of the catalysts
were measured by an X’pert (PANalytical) diffractometer, using
CuKα radiation at 40 kV and 40 mA, 2θ ranges were 10°-70°.
The X-ray photoelectron spectroscopy (XPS) spectra was
obtained with an X-ray photoelectron spectrometer (ESCALAB250,
Thermo-VG Scientific, USA) at room temperature under a vacuum
of 10-8-10-9 Torr using monochromated Al Kα radiation (1486.92
eV). The binding energies (BE) were calibrated to carbon with a C
1s band at 284.6 eV.
OH OH OH
HO
H
OH OH
Hexitols
or
Ru RuW
O
OH OH OH
H
HO
HO
OH
O
OH
OH
Ru-WOx/HAP
Ru-WOx/HAP
HO
HO
HO
OH
OH
O
propanol
1,2-PG
Fructose
C3 intermediates
Acidic sites
Humins
Conclusions
In conclusion, multifunctional Ru-WOx/HAP catalyst was
designed and employed for the one-pot selectively chemocatalytic
conversion of fructose to 1,2-propylene glycol, and reached up to
91.3% yield at 180 °C, 1 MPa initial hydrogen for 8 h in water.
Various characterizations revealed that in this catalyst, Ru and WOx
were highly dispersed on HAP support and they interacted with
each other to form a special catalytic center. The lack of isolated Ru
or RuW alloy site led to a moderate activity for hydrogenolysis and
hindered the further conversion of PG to propanol. The weak basic
HAP support efficiently prevented the humin formation. This
precisely controlled catalyst has potential in green production of
1,2-propylene glycol.
Experimental
Reagents
Fructose (AR, >99%), pentanol (AR, >99.8%), Ruthenium
trichloride
hydrate
(RuCl3·xH2O)
(AR,
35.0-42.0%),
ammonium metatungstate (AR, >99%), hydroxylapatite (HAP)
were purchased from Aladdin Chemical Reagent Co., Ltd; high-pure
H2 and high-pure N2 were purchased from Nanjing Special Gas
Factory Co. Ltd. All these chemicals were used without further
purification.
The chemical composition of catalysts was analyzed by an
Optima 7300 DV ICP-AAS. ICP-AAS was performed on a PerkinElmer
Corporation Analyst 800 instrument. The catalyst sample handling
process is as follows: 10 mg of catalyst was added into a 10 mL
round-bottom flask with 4 mL of aqua regia and stirred at 80 °C for
24 h until metal is completely dissolved. Then the mixture was
diluted to 25 mL in a volumetric flask for characterization.
Catalyst Test
All catalytic reactions for the conversion of fructose to PG were
performed in a 25 mL Parr reactor. In a typical experiment, 100 mg
of fructose, 65 mg of the reduced catalyst and solvent (10 mL of
deionized water) were added into the reactor. After purged for 4
times, H2 was filled to corresponding pressure at ambient
temperature. The reaction temperature and the reaction time
were kept at certain values with magnetic stirring. After the
reaction, the reactor was cooled to room temperature, and the
products were separated from the catalyst by an external magnet
and then diluted with methanol. Finally, the collected sample
Catalysts Preparation
A series of Ru-WOx/HAP catalysts with different amounts of Ru
loading and Ru/W mass ratios were prepared by co-precipitation
method. The catalysts were labeled as (x)Ru-(y)WOx/HAP (x, y
represent the mass percentage of Ru and W, respectively). A
typical catalyst preparing procedure was as follows: 1.2 g of HAP
was added into 100 g of deionized water in a 250 mL round-bottom
flask and stirred at 60 °C. A certain amount of RuCl3·xH2O and a pre-
calculated amount of ammonium metatungstate were well
dissolved in deionized water (20 g) and then dropwisely added into
the above catalyst/water mixture under magnetic stirring. The
mixture was stirred vigorously for 24 h. After that, water is
removed by rotary evaporator. Subsequently, the solid was
transferred into an oven and dried at 105 °C for 12 h. After drying,
the samples were reduced in H2 atmosphere at 600 °C for 2 h with
a heating rate of 1 °C/min before reaction.
solution was identified by
a
gas chromatograph-mass
spectrometer combination (GC-MS, Agilent 5975C) and quantified
by a gas chromatograph (Kexiao 1690) with HP-INNOWAX capillary
column (30 m*0.250 mm*0.25 μm) as well as a high-performance
Catalyst characterization
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
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liquid chromatography (HPLC, Hitachi L2000) with Sugar 2011
column. The GC detecting conditions were as follows: nitrogen as
carrier gas; injection port temperature: 280 °C; detector (FID)
temperature: 280 °C; column temperature: 40 °C, heating up to
250 °C with a heating rate of 10 °C/min. Pentanol was used as
internal standard to quantify the products. Meanwhile, HPLC
analyses were conducted at the column temperature of 323 K using
water as the mobile phase with a flow rate of 0.5 mL·min-1. The
injected sample volume was set at 20 μL. In this paper, the
experiments were repeated for at least three times and the data
were the average value with experimental error less than 1%.
The conversion and yield were calculated as follows:
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

mass of carbon in fructose after reaction
mass of carbon in fructose put in the reactor
Conv. (%) = 1−
×100%




mass of carbon transferred from fructose to the target product
mass of carbon in fructose put into the reactor
Yield (%) =
×100%
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement
This work was supported by the National Key R&D Program of
China (2018YFB1501600), the National Natural Science Foundation
of China (21572212, 51821006, 51961135104), the Major Science
and Technology Projects of Anhui Province (18030701157), the
Strategic Priority Research Program of the CAS (XDA21060101),
and the Local Innovative and Research Teams Project of
Guangdong Pearl River Talents Program (2017BT01N092).
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Chin. J. Chem.
Accepted manuscript online: XXXX, 2019
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Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Chin. J. Chem. 2019, 37, XXX－XXX
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Selectively chemocatalytic conversion of
fructose to 1,2-propylene glycol over Ru-
WOx/HAP catalyst
In this work, multifunctional Ru-WOx/HAP catalyst was employed for the conversion of fructose to
1,2-propylene glycol and reached up to 91.3% yield at 180 °C, 1 MPa initial hydrogen for 8 h in water.
a
Chuang Li,a# Guangyue Xu,a# Xiang Zhang and
Yao Fu*,a
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© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.