Perovskite type oxide-supported Ni catalysts for the production of 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural

Article abstract of DOI:10.1039/c6gc00432f

The hydrogenolysis of C-O and CO in 5-hydroxymethylfurfural for the production of furan biofuel 2,5-dimethylfuran (DMF) is of great importance for biomass refining. However, development of non-noble metal-based catalysts which perform stably for this process is still challenging. Here, perovskite-supported Ni catalysts were used for the hydrogenolysis of 5-hydroxymethylfurfural at 230 °C, with 98.3% yield of DMF being obtained. The effects of reaction conditions such as temperature and pressure were investigated and discussed, and the catalyst could maintain good activity after being used at least 5 times. In order to further explore the reaction mechanism, dynamic experiments at different times were carried out and a possible reaction pathway was proposed. The development of efficient perovskite-supported Ni catalysts verified their great potential in biomass conversion.

Full text of DOI:10.1039/c6gc00432f

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ARTICLE TYPE
Perovskite Type Oxide Supported Ni Catalysts for the Production of
,5-Dimethylfuran from Biomass-Derived 5-Hydroxymethylfurfural†
2
a
a
a
a
Meng-Yuan Chen, ‡ Chu-Bai Chen, ‡ Bakht Zada, and Yao Fu *
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
The hydrogenolysis of CꢀO and C=O in 5ꢀhydroxymethylfurfural for the production of furan biofuel
2
,5ꢀdimethylfuran is of great importance for biomass refining. However, development of nonꢀnoble metal
based catalysts which perform stably for this process is still challenging. Here, perovskite supported Ni
o
catalysts were used for the hydrogenolysis of 5ꢀhydroxymethylfurfural at 230 C, and 98.3% yield of
1
0
DMF was obtained. The effect of reaction conditions such as temperature and pressure were investigated
and discussed, and the catalyst could maintain good activity after used for at least 5 times. In order to
further explore the reaction mechanism, dynamic experiments at different time were carried out and a
possible reaction pathway was proposed. The development of efficient perovskite supported Ni catalysts
verified the great potential in biomass conversion.
favor of suppressing the vapor lock in the inlet and the cold
1
5
1 Introduction
starting performance at low ambient temperature respectively.
The water solubility of DMF at 20 C is just 0.26wt%, however
o
With the gradual decrease of the fossil resources which is not
sustainable, the demand for exploring the renewable feedstock for
the production of transportation fuel and chemicals is getting
more and more attention. Biomass, which is widespread,
abundant all over the world, inexpensive, and renewable, is
considered to be an ideal promising alternative to fossil resources
5
5
6
6
7
7
0
5
0
5
0
5
bioꢀethanol is miscible with water, the water solubility of
o
bioꢀbutanol is 7.7wt% at 20 C, this advantage makes DMF
harder to absorb water from air which will reduce the product
1
o
quality. The kinematic viscosity of DMF at 20 C (0.57 cSt) is
2
2
3
3
4
4
0
5
0
5
0
5
similar to that of gasoline (0.37ꢀ0.44 cSt), which is advantageous
to establishing the injection pressure of DMF in fuel system and
protecting the movements in the engine components, for
2
for the production of fuels and chemicals. However, because of
the high oxygenꢀcontent in biomassꢀderived compounds (e.g.
comparison, the kinematic viscosity of bioꢀethanol and
5
ꢀhydroxymethylfurfural (HMF), levulinic acid (LA), furfural,
o
bioꢀbutanol at 20
C
are 1.5 cSt and 3.6 cSt, respectively.
phenol and guaiacol, etc.), they could not be directly used as
12,5
Moreover, the research octane number (RON) of DMF (119) is
higher than that of bioꢀethanol, bioꢀbutanol and gasoline (110, 98,
3
renewable fuels. Hydrogenolysis is an important process for the
4
deoxygenation of these oxygenꢀcontaining compounds.
representative and important process is the hydrogenolysis of
HMF to afford the bioꢀfuel 2,5ꢀdimethylfuran (DMF). In this
A
9
0ꢀ100 respectively). These advantages mentioned above makes
DMF a promising bioꢀfuel.
5
Dumesic et al. firstly published the reaction pathway for the
case, HMF is an important bioꢀbased compound which is
affirmed as one of the top 10 platform molecules derived from
5
production of DMF from fructose, CuRu/C was used for the
hydrogenolysis of HMF with a yield of 76ꢀ79%. In general, the
subsequent reports on the selective hydrogenolysis of HMF were
6
7
biomass. It can be converted into 2,5ꢀfurandimethanol (FDM)
8
and furan 2,5ꢀdicarboxylic acid (FDCA) through hydrogenation
and oxidation, respectively, which could be used for the polymer
industry. DMF could be obtained through further hydrogenolysis
of HMF, which is considered as a highly promising new
generation of alternative liquid fuel.
Compare to bioꢀethanol and bioꢀbutanol, which are studied
1
3
14
mainly performed over noble metals (e.g. Pd/C , Ru/C ,
1
5
16
17
18
19
RuSn/C , RuꢀKꢀOMSꢀ2 , Pd Au /C , Pd/C/Zn , Pd/Fe O
,
x
y
2
3
20
21
22
23
PtCo@HCS , Ru/Co O
,
Ru/Cu/Fe O /NꢀrGO , Pt/C ,
3
4
3
4
2
4
25
12c
Ru/HT ,
RuꢀSn/ZnO ,
RuꢀNaY ).
Development
of
9
nonꢀprecious metal based catalysts for this hydrogenolysis
process is of great importance for the industrial application of
DMF. However, because of the generally low activity of
1
0
deeply as alternative energy sources, DMF shows a lot of
advantages. According to the previous report on the
physicochemical properties of DMF, bioꢀethanol and
26
nonꢀnoble metal catalysts , only few studies reported the
construction of nonꢀnoble metal catalysts for the hydrogenolysis
of HMF. Currently, the reported nonꢀnoble metal catalyst systems
for the conversion of HMF into DMF can be divided into two
11
bioꢀbutanol, DMF has higher lower heating value (LHV, 33.7
MJ/kg, 26.9 MJ/kg, 33.2 MJ/kg for DMF, bioꢀethanol and
bioꢀbutanol, respectively) which will cost less fuel. The boiling
2
7
categories: (1) nickel based catalysts, e. g. Raney Ni , NiꢀAl O
3
o
12a
2
point of DMF (93 C) is higher than that of bioꢀethanol (77.3
28
derived from hydrotalciteꢀlike compounds , nickel nanoparticles
o
o
C) and lower than that of bioꢀbutanol (117.25 C), which is in
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2
9
30
31
inlaid nickel phyllosilicata (NiSiꢀPS) , Ni/Co O , NiꢀFe/CNT ;
diffractometer was used to measure the Xꢀray power diffraction
3
4
(
2) copper based catalysts, e. g. Cuꢀdoped porous metal oxide 55 (XRD) patterns of the catalysts at 40 kV and 40 mA.
3
2
33
(
CuꢀPMO) , copperꢀzine nanoalloy nanopowder (CuZn) ,
Transmission electron microscopy (TEM) was performed on a
JEOLꢀ2010 electron microscope. The samples were deposited on
a Cu grids after ultrasonic dispersion of the samples in ethanol.
Xꢀray photoelectron spectroscopy (XPS) analyses of the prepared
34
CuꢀZnO catalysts derived from minerals (e.g. malachite) .
Recent progress on the properties and production of DMF were
also reviewed in some reports
5
0
5
0
5
0
5
7
h,11,12a,35
. Nickel based catalysts are
more attractive because they are active for the cracking of the 60 catalysts were performed on a Thermo Scientific Escalab
CꢀO bonds in the biomass derived molecular under relatively
250ꢀXꢀray photoelectron spectrometer.
2
9
mild conditions . Recently, our group proposed the nonꢀnoble
2
.3 Catalysts preparation
1
1
2
2
3
3
bimetallic NiꢀW C/AC catalyst for the hydrogenolysis of HMF
2
3
6
and gave rise to a 96% yield of DMF . Nevertheless, the
establishment of novel nonꢀnoble catalyst systems which can be
The perovskite supported Ni catalysts were prepared by oneꢀstep
citricꢀcomplexing method . For a typical catalyst preparation, a
4
4
synthesized simply and perform steadily is particularly essential 65 precalculated amount of nickel nitrate (10.345 mmol), 10 mmol
for the industrial production of bioꢀfuel DMF.
of iron nitrate, 10 mmol of lanthanum nitrate were well dissolved
in deionized water in a 100 ml round bottom flask. A certain
amount of citrate acid (36.414 mmol) and polyethylene glycol
400 (7.283 mmol) which were 120 mol% and 24 mol% molar
Perovskiteꢀtype functional materials are widely studied in the
3
7
38
39
fields of catalysis , fuel cell and solar cell , especially
4
0
catalytic hydrogenation . And the high thermal and hydrothermal
stability of perovskite oxides enable them appropriate for 70 amount of all the metal cations respectively were added to the
3
7c
catalysis . Recently perovskiteꢀtype oxide catalysts which can
solution under magnetic stirring. Subsequently the mixture were
continued to stir vigorously for another 12 h. Then the mixture
was taken into an oil batch and kept at 80 C until spongy solids
4
1
be represented by the general formula ABO3 structures were
gradually found to be efficient for bioꢀrefinery process, for
instance, steam reforming of ethanol , hydrogenation etc. And
o
4
2
43
were formed. The spongy solids were transferred into an oven
43
o
it was reported that perovskiteꢀtype oxides could help to 75 and dried at 120 C for 24 h. Then the mixture was taken into a
stabilize the metal particles on the metallic oxides which will
effectively improve the activity and stability of the catalysts. In
consideration of the advantage of perovskiteꢀbased catalysts,
nonꢀnoble metal nickel supported on perovskteꢀtype oxide
furnace and the temperature was raised from room temperature
o
o
o
(RT) to 750 C at the rate of 10 C/min and kept at 750 C for
another 5 h to afford the catalyst precursor. The precursor was
reduced in a tube furnace under a N /H mixed gas, the flow rates
2
2
supports was synthesized for the investigation of the 80 were 100 ml/min and 20 ml/min respectively. The temperature of
o
hydrogenolysis process of biomassꢀderived HMF. The catalyst
showed high activity and selectivity towards DMF, and the
catalyst could maintain good activity after used for at least 5
times. The effect of different reaction conditions on the reaction
the tube furnace was raised from RT to 500 C at the rate of 10
o
o
C/min and kept at 500 C for 4 h. After cooling to RT, the
resulted powder was collected. The catalyst prepared by this
method was marked as LFꢀN20, in which the “20” represents the
was investigated and a possible reaction mechanism was 85 weight percent of Ni in the catalyst. And the preparation
proposed. The establishment of perovskiteꢀbased catalysts
highlights its great potential capability for biomass conversion.
procedures for the other catalysts in this work were similar to that
of LFꢀN20.
2
.4 Catalyst test
2
Experimental
The hydrogenolysis reaction of HMF was carried out in a 25 ml
Parr reactor equipped with a magnetic stirrer. In a typical
experiment, 1.0 mmol of HMF, 1.0 mmol of nꢀtetradecane (used
as internal standard), 100 mg of the catalyst, and 12 ml of ethanol
were added to reactor. Then the reactor was purged with
hydrogen for 5 times, and maintained at a specified hydrogen
2
.1 Materials
90
HMF, DMF, 2,5ꢀfurandimethanol (FDM), 5ꢀmethylfurfuryl
alcohol (MFA), 2,5ꢀdihydroxymethyltetrahydrofuran (DHMTHF),
and 5ꢀmethylfurfural (MF) were generously gifted by Hefei Leaf
Energy Biotechnology Co., Ltd (www.leafresource.com). Nickel
4
0
nitrate hexahydrate (99.9+%) was supplied by Strem Chemical, 95 pressure (e.g. 5.0 MPa) at ambient temperature. The reaction
o
Inc. Iron nitrate nonahydrate (AR), citrate acid monohydrate
AR), polyethylene glycol 400 (CP) and ethanol (AR) were
purchased from Sinopharm Chemical Reagent Co., Ltd.
Lanthanum nitrate hexahydrate (99.99%) was supplied by Energy
temperature was kept at a certain value, for instance, 230 C.
After the reaction, when the reactor was cooled to RT, the
mixture of the products was collected and analyzed by gas
(
4
5
chromatographꢀmass
spectrometer
(GCꢀMS)
and
gas
Chemical. Tetradecane (99%) was obtained from Aladdin 100 chromatograph (GC).
Reagent Co., Ltd.
3
Results and discussion
2
.2 Catalyst characterization
3
.1 Characterization of the catalysts
5
0
The nitrogen adsorption/desorption of the catalysts was measured
on a Micromeritics ASAP 2020 analyzer. The specific surface
areas of the catalysts were determined through the
The Xꢀray powder diffraction (XRD) patterns of perovskite type
oxides (PTO) supported Ni catalysts were displayed in Fig. 1.
BarrettꢀEmmetꢀTall (BET) method. An X’pert (PANalytical) 105 The characteristic peaks corresponding to the perovskite type
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Fig. 2 The TEM images of perovskite supported Ni catalysts with
different Ni contents (a) LFꢀN5; (b) LFꢀN10; (c) LFꢀN15; (d) LFꢀN20; (e)
LFꢀN25; (f) LFꢀN30
reflections of LaFeO3 (labeled as LF) could be obviously
discovered in the XRD patterns of different supported Ni
catalysts (labeled as LFꢀN5, LFꢀN10, LFꢀN15, LFꢀN20, LFꢀN25,
LFꢀN30, respectively). And the reflection peaks corresponding to
metallic Ni phase were found in all the supported Ni catalysts, the
intensity of metallic Ni phase reflection signals enhanced with the
Ni contents in catalysts. The XRD results of the catalysts were
30
The Xꢀray photoelectron spectroscopy (XPS) analysis of the
supported Ni catalysts was displayed in Fig. 3. Considering that
the binding energy (BE) position of La 3d overlapped the BE
5
45
position of Ni 2p , it was hard to measure the BE of Ni 2p,
4
4c
similar to the previous reports . The dimensions of the metallic 35 therefore the XPS signals of Ni 3p was analysed. It has been
4
5
Ni phase (DMP) were caculated using the Scherrer formula (Table
1). The XRD results of the iron oxides supported Ni catalyst and
lanthanum oxides supported Ni catalyst prepared using the same
method were presented in the supporting information and the
reported that the BE of Ni 3p for metallic Ni is 67 eV .
According to the XPS results of the supported Ni catalysts in Fig.
3, the BE of metallic Ni 3p were detected in all the perovskite
supported Ni catalysts, indicating the formation of active metallic
1
0
reflection peaks of the metallic Ni phase could be discovered 40 Ni for the hydrogenolysis of HMF. The BarettꢀEmmetꢀTall (BET)
obviously.
analysis results of the supported Ni catalysts were presented in
Table 1.
1
5
Fig. 1 XRD patterns of perovskite supported Ni catalysts
The TEM images of perovsktite supported catalysts with
different Ni contents were also investigated. It could be
determined from the TEM images (Fig. 2) that the proper
morphologies of the perovskites were prepared in accordance
with the previous reports. However, the Ni particles could hardly
be observed because it was relatively hard to distinguish the
supports and the metallic phase from these TEM images. The
TEM images of the iron oxides supported Ni catalyst, lanthanum
Fig. 3 XPS spectra in the Ni 3p region for perovskite supported Ni
catalysts
45
Table 1 Physicoꢀchemical properties of catalysts
2
0
a
Sureface
Pore
Pore
Size /
nm
Ni /
wt%
D
MP
/
b
c
d
Catalyst
Area /
Volume /
nm
2
3
m /g
cm /g
LFꢀN5
LFꢀN10
LFꢀN15
LFꢀN20
LFꢀN25
LFꢀN30
FꢀN20
LꢀN20
LF
5
15.6
16.4
18.4
21.0
24.7
26.4
26.6
31.8
ꢀ
2.54
5.55
4.67
3.35
5.88
3.76
12.09
1.74
4.88
0.043
0.054
0.051
0.039
0.045
0.025
0.085
0.009
0.045
40.2
61.7
53.8
53.9
51.1
37.2
22.2
27.2
42.4
10
15
20
25
30
20
20
0
2
5
oxides supported Ni catalyst and LaFeO were presented in the
3
supporting information.
a. Crystal size of the metallic Ni phase, calculated from XRD results with
Scherrer formula; b. BET Surface Area; c. BJH desorption cumulative
volume of pores between 17.0 Å and 3000.0 Å diameter; d. BJH
desorption average pore diameter (4V/A).
50
3
.2 Selective hydrogenolysis of HMF
Selective hydrogenolysis of HMF over different catalysts was
performed and the products were analyzed by GCꢀMS and GC. It
could be found that 69.3% DMF could be obtained (Table 2,
entry 1) when the Ni content in the catalyst was only 5% (catalyst
marked as LFꢀN5), and the byꢀproducts were primarily
55
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a
Table 2 Catalytic performance of various catalysts for the selective hydrogenolysis of HMF
Yield / %
DHMTHF
Entry
Catalyst
Conv. / %
DMF
FDM
MFA
MF
Others
0.1
2.2
2.6
0.9
0.8
1.5
3.1
57.3
3.4
1
2
3
4
5
6
7
8
9
LFꢀN5
LFꢀN10
LFꢀN15
LFꢀN20
LFꢀN25
LFꢀN30
FꢀN20
LꢀN20
LF
＞99
＞99
＞99
＞99
＞99
＞99
＞99
＞99
96.6
69.3
74.2
85.9
98.3
86.0
78.1
67.4
0
0
0
0
0
0
0
0
0.1
36.5
0
0
0
28.7
21.8
10.6
0.7
5.6
2.2
27.8
0
38.5
1.9
1.8
0.9
0.1
0
0.1
0.7
0.5
2.9
0
7.6
18.1
1.0
42.1
0
15.3
o
2
a. Reaction conditions: 1.0 mmol of HMF, 1.0 mmol of nꢀtetradecane, 100 mg of the catalyst, 12 ml of ethanol, P(H )= 5.0 MPa, T= 230 C, t= 6.0 h; DMF
:
5
2,5ꢀdimethylfuran; FDM : 2,5ꢀfurandimethanol; DHMTHF : 2,5ꢀdihydroxymethyltetrahydrofuran; MFA :5ꢀmethylfurfuryl alcohol; MF :
ꢀmethylfurfural.
5
0
5
0
5
0
5
5ꢀmethylfurfuryl alcohol (MFA) and 5ꢀmethylfurfural (MF)
from Figure 4 that the activity was quite low at lower temperature
such as 200 C, although the conversion of HMF reached to
98.6%, DMF yield was only 8.7% at this condition, and the main
products were MFA and FDM with yields of 61.9% and 18.1%,
o
which could be converted into DMF by further hydrogenolysis.
With increasing the Ni content to 10%, the yield of DMF
increased slightly to 74.2%, and there was still 21.8% MFA kept
unconverted (Table 2, entry 2). The yield of DMF reached to 45 respectively. MFA and FDM could be converted into DMF
1
1
2
2
3
3
85.9% when the Ni content was 15%, and only 10.6% MFA and
.9% MF were remained (Table 2, entry 3). In order to further
through the cleavage of CꢀO bonds, this result indicted that
hydrogenolysis of HMF was incomplete. Continue to increase the
0
o
improve the product yields, we synthesized catalysts with higher
Ni content. Nearly quantitative DMF (Table 2, entry 4) was
obtained using the LFꢀN20 as catalyst, which means that the
higher Ni contents afford for more active metal sites. However,
further increased the Ni contents in the catalysts resulted in
overꢀhydrogenation of HMF. When LFꢀN25 was used for the
hydrogenolysis of HMF, 2,5ꢀdihydroxymethyltetrahydrofuran
temperature to 210 C, the yield of DMF rose to 45.8%, showed
(
DHMTHF) was formed with a yield of 7.6%, and the yield of
DMF decreased to 86.0% with 5.6% MFA remained unconverted
Table 2, entry 5). The yield of DHMTHF reached to 18.1%
(
when LFꢀN30 was used for the hydrogenation of HMF, which
indicated more active Ni sites resulted in the overꢀhydrogenaion
(Table 2, entry 6). For comparison, the reaction using iron oxides
supported Ni and lanthanum oxides supported Ni (labeled as
FꢀN20 and LꢀN20, respectively) as catalysts were also
investigated, resulted in the yields 67.4% and 0% of DMF, which
proved that only the perovskite supported Ni particles was
responsible for the better yields. In the case of FꢀN20, 27.8%
MFA and 0.7% MF were the main byꢀproducts, which meant the
LFNꢀ20 was more efficient for the hydrogenolysis of CꢀO bonds
of MFA. And LaFeO (marked as LF) was also investigated for
3
the hydrogenolysis of HMF, DMF yield of 12.2% was obtained
suggestting low activity. And 36.5% 2,5ꢀfurandimethanol (FDM),
38.5% MFA and 2.9% MF were obtained, which indicated that
active Ni particles was necessary for the formation of DMF.
5
0
Fig. 4 Effect of different temperature on the conversion of HMF to DMF,
Reaction conditions: 1.0 mmol of HMF, 1.0 mmol of nꢀtetradecane, 100
mg of the LFꢀN20, 12 ml of ethanol, P(H
,5ꢀdimethylfuran; FDM : 2,5ꢀfurandimethanol; MFA :5ꢀmethylfurfuryl
alcohol; MF : 5ꢀmethylfurfural.
2
)= 5.0 MPa, t= 6.0 h; DMF :
3
.3 Effect of reaction temperature
2
55
Temperature is one of the important factors for the conversion of
HMF to DMF, so the effect of different temperature on the
hydrogenolysis of HMF was investigated. It could be confirmed
that higher temperature was necessary for the better activity. And
the yields of the main byꢀproducts MFA and FDM decreased to
4
0
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3
8.9% and 8.4%, respectively, which indicated that MFA and
was above 2 MPa, the conversions of HMF were >99%. Further
FDM might be the intermediates in this reation. In order to
increasing the H pressure to 3 MPa led to an improvement of
2
further improve the yield of DMF, we increased the reaction
temperature to 220 C, and 71.3% of DMF was obtained, 40 unconverted. To further improve the yield of DMF, reaction
DMF yield (79.7%), however, 12.6% of MFA still remained
o
5
however, FDM was completely converted and the yield of MFA
further decreased to 24.7%. The hydrogenolysis reaction reached
a maximum yield of 98.3% when the temperature reached to 230
under higher H pressure was investigated, and 87.9% of DMF
could be obtained under the pressure of 4 MPa. The yield of
2
DMF reached to nearly equivalent (98.3%) under a H pressure of
2
o
C, and the yield of MFA was only 0.7% at this point. Further
5 MPa. However, higher reaction pressure (e.g. 6 MPa) did not
o
increasing the reaction temperature to 240 C resulted in a slight 45 result in the higher yield of DMF, and 94.6% of DMF was
1
0
decrease of the DMF yield which might be attributed to the
hydrogenation of DMF to afford 2,5ꢀdimethyltetrahydrofuran
collected, which might be due to the hydrogenation of DMF. The
survey on the H2 pressure revealed that a relatively high H2
pressure (e.g. 5 MPa) was essential to afford DMF, however, too
high pressure was not always desired.
(DMTHF), suggesting that side reactions occurred at higher
temperature. The investigation on the reaction temperature
indicated that temperature had an important impact on the
products distribution and a proper temperature was necessary to
afford the highest yield of DMF.
50
3.5 Recyclability of the catalyst
1
5
3
.4 Effect of hydrogen pressure
Fig. 6 The recyclability of perovskite supported Ni catalyst. Reaction
conditions: 1.0 mmol of HMF, 1.0 mmol of nꢀtetradecane, 100 mg of the
o
LFꢀN20, 12 ml of ethanol, P(H
2
)= 5.0 MPa, T= 230 C, t= 6.0 h.
55
The stability of the catalyst is great importance for the
commercial application of the heterogeneous catalysts. To test the
stability of the perovskite supported Ni catalyst, the LFꢀN20
catalyst was collected by centrifugation after the reaction and
washed with ethanol for at least five times. Then the catalyst was
2
Fig. 5 Effect of H pressure on the hydrogenolysis of HMF to afford DMF,
2
0
Reaction conditions: 1.0 mmol of HMF, 1.0 mmol of nꢀtetradecane, 100
o
60 directly used for the next run. It could be informed from Fig. 5
that the catalyst maintained good activity for the hydrogenolysis
of HMF after used for five times. The yield of DMF after the fifth
run was still 90.2%, and a possible explanation for the decrease
of the DMF yield was the mass loss of the catalyst during the
mg of the LFꢀN20, 12 ml of ethanol, T= 230 C, t= 6.0 h; DMF :
2
,5ꢀdimethylfuran; FDM : 2,5ꢀfurandimethanol; MFA :5ꢀmethylfurfuryl
alcohol; MF : 5ꢀmethylfurfural.
The effect of hydrogen pressure on the hydrogenolysis of HMF
was investigated to better understand the reaction process. It
could be informed from Fig. 5 that the hydrogenolysis of HMF
could proceed even under relatively low hydrogen pressure.
When the reaction was carried out under a H pressure of 1MPa,
the conversion of HMF reached to 97.9%, and the yield of DMF
was 60.0%, the byꢀproducts were MFA (23.1%), FDM (11.6%)
2
3
3
5
0
5
65
washing process and the formation of byꢀproducts on the metal
sites of the catalyst, which is in accordance with the previous
27
reports .
.6 Mechanism
The main detected byꢀproducts for the hydrogenolysis of HMF
2
3
and MF (2.1%), which were not completely hydrogenolysed. 70 were FDM, MF and MFA. In order to establish the reaction
When the H pressure increased to 2 MPa, the conversion of
sequence, the effect of reaction time on the products distribution
for the hydrogenolysis of HMF was investigated. As showed in
Fig. 7, at the initial time of the reaction (e.g. 0.5 h), HMF was
almost completely converted (96.1%). However, the yield of
2
HMF was 98.9%, the yield of DMF slightly increased to 69.6%,
however, the yields of MFA and FDM decreased to 18.7% and
5.1%, respectively, which implied that high pressure favored the
hydrogenolysis of reaction intermediates. When the H pressure 75 DMF was just 8.3%, the main products were FDM (30.3%) and
2
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Journal Name, [year], [vol], 00–00
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Green Chemistry
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DOI: 10.1039/C6GC00432F
MFA (51.6%), it should be noticed that MF was detected with a
were obtained, respectively. DMF was also reacted under the
yield of 2.4% which meant that HMF was transformed into MF 40 same conditions and the recovery ration was 98.4%. Based on the
directly or indirectly during the hydrogenolysis process.
Prolonging the reaction time to 1.0 h resulted in the nearly
completely conversion of HMF, and the yield of DMF increased
to 31.3%. The yield of MFA reached a maximum (59.4%) during
above results, a possible reaction pathway was proposed, which
27
was similar to the previous reports (Fig. 8). HMF was converted
into FDM and MF through two distinctive ways: hydrogenation
of C=O bond and hydrogenolysis of CꢀO bond. Both of FDM and
5
0
5
0
the entire duration of the reaction, whereas FDM yield decreased 45 MF were transformed into the main reaction intermediate MFA
to 6.3%. Since FDM could be converted into MFA and DMF
through selectively cleavage of the CꢀO bond, therefore the
conversion of FDM to MFA and the hydrogenolysis of MFA to
DMF were the dominated processes during this period. The DMF
through the hydrogenolysis of CꢀO bond and hydrogenation of
C=O bond, respectively. And DMF was obtained through
hydrogenolysis of CꢀO bond of MFA.
1
1
2
Table 3 Hydrogenolysis of the reaction intermediates for the mechanism
a
yield increased to 53.4% when the reaction time was 2.0 h, 50 investigation
meanwhile MFA yield and FDM significantly decreased to
1.8% and 2.2%, respectively. When the reaction time was
Entry
Substrate
Conv. / %
DMF yield / %
4
1
2
3
4
FDM
MF
＞99
＞99
＞99
＞99
95.6
96.5
99.6
98.4
extended to 4.0 h, 81.5% of DMF was obtained, however, the
yield of MFA decreased to 14.9%, which suggested that MFA
was an important precursor to be converted into DMF. The yield
of DMF increased to 98.3% at a reaction time of 6.0 h, and the
yield of the main byꢀproduct MFA was only 0.7%. The yield of
DMF slightly decreased to 97.3% after further prolonging the
reaction time to 10.0 h, which indicated that DMF could existed
stably under this kind of reaction conditions.
MFA
DMF
Reaction conditions: 1.0 mmol of substrate, 1.0 mmol of
nꢀtetradecane, 100 mg of the LFNꢀ20, 12 ml of ethanol, P(H
2
)= 5.0
o
MPa, T= 230 C, t=6.0h.
Fig. 8 Possible reaction pathway for the hydrogenolysis of HMF
4
Conclusions
5
5
In conclusion, the hydrgenolysis of biomassꢀderived HMF into
DMF has been performed over perovskite supported Ni catalyst
system. Under optimized conditions, >99% conversion of HMF
with a high DMF yield (98.3%) was achieved. The perovskited
catalyst system showed a high stability, it kept the activity after
recycled for at least 4 times. The kinetic experiments revealed
that HMF was converted into MFA through the reaction
intermediates FDM and MF. The current research emphasized an
efficient perovskiteꢀbased catalyst system for transforming
biomassꢀderived platform compounds into bioꢀfuels.
60
65
Fig. 7 Effect of time on the conversion of HMF to DMF, Reaction
2
5
conditions: 1.0 mmol of HMF, 1.0 mmol of nꢀtetradecane, 100 mg of the
Acknowledgements
o
LFꢀN20, 12 ml of ethanol, P(H
2
)= 5.0 MPa, T= 230 C; DMF :
2
,5ꢀdimethylfuran; FDM : 2,5ꢀfurandimethanol; MFA :5ꢀmethylfurfuryl
This work was supported by the 973 Program (2012CB215305,
2012CB215306, 2013CB228103), NSFC (21325208, 21172209,
alcohol; MF : 5ꢀmethylfurfural.
2
1272050, 21402181, 21572212), CAS (KJCX2ꢀEWꢀJ02),
IPDFHCPST (2014FXCX006), CPSF (2014M561835), SRFDP
20123402130008), FRFCU (WK2060190025, WK2060190033)
and PCSIRT. Thanks for the support by
To further investigate the reaction mechanism, the reaction
intermediates FDM, MFA, and MF were hydrogenolysed.
Reactions using these substrates were carried out under the same
reaction conditions to verify that these intermediates could be
converted into DMF. As shown in Table 3, FDM, which was
obtained through the hydrogenation of C=O bond, could be
converted into DMF with a yield of 95.6%. HMF could be
transformed into MF through the cleavage of CꢀO and
subsequently hydrogenation of C=O to get MFA, both MF and
MFA were hydrogenolysed and high yields of 96.5% and 99.6%
7
0
3
0
(
the Program for Changjiang Scholars and Innovative Research Te
am in University of the Ministry of Education of China
75
and the Fundamental Research Funds for the Central Universities
WK 2060190040)
3
5
(
Notes and references
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Journal Name, [year], [vol], 00–00
|
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DOI: 10.1039/C6GC00432F
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Page 9 of 9
Green Chemistry
View Article Online
DOI: 10.1039/C6GC00432F
Hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran was performed
over perovskite type oxide supported Ni catalysts, 98.3% of 2,5-dimethylfuran was obtained.