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Direct catalytic conversion of cellulose to levulinic acid (LA) by niobium-based solid acids and further
upgrading to -valerolactone (GVL) on a Ru/C catalyst were realized through sequential reactions in a
reactor. Firstly, using aluminium-modied mesoporous niobium phosphate as a catalyst, cellulose can be
directly converted to LA with as high as 52.9% yield in aqueous solution, even in the presence of the Ru/C
catalyst. To the best of our knowledge, this is the best result over a heterogeneous catalyst so far. It was
found that the type of acid (Lewis and Brnsted acids) and acid strength had an inuence on the yield of
LA; the doping of aluminium can enhance the strong Lewis and Brnsted acids, especially the strong
Lewis acid, thus resulting in the increase of LA yield from cellulose as well as from glucose and HMF. Such
an enhancement by a Lewis acid on LA yield from HMF was further conrmed by adding lanthanum
triuoroacetate [(TfO)3La], a strong Lewis acid, in the catalytic system (HCl, (TfO)3H, niobium phosphate),
Received 24th April 2014, indicating that a suitable ratio of Lewis/Brnsted acid is important for higher selectivity to LA from HMF, as
Accepted 1st June 2014
well as from cellulose. Then, after replacing N2 with H2, the generated LA in the reaction mixture can
DOI: 10.1039/c4gc00737a be directly converted to -valerolactone through hydrogenation over the Ru/C catalyst without further
www.rsc.org/greenchem separation of LA.
3846 | Green Chem., 2014, 16, 38463853 This journal is The Royal Society of Chemistry 2014
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similar to the above procedure except for the addition of a cal- stirring. N2 was used as a protective gas and kept at a pressure
culated amount of aluminium precursor, which was prepared of about 0.8 MPa. The zero time was taken when the Teflon-
by dissolving aluminium hydroxide in 10 mL of 1.5 M oxalic lined stainless steel autoclave was placed in the heating
acid solution. mantle under magnetic stirring, which had already been
heated to the set temperature. After reaction, the catalyst was
Characterizations collected by centrifugation and washed with water and ethanol
several times, and then dried at 100 C for 24 hours for the
Nitrogen adsorptiondesorption isotherms of the catalysts
next run. The supernatant liquid in the centrifugation tube
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3848 | Green Chem., 2014, 16, 38463853 This journal is The Royal Society of Chemistry 2014
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rate and enhance LA yield.13,14 Hence, in this work, the reac- Table 1 Chemical composition and BET properties of porous niobium
tion temperature was increased to 180 C, and ca. 40% yield of catalyst synthesized with dierent amounts of aluminium
LA was obtained after 24 h from 5 wt% cellulose solution cata-
SBET/ Pore size/
lyzed by mesoporous niobium phosphate. This yield of LA Catalyst m2 g1 nm Nb/at% Al/at% P/at%
was comparable with that of 38.6% using 0.9 mol L1 HCl as a
catalyst under 160 C from ca. 0.8 wt% cellulose solution14 and H-ZSM-5 318 0.55
NbOPO4 (A) 233 3.8 20.94 20.95
higher than those reported by R. Weingarten et al.,42 in which Al-NbOPO4 (B) 145 7.6 21.01 1.12 21.39
zirconium (ZrP) and tin (SnP) phosphates, or other solid acid Al-NbOPO4 (C) 102 7.3 18.98 2.12 20.82
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catalysts such as metal oxides and heteropoly acid containing Al-NbOPO4 (D) 50 9.6 17.45 2.49 18.61
Al, W, Zr, Cs and Sn were used as catalysts for glucose conver-
sion to LA under 160 C.25 Such an excellent performance may
be attributed to the unique Brnsted and Lewis acid property
of niobium phosphate.
Considering pure niobium phosphate with a high B/L
molar ratio (ca. 1.8), we would like doping of aluminium in
niobium phosphate to enhance Lewis acid because aluminium is
always considered as a strong Lewis acid site, and samples with
dierent amounts of aluminium were prepared using the same
method. The samples doped with 5 and 10% aluminium were
referred to as samples B and C; as a comparison, pure
niobium phosphate was named A. Another catalyst D was also Fig. 2 Py-FTIR spectra of catalyst A (a) and catalyst D (b).
prepared by lowering the amount of CTAB (ca. a quarter of the
initial on catalyst D) during the hydrothermal synthesis
process. ICP analysis and N2 sorption were conducted to inves-
tigate the change of the composition and structural para- Table 2 The weak/medium/strong acid sites amounts of catalysts A, B,
meters after aluminium introduction and the results are C and D calculated from pyridine adsorption infrared (Py-FTIR) spectra
presented in Fig. 1 and Table 1, respectively. It is found that
Niobium phosphate A B C D
the molar ratios of Nb/P in dierent samples were nearly the
same, close to 1, while the surface area decreased gradually Brnsted acid/ Weak 373473 K 113.0 127.9 109.3 122.4
with the doping of aluminium. The acidic properties (type, mol g1 Medium 473673 K 397.6 268.0 253.4 136.1
Strong >673 K 130.9 215.2 323.7 234.1
strength and amount) were also studied through pyridine Total 641.5 611.1 686.4 492.6
adsorbed infrared spectra (Py-FTIR) and the data are collected Lewis acid/ Weak 373473 K 68.2 57.9 51.7 31.2
in Fig. 2 and Table 2. It is found that the strong Brnsted and mol g1 Medium 473673 K 231.3 201.2 75.2 119.4
Strong >673 K 45.6 112.7 296.9 318.7
Lewis acid sites increased with increasing the amount of Al, Total 345.1 371.8 423.8 469.3
especially the strong Lewis acid sites, which increased from
45.6 to 296.9 mol g1, indicating that aluminium is indeed a
good strong Lewis acid centre, while the medium acid sites fer from a medium acid site to a strong acid site, which is
decreased with increasing the Al doping, maybe due to a trans- unclear till now.
The catalytic performances of various catalysts including
H-ZSM-5, a strong solid acid with a molar ratio of Si/Al = 25, in
the conversion of cellulose to LA are presented in Fig. 3. It can
be seen that the LA yield increased with the increase of alu-
minium amount in the catalyst, but the conversions of cellu-
lose are similar, all above 90%. This kind of tendency may
imply that the increase of strong Brnsted and Lewis acids by
aluminium doping will promote the generation of LA from
cellulose and the highest LA yield of 52.9% can be obtained by
using catalyst D, which contains 2.49% aluminium. This value
is 12% higher than that from pure mesoporous niobium phos-
phate as a catalyst, and 24% higher than that from H-ZSM-5.
Even though such a value of LA yield is still lower than that of
6070% from liquid acids (e.g., HCl) in the biphasic phase,9 it
is already much higher than those obtained from any other
kind of solid acid catalyst investigated so far. The analytical
data were the average from three repeated reactions, and the
Fig. 1 N2 adsorption/desorption isotherms of catalysts A, B, C and D. error was less than 1% compared with the average data.
This journal is The Royal Society of Chemistry 2014 Green Chem., 2014, 16, 38463853 | 3849
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SBET/ Pore
m2 g1 size/nm Nb/at% Al/at% P/at%
carbon in humins and soluble polymers are ca. 60% and 44%,
respectively, the former of which was separated and analyzed
by EDS and are shown in Table 3, and the latter was calculated
from the structure of humins41 and monomers of oligo-
saccharides. In addition, no lactic acid, HMF, glucose or other
small organic molecules were detected in the reaction solu-
Fig. 3 Cellulose conversion and LA yield from catalysts A, B, C, D, and
H-ZSM-5 (Al/Si = 1/25). Reaction conditions: 0.5 g of cellulose, 0.4 g of tion, and the main by-products are humins and soluble poly-
catalyst, 10 g of H2O, 180 C, 24 h. Calculated from the conversion of saccharides. According to previous studies,25,39 it is believed
anhydroglucose unit in cellulose. that small molecules, such as lactic acid would appear only
when there is not enough Brnsted acid in the reaction
system. Once again, the importance of the bonding between
Brnsted and Lewis acids is emphasized. It is also notable that
in the products distribution catalyzed by these four niobium-
based catalysts, the percentage of soluble oligomers and poly-
mers remains stable, and the increase of FA and LA would
result from the decrease of humins.
To investigate the influence of strong acidity, especially
strong Lewis acids on the selectivity/yield of LA, the LA selecti-
vity/yield from glucose and HMF catalyzed by these four cata-
lysts were investigated and compared with cellulose conversion
and presented in Fig. 5. In all cases, the conversion of all sub-
strates is above 95%. It is found that the LA yield from HMF
had the same tendency as that from cellulose, indicating that
the solid acid catalyst with more aluminium content, that is,
stronger Lewis acid sites could increase the LA yield. The
strong Lewis acid would enhance the selectivity to LA in HMF
conversion was never mentioned before and will be further
confirmed by using a strong liquid Lewis acid later. The result
from glucose has the same tendency, too, but conflicted with
the previous reports,25,39,43 especially the studies reported by
V. V. Ordomsky et al.,43 where the high molar ratio of B/L acid
would promote the formation of LA from glucose. This surpris-
Fig. 4 The distributions of carbon elements in the products by using
ing result may be due to the high B/L molar ratio (ca. 1.21.8)
various acid catalysts under the same conditions as in Fig. 3. Calculated
from the total number of carbon atoms. in niobium phosphate, much higher than those other reported
catalysts (lower than 1.0), so the addition of aluminium
increased the strong Lewis acid and thus enhanced the selecti-
The distribution of carbon element in the products was vity to LA from HMF. It means that there is a balance of Lewis
analyzed by HPLC and thermal analysis, and the result is pre- and Brnsted acids for the conversion of HMF/glucose/cellu-
sented in Fig. 4. Cellulose conversion is above 95% when lose to LA, not the higher B/L ratio, a better selectivity to LA.
using a niobium-based catalyst and 93% for H-ZSM-5, indicat- On the other hand, the final LA yield from glucose is lower
ing that cellulose can be fully converted using these solid acid than that from cellulose with all four catalysts. This may be
catalysts. The ratio of carbon atoms in formic acid and levuli- due to the side reactions during the conversion of glucose to
nic acid analyzed by HPLC is always 1 : 5 in solution (of equal HMF, which happens much easier at a high concentration of
molecule amounts), which is consistent with the report that glucose. While in the conversion of cellulose, glucose just
LA and formic acid are equimolarly produced. The contents of existed as an intermediate with very low concentration, which
3850 | Green Chem., 2014, 16, 38463853 This journal is The Royal Society of Chemistry 2014
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Acknowledgements
This project was supported financially by the NSFC of China
(no. 21101063 and 21273071), the Science and Technology
Commission of Shanghai Municipality (13520711400,
13JC1401902, 10dz2220500) and the Fundamental Research
Funds for the Central Universities, China.
3852 | Green Chem., 2014, 16, 38463853 This journal is The Royal Society of Chemistry 2014
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