DOI: 10.1002/cssc.201600116
Communications
Conversion of Xylose to Furfuryl Alcohol and
2-Methylfuran in a Continuous Fixed-Bed Reactor
Jinglei Cui,[a, b] Jingjing Tan,[a, b] Xiaojing Cui,[a] Yulei Zhu,*[a, c] Tiansheng Deng,[a]
Guoqiang Ding,[c] and Yongwang Li[a, c]
An efficient process was designed for the synthesis of furfuryl
alcohol and 2-methylfuran from xylose using a continuous
fixed-bed reactor over a catalyst combining Hb zeolite and Cu/
ZnO/Al2O3 in g-butyrolactone (GBL)/water as solvent. The coop-
erative effect of Hb zeolite and GBL facilitated the dehydration
of xylose and enhanced largely the furfural yield. The produc-
tion of furfuryl alcohol and 2-methylfuran can be simply tuned
by changing the hydrogenation temperature for furfural over
the Cu/ZnO/Al2O3 catalyst. The yield for furfuryl alcohol
reached 87.2% at 1508C whereas a yield of 86.8% was ach-
ieved for 2-methylfuran at 1908C.
dehyde emission.[8] The current industrial production processes
of FFA and 2-MF from biomass resources contain several steps.
Specifically, furfural is produced from the dehydration of pen-
tose (xylose) in hemicellulose over mineral acid catalysts and
the further hydrogenation of the carbonyl bond (C=O) in furfu-
ral yields FFA; 2-MF, on the other hand, can be obtained
through the hydrogenolysis of FFA (Scheme 1). Compared with
the multi-step process, the efficient conversion of xylose to
FFA or 2-MF using a one-step method is promising as it is
more economical and the energy-intensive separation of furfu-
ral is not necessary. Although many efforts have been made to
improve the efficiencies of the separate steps in the multi-step
process, those to enhance the efficiencies of the direct conver-
sion of xylose to FFA and 2-MF are scarce. Particularly, the con-
trollable production of FFA and 2-MF from xylose still remains
a challenge. Perez and Fraga investigated the one-pot produc-
tion of FFA from xylose over combined Pt/SiO2 and sulfated
ZrO2 catalysts in a batch reactor, and a considerable yield of
51% for FFA was obtained.[7] Ordomsky et al. reported the de-
hydration of xylose and the consecutive furfural hydrogenation
over Amberlyst-15 and a Ru/C catalyst, and the main product
was tetrahydrofurfuryl alcohol with a selectivity of 50% at
a xylose conversion of 32%.[9] Several problems are faced for
the direct conversion of xylose using a batch reactor. One
problem is that besides contacting with the first catalyst (the
acid catalyst), xylose molecules have equal possibilities to con-
tact with the second catalyst, that is, the hydrogenation cata-
lyst. In this case, xylose is readily converted into xylitol over
the hydrogenation catalyst, which cannot be converted to fur-
fural.[9] Another problem is that a longer reaction time is usual-
ly required in the batch reactor compared with that in the con-
tinuous reactor, which would inevitably promote the side reac-
tions between xylose, xylose dehydration intermediates ,and
FFA.[10] All these problems would lead to a complexity in the
product distribution and a large reduction in the yield for the
overall process. It would be, therefore, more desirable but
highly challenging to develop a more efficient process to pro-
duce FFA and 2-MF directly from xylose with improved overall
yield under mild reaction conditions.
With the growing requirement of fuels and chemicals, the
strategies to cope with the depletion of fossil resources and
environment pollution become increasingly important.[1] The
utilization of biomass resources is considered as a beneficial
solution due to their renewable and abundant nature.[2] One of
the key strategies for biomass utilization is to convert the bio-
mass-derived carbohydrates to platform chemicals, followed
by the transforming of these platform chemicals to fuels and
fine chemicals.[3] Among the various pathways for carbohy-
drate conversions, the conversion of xylose to furfural and the
subsequent hydrogenation of furfural have been identified as
a promising route in industry.[4]
As one of the top-value platform chemicals, furfural is the
feedstock for many valuable chemicals, including furfuryl alco-
hol (FFA), 2-methylfuran (2-MF), tetrahydrofurfuryl alcohol, and
2-methyltetrahydrofuran.[5,6] More than 50% of furfural is con-
sumed to produce FFA, which is an important monomer in the
polymer industry.[7] 2-MF is considered as a promising liquid
fuel as it has several excellent properties such as comparable
energy density, better knock suppression ability, and lower al-
[a] Dr. J. Cui, Dr. J. Tan, Dr. X. Cui, Prof. Y. Zhu, Dr. T. Deng, Prof. Y. Li
State Key Laboratory of Coal Conversion
Institute of Coal Chemistry
Chinese Academy of Sciences
Taiyuan 030001 (P.R. China)
Fax: (+86)351-7560668
Herein, an efficient process was designed to produce FFA
and 2-MF from xylose under mild conditions. The efficient pro-
duction of FFA and 2-MF can be realized through the utiliza-
tion of a continuous fixed-bed reactor system over a catalyst
utilizing a combination of acidic Hb zeolite and Cu/ZnO/Al2O3
in a mixture of g-butyrolactone (GBL)/water as solvent. The
production of FFA and 2-MF can be simply tuned by changing
the hydrogenation temperature for furfural. Interestingly, a co-
[b] Dr. J. Cui, Dr. J. Tan
University of Chinese Academy of Sciences
Beijing, 100049 (P.R. China)
[c] Prof. Y. Zhu, Dr. G. Ding, Prof. Y. Li
Synfuels China Co. Ltd.
Beijing (P.R. China)
Supporting Information for this article can be found under http://
ChemSusChem 2016, 9, 1259 – 1262
1259
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