The direct conversion of sugars into 2,5-furandicarboxylic acid in a triphasic system

Article abstract of DOI:10.1002/cssc.201500118

A one-pot conversion of sugars into 2,5-furandicarboxylic acid (FDCA) is demonstrated in a triphasic system: tetraethylammonium bromide (TEAB) or water - methyl isobutyl ketone (MIBK) - water. In this reaction, sugars are first converted into 5-hydroxymethylfurfural (HMF) in TEAB or water (Phase I). The HMF in Phase I is then extracted to MIBK (Phase II) and transferred to water (Phase III), where HMF is converted into FDCA. Phase II plays multiple roles: as a bridge for HMF extraction, transportation and purification. Overall FDCA yields of 78% and 50% are achieved from fructose and glucose respectively. You cant win if you dont tri: The one-pot conversion of sugars into 2,5-furandicarboxylic acid (FDCA) is demonstrated in a triphasic reactor. Sugars are first converted into 5-hydroxymethylfurfural (HMF) in Phase I, the HMF in Phase I is then extracted into Phase II and transferred to Phase III, where it is converted into FDCA. Overall FDCA yields of 78% and 50% are achieved from fructose and glucose, respectively.

Full text of DOI:10.1002/cssc.201500118

DOI: 10.1002/cssc.201500118
Communications
The Direct Conversion of Sugars into 2,5-Furandicarboxylic
Acid in a Triphasic System
[
a]
Guangshun Yi,* Siew Ping Teong, and Yugen Zhang*
[
24]
A one-pot conversion of sugars into 2,5-furandicarboxylic acid
FDCA) is demonstrated in a triphasic system: tetraethylammo-
nium bromide (TEAB) or water—methyl isobutyl ketone
MIBK)—water. In this reaction, sugars are first converted into
-hydroxymethylfurfural (HMF) in TEAB or water (Phase I). The
enzyme. The catalytic oxidization of HMF to FDCA is usually
conducted in basic environment. The reaction is very sensitive
(
[12,21]
to the purity of the HMF feedstock.
Acidic residues or
(
other impurities, such as humins, in newly prepared biomass-
derived HMF deactivate the catalyst in the HMF oxidization re-
5
[
21,25]
HMF in Phase I is then extracted to MIBK (Phase II) and trans-
ferred to water (Phase III), where HMF is converted into FDCA.
Phase II plays multiple roles: as a bridge for HMF extraction,
transportation and purification. Overall FDCA yields of 78%
and 50% are achieved from fructose and glucose respectively.
action.
As a result, prior to the second reaction step, sepa-
[12,21]
ration and purification of HMF are usually required.
This
multistep process inevitably leads to high costs, making the
price of FDCA less competitive than terephthalic acid. There-
fore, a more efficient process for the direct conversion of bio-
mass derivatives into FDCA is highly demanded.
The direct conversion of sugars to FDCA has been a great
challenge. Given the conditions for the two-step process are in
conflict with each other, Kroger et al. reported a one-pot con-
At the current rate of consumption, the world’s crude oil re-
[
1]
serves can only last for several more decades. Therefore there
is an urgent need to develop renewable and sustainable alter-
version of fructose to FDCA by using a specific membrane to
[
2–10]
[26]
natives for fuels and chemicals.
The use of renewable bio-
separate the reactor.
The reaction lasted for 7 days, with
mass, that is, lignocellulose, would be a good choice for the
a total FDCA yield of 25%. In another attempt, by Schuchardt
et al., cobalt acetylacetonate encapsulated in silica was used to
[
11–14]
production of biofuels and biochemicals.
Recently, the use
[27]
of biomass-derived 2,5-furandicarboxylic acid (FDCA) to replace
terephthalic acid for the production of polyethyene terephtha-
convert fructose to FDCA directly with a total yield of 72%.
However, the reaction was conducted in harsh conditions
(1608C, 20 bar of air) and no mechanistic details were report-
ed. Both processes used fructose as the starting material,
where glucose is a more favourable starting material owing to
its abundance and lower cost.
[
15]
late (PET) has received significant attention. PET is usually
used for the making of films, fibers, and in particular bottles
for the packaging of soft drinks, water, and fruit juices. The PET
bottle market alone amounts up to ca. 15 Mt per year, which is
ca. 5.9% of the total global plastics production and consumes
For the production of HMF from sugars, a two-phase reactor
[
16]
[28]
ca. 0.2% of the global energy supply. A furan-based polymer
poly(ethylene-2,5-furandicarboxylate) (PEF) was prepared from
biomass-derived FDCA, which has demonstrated comparable
system has been widely studied. In general, sugars are dehy-
drated to HMF in an aqueous layer with an acid catalyst,
where HMF was extracted in-situ to the organic layer. HMF
production has been demonstrated in biphasic systems with
[
15,17]
properties to petroleum-based PET.
The Coca Cola compa-
[11]
ny has collaborated with Avantium, Danone, and ALPLA to de-
glucose, fructose, and even starch and cellulose feedstock.
[
18]
velop and commercialize PEF bottles.
Their research has
Herein, we report a triphasic reactor, which can convert bio-
mass sugars to FDCA in one-pot. This reaction setup consists
of three phases (Phase I, II, and III) as illustrated in Scheme 1.
In the designed triphasic setup, sugars (fructose or glucose)
were first dehydrated to 5-hydroxymethylfurfural (HMF) in
Phase I. HMF was then extracted, purified, and transferred to
Phase III via a bridge (Phase II). Finally, HMF was converted to
FDCA in Phase III. With this setup, overall FDCA yields of 78%
shown that PEF bottles outperform PET bottles in many
[
18,19]
areas.
In view of this application, as well as its broad po-
tential as versatile platform chemical, FDCA is listed as one of
the top-12 value added chemicals from biomass by the US De-
[
20]
partment of Energy.
Biomass-derived FDCA is usually produced by a two-step
[
12,21]
process from sugars or biomass.
5-Hydroxymethylfurfural
(
HMF) was first prepared by acid dehydration of C6 sugars (like
[
22]
fructose and glucose) or cellulose. HMF was then oxidized to
[
11]
[1,23]
FDCA with stoichiometric oxidants,
metal catalysts,
or
[
a] Dr. G. Yi, S. P. Teong, Dr. Y. Zhang
Institute of Bioengineering and Nanotechnology
1 Biopolis Way, The Nanos
3
Singapore 138669 (Singapore)
E-mail: ygzhang@ibn.a-star.edu.sg
gsyi@ibn.a-star.edu.sg
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201500118.
Scheme 1. The triphasic system for the direct conversion of sugars to FDCA.
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Figure 1. A) The triphasic reaction setup, and B) FDCA yield vs reaction time.
Scheme 2. Triphasic reactors: Phase I (grey): TEAB or water, for the conver-
sion of sugar to HMF; Phase II (red): MIBK, for HMF extraction and transpor-
tation; Phase III (blue): water, for the conversion of HMF to FDCA.
smashed Amberlyst-15 were added into the reactor (Phase I).
Au Pd /HT catalyst, Na CO , and water were added to the other
8
2
2
3
side of the reactor (Phase III, right side of Figure 1a) and MIBK
was added on top of Phase I and Phase III. The reactor was
placed in an oil bath preheated to 958C, where oxygen gas
was bubbled into Phase III of the reactor throughout the reac-
tion. Aliquots of the solution from left and right sides of Pha-
se III were taken out and combined every 5 h for HPLC analy-
sis. Figure 1b shows the time study for FDCA yield. For the
first 10 h, FDCA yield increased almost linearly over time,
reaching a maximum overall FDCA yield of 78% at 20 h. After
which, the FDCA yield decreased slightly, which may be due to
the degradation of FDCA over prolonged reaction time.
and 50% were achieved from fructose and glucose, respective-
ly, in one pot.
Several types of triphasic reactors were designed and tested,
as shown in Scheme 2 and Figure S1 (Supporting Information).
Setup A is not robust enough for the reaction conditions. For
the HMF oxidization step in Phase III, the reaction was con-
ducted under O bubbling and stirring with solid Au Pd /HT
2
8
2
[
21]
catalyst. As the result, setup A failed to separate Phase I and
III completely. During this process, O2 bubbling in Phase III
brought the reaction solution as well as catalyst up to Phase I
and II. As a result, Phase I was interrupted and led to incom-
plete reaction. This also led to lower catalytic activity of
Au Pd /HT in Phase III. An H-type reactor was then designed,
To study the detailed kinetic process in this triphasic reactor,
step-by-step reactions were conducted. Firstly, the conversion
of fructose to HMF in TEAB was carried out based on a modi-
8
2
[29]
as shown in Scheme 2(B) and Figure S1 to avoid the phase
mixing issue. However, the HMF mass transfer efficiency was
low. Therefore, an improved setup C was designed as shown in
Scheme 2(C) where the problems observed in the previous
setups were eliminated. Reactions in Phase I and Phase III were
well-controlled and no mixing of reactants was observed. With
that, the triphasic setup C was used for optimization.
The one-pot conversion of fructose to FDCA in the triphasic
reactor was then conducted as shown in Figure 1A. 0.18 g
fructose (1 mmol), 0.91 g TEAB, 0.09 mL water, and 0.018 g
fied literature procedure at a lower reaction temperature of
958C. The selection of 958C in Phase I was in consideration of
the reaction in Phase III, where the optimized reaction temper-
[21,23a]
ature is 958C.
The conversion of fructose to HMF in TEAB
is a fast reaction. It was completed in 30 min with HMF yield of
86%, similar to Afonso’s results (reaction completed in
[29]
20 min). Concurrently, a control reaction was conducted in
a biphasic system, with 4 mL of MIBK as the extraction solvent.
As TEAB is immiscible with MIBK, a clear interface between
TEAB and MIBK was formed during the reaction. After 30 min
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at 958C, 0.6 mmol and 0.22 mmol of HMF were detected in
TEAB and MIBK, respectively, when 1 mmol of fructose was
used. The detected HMF distribution ratio between MIBK and
TEAB was about 1:2.7. In parallel, the conversion of HMF (pre-
pared from fructose and purified by a water extraction
A large triphasic reactor was also designed (OD=35 mm,
height=80 mm, plate separator height=20 mm, Figure S1) to
test for a scale-up reaction by a factor of 5. Under the same re-
action conditions, we have achieved 74% FDCA yield over
20 h. This shows the feasibility of a large-scale FDCA produc-
[
21]
[31]
method ) to FDCA was also conducted separately in 10 mL of
water, with Au Pd /HT catalyst and Na CO . The reaction was
tion using this triphasic reactor.
The direct conversion of glucose to FDCA in the triphasic re-
actor is challenging, however, more desirable as compared to
fructose. To convert glucose to HMF in Phase I, TEAB was used
8
2
2
3
conducted at 958C with O bubbling and completed in 7 h
2
[
21]
with an almost quantitative yield of FDCA.
Au Pd /HT is
8 2
a very efficient and robust catalyst for the conversion of HMF
as reaction media and Amberlyst-15/CrCl were selected as cat-
3
[
21,23a,30]
[32]
to FDCA,
however, from Figure 1, the whole process
alysts. CrCl is important for the isomerization of glucose to
3
from fructose to FDCA was completed at nearly 20 h, with
a total yield of 78%. This indicates that the bottleneck of the
reaction is the mass transfer of HMF from Phase I to Phase III
via MIBK, slowing down the whole process. HMF concentration
in Phase I and II at different reaction time further confirmed
the mass transfer limitation (Table S1, Supporting Information).
The reaction progress of the triphasic system was also moni-
tored by analyzing the FDCA yield in Phase III with HPLC. As
shown in Figure S2 (Supporting Information), the FDCA yield
was gradually increased from 5 h to 20 h and reached a maxi-
mum yield of 78% at 20 h. As shown in Figure 2a, only HFCA
fructose, and together with Amberlyst-15 made the system
[32]
more efficient in the dehydration of glucose to HMF. The
first attempt was conducted at 958C. However, after 7 h, only
negligible amount of FDCA was detected, with the glucose
conversion of only 7.2%. The low glucose conversion may be
due to the lower reaction temperature in Phase I. As reported
in the literatures, the conversion of glucose to HMF in TEAB
[29,31]
was conducted at 1208C.
Therefore, the experimental
setup was improved by tilting the reactor and heating only
Phase I at 1208C for 30 min. After that, the temperature was
lowered and the whole reactor was heated at 958C. With O2
bubbling in Phase III, the reaction proceeded smoothly and
50% FDCA yield was achieved with full glucose conversion, as
shown in Table 1.
[
a]
Table 1. The conversion of glucose into FDCA in a triphasic reactor.
Entry
Reaction time
h]
HFCA yield
[%]
FDCA yield
[%]
[
1
2
3
4
5
10
20
30
40
50
28
17
7
3
1
26
43
50
49
48
Figure 2. A) HPLC results for Phase III after 5 h reaction, and B) conversion
pathway from HMF to FDCA in Phase III.
[
a] Reaction conditions: 0.18 g glucose, 0.91 g TEAB, 0.09 g water, 18 mg
Amberlyst-15, 26.6 mg CrCl .6H O (10% mol), 0.25 g Au-Pd/HT catalyst,
0 mL water, 1 mmol Na CO . 1208C 30 min, then 958C for 0–50 h with
bubbling.
3
2
1
O
2
3
(retention time=24 min) and FDCA (retention time=21 min)
2
were detected in Phase III where no HMF was observed (reten-
tion time=37 min). As expected, high content of HMF was de-
tected only in MIBK (Phase II) and TEAB (Phase I). This indicates
that the conversion of HMF to FDCA occurs via HFCA (as
showed in Figure 2b) intermediate, and fast conversion from
HMF to HFCA was observed. This was attributed to the easy
In the current triphasic reactor, we have selected TEAB as
the reaction media for the conversion of sugars to HMF. The
reason for this selection is due to the relatively high HMF yield
(86% from fructose) that can be obtained under mild reaction
[
30]
[29,32]
oxidization nature of the aldehyde group of HMF. Once HMF
diffused to Phase III, it was quickly converted to HFCA, which
then converted to FDCA slowly. As a result, only FDCA and
HFCA were detected in Phase III during the process.
conditions (958C for fructose and 1208C for glucose).
Moreover, the price of TEAB is much lower as compared to imi-
[33]
dazolium salts. However, it would be advantageous if this re-
action can be carried out in water. Dumesic et al. has reported
a biphasic reaction system, using acid aqueous solution for
sugar dehydration reaction and an organic layer for HMF ex-
The mass movement in this triphasic reactor was rather
clear. In the reactor, fructose was converted to HMF which was
extracted to MIBK. HMF in MIBK was diffused to Phase III
where it was converted to HFCA and FDCA. HFCA and FDCA
are highly soluble in Phase III in the presence of Na CO , but
[28]
traction. Similarly, we have tested to use NaCl-saturated HCl
aqueous solution as the reaction media in Phase I in our tri-
phasic system. The reaction was conducted at 958C and an
overall FDCA yield of 41% was achieved, as shown in Table 2
below.
2
3
are insoluble in MIBK. Hence, the final product of FDCA was
only found in Phase III. As HMF was continually consumed in
Phase III, it drove the mass flow of HMF which led the overall
reaction to completion.
The low overall FDCA yield is due to the low HMF yield in
the current reaction system. In a typical HCl/MIBK biphasic
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on top of Phase I and Phase III. Oxygen gas was piped into the
bottom of Phase III through a Pasteur glass pipette (230 mm long
with open tip), with oxygen flow rate of 1 mLmin . Water was
Table 2. The conversion of fructose into FDCA in a triphasic reactor with
an aqueous solution as Phase I.
[
a]
À1
added if the water level decreased. The reaction was carried out
for 1–30 h.
Entry
Reaction time
HFCA yield
[%]
FDCA yield
[%]
[
h]
General reaction procedure for glucose to FDCA: In the triphasic
reactor, 0.18 g glucose (1 mmol), 0.91 g TEAB, 0.09 mL water,
1
2
3
4
5
13
15
3
12
26
41
38
10
20
30
0
.018 g smashed Amberlyst-15 and 0.027 g CrCl .6H O (0.1 mmol)
3 2
were added into the reactor (Phase I) 0.25 g Au Pd /HT catalyst,
1
8
2
0
.106 g of Na CO3 (1 mmol) and 10 mL of water were added to
2
[
a] Reaction conditions: 0.18 g fructose, 0.6 mL 0.25m HCl (NaCl saturat-
Phase III of the reactor. The reactor was tilted and Phase I of the re-
actor was heated to 1208C for 30 min under magnetic stirring.
After that, the reactor was placed in an oil bath pre-heated to
ed), 4 mL MIBK, 0.25 g Au-Pd/HT, 10 mL H O, 1 mmol Na CO , 958C.
2
2
3
9
58C, where MIBK was added on top of Phase I and Phase III.
Oxygen was bubbled into Phase III of the reactor, where water was
added if the water level decreased.
Product analysis: HMF and FDCA yields were analyzed by HPLC
(Agilent Technologies, 1200 series) and confirmed with isolated
[
28]
system, the HMF yield is ~50–70%, which was achieved in
a closed reactor under reaction temperature of 150–1808C.
The current triphasic system was an open system with a low
reaction temperature of 958C. In a control experiment, fructose
was converted in a similar open biphasic system at 958C and
only 48% HMF was obtained after 20 h reaction. It is clear that
the lower reaction temperature of Phase I lowered the HMF
yield in the water/MIBK system and eventually led to a lower
overall FDCA yield.
yields. HPLC working conditions: column (Agilent Hi-Plex H, 7.7ꢁ
À1
3
00 mm, 8 mm), solvent 10 mm H SO , flow rate 0.7 mLmin , 258C,
2
4
UV detector, 280 nm for HMF and 254 nm for FDCA and HFCA. The
retention times for detected compounds were 20.7 min, 24.4 min,
and 36.5 min for FDCA, HFCA, and HMF respectively. Fructose and
glucose conversions were measured using a Sugar Analyzer (DKK-
TOA Corporation, Japan. Model: SU-300). For sugar analysis, during
the reaction or after reaction, 10 ml of Phase I was taken out and
diluted in 1 mL water (100 times dilution). The sugar concentration
was measured with sugar analyzer. Before the measurement cali-
bration was conducted with standard solution as a system require-
ment. Sugar conversion was then calculated based on the testing
results.
In conclusion, a triphasic reactor that can convert sugars
into 2,5-furandicarboxylic acid (FDCA) in a one-pot process has
been demonstrated. Overall FDCA yields of 78% and 50%
were achieved with fructose and glucose feedstock, respective-
ly. Kinetic studies revealed that mass transfer of HMF from
Phase I to Phase III was the main bottleneck that impeded the
overall reaction. This bottleneck may be overcome by better
1
Characterization: The product was characterized by H and
13
C NMR (Bruker AV-400). Au Pd /HT catalyst was characterized by
8
2
[
31]
Phase II design.
TEM (FEI Tecnai F20) and XRD (PANalytical X-ray diffractometer,
X’pert PRO, with CuKa radiation at 1.5406 ꢂ). The characterization
results are shown in the Supporting Information (Figure S3 and
S4).
Experimental Section
Materials: d-Glucose and d-fructose were purchased from Alfa
Aesar. TEAB, HMF, FDCA, and Amberlyst-15 were purchased from
Sigma–Aldrich. MIBK was purchased from Merck. All the chemicals
were used directly without any pretreatment.
The triphasic reactor was custom-made by UFO Labglass (S) Pte
Ltd. Two sizes were made; the smaller one with OD=23 mm and
height=75 mm, and the larger one with OD=35 mm and
height=80 mm. Both reactors consist of glass plate separator with
height=20 mm. Pictures are shown in the Supporting Information,
Figure S1.
Acknowledgements
This work was supported by the Institute of Bioengineering and
Nanotechnology (Biomedical Research Council), Biomass-to-
Chemicals program (Science and Engineering Research Council),
Agency for Science, Technology and Research, Singapore.
Keywords: biomass · carbohydrates · extraction · phase-
transfer catalysis · renewables
Preparation of Au Pd /HT catalyst: Au Pd /HT was prepared
8
2
8
2
[21]
based on our previous work. Briefly, 0.1 mmol of HAuCl4 and
.025 mmol of NaPdCl were dissolved in 40 mL of water. To this
0
4
solution, 1 g of hydrotalcite was added, followed by addition of
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was vigorously stirred for 6 h and refluxed for 30 min at 373 K. The
resulting solid was filtered, washed thoroughly with water and
heated at 473 K overnight.
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reactor, 0.18 g fructose (1 mmol), 0.91 g TEAB, 0.09 mL water, and
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Received: January 22, 2015
Revised: February 17, 2015
Published online on && &&, 0000
ChemSusChem 0000, 00, 0 – 0
www.chemsuschem.org
5
ꢀ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

COMMUNICATIONS
G. Yi,* S. P. Teong, Y. Zhang*
You can’t win if you don’t tri: The one-
pot conversion of sugars into 2,5-furan-
dicarboxylic acid (FDCA) is demonstrat-
ed in a triphasic reactor. Sugars are first
converted into 5-hydroxymethylfurfural
(HMF) in Phase I, the HMF in Phase I is
then extracted into Phase II and trans-
ferred to Phase III, where it is converted
into FDCA. Overall FDCA yields of 78%
and 50% are achieved from fructose
and glucose, respectively.
&& – &&
The Direct Conversion of Sugars into
,5-Furandicarboxylic Acid in
2
a Triphasic System
&
ChemSusChem 0000, 00, 0 – 0
www.chemsuschem.org
6
ꢀ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!