Synthesis of maleic and fumaric acids from furfural in the presence of betaine hydrochloride and hydrogen peroxide

Article abstract of DOI:10.1039/c6gc02620f

Here we report the successful valorisation of furfural into maleic acid (MA) and fumaric acid (FA) with a total yield above 90% using an aqueous solution of betaine hydrochloride (BHC) in the presence of hydrogen peroxide. BHC can be recycled for at least 4 cycles and it can be used to directly convert xylose to MA and FA.

Full text of DOI:10.1039/c6gc02620f

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Synthesis of maleic and fumaric acids from furfural in the
presence of betaine hydrochloride and hydrogen peroxide
N. Araji,a D. D. Madjinza,a G. Chatel,a* A. Moores,b F. Jérômea and K. De Oliveira Vigiera*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Here we report the successfully valorisation of furfural into maleic pathways: (1) abstraction of hydrogen to produce furfural
acid (MA) and fumaric acid (FA) with a total yield above 90% using radical intermediate affording 4-hydroxyfurfural; (2)
an aqueous solution of betaïne hydrochloride (BHC) in the decarbonylation of furfural to furan, leading to 2-furanone as
presence of hydrogen peroxyde. BHC can be recyclable at least 4 an intermediate; or by (3) a Baeyer–Villiger oxidation of
cycles and it can be used to directly convert xylose to MA and FA.
furfural to furan-2-ol and then to MA through furan-2(5H)-one
intermediate. In all the proposed mechanism, bifunctional
catalysts are required to obtained MA and FA from furfural.
The catalytic aerobic oxidation of furfural was studied by Yin et
al. in the presence of phosphomolybdic acid catalyst (under 20
atm. of O2, at 383 K and during 14 h).8 In this study, 69% of
selectivity to MA was reached while the conversion of furfural
was 50% in the optimized conditions (i.e. 34% yield). In a
biphasic system, oxidation reaction occurred in the aqueous
phase while the organic phase constituted a reservoir to
gradually release the substrate through the phase equilibrium.
The same group reported the combination of
phosphomolybdic acid with copper nitrate to selectively
oxidize furfural into maleic acid with 51% selectivity and 95%
conversion of furfural.9 However, the recycling of this catalytic
system was not reported. Hydrogen peroxide has been also
used as an oxidant for the oxidation of furfural in the presence
of Cr(VI) and Mo(VI)-based catalysts,10 or acid catalysts such as
Amberlyst-15, Nafion NR50, Nafion SAC13, hydrochloric acid,
acetic acid, sulfuric acid or p-toluenesulfonic acid.11
A lot of studies are nowadays devoted to the catalytic
conversion of biomass to bio-based chemical platforms , which
can be further converted to a wide range of valuable
products.1 Among these renewable chemical platforms,
furfural, is one of the most important building blocks than can
be obtained from hemicellulose.2 From this building block,
catalytic oxidation affords a number of chemical intermediates
and end products.3 Most of the current studies focus on the
selective oxidation of furfural to diacids or anhydride acids
(succinic acid, fumaric acid (FA), maleic acid (MA) and maleic
anhydride). Owing to the fact that MA and FA are used as
important intermediates in the chemical industry, their
production is constantly increasing, the annual production of
MA and FA being 1,800,000 ton/year and 90,000 ton/year,
respectively. These two C4 dicarboxylic acids are involved in
the synthesis of copolymers, surface coatings, lubricant, food
and beverage additives, plasticizers, resins (paper, alkyd and
unsaturated polyester resins), and agricultural chemicals.4
Industrially, MA is produced via aerobic oxidation of benzene,
butane or butadiene.5 FA is essentially manufactured by
chemical conversion of maleic anhydride or biological
conversion by fungi.6 The production of MA was previously
investigated in aerobic conditions or in the presence of
hydrogen peroxide in liquid phase. The exact mechanism of
the reaction (role and nature of catalytic sites) are still under
discussion.7 MA can be synthesized from furfural via different
a.IC2MP UMR CNRS 7285, Université de Poitiers, ENSIP, B1, 1 rue Marcel Doré TSA
41105, 86073 POITIERS Cedex 9, France, E-mail : karine.vigier@univ-poitiers.fr
and gregory.chatel@univ-poitiers.fr
Scheme 1. Catalytic oxidation of furfural to MA and FA.
b.Centre for Green Chemistry and Catalysis, Department of Chemistry, McGill
University, 801 Sherbrooke St. W., Montreal, Canada.
In a previous study carried out in our group, reaction media
containing water and betaine hydrochloride (BHC), a co-
product of sugar beet industry, were used to produce i)
Electronic Supplementary Information (ESI) available: general procedure for the
syntheses of MA and FA and BHC characterization after the recycling.
See DOI: 10.1039/x0xx00000x
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furfural from hemicellulose and ii) 5-hydroxymethylfurfural the presence of an aqueous solution of 10 wt% of BHC, 12% of
(HMF) from fructose and inulin.12 High yield to furfural and to MA was observed after 30 min of reaction (Table 1, entry 1).
HMF were obtained and BHC was recyclable. Based on these Upon prolonged reaction time (up to 120 min) the yield of MA
results it was interesting to investigate the oxidation of furfural reached 29% along with a FA yield of 6% (Table 1, entries 2 and
to MA and FA in the presence of an aqueous solution of BHC 3). When the amount of BHC was increased up to 20 wt%,
and hydrogen peroxide.
similar yields were observed (Table 1, entries 4–6). However, a
Here we report that in a BHC/H2O2 system, MA and FA can be further increase of BHC content to 40 wt% afforded 56% of MA
obtained with a total yield of 92% (Scheme 1). BHC could be and 14% of FA (Table 1, entry 7). If the BHC amount was higher
recycled 4 times, and used to convert directly xylose to MA than 40 wt%., a decrease in the MA and FA yields was
and FA with a total yield of 21% from xylose (i.e. 35% of MA observed due to dominant side decomposition of furfural
and 8% of FA from furfural). These results are highly appealing (Table 1, entry 8).15 It can be concluded that an aqueous BHC
because (i) BHC contrary to homogeneous mineral acid was content of 40 wt% is optimal to produce FA and MA from
recyclable, (ii) BHC is readily available from biomass itself, and furfural with the highest yields. Moreover, “2-furanone was
the process no longer relies on the use of metals; (iii) access of detected in all the experiment suggesting that the reaction
MA and FA directly from a sugar in the form of xylose allows to mechanism could involve the in situ production of furan as
skip isolation of furfural. These promising results are very described previously.16 In order to confirm this hypothesis, 2-
encouraging for the valorization of furfural into valuable furanone was used as a substrate instead of furfural and after
acids.13
30 min under optimized conditions, only 6% of MA and 1% of
FA. A prolonged reaction time up to 17h led to an increase of
In a first set of experiments, 0.5 g of furfural was added to 5 g the conversion to 50% but only 3% of MA and 7% of FA were
of water containing 40 wt% of BHC (2g of BHC, pH = 1) in the observed. These results suggest that 2-furanone is not the
,
presence of 10 eq. of H2O2 (35 wt% aqueous solution). The main intermediate in the production of MA and FA from
reaction was carried out at for 2 h at 90°C. Yields and furfural using BHC and H2O2 aqueous solution.”
conversions were determined by HPLC using commercial Table 1: Effect of the BHC and H2O2 content, the reaction
standard. Interestingly, the conversion of furfural was total, temperature in the synthesis of FA and MA from furfural.
Yield (%)
and 44% of MA and 10% of FA were produced after only 30
min of reaction (Table 1, entry 7) along with 10% of FA and 5%
of 2-furanone. These results demonstrated that an aqueous
solution of BHC and H2O2 is capable of producing C4-
dicarboxylic acids from furfural. A kinetic study was then
performed (Figure 1).
H2O2
BHC
Time Conv.
Entry
T (°C)
2-
(eq.) (wt%.)
(min)
(%)
MA FA
Furanone
1
2
30
60
82
12
30
29
26
27
36
-
8
7
10
100
100
99
5
6
3
8
5
3
120
30
5
4
13
5
10
20
90
5
60
100
100
100
100
100
100
100
100
100
6
120
30
4
7
40
44 10
5
8
50
30
44
49
4
2
3
9
10
50
240
30
1
10
11
12
13
10
40
5
100
100
100
100
61 31
36 30
3
60
4
2
2
60
9
20
3
120
10 48
2
The effect of the reaction temperature was also studied (Table
1, entries 9 and 10). It was shown that a decrease of the
reaction temperature from 90 to 50 °C led to a similar yield of
MA yield (49% vs. 44%) while the yield of FA remained rather
low (2% at 50 °C). The reaction time was higher (240 min) at 50
°C than at 90 °C (30 min) to reach similar yield of MA.
However, the decrease of the reaction temperature inhibited
the formation of FA since the FA yield decreased from 14 to 2
% when going from 90 to 50 °C, the total yield (MA+FA) being
smaller at 50°C than at 90°C. An increase of the temperature
increases the selectivity to the C4 acids. This claim was further
supported by the increase of the reaction temperature up to
100°C which afforded 61% of MA along with 31% of FA. It can
be pointed out that at 100 °C a total yield of FA and MA over
90% was observed. If the amount of H2O2 is decreased from 10
to 5 eq., the yield to MA was decreased from 61 to 36% while
Figure 1. Oxidation of furfural (0.5 g) to MA and FA in the presence of 2,5 eq. of BHC in
5 g of water and 10 eq. of H2O2 at 90 °C (2-one: 2-furanone).
In these conditions, the furfural conversion was total and MA
was produced with 12% yield after 15 min of reaction. One can
note that after 30 min of reaction, the isomerization of the cis
isomer (MA) into the trans isomer (FA) occurred (Figure 1)
since It is known that in acidic conditions and with heating, the
reversible addition of proton leads to free rotation about
central C–C bond and formation of the more stable and less
soluble fumaric acid.14
The effect of the BHC content (Table 1, entries 1-8) was then
studied at 90 °C in the presence of 10 eq. of aqueous H2O2. In
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the yield to FA was similar, around 30%. A further decrease of performed without significant loss in MA and FA yields. After
1
the amount of H2O2 from 5 to 2 eq. led to a decrease of the the 6th recycling, BHC was recovered and analyze by H NMR
MA yield to 10% while the FA yield was increased up to 48%, and the pH of the aqueous solution of BHC was measured.
the main product formed being FA. These results show that Similar NMR spectra were obtained between fresh and used
H2O2 plays an important role in the isomerization reaction as BHC (Figure S1) and the pH was only 1. Moreover, titration of
well as in the selectivity of the reaction. The decrease of the chlorine in BHC was also performed and no change in chlorine
H2O2 content led to a decrease in the selectivity of the reaction content was observed between commercial BHC and
to MA and FA with an increase of the FA yield. In order to recovered BHC. These results show that BHC was not degraded
selectively produce fumaric acid, low amount of hydrogen during the reaction
peroxide and high reaction temperature are required.
To the best of our knowledge, this is the first time that such the conversion of xylose to furfural, we explored the direct
yields to MA and FA are reported in the literature.
transformation of xylose into MA and FA.12 To this end the
As we have established before that BHC was efficient towards
BHC is a strong organic acid, providing pHs around 1 under the dehydration of xylose to furfural was carried out in the
studied conditions. In order to understand the role of BHC in presence of 0.1 g of xylose and 1g of BHC and 5 mL of water at
the reaction, we compared its activity with two comparable 180 °C according to our previous results. A furfural yield of
inorganic acids, HCl and H2SO4. All the reactions were carried 48% was obtained after 60 min of reaction. The reaction media
out under reflux at 90 °C in the presence of 10 eq. of aqueous was cooled down to room temperature and 5.8 g of H2O2 was
H2O2 for 30 min.
added as well as 1 g of BHC. The reaction temperature was
increased up to 90 °C and 17% of MA along with 4% of FA
(yield in accordance with the xylose content) were observed
after 30 min of reaction.
Table 2: Comparison of BHC and HCl in the synthesis of FA and MA from furfural at 90
°C under reflux in the presence of 10 eq. of H2O2.
Entry
Acid
Yield (%)
MA
44
FA
10
2
1
2
3
BHC (pH~1)
HCl (pH~1)
H2SO4
35
30
7
Scheme 2. Synthesis of MA and FA from xylose in the presence of BHC and hydrogen
peroxide in a one pot two steps process
In a reaction test in absence of BHC, the pH was adjusted to 1
by addition of HCl or H2SO4 (Table 2, entries 2-3) before
reaction was performed. This reaction provided lower yields to
MA and FA compared to the ones observed in the presence of
BHC. These results suggest the main role of BHC is to act as a
strong acid.
It can be pointed out that if the yield of MA was calculated
from furfural produced from xylose, 35% of MA was obtained,
showing a similar yield that those observed from commercial
furfural, the BHC content in water being 40 wt%.
The recycling of the BHC was explored, to show the benefit of
using BHC instead of HCl (Figure 2). The recycling of BHC was
evaluated under optimized conditions 90 (100°C under reflux,
10 eq. of H2O2, 2g of BHC in 5 mL of water (40 wt% of BHC in
water).
Conclusions
Here, we have demonstrated that BHC can be used to
selectively convert furfural to maleic and fumaric acids, with
high yields (above 90%). BHC yields similar results than HCl,
but its main advantage relies on its recyclability. Particularly,
BHC was recyclable up tot 4th cycle without significant loss in
MA and FA yields. The analysis of the BHC after the recycling
study has shown that BHC was not decomposed during the
reaction proving the interest of this media for this reaction.
Moreover, BHC is capable of producing MA and FA directly
from xylose in a one pot two steps process, thus streamlining
the production of important industrial intermediates directly
from sugars.
Acknowledgement
Figure 2. Recyclability of BHC in the oxidation of furfural (0.5 g) to MA and FA in the
presence of 2.5 eq. of BHC in 5 g of water and 10 eq. of H2O2 at 100 °C.
The authors would like to thank the French Ministry of
National Education, Higher Education and Research as well as
the France-Canada Research Fund for the funding of the PhD
grant of NA. Funding from the International Consortium on
Eco-conception and Renewable Resources (FR CNRS INCREASE
After 30 min of reaction, BHC was recovered by precipitation
upon addition of acetone with high purity in the reaction
media. BHC was separated by filtration and reused as
collected. We were pleased to see that up to 6 cycles can be
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3707) is also acknowledged for its financial support for this
study.
References
1
(a) L. Hu, G. Zhao, W. Hao, X. Tang, Y. Sun, L. Lin, S. Liu, RSC
Adv., 2012, , 11184; (b) P. Gallezot, Chem. Soc. Rev., 2012,
41, 1538 ; (c) S. Dutta, S. De, B. Saha, M.I. Alam, Catal. Sci.
Technol., 2012, , 2025; (d) P. Gallezot, Catal. Today, 2007,
2
2
121, 76; (e) I. Agirrezabal-Telleria, I. Gandarias, P.L. Arias,
Catal. Today, 2014, 234, 42.
(a) J.P. Lange, E. van der Heide, J. van Buijtenen, R. Price,
2
3
ChemSusChem, 2012,
Kim, I.T. Hwang, N.J. Park, Y.K. Hwang, J.S. Chang, J.S. Hwang,
Biofuels Bioprod. Bioref., 2008, , 438 ; (c) K. Yan, G. Wu, T.
5, 150; (b) A.S. Mamman, J.M. Lee, Y.C.
2
Lafleur, C. Jarvis, Renew. Sustain. Energy Rev., 2014, 38, 663.
(b) R. Cao, C. Liu, L. Liu, Org. Prep. Proced. Int., 1996, 28
,
215; (c) M. Krystof, M. Perez-Sanchez, P. Dominguez de
Maria, ChemSusChem, 2013, , 826; (d) J. Lan, Z. Chen, J. Lin,
G. Yin, Green Chem., 2014, 16, 4351; (e) N. Alonso-Fagúndez,
6
I. Agirrezabal-Telleria, P.L. Arias, J.L.G. Fierro, R.
Mariscal,M.L. Granados, RSC Adv., 2014,
Alonso-Fagundez, M.L. Granados, R. Mariscal, M. Ojeda,
ChemSusChem, 2012, 1984; (g) H. Choudhary, S.
4, 54960; (f) N.
5,
Nishimura, K. Ebitani, Appl. Catal. A: Gen. 2013, 458, 55; (h)
F. Cherubini, Energy Convers. Manage. 2010, 51, 1412; (i) R.
A. Sheldon, Green Chem. 2014, 16, 950.
4
5
C. A. Roa Engel, A. J. J. Straathof, T. W. Zijlmans, W. M. van
Gulik and L. A. M. van der Wielen, Appl. Microbiol.
Biotechnol. 2008, 78, 379–388.
K. Lohbeck, H. Haferkorn, W. Fuhrmann and N. Fedtke,
Maleic and Fumaric Acids, Ullmann's Encyclopedia of
Industrial Chemistry, 2000.
6
7
Z. Zhou, G. Du, Z. Hua, J. Zhou and J. Chen, Bioresour.
Technol. 2011, 102, 9345–9349.
R. Wojcieszak, F. Santarelli, S. paul, F. Dumeignil, F. Cavani,
R.V. Gonçalves, Sustain. Chem. Process, 2015, 3, 9.
H. Guo and G. Yin, J. Phys. Chem. C 2011, 115, 17516.
S. Shi, H. Guo and G. Yin, Catal. Commun. 2011, 12, 731.
8
9
10 (a) L. A. Badovskaya, V. M. Latashko, V. V. Poskonin, E. P.
Grunskaya, Z. I. Tyukhteneva, S. G. Rudakova, S. A. Pestunova
and A. V. Sarkiisyan, Chem. Heterocycl. Compd. 2002, 38
,
1040–1048; (b) E. P. Grunskala, L. A. Badovskaya, V. V.
Poskonin and Y. F. Yakuba, Chem. Heterocycl. Compd. 1998,
34, 775–780.
11 H. Choudhary, S. Nishimura and K. Ebitani, Chem. Lett. 2012,
41, 409–411.
12 (a) F. Liu, F. Boissou, A. Vignault, L. Lemée, S.Marinkovic, B.
Estrine, K. De Oliveira Vigier, F. Jérôme, RSC Adv., 2014,4,
8836-28841 ; (b) K. De Oliveira Vigier, A. Benguerba, J.
Barrault and F. Jérôme, Green Chem. 2012, 14, 285
13 M. D. Sutton and J. B. D. Peterson, J. Sugar Beet Res. 2001,
38, 19–34.
14 K. Nozaki and R. Ogg Jr, J. Am. Chem. Soc. 1941, 63, 2583.
15 D. Montané, J. Salvadó, C. Torras and X. Farriol, Biomass
Bioenergy, 2002, 22, 295.
16 J. Lan, Z.i Chen, J.Lin, G. Yin, Green Chem. 2014, 16, 4351
.
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Graphical abstract
Maleic acid (MA) and fumaric acid (FA) was produced from furfural with a total yield above 90% in the presende of an
aqueous solution of betaïne hydrochloride (BHC) and hydrogen peroxyde. BHC can be recyclable and can be used to
convert xylose to MA and FA.