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DOI: 10.1002/cssc.201300367

Waste Not, Want Not: Mild and Selective Catalytic


Oxidation of Uronic Acids
Frits van der Klis, Augustinus E. Frissen, Jacco van Haveren, and Daan S. van Es*[a]
Driven by growing concerns about climate change as well as
so is the importance of developing sustainable and effective
the decreasing availability of cheap fossil-based feedstocks, remethods for the production of resin-grade FDCA. Currently,
newable biomass is increasingly explored as alternative feedmost research efforts focus on the oxidation of 5-(hydroxymestock for the production of energy and chemicals. In order to
thyl)furfural (HMF), obtained by cyclodehydration of fructose
prevent undesirable competition with food supply, biomass
or glucose.[8] Although C6 sugars (such as glucose or fructose)
sources should preferably be restricted to nonfood crops (e.g.,
are the most abundant monomeric carbohydrates, they are
wood, grasses, jatropha, microalgae) and agrofood residues or
also an important food component, and as such subject to
waste from the food supply chain.[1] Furthermore, to minimize
ethics considerations. Therefore alternative feedstocks such as
waste and maximize economic viability a biorefinery approach
aldaric acids should be considered. These can be converted
should be followed, directed at the valorization of all available
into FDCA by acid-catalyzed cyclodehydration.[9]
components in a biomass feedstock stream. The conversion of
The preferred biobased feedstock for aldaric acid producbiomass into chemicals and building blocks (either existing
tion, pectins, are found in nondigestible hemicellulose fracones, so called drop-in replacement, or new biobased chemicals with unique structures) is
a crucial element in the transition towards a sustainable biobased economy.[2]
Aldaric acids are sugar acids
characterized by the formula
HOOC (CHOH)n COOH,
and
have very interesting properties
and applications. Although historically somewhat overlooked,
aldaric acids can serve as platform chemicals for a host of
high-value products, ranging
from sequestering agents[3] and
corrosion inhibitors[4] to monomers for polyaldaramides[5] and
-esters[6] (Scheme 1). Currently,
building blocks for condensation
polymers such as furan-2,5-dicarboxylic acid (2,5-FDA or FDCA)
attract considerable attention.
This furan diacid is increasingly
Scheme 1. Route from pectins/alginates to aldaric acids; derived products and main applications. Hydr. = hydrolypromoted as a biobased alterna- sis, [O] = oxidation, CDH = cyclodehydration.
tive to terephthalic acid (TA).[2a]
Recent reports show that FDCAtions. They are contained in the residues from agrofood probased polymers are in many aspects comparable or superior to
duction [e.g., sugar beet and chicory pulp and (citrus) fruit
their TA analogues.[7] As interest in furan polyesters is growing,
peels]. For example, in the EU alone in 2012 approx. 10 million
tonnes of sugar beet pulp (suppressed pulps reduced to 22 %
[a] F. van der Klis, Dr. A. E. Frissen, Dr. J. van Haveren, Dr. D. S. van Es
of dry matter) were produced, containing ca. 23 % of pectin
Food and Biobased Research
Wageningen University and Research Centre
sugars.[10] Pectins contain uronic acids (predominantly d-galacP.O. Box 17, 6700 AA Wageningen (The Netherlands)
turonic acid and d-glucuronic acid) and pentoses (predomiFax: (+ 31) 317-483011
nantly d-arabinose).[11] Interestingly, macroalgae such as brown
E-mail: daan.vanes@wur.nl
algae contain anionic polysaccharides called alginates, which
Supporting Information for this article is available on the WWW under
also mainly consist of uronic acids (predominantly d-mannurhttp://dx.doi.org/10.1002/cssc.201300367.
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onic acid and l-guluronic acid).[12] Macroalgae are currently
widely investigated as potential aquatic biomass source of carbohydrates and proteins. Uronic acids are sugar acids with an
aldehyde group at C-1 and a carboxylic acid group at C-6
(Scheme 1). While oxidation of these uronic acids would be
a simple route towards aldaric acids, the acid-sensitive nature
of, for example, d-galacturonic acid[13] prohibits the use of
standard sugar oxidation methods such as oxidation with
HNO3, used for example for the production of glucaric acid
from glucose.[14] To the best of our knowledge, only one process currently exists for the (small-scale) batch industrial production of galactaric acid; the electro-oxidation of d-galacturonic acid.[15]
Given the broad range of potential applications of aldaric
acids, there is a need for a new mild catalytic method for the
oxidation of uronic acids. In order for such a method to be sustainable and green, as well as industrially and economically
viable, various requirements have to be met: low temperature
(preferably no heating or cooling required); mild pH (avoid
substrate decomposition, as well as excessive salt production);
use of an efficient, selective, and recyclable catalyst (i.e., a heterogeneous oxidation catalyst); efficient down-stream processing (DSP); the use of an environmentally benign cost effective
solvent (preferably water); and the use of a cheap, waste-free
oxidant (like O2 or compressed air). Herein, we report a mild,

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selective and highly atom-efficient catalytic oxidation of uronic
acids to the corresponding aldaric acids using supported gold
catalysts.
Supported gold catalysts have proven effective in various
carbohydrate oxidation reactions.[16] Hence, we started our investigations on the oxidation of d-galacturonic acid by screening commercially available supported gold catalysts: Au/TiO2,
Au/Al2O3, and Au/ZnO. Previous work on glucose oxidation has
shown that reactivity as well as product selectivity are optimal
in the pH range 79.[17] Given the sensitivity of galacturonic
acid towards high base concentrations as well as the desire to
minimize the amounts of salts formed in the process, we initially used a base concentration of 0.1 n, corresponding to
1 equiv base relative to the galacturonic acid substrate. By performing the reactions in D2O/NaOD, we were able to conveniently follow the reaction progress by 1H NMR spectroscopy. Initial tests using Au/TiO2 showed that at 1 bar O2 pressure full
conversion of the starting material was obtained in 3 h at RT,
with the selective formation of galactaric acid and negligible
formation of byproducts as was observed by 1H NMR spectroscopy and confirmed by HPLC analysis (see Figure 1, and
Table 1, entry 1).
A control experiment performed in the absence of base
showed no conversion of the starting material even after 5 h,
proving that base is required, yet 1 equiv is sufficient for the

Figure 1. 1H NMR spectra in D2O/NaOD: a) 0.1 m d-galactaric acid reference; b) reaction mixture 0.1 n NaOD 3 h. HPLC (UV, 210 nm): c) d-galactaric acid reference; d) reaction mixture 0.1 n NaOD 3 h.

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Table 1. Oxidation of sodium galacturonate over various catalysts; effects


on conversion and selectivity.[a]
Entry

Catalyst

Base
[equiv]

t
[h]

pO2
[bar]

Conv.[b]
[mol %]

Select.[b]
[mol %]

1
2
3
4
5
6
7
8
9
10
11

Au/TiO2
Au/TiO2

TiO2
ZnO
Al2O3
Au/ZnO
Au/Al2O3
Pd/Al2O3
Pt/Al2O3
Ru/Al2O3

10
1
1
1
1
1
1
1
1

3
5
5
3
3
3
3
3
3
3
3

1
3
3
1
1
1
1
1
1
1
1

> 99

> 95
> 99

97

96
96

for a 3rd run. All reaction mixtures were analyzed by 1H NMR


spectroscopy. This showed that the catalyst remained highly
active over these 3 runs, as was apparent by the almost complete conversion to galactaric acid during all the reactions (see
Table 2 and Supporting Information).

Table 2. Catalyst stability (3 consecutive runs) for the oxidation of


sodium galacturonate over Au/TiO2.[a]
Run

Conversion
[mol %][b]

Selectivity
[mol %][b]

1
2
3

> 99
98
97

97
97
95

[a] Reaction conditions (75 mL pressure reactor): sodium galacturonate


(1.0 mmol), catalyst (0.2 mol % metal on support), 10 mL D2O, 500 rpm,
RT. [b] Conversion of substrate and selectivity towards disodium galactarate determined by 1H NMR spectroscopy.

[a] Reaction conditions (75 mL pressure reactor): sodium galacturonate


(1.0 mmol), catalyst (0.2 mol % Au/TiO2), 10 mL D2O, 500 rpm, RT. [b] Conversion of substrate and selectivity towards disodium galactarate determined by 1H NMR spectroscopy.

reaction to proceed smoothly (Table 1, entry 2). In the absence


of catalyst none of the starting material was converted after
5 h, even when the amount of base was increased to 10 equiv
(entry 3). In the presence of the support materials only (TiO2,
ZnO, and Al2O3), again no starting material was converted (entries 46). These experiments confirm the catalytic activity of
the supported gold nanoparticles (Scheme 2).

Whereas the results thus far are encouraging, an assessment


of the technical viability of the process still requires more data
on several process parameters. Although the in situ NMR experiments and HPLC analysis indicate high yields (i.e., conversion + selectivity), confirmation is required by quantitative isolation. In order to minimize mass losses due to small-scale
work-up, 6 reactors were used in parallel under our standard
conditions (Au/TiO2, 1 bar O2, 0.1 n NaOH, RT). Because the reaction under these conditions gives selective formation of galactarate, the reaction progress was monitored by O2 consumption. After completion of the reaction after 4 h, the reaction
mixtures were combined, filtered, acidified to pH 23 with HCl,
and the product was left to precipitate overnight at 4 8C. In
this way 4 g (ca. 80 mol %) of high-purity (> 97 %) galactaric
acid was isolated. Since a recovery experiment using galactaric
acid disodium salt at the same scale gave a mass recovery of
87 %, the actually isolable yield should amount to almost 92 %
or higher, after optimizing the conditions.
In addition, we investigated the possibility to use compressed air as oxidizing agent, since the use of high-pressure
oxygen on industrial scale can be considered undesirable from
both a hazard as well as a cost point-of-view. Running the reaction under 5 bar synthetic air pressure (i.e., 1 bar O2 partial
pressure) for 3 h at RT (0.1 n NaOH) gave full conversion to
galactaric acid, with negligible byproduct formation, comparable to 1 h under 1 bar O2.
While working under elevated pressure is common industrial
practice, it would be even more desirable to work under atmospheric pressure. Hence, oxidation of sodium galacturonate
was conducted in normal glassware by bubbling O2 through
the reaction mixture (ca. 100 mL min 1) at RT. After 3 h the reaction was complete, with 97 % selectivity (NMR) towards galactaric acid. A similar experiment conducted with synthetic air
gave comparable conversion and selectivity after 3 h.
In order to obtain further insight into the process window
and selectivity of the reaction, next the base concentration
was increased. Based on the previous experiments without

Scheme 2. Oxidation of d-galacturonic acid to galactaric acid by supported


gold catalysts. s = support material.

The unique catalytic properties of the supported gold catalysts in this oxidation reaction became apparent after comparison to other catalysts. Whereas no significant differences were
found between the performances of the three different supported gold catalysts (Table 1, entries 1, 7, and 8), surprisingly
no conversion was found when using either Pd, Pt or Ru supported on alumina (under our optimized conditions), in contrast to previous results using, for example, arabinose as substrate.[16a]
For the Au/TiO2 catalyst, catalyst recyclability was investigated by performing 3 consecutive runs (0.1 m d-galacturonic
acid, 1 equiv NaOD base, 3 bar O2, RT, 3 h). The first run was
performed by running 3 parallel reactions using 1 mmol d-galacturonic acid. After this run, the catalysts were combined,
washed, and dried, and re-used for the 2nd run, which was performed in 2 parallel reactions. Again the catalysts were combined, washed, and dried, and the recovered catalyst was used
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base (Table 1, entries 1 and 2) it was expected that a further increase of the base concentration might also lead to an increased reaction rate. Although the reaction proceeds highly
selective under mild conditions, it was found that increasing
the base concentration from 0.1 n to 1.0 n resulted in lower
selectivity towards galactaric acid, as was evident by additional
proton resonances at 1.9 and 3.3 ppm, whose intensity increased over a period of 4 days at the expense of the galactaric acid signals. A control experiment starting from a 0.1 m solution of galactaric acid under identical conditions (1 n NaOD,
0.2 mol % Au/TiO2, 3 bar O2, RT) already showed significant,
and apparently selective conversion to a secondary product
after 5 h (see Supporting Information), indicating that the desired product is unstable under the reaction conditions.
Prolonging the reaction time to 96 h showed 1H NMR resonances indicative of sodium acetate (d = 1.90 ppm,[18] and acetone
(d = 2.15 ppm see Supporting Information) at 1 n NaOD. Due
to extensive HD exchanges, signal-to-noise ratios are low,
making it difficult to exactly identify the secondary/tertiary
products. 13C NMR analysis of a concentrated solution of degraded galactaric acid confirmed the presence of sodium acetate (d = 181.4 ppm, and d = 23.3 ppm, see Supporting Information), and indicated the presence of sodium oxalate (d =
168.3 ppm). In order to have an alternative identification
method for the observed (secondary) products, HPLC analysis
was performed on these samples (see Supporting Information).
Furthermore, reactions were run in H2O to allow for HPLC-MS
analysis (avoiding problems due to HD exchange). HPLC-MS
analysis of the reaction mixtures confirmed the formation of
galactarate and the presence of acetate and oxalate in the
samples. Additionally, small amounts of other compounds such
as tartronic acid, glyceric acid, glycolic acid, and formic acid
were detected. These secondary products probably result from
a combination of (base-catalyzed) dehydrations, decarboxylations, and retro-aldol reactions, followed by oxidation of reactive intermediates and further decomposition (see Scheme 3
for suggested pathways).
While the suggested intermediate alpha-keto acids shown in
Scheme 3 are probably stable in basic solution, they are highly

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reactive in the presence of hydrogen peroxide, readily undergoing decarboxylation.[19] Under our reaction conditions H2O2
is believed to be formed as intermediate reaction product.[20]
Remarkably significant differences between the three supports used for the gold catalysts are observed when the intended product (galactaric acid) was exposed to oxidizing conditions at high base concentration (10 equiv) for prolonged
time. Whereas Au/TiO2 and Au/Al2O3 showed acetate (d =
1.90 ppm, Figure 2) as the main degradation product, Au/ZnO
gave rise to a different secondary product at d 3.32 ppm,
which was identified as methanol (see Figure 2). Although the
exact reaction pathway to methanol is unknown, it might
result from the (oxidative) decarboxylation of acetic acid.[21]
As the work in this paper is part of a biorefinery programme
directed at the valorization of sugarbeet pulp in nonfood applications, it is important to obtain insight into the influence of
other beet pulp components on the uronic acid oxidation.
Since sugar beet pulp also contains significant amounts of arabinose, we investigated the influence of (residual) arabinose
on the catalytic oxidation of galacturonic acid by the Au/TiO2
catalyst.
Mirescu et al. already reported the selective (> 99.5 %) oxidation of arabinose using a gold catalyst, albeit in somewhat different conditions (0.01 m arabinose, 0.45 % Au/TiO2, 40 8C, pH 9,
O2 continuous flow 500 mL min 1).[16a] Also the group of Murzin
reported the oxidation of l-arabinose using several types of
supported gold catalysts (0.1 m arabinose, 0.45 % Au/TiO2, 60
70 8C, pH 8, O2 continuous flow 2.5 mL min 1 diluted in
17.5 mL min 1 N2).[22] When we tested both l- and d-arabinose
under our conditions (0.1 m arabinose, 1.2 % Au/TiO2, 0.2 mol %
Au, 1 bar O2, 0.1 n NaOD, 10 mL D2O, RT) complete conversion
of the substrates was observed in 3 h, with a high selectivity
towards arabinonic acid (> 97 %). Comparable results were obtained when the reaction was performed in normal glassware
under a continuous flow of oxygen. The next step was to combine both types of pectin derived substrates, that is, d-galacturonic acid (sodium salt) and l-arabinose. Subjecting this mixture in a 1:1 molar ratio to our standard conditions for 5 h
showed incomplete conversion (> 85 %) with by-product for-

Figure 2. 1H NMR spectra in D2O/NaOD. 0.1 m d-galacturonic acid, reaction mixture 1.0 n NaOD 72 h RT over a) Au/TiO2, and b) Au/ZnO.

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mation over time (see Supporting Information). For comparison; oxidation of sodium d-glucuronate under standard conditions also showed incomplete
conversion (> 85 %) after 5 h, yet
with high selectivity (> 98 %, see
Supporting Information). Whereas Zope et al. reported a strong
catalyst inhibition effect of sugar
acids (glyceric acid, xylonic acid
and gluconic acid) in the gold
catalyzed oxidation of glycerol
to glyceric acid, the apparently
higher reactivity of the aldehyde
group in uronic acids reduces
the influence of possible chelating effects.[23] Further investigations toward the product degradation mechanism, substrate selectivity, selectivity towards feedstock composition, and catalyst
stability are currently in progress.
In conclusion, we have successfully developed a mild,
highly selective method for the
catalytic oxidation of uronic
acids. The application of highly
effective supported gold catalysts and air as oxidant allow for
the further development of an
industrially viable continuous
process. Preliminary results on
a mixture of pectin constituents
show that conversion and selectivity are largely maintained.
Hence, this procedure is a valuable new contribution to the valorization of agrofood residues
and the development of biobased chemicals.

Experimental Section

Scheme 3. Suggested network of secondary reactions. The presence of the compounds in frames was confirmed
by HPLC or NMR spectroscopy.

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Reactions were performed in


a Parr MRS5000 parallel reactor
system (6  5 mL, Hastelloy C-276)
equipped with glass liners and
magnetic stirring. The reagents
were dissolved in NaOD/D2O or
NaOH/H2O and the resulting clear
solutions were transferred to the
glass liners. Next, the catalyst was
added (catalyst extrudates were
pulverized in a mortar to a fine
powder) and the reactors were
closed. Subsequently, the reactors

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were flushed 3 times with O2 or synthetic air at 3 bar. Next the reactors were pressurized to the desired O2 or synthetic air pressure,
and magnetic stirring (500 rpm) was started. After the desired reaction time, samples of the reaction mixture were taken to determine
the conversion. Samples were filtered over a 0.45 mm Minisart NML
syringe filter to remove the catalyst and 1H NMR spectra were measured without any further work-up.
See the Supporting Information for detailed experimental procedures.

Acknowledgements
The authors would like to thank R. P. Purushothaman and A. van
Zeeland for the HPLC-(MS) analysis and Royal Cosun B.V. for its
technological and financial support. This project is jointly financed by the European Union, European Regional Development
Fund and The Ministry of Economic Affairs, Agriculture and Innovation, Peaks in the Delta, the Municipality of Groningen, the
Provinces of Groningen, Frysln and Drenthe as well as the
Dutch Carbohydrate Competence Center (CCC WP10).
Keywords: gold heterogeneous catalysis oxidation
pectins renewable resources
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Received: April 19, 2013
Revised: June 27, 2013
Published online on August 12, 2013

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