High Catalytic Performance of Aquivion PFSA, a Reusable Solid Perfluorosulfonic Acid Polymer, in the Biphasic Glycosylation of Glucose with Fatty Alcohols

Article abstract of DOI:10.1021/acscatal.6b03561

The catalytic performance of Aquivion PFSA, a solid superacid, was investigated in the catalytic glycosylation of glucose with fatty alcohols. Four main criteria were considered to evaluate the catalytic performance of Aquivion PFSA: (1) the selectivity of the reaction, (2) the turnover frequency, (3) the reactor productivity, and (4) the catalyst stability/recycling. To shed light on the catalytic performance of Aquivion PFSA, it was systematically compared to H₂SO₄, which is industrially employed in such reactions. We discovered that Aquivion PFSA surpassed the catalytic performance of H₂SO₄ in terms of activity, selectivity, and reactor productivity. In particular, Aquivion PFSA selectively converted glucose to alkyl polyglucosides (DP = 1.2) with 85% yield, which corresponded to a reactor productivity as high as 477 kg/(m³ h). Conversely to H₂SO₄, Aquivion PFSA was also capable of selectively producing alkyl polyglucosides directly from glucose syrup, a cheap source of glucose. This result was ascribed to the amphiphilic nature of Aquivion PFSA, which facilitated the Pickering-like emulsification of the biphasic reaction medium. Finally, owing to its high chemical and mechanical properties, Aquivion PFSA was highly stable under our working conditions and could be recycled at least 10 times without obvious loss of its catalytic performance.

Full text of DOI:10.1021/acscatal.6b03561

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Article
High catalytic performances of Aquivion® PFSA, a
reusable solid perfluorosulfonic acid polymer, in the
biphasic glycosylation of glucose with fatty alcohols
Ayman KARAM, Karine De Oliveira Vigier, Sinisa Marinkovic,
Boris Estrine, Claudio Oldani, and François Jerome
ACS Catal., Just Accepted Manuscript • Publication Date (Web): 15 Mar 2017
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High catalytic performances of Aquivion® PFSA, a
reusable solid perfluorosulfonic acid polymer, in the
biphasic glycosylation of glucose with fatty alcohols
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Ayman Karam,a Karine De Oliveira Vigier,a Sinisa Marinkovic,b Boris Estrine,b Claudio Oldanic
and François Jérôme*a
a Institut de Chimie des Milieux et Matériaux de Poitiers, CNRS/Université de Poitiers, 1 rue
Marcel Doré, ENSIP, TSA 41105 86073 Poitiers cedex 9 (France).
b ARDꢀAgroꢀindustrie Recherches et Développements, Green Chemistry Department, Route de
Bazancourt, Fꢀ51110 Pomacle, France
c Solvay Speciality Polymers, Viale Lombardia 20, 20021 Bollate MI, Italy
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ABSTRACT: The catalytic performances of Aquivion PFSA, a solid super acid, were
investigated in the catalytic glycosylation of glucose with fatty alcohols. Four main criteria were
considered to evaluate the catalytic performances of Aquivion PFSA (1) the selectivity of the
reaction, (2) the Turn Over Frequency, (3) the reactor productivity and (4) the catalyst
stability/recycling. To shed light on the catalytic performances of Aquivion PFSA, it was
systematically compare to H2SO4 which is industrially employed in such reaction. We
discovered that Aquivion PFSA surpassed the catalytic performances of H2SO4 in terms of
activity, selectivity and reactor productivity. Particularly, Aquivion PFSA selectively converted
glucose to alkyl polyglucosides (DP = 1.2) with 85% yield which corresponded to a reactor
productivity as high as 477 kg/m3/h. Conversely to H2SO4, Aquivion PFSA was also capable of
selectively producing alkyl polyglucosides directly from glucose syrup, a cheap source of
glucose. This result was ascribed to the amphiphilic nature of Aquivion PFSA which facilitated
the Pickeringꢀlike emulsification of the biphasic reaction medium. Finally, owing to its high
chemical and mechanical properties, Aquivion PFSA was highly stable under our working
conditions and was recycled at least 10 times without obvious loss of its catalytic performances.
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KEYWORDS: Biphasic catalysis, Acid catalysis, Carbohydrates, Glycosides, Aquivion® PFSA,
Alkyl polyglycosides
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Introduction
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Acids are widely employed in industry to catalyze diverse reactions from carbohydrates such
as dehydration, esterification, glycosylation, polyꢀ or depolymerization among many other
examples.1 In most cases, these reactions imply water either as a solvent, reactant or coꢀproduct.
Industrially, H2SO4 is often a preferred catalyst for carbohydrate processing because it is cheap
(0.15 $/kg), highly active and it also leads to high reactor productivities. From a sustainable point
of view, solid acid catalysts are obviously more desirable owing to their possible recycling, the
absence of neutralization step at the end of the reaction and also due to their lowest
corrosiveness.1gꢀh Solid acid catalysts however often suffer from a low productivity and/or
deactivation caused by the presence of water or thermal instability.2 All these aspects currently
hamper the industrial deployment of solid acid catalysts for carbohydrate processing.
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The catalytic glycosylation of glucose with alkyl alcohols is a typical example.3 This reaction
is of prime importance in industry. In particular, the glycosylation of glucose with long chain
alkyl alcohols affords Amphiphilic Alkyl monoGlycosides (AAG) that are valuable nonꢀionic
bioꢀbased surfactants.3a Thanks to their low toxicity, biodegradability and stability (even in
alkaline conditions), these nonꢀionic surfactants are receiving many interests in food, detergence,
cosmetic and pharmaceutical industries. For instance, AAG are the main constituents of
Glucopon 600® and Milcoside 200® produced by BASF and LG, respectively.
The production of AAG is industrially achieved by glycosylation of glucose with an excess of
fatty alcohols (10 eq.) in the presence of 1 wt% of H2SO4.4 This reaction releases a
stoichiometric amount of water. The reaction is conducted under vacuum (100 mbar) to distill
water out of the reactor and to shift the process towards the formation of AAG. At the end of the
reaction, H2SO4 is neutralized by NaOH leading to the production of Na2SO4. This salt being
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nonꢀtoxic and present in a low quantity, it is not separated at the end of the reaction and thus
remains with AAG. Industrial processes generally afford AAG with 70% yield. Other products
are mostly alkyl polyglycosides (APG). In average, the final product contains 1.1 to 1.5 glucose
unit per fatty chains. According to the experimental conditions, glucose may also partly
polymerize leading to the formation of unwanted polydextroses.
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Scheme. 1. Synthesis of amphiphilic alkyl glycosides
According to the grade of glucose, there are two different pathways to produce AAG in large
scale (Scheme 1). From refined glucose (anhydrous or monohydrate crystalline powder, 0.45
$/kg), AAG are produced by a direct glycosylation of glucose with fatty alcohols in the presence
of H2SO4. From glucose syrup (0.30 $/kg), the direct glycosylation with a fatty alcohol is not
efficient due to the very low solubility of the fatty alcohol in the syrup leading to uncontrolled
and dominant polymerization of glucose to polydextroses. In this case, transglycosylation
reactions are thus generally preferred. Typically, the syrup is first glycosylated with nꢀbutanol
followed by a transglycosylation with a fatty alcohol, both reactions taking place subsequently in
the same reactor generally with H2SO4 as a homogeneous catalyst.
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Nowadays, the price of AAG is a critical issue (about 2.0 $/kg) and it is too high as compared
to fossilꢀderived surfactants (<1$ /kg) to deeply penetrate the market. The reactant price accounts
for about 60% of the full manufacturing cost of AAG. Hence, there are two options to lower the
price of AAG.
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The first strategy consists in optimizing the current processes by searching novel and
recyclable heterogeneous catalytic systems capable of producing AAG with a high selectivity
and productivity, particularly from glucose syrup. Obviously, solid acid catalysts should also
lower equipment and process costs in a significant way.
The second strategy consists in starting from a cheapest source of raw material such as waste
biomass (< 0.1 $/kg) instead of edible glucose as it is nowadays the case. If amphiphilic alkyl
xylosides can be produced in large scale from the hemicellulosic fraction of biomass,5 the
production of AAG from the cellulosic part is however scientifically more relevant. In 2010, D.
E. de Vos and A. Corma independently reported the acidꢀcatalyzed conversion of cellulose to
AAG in ionic liquids at 110°C.6 In 2015, our group has reported the glycosylation of cellulose
assisted by ballꢀmilling.7 Although good yields (60ꢀ80%) were claimed starting from C4 to C8
alkyl alcohols, these processes remain at the moment too costly for implementation at a larger
scale.
In this work, we focused on the first strategy i.e. the search of a solid acid catalyst. Despite
many studies on the catalytic glycosylation of glucose in the presence of a heterogeneous
catalyst, examples of heterogeneouslyꢀcatalyzed glycosylation of glucose with fatty alcohols (C8
to C24) are very scarce due to the biphasic nature of the reaction medium inducing mass transfer
problem and, thus poor selectivity. N. S. Chaubal et. al. reported the heterogeneouslyꢀcatalyzed
glycosylation of glucose with myristyl alcohol in the presence of spinels of the type ZnFe2O4
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supported on ZrO2.8 The reaction was carried out in toluene and myristyl glycosides were
obtained with 87% yield. Y. Wu et al. reported the synthesis of octyl glycosides over
H2SO4/SiO2 affording APGs with an average degree of polymerization of 1.37.9 Same catalyst
was employed by I. A. Amin et al. for the glycosylation of dextrose with nꢀoctanol.10 In another
example, H. Kim et al. investigated the glycosylation of glucose with nꢀoctanol in the presence
of polyvinyl bound trisulfonate ethylamine chloride and polyvinyl bound disulfonate ethylamine
as Brønsted solid acid catalysts.11 Under optimized conditions, APGs were obtained with
excellent yields. Although excellent selectivity to APGs was claimed in all these examples, the
deactivation/leaching of solid catalysts and the low reactor productivity remain important
obstacles for implementation at a larger scale. To date, there is no commercialized
heterogeneouslyꢀcatalyzed process for the glycosylation of carbohydrates and, in this field,
H2SO4 remains the reference in terms of activity, selectivity, productivity and costꢀefficiency.
Aquivion® PFSA PW98 is a perfluorosulfonic acid ionomer which is synthesized by the freeꢀ
radical copolymerization of tetrafluoroethylene and sulfonyl fluoride vinyl ether CF2=CFꢀOꢀ
(CF2)2ꢀSO2F. The ꢀSO2F moieties are then converted to ꢀSO3H groups by a treatment with a
mineral base (NaOH or KOH) followed by a cation exchange in acid conditions.12 Thanks to the
presence of perfluorinated chains, Aquivion® PFSA is considered as a solid superacid with a
Hammett acidity function of ꢀ12 which is similar to that of H2SO4 and higher than that of
classical sulfonated polystyrenes such as Amberlystꢀ15 for instance (H0 = ꢀ2).13 The structure of
Aquivion® PFSA PW98 is provided in the supporting information (Figure S1). The proton
exchange capacity of Aquivion® PFSA PW98 used in this study is 1.0 mmol/g. In contrast to
Nafion NRꢀ50, the mechanical and chemical integrity of Aquivion® PFSA PW98 are preserved
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at high temperature (up to 150ꢀ160°C).14 This large operating temperature window is an
important aspect with respect to the long term recycling.
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In this work, we report that Aquivion® PFSA PW98 is not only a highly robust and recyclable
heterogeneous catalyst under our working conditions but it is also markedly more selective and
more productive than H2SO4. Importantly, in contrast to H2SO4, Aquivion® PFSA PW98 is also
capable of producing amphiphilic AAG by a direct glycosylation of glucose syrup with fatty
alcohols. To the best of our knowledge, this work is one of the rare examples where a solid acid
catalyst surpasses the industrial performances of H2SO4 in terms of selectivity, productivity and
that, whatever the grade of glucose.
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Results and Discussion
In a first set of experiments, the glycosylation of anhydrous glucose with nꢀdodecanol was
investigated in the presence of Aquivion® PFSA PW98. Three main criteria were considered to
evaluate the catalytic performances of Aquivion® PFSA PW98 (1) the selectivity of the reaction,
(2) the Turn Over Frequency (TOF) (molconverted glucose / molH+ /h expressed hereafter in hꢀ1) and
(3) the reactor productivity expressed in kg/m3/h. To shed light on the contribution of Aquivion®
PFSA PW98, it was systematically compared to H2SO4 but also to heterogeneous acid catalysts
such as sulfonated SBAꢀ15 mesoporous silica (SBAꢀSO3H), Amberlystꢀ15 and a zeolite HꢀBEAꢀ
25. For the sake of clarity, we first focused the discussion on AAG. The formation of alkyl
polyglucoside (APG) is discussed later.
In a typical procedure, anhydrous glucose was mixed with 3 eq. of nꢀdodecanol and the
resulting mixture was heated at 120°C in the presence of 1.5 mol% of H+. The reaction was
carried out under vacuum (50 mmHg) to distill water out of the reaction vessel and to enhance
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the formation of AAG. As usual for this kind of reaction, the yield of AAG reached a maximum
and then decreased due to the formation of APGs. A detailed identification of the different
reaction products formed is provided later. Results are summarized in Table 1. A typical kinetic
profile and gas chromatogram are provided in the supporting information (Figure S2, S3).
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Table 1. Catalytic glycosylation of glucose with nꢀdodecanol in the presence of acid catalystsa
Entry
Catalyst
Time
Conv.
(%)
TOF
(hꢀ1)c
Yield
(%)d
Sel.
(%)
Productivity
(kg/m3/h)
(min)b
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5
H2SO4
60
300
240
600
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70
94
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38
85
145
102
ꢀ
50
35
9
71
37
53
26
82
290
41
13
6
SBAꢀSO3H
Amberlystꢀ15
HꢀBEAꢀ25
ꢀ
10
70
Aquivion®
46
350
PFSA PW98
6e
7f
H2SO4
90
30
90
86
74
47
75
47
86
Aquivion®
100
456
546
PFSA PW98
8g
9h
Aquivion®
PFSA PW98
1080
100
98
96
<1
40
52
53
38
17
Aquivion®
36
125
PFSA PW98
b
a 120°C, 1.5 mol% of H+, nꢀdodecanol/glucose molar ratio = 3, time of the reaction to reach
c
the maximum yield to AAG; measured at the initial stage of the reaction (conv. Glucose < 20
d
e
f
g
h
%); maximum yield to AAG; nꢀdodecanol/glucose molar ratio = 10; at 150°C; at 90°C;
under closed vessel
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Under our working conditions, H2SO4 exhibited a TOF of 145 hꢀ1 and afforded AAG with a
maximum yield of 50 % at a conversion of glucose of 70% (i.e AAG selectivity of 71%) (Table
1, entry 1). As expected, the reactor productivity was high with H2SO4 and it reached 290
kg/m3/h. Among tested heterogeneous catalysts, SBAꢀSO3H exhibited a TOF of 102 hꢀ1 but
unfortunately it was deactivated during the reaction due to the partial hydrolysis of the siliceous
surface at 120°C (Table 1, entry 2, see also kinetic profile in the Figure S4). A maximum yield of
AAG of 35% was however obtained at a conversion of glucose of 94% (after 300 min of
reaction) which corresponded to an AAG selectivity and a reactor productivity of 37% and 41
kg/m3/h, respectively (i.e. selectivity and productivity were 1.9 times and 7 times lower than that
of H2SO4). Other products are mostly polydextroses in this case. Their formation is indeed
strongly favored over hydrophilic catalytic surface. As expected, due to its low thermal stability,
Amberlystꢀ15 was poorly active under our working conditions (Table 1, entry 3). In contrast to
what was previously observed with nꢀbutanol,15 HꢀBEA (Si/Al = 25) was poorly active from
fatty alcohols at 120°C presumably due to the biphasic nature of the medium that induced mass
transfer problems (Table 1, entry 4). These selected examples illustrate well the difficulty facing
by heterogeneous catalyst to compete with H2SO4 in such reaction.
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To our delight, Aquivion® PFSA PW98 afforded the highest yield of AAG (i.e. 70%) (Table 1,
entry 5). This yield was obtained at a conversion of glucose as high as 85% indicating that
Aquivion® PFSA PW98 was markedly more selective than H2SO4 (82% vs 71%). A kinetic
effect can be ruled out to explain this greatest selectivity since Aquivion® PFSA PW98 has a
TOF of 46 hꢀ1 which is 2 to 4 times lower than those of H2SO4 or SBAꢀSO3H. From the state of
the art, the amphiphilic nature of Aquivion® PFSA PW98 was presumably responsible for this
high selectivity by favoring a better contact between glucose (hydrophilic) and nꢀdodecanol
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(hydrophobic), thus contributing to limit the side oligomerization of glucose. This aspect is
discussed later. The reactor productivity was also higher with of Aquivion® PFSA PW98 than
with H2SO4 since it reached 348 kg/m3/h (Table 1, entry 5).
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To more accurately compare the reactor productivity between Aquivion® PFSA PW98 and
H2SO4, the H2SO4ꢀcatalyzed process was optimized in order to find the suitable experimental
conditions to compare both catalysts at a similar selectivity and conversion. To this end, it was
necessary to increase the nꢀdodecanol/glucose ratio from 3 to 10 with H2SO4. Under these more
diluted conditions, the TOF of H2SO4 was logically reduced from 145 hꢀ1 to 86 hꢀ1 but the AAG
yield was increased to 74% for a conversion of glucose of 90% (Table 1, entry 6). These
conditions are actually very close to the industrial ones. At 82% of selectivity and 85ꢀ90%
conversion, we were pleased to see that the reactor productivity was much higher with
Aquivion® PFSA PW98 than with H2SO4 (350 vs 85 kg/m3/h) highlighting the efficiency of
Aquivion® PFSA PW98 in glycosylation of glucose.
Next, the impact of the temperature on the Aquivion® PFSA PW98 performances was checked.
In accordance with the Arrhenius law, when the temperature was increased from 120°C to
150°C, the TOF of Aquivion® PFSA PW98 was concomitantly increased from 46 hꢀ1 to 456 hꢀ
1(Table 1, entries 1 and 7). At 150°C, the maximum yield of AAG (47%) was however markedly
lower than at 120°C (70%) due to dominant acidꢀcatalyzed degradation of glucose and
glycosides as supported in this case by the formation of unidentified black materials. Conversely,
a decrease of the reaction temperature from 120°C to 90°C decreased the reaction rate to an
unacceptable level (Table 1, entry 8). Hence, 120°C was selected in the following experiments.
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Continuous removal of water was also mandatory to shift the reaction (equilibrium) to the
formation of AAG. For instance, when the same reaction was conducted in a closed reactor, the
yield of AAG reached a maximum of only 36% (Table 1, entry 9).
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Next, Aquivion® PFSA catalyst with different sulfonic loadings were checked to evaluate the
impact on the TOF, the selectivity and the reactor productivity. To this end, Aquivion® PFSA
with a proton exchange capacity of 1.0, 1.15, 1.26 and 1.45 mmol/g were tested. Results are
summarized in Table 2.
Table 2. Influence of the proton exchange capacity on the Aquivion® PFSA catalytic
performancesa
Catalyst
H+ exchange
capacity
(mmol/g)
Conv.
(%)
TOF (hꢀ1)
AAG
AAG
Productivity
(kg/m3/h)
yield (%) selectivity
(%)
Aquivion®
PW98
1.0
85
80
80
85
46
42
55
83
70
65
75
75
82
81
87
88
350
378
433
523
Aquivion®
PW87
1.15
1.26
1.45
Aquivion®
PW79
Aquivion®
PW66
a 120°C, nꢀdodecanol/glucose molar ratio = 3, 1.5 mol% of H+
Whatever the H+ loading, the selectivity to AAG remained similar (81ꢀ88%). The H+ loading
has however a significant effect on the TOF of Aquivion®. The TOF of Aquivion® was indeed
increased from 46 to 83 hꢀ1 when the H+ loading was concomitantly increased from 1.0 to 1.45
mmol/g. Considering that the selectivity was not changed, this result may reflect a possible
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cooperativity between ꢀSO3H sites at high loading. It was indeed previously shown that the
mobility of H+ on Aquivion® was significantly affected by an increase in the ꢀSO3H loading
owing to the formation of wellꢀconnected water clusters.16 Furthermore, the formation of these
water clusters may also impacts the swelling of Aquivion® and thus the accessibility of ꢀSO3H.
Among the different tested Aquivion® PFSA, Aquivion® PFSA PW66 was the most performant
one affording AAG with 75% yield (i.e. 88% selectivity) after only 50 min of reaction which
corresponds to unprecedented reactor productivity as high as 523 kg/m3/h.
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The reaction mixture was next carefully analyzed by means of different characterization
methods in order to determine the nature of other products formed. At the end of the reaction,
Aquivion® PFSA PW98 was filtered off and, as industrially performed, the excess of nꢀ
dodecanol was removed by vacuum distillation. The crude product was next analyzed by GC
analyses and revealed that the APG sample contained 14% of glucose which is in line with a
determined conversion of 85%. It also means that less than 1% of glucose was converted to
polydextrose. This result was also confirmed by titrating the reducing sugar present in the sample
by 2,6ꢀdinitrosalicylic acid (DNS method).17 AAG were then analyzed by mass spectrometry
(electrospray) and the formation of alkyl polyglucosides (APG) was clearly observed.
Particularly, APGs with a degree of polymerization (DP) going from 1 to 4 were formed.
Determination of the average DP was achieved by 1H NMR (in d6ꢀDMSO) and revealed a DP of
1.2 which is a similar value with industrial products (Figure S5, S6). One should note that such
DP also indicated that glucose was exclusively converted to APG which agrees well with the
absence of side oligomerization of glucose. Note that all these results were doubleꢀchecked by
separating nꢀdodecanol, glucose and APGs by filtration over a plug of silica using consecutively
ethyl acetate/heptane (1/1) and methanol/H2O (1/1) as eluents. This separation also confirmed
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the exclusive conversion of glucose to APG with a DP of 1.2. Finally, GC analyses showed that
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AAG was formed as a mixture of furanoside and pyranoside forms, both forms coꢀexisted as α
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and β isomers which agrees well with a classical reaction mechanism i.e. in situ formation of an
oxocarbenium cation.18 The pyranoside form was dominant and the pyranoside/furanoside ratio
was 2.5. The α/β ratios for the pyranoside and furanoside forms were 4.72 and 3.38, respectively
which is consistent with previous works of the field.4,19 It is worth mentioning that during the
monitoring of the catalytic reaction by GC, we observed that 7% of nꢀdodecanol was also
converted to didodecylether during the reaction but this later was not found in APG samples. It
was presumably distilled out at the same time with nꢀdodecanol (or hydrolyzed back to nꢀ
dodecanol during the distillation process).
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When nꢀdodecanol was replaced by nꢀhexadecanol or nꢀoctadecanol which are both available
in larger scale from biomass, the reaction also proceeded well. After purification by filtration
over a plug of silica, the corresponding APGs were obtained with 50% and 60% isolated yield,
respectively (not optimized results, product was lost during the purification process) showing the
attractiveness of Aquivion® PFSA PW98 for the synthesis of APG from biomass.
Considering both the selectivity and the reactor productivity, Aquivion® PFSA PW98 appeared
as a more performant catalyst than H2SO4. Aquivion® PFSA PW98 was also more performant
than betaꢀzeolite previously reported in the literature.15 While the yields and selectivity were in
this case in a similar range between both solid catalysts, the reactor productivity was however
nearly 10 times higher with Aquivion® PFSA PW98 than with beta zeolite. The best conditions
found for Aquivion® PFSA PW98 are 120°C, a nꢀdodecanol/glucose molar ratio of 3 and a
reaction time of 70 min. Applying these conditions led to the synthesis of AAG with 70% yield
(i.e. APG with 85% yield, 100% selectivity to APG) and a reactor productivity to AAG of 350
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kg/m3/h (i.e. 477 kg/m3/h based on APG) which is in line with industrial specifications.
Transposition of these results to a batch reactor of 10 m3 running for 8000 h per year (typical
reactor size in fine chemistry) suggests a production capacity of 38 kT per reactor which is also
in accordance with industrial specifications of the field. Note that an even higher productivity
may be expected using Aquivion® PFSA PW66 as a solid acid catalyst (Table 2).
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Although Aquivion® PFSA PW98 surpasses the performances of H2SO4, its recycling is
mandatory since solid acid catalysts are generally more expensive than H2SO4. In this context,
recycling experiments were undertaken. At the end of the first cycle, Aquivion® PFSA PW98
was filtered off and reused for another run after washing with water and ethanol to remove most
of adsorbed glucose and APGs. As expected, owing to its high chemical stability, Aquivion®
PFSA PW98 was successfully recycled at least 10 times without noticeable decrease in
selectivity, activity and productivity (Fig. 1).
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Figure 1. Recycling of Aquivion® PFSA PW98
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After filtration of Aquivion® PFSA PW98, the reaction medium was carefully analyzed by ICP
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and F NMR. No trace of fluorine or sulfur was observed in the sample of AAG which agree
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well with the high stability of Aquivion® PFSA PW98 under our working conditions.
To further support the integrity of Aquivion® PFSA PW98 after 10 consecutive runs, this later
was analyzed by FTꢀIR and CP/MAS NMR. In Figure S7 are reported the FTꢀIR spectrum of the
fresh Aquivion® PFSA PW98 and the overlapped spectra of the spent Aquivion® PFSA PW98
after one and 10 catalytic cycles. The FTꢀIR spectra show that the characteristic bands of
Aquivion® PFSA (namely the SꢀO stretching at about 1000 cmꢀ1 and the CꢀC and CꢀF stretching
at 1100ꢀ1300 cmꢀ1) were conserved over the catalytic runs. Besides, bands associated to
compounds adsorbed onto the catalyst surface were also evident at 2800ꢀ3000 cmꢀ1 (CꢀH
stretching) and at 1380ꢀ1480 cmꢀ1 (CꢀH bending) in the spent Aquivion® PFSA PW98 samples.
As expected, the intensity of such bands increased with the number of catalytic runs and is
presumably related to the increase amount of AAG or APG material deposited onto the catalyst
surface over the runs.
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Next, the spent Aquivion® PFSA PW98 was analyzed by 13C MAS NMR (Figure 2). Fresh
Aquivion® PFSA is characterized by an intense signal at 111 ppm, ascribed to the ꢀCF2ꢀ groups,
and by two very small signals blurred in the feet of the main signal at 117 and 108 ppm and
ascribed to ꢀOCF2ꢀ and ꢀCFꢀ groups respectively. The 13C MAS NMR spectrum recorded for the
spent Aquivion® PFSA PW98 (after ten catalytic runs) showed additional signals and particularly
a broad signal centered at 70 ppm, which could be assigned to adsorbed glucose. This claim is
supported by the presence of very weak signals in the 15ꢀ30 ppm range, which could be ascribed
to aliphatic ꢀCH2ꢀ groups. A trace of the signal at 70 ppm was already present after one catalytic
run (Figure 2).
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Figure 2. 13C{1H} one pulse MAS NMR spectra (left side) and 19F one pulse MAS NMR
spectra (right side) of (a) fresh Aquivion® PFSA PW98 (b) Aquivion® PFSA PW98 after one
catalytic run and (c) Aquivion® PFSA PW98 after ten catalytic runs
The 19F one pulse MAS NMR spectra of the fresh and spent Aquivion® PFSA PW98 samples
are also reported in Figure 2. Fresh Aquivion® PFSA PW98 shows signals that can be ascribed to
ꢀOCF2ꢀ (ꢀ79 ppm) and ꢀCFꢀ (ꢀ138 ppm) groups, whereas the signals in the range between ꢀ105
and ꢀ123 ppm are assigned to ꢀCF2ꢀ groups. Spent Aquivion® PFSA PW98 collected after one or
ten catalytic runs did not show additional signals, corroborating the chemical stability of
Aquivion® PFSA PW98 already observed with other techniques. Finally, TGA analysis of the
fresh and spent Aquivion® PFSA PW98 was carried out (Figure S8). This analysis confirmed
that 9 wt% of materials were absorbed on the recycled Aquivion® PFSA PW98 which agrees
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well with CP/MAS NMR and FTꢀIR investigations. The decomposition temperature of the fresh
and recycled Aquivion® PFSA PW98 was the same (starts at 300°C) which further supported the
integrity of the polymer structure during catalysis.
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Having all these data in our hands, we then evaluated the possibility to produce AAG from
glucose syrup (typically 70 wt% of glucose in water) which is a cheaper source of glucose. As
aboveꢀmentioned, the H2SO4ꢀcatalyzed glycosylation of glucose syrup with fatty alcohols is not
directly feasible at an industrial scale and it requires a twoꢀstep process involving (1) a catalytic
glycosylation of glucose syrup with nꢀbutanol followed by (2) a transglycosylation of butyl
glycosides with nꢀdodecanol. Despite acceptable yields of APGs, this industrial process is
however more costly than the direct glycosylation with fatty alcohols.
In this context, the direct glycosylation of glucose syrup with nꢀdodecanol was investigated
either in the presence of Aquivion® PFSA PW98 or H2SO4 (Table 3). Similar conditions than
those described above (Table 1, entry 5) were employed. As expected, in the presence of H2SO4,
AAG were produced with only 30% yield at total conversion after 90 min of reaction and the
stirring was rapidly hampered by the formation of a sticky gel (polydextrose, Figure S9). To our
delight, when Aquivion® PFSA PW98 was employed, AAG was produced with 64 % yield (at a
glucose conversion of 90%) and no formation of polydextroses was visually observed. Other
products were mostly APG. The selectivity to AAG was 71% (vs 30% with H2SO4) and the
reactor productivity to AAG reached 223 kg/m3/h (vs 106 kg/m3/h for H2SO4) which represent an
important advance in the field. Aquivion® PFSA PW66 also afforded similar results (66% yield
to AAG, Table 3).
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Table 3. Catalytic glycosylation of glucose syrup with nꢀdodecanola
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Catalyst
Conv. (%)
AAG yield
(%)
AAG selectivity
(%)
Productivity
(kg/m3/h)
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H2SO4
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223
300
Aquivion® PFSA PW98
Aquivion® PFSA PW66
a 120°C, 1.5 mol% of H+, nꢀdodecanol/glucose molar ratio = 3, 90 min
Previously, it has been well documented that the concomitant presence of perfluoroakyl chains
and ꢀSO3H groups conferred to Aquivion® PFSA PW98 amphiphilic properties.20 One may thus
suspect that Aquivion® PFSA PW98 facilitated a more intimate contact between glucose syrup
and the nꢀdodecanol phases than in the case of H2SO4. This kind of Pickeringꢀlike emulsification
of the reaction medium by Aquivion® PFSA PW98 is expected to inhibit the side
oligomerization of glucose. To support this claim, the glucose syrup was stirred in the presence
of nꢀdodecanol (ratio 1:3) at 40°C for 15 min at 24 000 rpm in the presence of 1.5 mol% of H+
(relative to glucose) either with H2SO4 or Aquivion® PFSA PW98. After emulsification of the
reaction medium, it was progressively cooled down to room temperature within 30 min. At room
temperature, nꢀdodecanol crystallized, thus providing a clear frozen image of the emulsion.
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Figure. 3. Frozen image of the emulsification of the reaction medium with (A) H2SO4 and (B)
Aquivion® PFSA PW98
In the case of H2SO4, a clear phase separation was observed between crystallized nꢀdodecanol
and the glucose syrup (Figure 3). Conversely, in the case of Aquivion® PFSA PW98, the glucose
syrup remained fully dispersed in nꢀdodecanol. The sample was even kept overnight without
obvious decantation of the syrup. These results strongly support the effect of the Aquivion®
PFSA PW98 polymeric structure on the emulsification of the reaction medium which may
rationalize the better selectivity observed with Aquivion® PFSA PW98.
Conclusion
We report here that Aquivion® PFSA, a perfluorosulfonic acid polymer, surpasses the
performances of H2SO4 industrially employed in the glycosylation of glucose with fatty alcohols.
Under close conditions with industrial processes, Aquivion® PFSA was found markedly more
selective than H2SO4 and led to higher reactor productivities. Furthermore, its high chemical
stability allowed its recycling for at least 10 consecutive catalytic cycles. Under optimized
conditions, Aquivion® PFSA provided selectively APGs (DP of 1.2) with a reactor productivity
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of 477 kg/m3/h which is in line with the industrial specifications of the yield. Origin of these
superior performances of Aquivion® PFSA not only stems from its super acid properties but also
from its amphiphilic properties leading to an emulsification of the biphasic medium, a pivotal
aspect to limit the unwanted oligomerization of glucose to polydextroses. Conversely to H2SO4,
owing to this amphiphilic property, Aquivion® PFSA was even capable of catalyzing the direct
glycosylation of glucose syrup with nꢀdodecanol, thus opening a straightforward access to APGs
from a cheaper source of glucose.
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Aquivion PFSA has a clear potential to induce a cut of cost as no catalyst or base are
consumed in the process. As a consequence, Aquivion® PFSA allows producing APG without
any ashes, an important point with respect to their physicoꢀchemical properties. At this stage, the
cost of this process is however difficult to be correctly worked out because of the lack of reliable
data and the difficulty to weight the different costs (capex, catalyst recycling, purification steps,
idle time due to catalyst maintenance, etc..). In our views, as compared to current routes,
Aquivion® PFSA should not induce supplemental cost as it is conveniently recovered by
filtration and reused as collected without any treatment and it does not require any new
equipment or investments.
Experimental section
Chemical and reagents: nꢀDodecanol, nꢀHexadecanol, nꢀOctadecanol and H2SO4 were
purchased to SigmaꢀAldrich and used without further purification. Aquivion® PFSA PW98,
Aquivion® PFSA PW66ꢀS, Aquivion® PFSA PW79ꢀS and Aquivion® PFSA PW87ꢀS were
kindly provided by Solvay Specialty Polymers. Amberlystꢀ15 was purchased to ACROS and
SBAꢀ15ꢀSO3H was prepared according to a known procedure.21
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Gas Chromatography analyses: AAGs were analyzed on a Varian 3350 equipped with a flame
ionization detector. Before analysis, AAGs were silylated. Typically, a sample (0.1 g) was taken
from the reactor and diluted in 2 mL of a solution of pyridine containing 1 mg.mLꢀ1 of sorbitol
(internal standard). After solubilization, 1.0 mL of HDMS and 1.0 mL of TMSCl were
successively added. The solution was then centrifuged for 10 minutes and 0.5 µL of the solution
was injected. A HT 5 column was used (L = 30 m, Ø = 0.32 mm, e = 0.25 µm). The oven was
heated from 50°C to 220°C with a heating ramp of 10°C/min and then to 320°C with a heating
ramp of 10°C/min.
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Solid State MAS NMR: experiments were acquired on an Agilent DirectDrive2 400 MHz NB
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spectrometer operating at 399.81 MHz for H, 376.62 MHz for 19F and 100.50 MHz for 13C,
using a 1.6 mm T3 MAS special HFXY probe. 1H one pulse MAS experiments were acquired at
25 kHz using a 90° pulse of 4.2 ꢁs, a recycle delay of 4 s and 64 scans. 19F one pulse MAS
experiments were acquired at 25 kHz using a 90° pulse of 3.5 ꢁs, a recycle delay of 8 s and 64
scans. 13C(1H) dipolar decoupled one pulse experiments were acquired at 20 kHz, using a 90°
pulse of 4.0 µs, a TPPM 1H decoupling scheme, a recycle delay of 6 s and 8800 scans. Chemical
1
shifts (δCS) for H and 13C are reported relative to TMS, using adamantane as secondary
standard. 19F δCS are reported relative to CFCl3, using PTFE (δCS= ꢀ123 ppm) as secondary
standard.
Catalytic glycosylation of glucose: Typically, glucose (1.08 g, 6 mmol) was mixed with nꢀ
dodecanol (3.35 g, 18 mmol) in a 50 mL round bottom flask, equipped with a magnetic stirring
bar. Then an acid catalyst (1.5 mol% of H+ relative to glucose) was added and the solution was
heated in an oil bath at 120°C under vacuum (15 mmHg) for the desired reaction time. The
reaction was monitored by GC as mentioned above. In the case of Aquivion® PFSA, this later
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was filtered off at the end of the reaction and the excess of nꢀdodecanol was removed under
vacuum using an industrialized standard procedure. Alternatively, APGs can be also purified by
filtration on a plug of silica using consecutively ethyl acetate/heptane (1/1) and methanol/H2O
(1/1) as eluents. The same procedure was used from nꢀhexadecanol and nꢀoctadecanol.
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Note: filtration of the Aquivion® PFSA solid acid catalyst should be performed at 100°C to avoid
the solidification of nꢀdodecanol. Alternatively, the reaction medium can be also diluted with
ethanol to facilitate the filtration of Aquivion® PFSA at room temperature.
Recycling experiments: After the catalytic first run, the Aquivion® PFSA was filtered off at
100°C. Then, Aquivion® PFSA was washed with water and with ethanol to remove most of
adsorbed glucose and APGs. The recovered catalyst was then dried for one hour at ambient
temperature under vacuum (15 mHg) and directly reꢀengaged in the next catalytic run without
any further purification. Experimental parameters (reaction time, temperature, nꢀ
dodecanol/glucose ratio, catalyst loading,etc.) remained unchanged between each run.
ASSOCIATED CONTENT
Supporting Information Available: http://pubs.acs.org Selected kinetic profiles, a representative
chromatogram, copies of NMR spectra of APGs, copies of FTꢀIR, 13C and 19F MAS NMR
spectra of fresh and spent Aquivion® PFSA PW98 and a picture of the reaction medium during
the H2SO4ꢀcatalyzed glycosylation of glucose syrup with nꢀdodecanol.
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Author information:
*Corresponding
Author:
Tel:
+33ꢀ549ꢀ454ꢀ052;
Eꢀmail:
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francois.jerome@univꢀpoitiers.fr
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Author Contributions: The paper was written through contributions of all authors. All authors
have given approval to the final version of the paper. A. Karam, K. De Oliveira Vigier, and F.
Jérôme contributed equally to catalytic experiments. S. Marinkovic, B. Estrine contributed
equally to the purification and characterization of APG. C. Oldani contributed to the
characterization of Aquivion PFSA before and after use.
Notes: The authors declare no competing financial interest.
Acknowledgement: This work was supported by the CNRS, the French Ministry of Research,
ARD and ADEME (project APGꢀ2G). G. Canil (FTꢀIR analyses), R. Biancardi and A. Cattaneo
(MAS NMR spectroscopy) are gratefully acknowledged.
Abbreviations: AAG, Amphiphilic Alkyl monoGlycosides; APG, Alkylpolyglycosides, PFSA,
perfluoro sulfonic acid; DP, Degree of Polymerization, TOF, Turn Over Frequency; GC, Gas
Chromatography, NMR, Nuclear Magnetic Resonance; FTꢀIR, Fourier TransformationꢀInfra
Red.
REFERENCES
(1)
As selected examples see a) Yabushita, M.; Kobayashi, H.; Fukuoka, A. Appl. Catal. Sci.
B Env. 2014, 145, 1ꢀ9; b) Gallezot, P. Chem. Soc. Rev. 2012, 41, 1538ꢀ1558; c) Rinaldi,
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R.; Schüth, F. ChemSusChem 2009, 2, 1096ꢀ1107; d) Dhepe, P. L.; Fukuoka, A.
ChemSusChem 2008, 1, 969ꢀ975; e) Luterbacher, J. S.; Martin Alonso, D.; Dumesic, J.A.
Green Chem. 2014, 16, 4816ꢀ4838; f) Corma, A.; Iborra, S.; Velty, A. Chem. Rev. 2007,
107, 2411ꢀ2502; g) Climent, M. J.; Corma, A.; Iborra, S. Green Chem. 2011, 13, 520ꢀ
540; h) Van De Vyver, S.; Geboers, J.; Jacobs, P. A.; Sels, B. ChemCatChem 2011, 3, 82ꢀ
94; i) Zhou, C. H.; Xia, X.; Lin, C.ꢀX.; Tong, D.ꢀS.; Beltramini, J. Chem. Soc. Rev. 2011,
40, 5588ꢀ5617.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
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34
35
36
37
38
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40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(2)
(3)
Lange, J.ꢀP. Catal. Sci. Technol. 2016, 6, 4759ꢀ4767.
(a) Balzer, D., Lüders, H., In Nonionic surfactants: alkyl polyglucosides, Marcel Dekker:ꢂ
New York and Basel, Switzerland, 2000, vol. 91, p19; (b) von Rybinski, W.; Hill, K.
Angew. Chem. Int. Ed. 1998, 37, 1328ꢀ 1345; (c) Martel, F.; Estrine, B.; PlantierꢀRoyon,
R.; Hoffmann, N.; Portella, C. Top. Curr. Chem., 2010, 294, 79ꢀ115; (d) Ismail, A.;
Soultani, S.; Ghoul, M. J. Biotechnol., 1999, 69, 135–143; (e) Ismail, A.; Soultani, S.;
Ghoul, M. J. Biotechnol., 1999, 69, 145–149; (f) Li, J. Y.; Liu, Y. J.; Zheng, G.; Sun, Y.;
Hao, Y. N.; Fu, T. Adv. Mater. Res., 2012, 550ꢀ553, 75ꢀ79; (g) Böge, K.; Tietze, L. F.,
Fett/Lipid, 1998, 100, S. 36–41.
(4)
(5)
Hill, K., von Rybinski, W., Stoll, G., In Alkyl Polyglycosides: Technology, Properties
and Applications, Eds VCH Verlagsgesellschaft mbH Weinheim, 1997, 9ꢀ22.
(a) Bouxin, F.; Marinkovic, S.; Le Bras, J.; Estrine, B. Carbohydrate Res. 2010, 345,
2469ꢀ2473; (b) Hausser, N.; Marincovic, S.; Estrine, B. Cellulose 2013, 20, 2179ꢀ2184
and references cited therein.
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Page 25 of 28
ACS Catalysis
1
2
3
4
5
6
7
8
9
(6)
(7)
(a) Ignatyev, I. A.; Mertens, P. G. N.; Van Doorslaer, C.; Binnemans, K.; de Vos, D. E.
Green Chem. 2010, 12, 1790; (b) Villandier, N.; Corma, A. Chem. Commun. 2010, 46,
4408ꢀ4410; c) Villandier, N.; Corma, A. ChemSusChem 2011, 4, 508ꢀ513.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Boissou, F.; Sayoud, N.; De Oliveira Vigier, K.; Barakat, A.; Marinkovic, S.; Estrine, B.;
Jérôme, F. ChemSusChem 2015, 8, 3263–3269.
(8)
(9)
Chaubal, N. S.; Joshi, V. Y.; Sawant, M. R. J. Mol. Cat. A: Chem. 2007, 267, 157–164.
Wu, Y.; Yu, J. G.; Ma, X. F.; Zhang, J. S. Chin. Chem. Let. 2007, 18, 1173–1175.
(10) Amin, I. A.; Yarm, M. A.; Yusoff, N. I. N.; Yusoff, M. Z.; Ayatillah, A. Adv. Mater. Res.
2013, 620, 446ꢀ452.
(11) Chaugule, A. A.; Jadhav, A. R.; Kim, H. RSC Adv. 2015, 5, 104715.
(12) SOLVAY home Page. http://www.solvay.com/en/marketsꢀandꢀproducts/featuredꢀ
products/Aquivion.html (accessed Feb 24, 2017)
(13) Olah, G.A.; Prakash, G.K.S.; Sommer, J.; Molnár, A. In Superacid Chemistry, John
Wiley & Sons, Inc.: Hoboken, NJ, 2009.
(14) (a) Fang, W.; Wang, S.; Liebens, A.; De Campo, F.; Xu, H.; Shen, W.; PeraꢀTitus, M.;
Clacens, J.ꢀM. Cat. Sci. Technol. 2015, 5, 3980ꢀ3990; (b) Tassini, R.; Rathod, V.D.;
Paganelli, S.; Balliana, E.; Piccolo, O. J. Mol. Catal. A : Chem. 2016, 41, 257ꢀ263; (c)
Bianchi, L.; Ballerini, E.; Curini, M.; Lanari, D.; Marrocchi, A.; Oldani, C.; Vaccaro, L.
ACS Sustainable Chem. Eng. 2015, 3, 1873ꢀ1880; (d) Karam, A., Sayoud, N.; De
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Page 26 of 28
1
2
3
4
5
6
Oliveira Vigier, K.; Lai, J.; Liebens, A.; Oldani, C.; Jérôme, F. J. Mol. Catal. A : Chem.
2016, 422, 84ꢀ88.
7
8
9
(15) Camblor, M. A.; Corma, A.; Iborra, S.; Miquel, S.; Primo, J.; Valencia, S. J. Catal. 1997,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
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42
43
44
45
46
47
48
49
50
51
52
53
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55
56
57
58
59
60
172, 76–84.
(16) (a) Likhomanov, V. S.; Primachenko, O. N.; Ivanchev, S. S. Rus. J. Appl. Chem. 2014,
87, 1314ꢀ1318; (b) Hiesgen, R.; Morawietz, T.; Handl, M.; Corasaniti, M.; Friedrich, K.
A. J. Electrochem. Sci. 2014, 161, F1214ꢀF1223; (c) Wang, C.; Duscher, G.; Paddison, S.
J. RSC Adv. 2015, 5, 2368ꢀ2373; (d) Wang, C.; Krishnan, V.; Wu, D.; Bledsoe, R.;
Paddison, S. J.; Duscher, G. J. Mater. Chem. A 2013, 1, 938ꢀ944; (e) Ferrari, M.ꢀC.;
Catalano, J.; Giacinti Baschetti, M.; De Angelis, M. G.; Sarti, G. C. Macromolecules
2012, 45, 1901ꢀ1912; (f) Wang, C.; Paddison, S. J. Soft Matter 2014, 10, 819ꢀ830 ; (g)
Mochizuki, T.; Kakinuma, K.; Uchida, M.; Deki, S.; Watanabe, M.; Miyatake, K.
ChemSusChem 2014, 7, 729ꢀ733.
(17) Miller, G. L. Anal. Chem. 1959, 31, 426ꢀ428.
(18) (a) Martin, A; Arda, A.; Désiré, J.; Marrot, J.; Probst, N.; Mingot, A., Sinaÿ, P.;
Thibaudeau, S.; Blériot, Y. Nature Chem. 2016, 8, 186ꢀ191 ; (b) Frihed, T. G.; Bols, M.;
Pedersen, C. M. Chem. Rev. 2015, 115, 4963–5013; (c) Crich, D. Acc. Chem. Res. 2010,
43, 1144ꢀ1153.
(19) van Es, D. S.; Marinkovic, S. ; Oduber, X.; Estrine, B. J. Surfact. Deterg. 2013, 16, 147ꢀ
154.
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7
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9
(20) (a) Zhou, W.ꢀJ.; Fang, L.; Fan, Z.; Albela, B.; Bonneviot, L.; De Campo, F.; PeraꢀTitus,
M.; Clacens, J.ꢀM. J. Am Chem. Soc. 2014, 136, 4869ꢀ4872; (b) Fang, W.; Wang, S.;
Liebens, A.; De Campo, F.; Xu, H.; Shen, W.; PeraꢀTitus, M.; Clacens, J.ꢀM. Catal. Sci.
Technol. 2015, 5, 3980ꢀ3990; (c) Fang, W.; Fan, Z.; Shi, H.; Wang, S.; Shen, W.; Xu, H.;
Clacens, J.ꢀM.; De Campo, F.; Liebens, A.; PeraꢀTitus, M. J. Mater. Chem. A 2016, 4,
4380ꢀ4385.
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58
59
60
(21) Karam, A.; Gu, Y.; Jérôme, F.; Douliez, J.ꢀP.; Barrault, J. Chem. Commun., 2007, 22,
2222ꢀ2224.
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SYNOPSIS
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Yield
Recyclability of
Aquivion PSFA
10Yi0%
eld
80
60
40
20
0
H2SO4
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SBA-15-SO3H
Amberlyst 15
H-BEA
Aquivion PFSA PW 98
Aquivion PFSA PW 87
Aquivion PFSA PW 66
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3
Selectivity
Productivity
100%
600 kg/m /h
Productivity
Selectivity
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