Catalysis Today 302 (2018) 87–93

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Chemical hydrolysis of cellulose into fermentable sugars through ionic T

liquids and antisolvent pretreatments using heterogeneous catalysts
⁎
Silvia Morales-delaRosa, Jose M. Campos-Martin , Jose L.G. Fierro
Sustainable Energy and Chemistry Group, Instituto de Catálisis y Petroleoquímica, CSIC, Marie Curie, 2, Cantoblanco, 28049 Madrid, Spain1

A R T I C L E I N F O A B S T R A C T

Keywords: We studied the use of heterogeneous catalysts with sulfonic groups in the hydrolysis of cellulose. The treatment
Acid hydrolysis based on dissolution/precipitation in ionic liquids yields a clear enhancement in the conversion of cellulose and
Heterogeneous catalysis glucose formation with heterogeneous catalysts. The activity results indicated that there is a relation between
Cellulose the acidity of the catalyst and its activity in the hydrolysis of cellulose. However, the nature of the surface groups
Glucose
on the catalysts seems to have a dramatic effect on the activity. The presence of hydroxyl groups (-OH) and Si-O-
Ionic liquic treatment
Functionalized silica
Si bonds at the surface of silica-based catalysts could favor the adsorption of cellulose chains and enhance the
activity of the catalysts. This study showed that the hydrolysis of cellulose treated with dissolution/precipitation
using an ionic liquid produces a glucose yield of approximately 50% at 140 °C in just 5 h. These results are a
promising starting point for further studies.

1. Introduction carried out in the homogeneous phase before initiating the hetero-
geneously catalyzed reactions. There is also the possibility that the
Although heterogeneous catalysis has been instrumental in the de- hydrolysis starts by reaction between solid biomass and the active sites
velopment of technology in the chemical and petroleum industries, the of the external surface of the catalysts, however, the reaction between
use of heterogeneous catalysts in existing biorefineries is rather limited two solid phases is difficult [3].
[1]. The conversion of renewable raw materials with heterogeneous Another issue to consider in the transformation of lignocellulose
catalyst-based processes provides new challenges in research. However, into biofuels and chemicals is that these processes involve the presence
to be competitive with biotechnology processes, catalysts must satisfy of water, either as a reactant, a product, or even as a solvent [3,4,7–9].
important demands, such as high activity and selectivity and long-term In addition, in these applications, only a few materials are suitable in
stability. Currently, there is an increasing attention paid to the appli- terms of acidity, stability, and insolubility. Some of the catalysts that
cation of heterogeneous catalysts for the transformation of biomass in meet these characteristics include activated carbon, functionalized re-
the production of biofuels for both transport and chemical products [2]. sins, functionalized silica, zeolites, some solid heteropolyacid com-
Because the separation of solid catalysts is quite easy after the reaction pounds, niobic acid, MoO3-ZrO2, tungstates zirconium phosphate, zir-
allowing its subsequent reuse, heterogeneous catalysts would provide conium phosphate, lanthanum phosphate niobium, and some other
the greatest advantages in biorefineries. In addition, solid acid catalysts materials [4,10].
are typically less aggressive in industrial plants than liquid mineral Heterogeneous catalysts are being studied for the preparation of
acids [3,4]. compounds derived from biomass [11]. The most important compounds
The hydrolysis of solid biomass with heterogeneous catalysts must are sugar alcohols obtained from saccharides [12] and cellulose
occur in two steps. First, the partial hydrolysis of biomass using [13–15], the hydration and dehydration of carbohydrates, trans-ester-
Brønsted acidic species released by either the solid material or formed ification [16,17], and the isomerization of carbohydrates [18], among
in the reaction [4–7]. Subsequently, reactions involving the hydrolysis others. In cellulose hydrolysis, some works using heterogeneous cata-
of biomass with a heterogeneous catalyst occur when oligomers are lysts have been published [9,19], with the use of metal oxides like
small enough to enter the pore system. Thus, the porosity of the solid HNbMoO6 [20], sulfonated groups, and carboxylic eOH supported on
catalyst may play a key role in the catalytic activity and selectivity amorphous carbon materials to obtain glucose [21]; the use of sulfo-
because it determines to what extent the initial hydrolysis has to be nated celluloses treated with activated carbon [22]; and sulfonated

⁎
Corresponding author.
E-mail address: [email protected] (J.M. Campos-Martin).
1
http://www.icp.csic.es/eqsgroup/.

http://dx.doi.org/10.1016/j.cattod.2017.08.033
Received 30 November 2016; Received in revised form 12 July 2017; Accepted 14 August 2017
Available online 19 August 2017
0920-5861/ © 2017 Elsevier B.V. All rights reserved.
S. Morales-delaRosa et al. Catalysis Today 302 (2018) 87–93

carbon catalysts under microwave irradiation [23]. Other hetero- (tosic acid) acids (Table 1). Two tosic acid silicas with different particle
geneous acid catalysts, such as zeolites, sulfated zirconia and Amber- sizes were chosen to study the effect of particle size on the hydrolysis
lyst-15 have lower activities. reaction; one of the samples is a powder (40–63 μm), and the other has
An interesting option is the use of silica based catalysts. It should be larger particles (500–1000 μm); the latter was specially fabricated for
noted that silica alone is not appropriate as the catalysts for the hy- this work with the same textural characteristics as the silica powder.
drolysis of cellulose, because its intrinsic aciditiy is very weak or even Cellulose was treated by dissolution/precipitation in the ionic liquid
negligible. However, the introduction of sulfonic groups (-R-SO3H) on (IL) using a method described in previous studies [29]. For this purpose,
silica surface modifies its acidity and makes it as an interesting catalysts we performed a complete dissolution of the cellulose (0.5 g) in the IL
for cellulose hydrolysis [4]. Several reports about hybrid carbon/ [EMIM]Cl (9.5 g) at 135 °C using a continuously stirred tank reactor
functionalized silica [24] or ordered mesoporous functionalized silica (Mettler Toledo Easy Max). The cellulose was completely dissolved
[4,25,26] indicated the feasibility of the hydrolysis of cellulose with within 15 min. Then, the cellulose was precipitated by the addition of
functionalized silica catalysts. water (50 mL). The precipitated solid was removed by filtration and
In this work, we propose the use of commercial functionalized subsequently was washed several times with distilled water in order to
amorphous silica with sulfonic groups as heterogeneous catalysts to eliminate the IL of the solid sample.
obtain sugars via the acid hydrolysis of cellulose. We have chosen these Cellulose, original and treated, samples were analyzed by X-ray
silicas for use as catalysts because they are acidic catalysts, which is diffraction (XRD). The profiles of samples were recorded using an X’Pert
indispensable for the hydrolysis process, and they contain eOH groups Pro PANalytical diffractometer equipped with a CuKα radiation source
on their surfaces, which provides a better approach to the cellulose fi- (λ = 0.15418 nm) and X’Celerator detector based on Real Time
bers by bridging hydrogen with the existing eOH. Multiple Strip (RTMS). The samples were ground and placed on a
The main objective of this work is to maximize the production of stainless-steel plate. The diffraction patterns were recorded in steps
fermentable sugars in the acid hydrolysis process of cellulose using a over a range of Bragg angles (2 θ) between 4° and 90° at a scanning rate
treatment of dissolution/precipitation with ionic liquids optimized in of 0.02° per step and an accumulation time of 50 s. The diffractograms
previous works [27–29] but using heterogeneous catalysts. The use of a were analyzed with the X’Pert HighScore Plus software.
treatment based on dissolution/precipitation with ionic liquid has the The scanning electron micrographs (SEM) of untreated cellulose and
advantage of using moderate conditions such as atmospheric pressure cellulose treated with the IL were recorded using a Hitachi S–3000 N
and temperature lower than 150 °C. instrument. The samples were treated with increasing concentrations of
ethanol to fix the structure and to dehydrate the samples. We then
proceeded to critical-point drying with a Polaron CPD7501 critical
2. Experimental section point drier. Finally, the samples were metallized in a Balzers SCD 004
gold-sputter coater; they were sputter-coated with a thin layer of gold.
All materials were used as received without any further purification. Hydrolysis reactions were carried out batchwise in a magnetically
Cellulose (powder from cotton fiber, reference C6288), the ionic liquid stirred 100 mL thermostated Teflon-lined steel Berghof reactor
(1-ethyl-3-methylimidazolium chloride, [EMIM]Cl, ≥95%) and sulfuric equipped with a pressure addition funnel [27]. The amount of catalyst
acid (H2SO4) were purchased from Sigma-Aldrich. The heterogeneous added was selected to keep the same concentration of acidic groups in
acid catalysts were commercially available. Amberlyst 70 was kindly the reaction media (0.1 mol L−1). In a typical run, 0.5 g of cellulose and
provided by Dow Chemical. Three catalysts based on silica functiona- 50 mL of water were added, and the reactor was heated to the reaction
lized with sulfonic groups, Si-propylsulfonic acid (40–63 μm), Si-tosic temperature (140 and 160 °C). After reaching the reaction temperature,
acid (40–63 μm) and Si-tosic acid (500–1000 μm), were purchased from stirring was started within the reactor, and the reaction time was re-
SiliCycle (Table 1). corded. Aliquots were periodically taken from the reactor. In all cases,
Amberlyst 70 was used as a reference; this compound is an ion- the reaction was stopped after 5 h, and the mixture was quickly cooled,
exchange resin obtained from a copolymer of styrene and divi- stopping and introducing the reactor into ice water (3 min). This cold
nylbenzene. This resin was selected because its chemical composition mixture was filtered off and washed with distilled water several times
can be used at temperatures up to 190 °C. Although the specific surface to separate the solid. Finally, the solid was dried at 80 °C overnight in
area of the resin is lower than the other silica-based catalysts, its an oven.
swellability and high pore diameter (22 nm) make Amberlyst 70 an The liquid aliquots obtained were analyzed using high-resolution
excellent liquid phase acid catalyst. Functionalized silicas with two chromatography on an Agilent Technologies series 1200 HPLC chro-
types of acid groups were selected: propylsulfonic and arylsulfonic matograph. The chromatographic separations were performed using an
Aminex HPX-87H Bio-Rad column at 65 °C and 0.6 ml·min−1 aqueous
Table 1
solution of sulfuric acid (0.01 mmol·L−1) as the mobile phase for the
The heterogeneous acid catalysts used in the hydrolysis of cellulose.
analysis of glucose, cellobiose, levulinic acid and 5-HMF. These com-
Heterogeneous Catalyst Acid Sites BET Pore Particle pounds were identified by comparing their retention times with those of
Conc. Surface Diameter Size (μm) commercial standards. In this work, the yield of 5-HMF is not shown
(mmol/g) Area (m2/ (nm) because the reaction is performed in aqueous phase, and the presence of
g)
high water concentration favors the 5-HMF decomposition to levulinic
Amberlyst 70 2,55 36 22 500 acid and formic acid, resulting in negligible amounts of 5-HMF in all
Si-Propylsulfonic Acid 0.66 470–530 6 40–63 samples analyzed. For this reason, only the results related to glucose
and levulinic acid were analyzed. The yields of glucose and levulinic
acid were calculated using the following equations:
Si-Tosic Acid (powder) 0.59 470–530 6 40–63 % yield of glucose = GCON·100/GMx (1)

% yield of levulinic acid = LCON·100/LMx (2)

Si-Tosic Acid (grain) 0.79 470–530 6 500–1000 GMx = (cellulose mass) factor ·factor·1000/volume solution (3)

LMx = (cellulose mass) factor ·mass·factor·1000/volume solution (4)

GCON is the glucose concentration measured by chromatography

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Fig. 1. XRD patterns of both treated and original cellulose samples:.

(g/L), GMx is the maximum glucose concentration (g/L) that can be

obtained based on the amount of cellulose that is added to the reactor,
LCON is the levulinic acid concentration measured chromato-
graphically (g/L) and LMX is the maximum concentration of levulinic
acid (g/L) that can be formed from cellulose added to the reactor. For
the calculations, the glucose and levulinic acid factors must be con-
sidered. They are 1.1 for glucose and 0.709 for the levulinic acid yield,
Fig. 2. SEM micrographs of the original and treated cellulose.
this factors are calculated directly from the hydrolysis reaction mass
balance.
cellulose. While the untreated cellulose did not exceed 2%, with the
3. Results and discussion treated sample the values exceeded 10%. However, when treated at a
temperature of 160 °C (Fig. 3), the glucose yield increased dramatically
XRD analysis of the original and treated cellulose samples showed in the treated cellulose sample, reaching a glucose yield of more than
that the dissolution/precipitation treatment produces a complete loss of 25%. In contrast, even at this elevated temperature, hydrolysis of the
diffraction peaks due to the fibrous cellulose crystalline structure untreated cellulose sample only yielded a little over 2% glucose. This
(Fig. 1). The SEM micrographs of the original and treated cellulose change was in agreement with previous works [29], which showed that
samples were completely different: the micrographs of the original a loss of the cellulose structure indicated much better glucose yields in
sample clearly showed cellulose fibers (Fig. 2), while the treated sample the IL-treated samples than in the untreated ones.
was completely amorphous (Fig. 2). The characterization data clearly Fig. 3 shows that formation of levulinic acid, which is the main
indicated that the initial cellulose structure is completely altered after byproduct of glucose decomposition, was very low at 140 °C (Fig. 3). In
treatment with IL. this case, the yield was less than 0.02% in the treated cellulose after 5 h
Initially, the first reactions were carried out with the Amberlyst 70 of reaction. This poor performance may be related to the low con-
catalyst, which is the most common type of catalyst used in the lit- centration of glucose in the solution reaction. However, when the re-
erature. The reaction was studied at three reaction temperatures: 120, action temperature was increased to 160 °C (Fig. 3), the formation of
140 and 160 °C. The concentration of the acid catalyst was 0.1 mol of levulinic acid was clearly detected. In the untreated cellulose sample,
acid groups/L of solution. The reaction results at 120 °C showed that the levulinic acid yields exceeded 1%, while when we work with treated
the conversion of original cellulose was very small and the yield to cellulose, this yield reached 7.5% at 160 °C.
cellulose lower than 1%, the conversion and yield to glucose with the The results obtained with Amberlyst 70 at different temperatures
treated one were a little higher but still very low. The untreated cel- showed that increasing the temperature increase the glucose yield and
lulose conversion values were low regardless of the reaction tempera- the cellulose conversion considerably, reaching 25% and 43%, respec-
ture employed, 11% for 140 °C and quite similar at 160 °C (Fig. 3). tively, at 160 °C in the sample of cellulose treated with IL (Fig. 3). Based
When treated cellulose was used, a clear increase in the conversion to on these results, the study was continued only with treated cellulose.
untreated cellulose was observed, 17% at 140 °C, and 43% at 160 °C The results of Si-propylsulfonic acid at 120, 140 and 160 °C (Fig. 4)
(Fig. 3); this phenomenon was observed too with the homogeneous showed an increase in the glucose yield from 120 to 140 °C, but sur-
catalysts in previous works [29]. The glucose yield followed a similar prisingly showed a decrease in the glucose yield when the temperature
trend to the conversion. At 140 °C (Fig. 3 (a)), a difference could be increase from 140 °C to 160 °C, reaching approximately 40% and 25%,
seen between the glucose yield values for the treated and untreated respectively, after 5 h of reaction. The formation of levulinic acid was

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S. Morales-delaRosa et al. Catalysis Today 302 (2018) 87–93

Fig. 3. Glucose yield, levulinic acid yield and cellu-

lose conversion in the hydrolysis of untreated cellu-
lose and cellulose treated with [EMIM]Cl and with
the heterogeneous catalyst Amberlyst 70 (0.1 mol/L)
for 5 h at different temperatures: 140 °C and 160 °C.

very small for 120 °C (< 0.15%), increasing for 140 °C, 12.5% after 5 h copolymer of styrene-divinylbenzene, showed a lower glucose yield of
of reaction, and reaching a 40% at 160 °C (Fig. 4). These results in- only approximately 10%. There were also differences in the levulinic
dicated that 120 °C was a very low temperature for this reaction, and acid yield, but the differences were much smaller (Fig. 5). A lower le-
the glucose was being consumed at the highest temperature (160 °C), vulinic acid yield was obtained with the Amberlyst 70 catalyst, perhaps
resulting in the formation of byproducts. The total product yields ob- because it was the less active catalyst and produced a lower glucose
tained with Si-propylsulfonic acid were higher than those obtained with concentration in solution. However, it was different for the other cat-
Amberlyst 70, indicating that the silica catalyst was clearly more active alysts, which were more active. We observed a different behavior in the
than the Amberlyst 70 resin (Figs. 3 and 4). The main objective of our production of levulinic acid between these catalysts. Si-propylsulfonic
project is the production of glucose. For this reason, we continued the acid was the catalyst that gave rise to the highest formation of levulinic
study at 140 °C. acid (13%), followed by sulfuric acid (6.7%), and finally, Si-tosic acid
The glucose yields for the different tested catalysts showed different (powder) (4.5%). A very interesting fact was that Si-propylsulfonic acid
values (Fig. 5). The highest yield was obtained with sulfuric acid, which produced a greater amount of levulinic acid and a lower glucose yield
had similar behaviors at short reaction times for both silica-based cat- (Fig. 5), while in the case of sulfuric acid, we obtained the highest
alysts (Si-propylsulfonic and Si-tosic acid), but at longer reaction times, glucose yield and a much lower levulinic acid yield. Finally, the be-
the yields with the homogenous catalysts were higher, but not so high havior of the Si-tosic acid (powder) was intermediate. Considering that
considering that we were comparing heterogeneous and homogenous levulinic acid was a byproduct produced from glucose, this fact in-
catalysts. We also detected some differences between the two silica dicated that the heterogeneous catalysts derived from silica favor sec-
catalysts. Si-tosic acid was clearly more active than Si-propylsulfonic ondary glucose reactions. The homogeneous catalyst gave rise to the
acid (Fig. 5). Finally, the Amberlyst 70 catalyst, which is based on a formation of levulinic acid but to a lesser extent than the heterogeneous

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Fig. 4. Glucose yield (a) and levulinic acid yield (b)

in the hydrolysis of treated cellulose with [EMIM]Cl
with the heterogeneous catalyst propylsulfonic acid
(0.1 mol/L) for 5 h at different temperatures: 120,
140 and 160 °C.

catalysts. centers (sulfonic groups) to be closer to the cellulose chains, thus fa-
As a general rule, the activities of the catalysts were related to the cilitating hydrolysis (Fig. 6). This effect had already been detected in
pKa of the acid groups (Fig. 5), (H2SO4: −6.6, Tosic acid and Amberlyst other types of substrates, such as carbons with functional groups
70: −2.8, propyl sulfonic acid: −1.9), for a lower pKa (higher acidity [21,30], carbons with defects [31], hybrid carbon-silica systems [24],
strength) resulted in a higher yield. The highest yield was obtained with chlorinated supports with sulfonic groups [32] or combining polymers
the most acidic catalyst (sulfuric acid), and lower yields were obtained with sulfonic groups with other polar functional groups [33].
for the less acidic catalysts (Si-propylsulfonic). However, this rule was Finally, we studied the effect of particle size on the heterogeneous
not followed by the reference catalyst Amberlyst 70, which had a low catalyst. To achieve this goal, we requested a substrate that had the
glucose yield. This behavior could be explained in terms of the differ- same textural characteristics as the Si-tosic acid (powder) catalyst from
ences in the BET surface areas of the catalysts, however as the BET the supplier (SiliCycle Inc.) but with a larger particle size. The change
surface area measured in dry conditions and Amberlyst 70 swells in the in the particle produced differences in the yield to glucose (Fig. 7). The
presence of solvents, BET surface area is not a good parameter to powder catalyst showed a higher glucose yield (50%) than the Si-tosic
compare catalysts. The difference in catalytic activity must be related to acid particle (40%) after 5 h of reaction. This difference was explained
the differences in the natures of the surfaces of the catalysts. While in by the increase in the particle size, which results in differences in the
the Amberlyst 70 catalyst, the surface is basically covered with aro- intraparticle mass transport and affects the reactivity. The trends in the
matic rings, the silica surface is mainly covered with hydroxyl groups levulinic acid yield were very similar to those of the glucose yield
(-OH) and Si-O-Si bonds. The presence of these groups promotes in- (Fig. 7). The powdered catalyst produced a higher yield of levulinic
teractions with the cellulose chains and, therefore, allows the active acid, but this levulinic acid yield was moderate in both cases, reaching

Fig. 5. Glucose yield (a) and levulinic acid yield (b)

in the hydrolysis of cellulose treated with [EMIM]Cl
and with different heterogeneous catalysts (0.1 mol/
L) for 5 h at 140 °C.

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Fig. 6. Schematic representation of the mechanism

of adsorption and hydrolysis of cellulose on the
surface of a functionalized heterogeneous silica cat-
alyst.

4.4% for the powdered catalyst and 3% for the particulate catalyst The glucose yield values obtained from the combination of solution
(Fig. 7). The results indicated that the heterogeneous catalyst based on treatment with an ionic liquid and subsequent precipitation of the
silica functionalized with sulfonic groups was a very interesting option cellulose and catalysts based on functionalized silica were very inter-
for the hydrolysis of cellulose to glucose. esting and clearly higher than those obtained by other authors with

Fig. 7. Glucose yield (a) and levulinic acid yield (b)

in the hydrolysis of cellulose treated with [EMIM]Cl
and with two heterogeneous Si-tosic acid catalysts
with different particle sizes (0.1 mol/L) for 5 h at
140 °C.

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