Selective Hydrolysis of Cellulose and Polysaccharides Into Sugars by Catalytic Hydrothermal Method Using Sulfonated Activated-Carbon

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Journal of the Japan Petroleum Institute, 55, (2), 73-86 (2012) 73

[Review Paper]

Selective Hydrolysis of Cellulose and Polysaccharides into Sugars by


Catalytic Hydrothermal Method Using Sulfonated Activated-carbon

Ayumu ONDA*

Research Laboratory of Hydrothermal Chemistry, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi 780-8520, JAPAN

(Received September 1, 2011)

Mildly hydrothermal reaction using solid acid catalysts for cellulose hydrolysis into glucose has potential abili-
ties to be one of the key technologies for a future sustainable society using cellulose biomass. Among the solid
acid catalysts tested, such as H-form zeolite catalysts and sulfated and sulfonated catalysts, sulfonated activated-
carbon (AC_SO3H) catalyst showed remarkably high yield of glucose in the hydrolysis of cellulose with β-1,4-
glycosidic bonds under hydrothermal conditions at temperatures around 423 K. The AC _SO3H catalyst with
hydrothermal pre-treatment had excellent catalytic properties attributed to the high hydrothermal stability and the
strong acid sites of the sulfo functional groups and the activated carbon surfaces for polysaccharide adsorption.
A bifunctional sulfonated activated-carbon supported platinum (Pt/AC_SO3H) was prepared by impregnation of
platinum on activated carbon (AC) and sulfonation of the prepared Pt/AC. Gluconic acid was produced from
polysaccharides, such as starch and cellobiose, in water at 393 K under air by a one-pot process using the Pt/AC_
SO3H catalyst.

Keywords
Cellulose, Glucose, Catalytic hydrothermal hydrolysis, Gluconic acid, Sulfonated activated carbon

1. Introduction enzyme cost, long residence times associated with the


necessary low reaction temperature, and severe controls
Biomass resources are promising as sustainable on enzymes and waste fluids. Sulfuric acid methods
chemical resources1),2). Cellulose is a polysaccharide are inexpensive and fast, but the large-scale use of sul-
consisting of a linear chain of β-1,4-glycosidic bonded furic acid generally suffers from energy inefficiency,
D-glucose units. Cellulose is the most abundant source catalyst recovery, and reactor corrosion, and requires
of biomass, and could become an alternative to fossil thorough separation and neutralization of the sulfuric
resources for sustainable production of chemicals and acid residue, resulting in high amounts of waste.
fuels, thus preventing global warming by decreasing Recently, cellulose hydrolysis methods using ionic
atmospheric CO2 generated from the consumption of liquid, such as 1-butyl-3-methylimidazolium chloride
fossil fuels1),3). Uses of cellulose have been limited to (BMImCl), have been reported18),19). Ionic liquid
timber, paper, wood fuel, and so on, because of its methods are fast and cause less reactor corrosion, but
robust structure with hydrogen bonds within and between also have problems with high cost and separation. On
cellulose molecules formed by the β-1,4-glycosidic the other hand, hydrothermal reactions are environmen-
bonds of D-glucose4). Glucose has been investigated tally friendly methods. Severe hydrothermal conditions,
as a renewable feedstock molecule, which can be such as supercritical water, result in the saccharization
efficiently converted into various chemicals, fuels, of cellulose within extremely short residence times of
foods, and medicines1),3),5)~8). Therefore, cellulose some seconds, so avoid further degradation and
hydrolysis into glucose is a key process for the wider de hydration of produced oligo-saccharides and glu-
use of cellulose. cose15)~17). However, control of reactions and effec-
Previous research has concentrated on the de- tive heat recovery are difficult to achieve in such short
gradation of cellulose with enzymes4),5), mineral acids residence times. Therefore, saccharification of ligno-
(H2SO43),9)~11), HCl12),13), and HF14)) and hydrothermal cellulosic materials has never been commercially
methods15)~17). Enzymatic processes and sulfuric acid implemented20).
processes have significant drawbacks such as high Mildly hydrothermal conditions and less short reac-
tion times are desirable for industrial applications of the
hydrolysis of cellulose into glucose. Mildly hydro-

E-mail: aonda@kochi-u.ac.jp thermal conditions will greatly decrease the reaction

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


74

Scheme 1 Catalytic Conversion of Cellulose into Glucose over AC_SO3H Catalyst

rates of cellulose hydrolysis. One possible solution is in water for the hydration of 2,3-dimethyl-2-butene at
to decrease the crystallinity of cellulose before the 343 K32), and the esterification of higher fatty acids at
hydrolysis, which is expected to accelerate the hydroly- 353 K33).
sis of cellulose as in the digestive system of ruminants. Here, we introduce an efficient green process to com-
Ball-milling treatment of microcrystalline cellulose bine mildly hydrothermal reactions and solid acid catal-
resulted in an insoluble material with β-1,4-glycosidic ysis for the selective hydrolysis of cellulose into glu-
bonds but containing large noncrystalline regions as cose at 373-450 K with autogenetic pressures34),35). A
confirmed by XRD and CP/MAS 13C NMR21). The re- sulfonated activated-carbon (AC_SO3H) was used as an
action rate of cellulose hydrolysis using dilute sulfuric effective solid acid catalyst below 450 K (Scheme 1).
acid at 448 K increased with decreasing cellulose crys- Activated carbon, which is common carbon substance
tallinity21). for catalysts, is used as the precursor because of its high
To reduce the effects on the environment, sulfuric acid hydrothermal stability and high surface area. We also
should be replaced by solid catalysts. Recent advances describe the hydrothermal stability of the AC_SO3H
in the catalytic conversion of cellulose were summa- catalyst and the negative effects of free sulfuric acid
rized in a review paper22). Heterogeneously catalytic ions on the glucose production from cellulose. In
processes for microcrystalline cellulose conversion into addition, we prepared a sulfonated activated-carbon
sugar_alcohols have been described23)~25), which are supported platinum (Pt/AC_SO3H) catalyst and demon-
expected to provide a renewable efficient hydrogen strated one-pot production of gluconic acid from poly-
source26),27), by combination of hydrolysis with instan- saccharides in hot water under air using this Pt/AC _
taneous hydrogenation on supported noble metal cata- S O 3H c a t a l y s t w i t h o u t p H a d j u s t m e n t a g e n t s
lysts, such as Pt/Al2O3 and Ru/C, in hot water with (Scheme 2)36).
compressed hydrogen gas. The disadvantages of these
heterogeneously catalytic processes are the requirement 2. Experimental
for hydrogen gas and noble metals and the uses of the
product sugar _ alcohols are limited, compared with 2. 1. Materials
glucose. Glucose production from soluble starch and The H-form zeolite materials, H-beta (12) (Si/Al=
p o l y s a c c h a r i d e s ove r s o l i d c a t a l y s t s h a s b e e n 12), H-beta (75) (Si/Al=75), H-mordenite (10) (Si/Al=
reported28),29), but production of glucose from insoluble 10), and H-ZSM5 (45) (Si/Al=45), sulfonated zirconia
cellulose using solid acid catalysts without hydrogen (JRC-SZ-1), and γ-alumina (JRC-ALO-2), were sup-
gas is less well understood. Therefore, a new hetero- plied by the Catalysis Society of Japan. Commercial
geneous catalytic process is a challenge for glucose for- silica (Cariact Q-6, Fuji Silysia), activated carbon (pow-
mation from cellulose by the combination of mildly der, Wako Pure Chemical Ind.), and ion-exchange resin
hydrothermal reactions and solid acid catalysis without (Amberlyst 15, Organo) were also used as catalysts.
hydrogen gas. Solid acid catalyst called sugar catalyst The other chemicals used in this article were reagent
has been prepared by the carbonization and sulfonation grade.
of saccharides30)~33). This catalyst has the high activity

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


75

Scheme 2 Catalytic Conversion of Starch into Gluconic Acid over Pt/AC_SO3H Catalyst

2. 2. Catalyst Preparation Procedures washing repeatedly with 3 L of distilled water at 353 K,


The sulfonated activated-carbon (AC_SO3H) was pre- the obtained powder was hydrothermally pre-treated at
pared by the following method based on a previous 473 K using two autoclaves lined with Teflon (70 mL)
report31). Typically, activated carbon (Wako Pure to prevent elution of SO42- ions during reaction under
Chemical Ind., powder, 1.0 g) was added concentrated hydrothermal conditions at 373-453 K. The product
H2SO4 (18 mol・L-1, 20 mL) and heated under argon flow was washed again until sulfate ions were no longer
(40 mL・min -1) at 423 K (5 K・min -1) for 16 h34),35). detected in the wash water.
The resultant sulfonated-activated carbon was washed The S content was determined with a CHNS analyzer
repeatedly with hot distilled water (3 L, 353 K). To (Thermo Finnigan, Flash EA1112). The Pt content was
prevent elution of SO42- ions during reactions under hy- determined with an inductively coupled plasma (ICP, SII,
drothermal conditions at 403-453 K, the black powder SPS7000A). A gas sorption analyzer (Quantachrome,
was hydrothermally treated at 473 K for 3 h, and then NOVA1000) was used for N2 physisorption to deter-
washed again with hot distilled water until sulfate ions mine the surface areas of solid catalysts. The acid
were no longer detected in the wash water. sites in the catalysts were determined by the titration
Pt/AC_SO3H catalyst was prepared by the impregna- method as follows. Sodium hydroxide aqueous solu-
tion and sulfonation method36). About 4 wt% Pt/AC tion (0.01 mol・L-1, 20 mL) was added to the catalyst
was prepared by the impregnation method using a com- (0.040 g). The mixture was stirred for 2 h at room
mercial activated carbon (AC) powder (Wako Pure temperature. After centrifugal separation, the super-
Chemical Ind.) and H2PtCl6_6H2O (Soekawa Chemical), natant solution was titrated with hydrochloric acid
with heating under hydrogen flow at 573 K for 6 h to (0.01 mol・L-1) aqueous solution using phenolphthalein.
form fine Pt particles on the AC. To confirm the me- X-ray diffraction analysis was carried out using a
tallic state of platinum by X-ray diffraction (XRD), the R i g a k u R o t a f l ex R A D - C u s i n g C u - K α s o u r c e
platinum loading was 4 wt%. Pt/AC_SO3H catalysts (0.154 nm).
were prepared by sulfonation of the Pt/AC (1.0 g) with 2. 3. Catalytic Reactions
concentrated (96 %) sulfuric acid (20 mL; Wako Pure A typical catalytic reaction procedure was as follows.
Chemical Ind.) at 423 K under flowing Ar (20 mL・min-1), Catalyst (50 mg) and water (5.0 mL) were introduced
as well as sulfonation of AC into AC _ SO3H. After into a steel autoclave lined with Teflon (25 mL) under

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


76

air at ambient pressure. White cellulose powders


treated by ball-milling, soluble starch, pullulan, cello-
biose, maltose, and glucose were used as reactants
(45 mg). Ball-milling experiments were performed
using ZrO2 balls (mass of 1.8 kg and diameter of 2 cm).
The balls were loaded with 20 g of cellulose (Fluka,
Avicel ® PH-101, microcrystalline) into a ZrO2 bottle
(2000 mL). The closed autoclave was heated at 393 K
in an electric oven with an axis to rotate the autoclaves
which were vertically rotated (22 rpm) to stir the reac-
tion media.
After the reaction, the reaction mixture was separated
by using normal filter paper. The filtrate solution was
analyzed with two HPLC systems (Hitachi, L-7490 RI Reaction conditions; reaction time 30 min, glucose 45 mg, distilled
water 5 mL, agitation.
detector, Shodex Sugar KS-802 column; Hitachi,
L-2035 UV-vis detector, Shodex RSpak KC-811 double Fig. 1 Hydrothermal Reactions of Glucose without Catalysts
columns) for saccharides and organic acids, and TOC
analyzer (Shimadzu, TOC 5000 A) for total amounts of
water soluble organic compounds. The dissolved and dehydration of the products15)~17). However, con-
SO42- ions in the filtrate solution were determined by trol of reactions is difficult in such short residence
ion chromatography (Dionex, DX-120, IonPac AS14A times. Mildly hydrothermal conditions and less short
column). The yields of products and total water solu- reaction times are desirable for industrial applications
ble organic compounds (WSOCs) were measured as of the hydrolysis of cellulose into glucose.
carbon % based on moles of carbon included in the To assess the range of the reaction temperature for
charged saccharides as determined by CHNS analyzer. high glucose yields from cellulose, the hydrothermal
For example, the yield of glucose was calculated as fol- stability of glucose was examined. The hydrothermal
lows: reactions of glucose were carried out without catalysts
Glucose yield (%)=(mol of glucose×6)/(mol of car- for 30 min (Fig. 1). The concentrations of glucose
bon included in charged saccharides determined by were constant at temperatures below 450 K, but drasti-
CHNS analyzer)×100. cally decreased under hydrothermal conditions at tem-
The yields of total WSOCs were determined by a peratures over 470 K. If the hydrolysis of cellulose is
TOC analyzer. The yields of total WSOCs and water carried out at over 470 K, the produced glucose may be
soluble by-products and the selectively of glucose were not stable and will react further. Consequently, glu-
calculated as follows: cose is stable under hydrothermal conditions below
Total WSOCs yield (C-%)=(mol of water soluble 450 K during less short residence times of products.
organic carbon)/(mol of carbon included charged cel- Therefore, cellulose hydrolysis was investigated using
lulose)×100. solid acid catalysts under mildly hydrothermal condi-
Water soluble by-products yield (C-%)=(yield of tions at temperatures below 450 K.
total WSOCs)−(yield of glucose). 3. 2. Effects of Ball-milling Treatments on the
The product yield at each reaction time was deter- Selective Hydrolysis of Cellulose
mined by high performance liquid chromatography The crystallinity of cellulose was characterized by
(HPLC), TOC, and IC analyzers for the filtrate solution XRD. Figure 2 shows the effects of ball milling on
of each reaction batch. The error of experimental data the XRD patterns of cellulose. After ball milling for
in this study, such as the amounts of sulfo groups, Pt over 24 h, the diffraction peaks attributed to cellulose
loading, surface area, and product yields, was within had almost disappeared, indicating that the crystallinity
10 %. of cellulose markedly decreased with ball-milling treat-
ment. Even after ball-milling treatment, all cellulose
3. Catalytic Hydrothermal Hydrolysis of Cellulose powders were white and insoluble in water. The
into Glucose degrees of polymerization of the cellulose molecular
chains might also not have decreased with the ball-
3. 1.◎R e a c t i o n B e h av i o r s o f G l u c o s e u n d e r milling treatment, which might not promote the hydro-
Hydrothermal Conditions lysis of glycoside bonds. Therefore, hydrothermal
The hydrothermal reactions of cellulose in super- hydrolysis of each cellulose using the AC_SO3H cata-
critical water resulted in easy saccharization into mix- lyst at 423 K was carried out. As shown in Figs. 2
tures of oligo-saccharides and glucose within extremely and 3, the crystallinity of cellulose affected the conver-
short residence times which avoided further degradation sion into glucose. Decreased cellulose crystallinity re-

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


77

sulted in increased glucose yield even in reactions using 3. 3.◎C a t a l y t i c H y d ro t h e r m a l H y d ro l y s i s o f


solid acid catalysts, as in the hydrothermal reactions of Cellulose over Various Catalysts
cellulose using diluted sulfuric acid21). Cellulose pow- 3. 3. 1. Characterizations
der pre-treated for 48 h was used in the following reac- The characterization data of the catalyst materials are
tions. summarized in Table 1, in which values given in
parentheses for the H-form zeolites are the Si/Al ratios.
In the case of H-form zeolites, the amounts of Al atoms
theoretically correspond to the amounts of Brønsted
acid sites. The acid sites were determined by the titra-
tion method in aqueous solutions and were inversely
proportional to the Si/Al ratios, except for H-mordenite
(20). The acid sites of H-mordenite were difficult to
accurately determine (20) because the powder was sus-
pended in NaOH aqueous solution and some parts of
the powder could not be separated from the aqueous so-
lution for the titration. The specific surface areas of
catalysts were measured without pre-heating treatment
(Table 1). The areas of the H-form zeolites were lower
than those after dehydration treatment at about 673 K.
In particular, the H-form of zeolites with lower Si/Al
Fig. 2●XRD Patterns of Cellulose Samples Pre-treated by Ball ratios, such as H-mordenite (10) and H-beta (13),
Milling for 0-144 h showed significantly lower specific surface area,
because the micropores of such hydrophilic zeolites
was filled by water molecules under air.
The activated carbon had high surface area of
1243 m2・g -1. The activated carbon was sulfonated
and then hydrothermally pre-treated at 473 K to
improve its tolerance to the hydrothermal catalytic reac-
tion media at around 423 K. Although the sulfonation
treatment of the activated carbon and the subsequent
hydrothermal treatment decreased the surface area, the
sulfonated activated-carbon (AC_SO3H) still had high
surface area of 806 m2・g-1. The XRD pattern showed
two broad peaks at around 24° and at around 42° attri-
buted to amorphous carbon consisting of aromatic car-
bon sheets oriented in a considerably random direc-
tions37) (Fig. 4). The XRD pattern was almost same
Reaction conditions; reaction time 24 h, catalyst 50 mg, cellulose as that before the sulfonation. AC _SO3H contained
45 mg, distilled water 5 mL, agitation.
0.63 mmol・g-1 of acidic sites, which was in good agree-
Fig. 3●Hydrothermal Hydrolysis of Cellulose in Fig. 2 Using AC_ ment with the sum of acidic sites of untreated activated-
SO3H Catalyst at 423 K carbon (0.25 mmol・g-1) and an S content of AC_SO3H

Table 1 Characterization Data

Si/Al S contents Acid sitesa) S. A.b)


[molar ratio] [mmol・g-1] [mmol・g-1] [m2・g-1]
SiO2 n.d. n.d. 0.095 407
γ-Al2O3 n.d. n.d. 0.049 140
H-mordenite (10) 10 n.d. 0.7 15
H-beta (13) 13 n.d. 1.05 105
H-ZSM-5 (45) 45 n.d. 0.30 124
H-beta (75) 75 n.d. 0.18 315
Activated carbon n.d. 0.0 0.24 1243
AC_SO3H n.d. 0.44 0.67 806
Sulfated zirconia n.d. 1.2 1.60 52
Amberlyst 15 n.d. 1.7 1.8 n.d.
a) Amounts of acid sites on catalysts were determined by a titration method.
b) Specific surface area was measured without pre-heating treatments of catalysts.

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


78

such as H-beta (75) and H-ZSM5 (45) showed higher


activity for glucose formation than the zeolite catalysts
with relatively low Si/Al ratio such as H-beta (13) and
H-mordenite (10). A similar relationship between Si/
Al ratios and glucose yields was reported in maltose
hydrolysis28). The zeolite catalysts with high Si/Al
ratios had relatively highly hydrophobic character, pre-
ferring organic compounds to water, which may be a
cause of the relatively high glucose yield.
The activated carbon (AC) and AC_SO3H catalysts
had higher hydrophobic character than zeolite catalysts.
However, the AC with acidic surface functional groups,
such as carboxylic groups, showed low catalytic activity
Fig. 4 XRD Patterns of Activated Carbon (AC) and the AC_SO3H for the cellulose hydrolysis. In the catalytic hydro-
thermal hydrolysis of cellulose at 423 K for 24 h,
AC_SO3H catalyst formed glucose in 40.5 C-% yield,
with minor water soluble by-products including C1-C2
carboxylic acids. The high catalytic activity was prob-
ably due to the sulfo groups. The product selectivity
was about 90 C-%, estimated as the ratio of the glucose
yield to the total yield of the water soluble compounds.
The AC_SO3H catalyst showed significantly higher cat-
alytic activity and glucose selectivity than the tested
H-form zeolite catalysts, which might be due to the
more hydrophobic graphene planes and strong acidic
SO3H surface functional groups of the AC_SO3H cata-
lyst.
Among the solid catalysts tested, sulfated zirconia
Reaction conditions: milled cellulose (45 mg), catalyst (50 mg), dis- and Amberlyst 15 also gave relatively high yields of
tilled water 5.0 mL, 24 h. glucose. However, the sulfated zirconia catalyst formed
a significant amount of water soluble by-products, such
Fig. 5●Cellulose Hydrolysis over Various Solid Acid Catalysts at as carboxylic acids, oligosaccharides, and sugar deriva-
423 K
tives. Amberlyst 15 catalyst consisting of an ion-
exchange resin with SO3H groups also showed consid-
(0.44 mmol・g-1). All S atoms in the sugar catalyst, a erable formation of water soluble by-products. In
sulfonated carbon material, are contained in SO3H addition, the ion-exchange resin colored to dark brown
groups according to X-ray photoelectron spectroscopy after reaction, due to the low hydrothermal stability.
(XPS) spectra31),32). The same would be true in the 3. 4.◎C a t a l y t i c H y d ro t h e r m a l H y d ro l y s i s o f
case of our AC_SO3H, and the high catalytic activity Cellulose over AC–SO3H Catalyst
would be due to the SO3H groups. The S contents of Figure 6 shows the effect of reaction temperature on
sulfated zirconia and Amberlyst 15 are 1.2 and cellulose hydrolysis with AC _ SO3H catalyst. The
1.7 mmol・g-1, which are larger than that of the AC_SO3H. yield of glucose increased with higher temperature in
Both AC and AC_SO3H particles had sizes between 5 the range of 403-433 K and reached 43 C-% at 433 K.
and 100 μm, according to SEM observations. These However, in the range of 433-453 K, the yield of glu-
particle sizes were almost the same as those of milled cose markedly decreased to 3 C-% at 453 K, the yield
cellulose, but were larger than the particles of the of by-products increased, and the total yields of glucose
H-form zeolites and the sulfated zirconia with sizes and water soluble by-products decreased. The reac-
between 0.5 and 20 μm. tion for 3 h at 453 K resulted in a relatively high glu-
3. 3. 2. Catalytic Hydrothermal Hydrolysis of the cose yield of 44 C-%, indicating that glucose sub-
Cellulose sequently reacted to form water soluble and insoluble
The catalytic results are summarized in Fig. 5. The by-products.
values given in parentheses for the H-form zeolites are After the first reaction run using AC_SO3H catalyst at
the Si/Al ratios. γ-Alumina and silica catalysts 423 K for 24 h, the solid catalyst was filtered with the
showed almost no activity. The H-form zeolite cata- cellulose residue. The fresh cellulose was added to the
lysts showed significantly higher activity than the blank filtrate solution, and then the reaction was carried out at
reaction. The zeolite catalysts with high Si/Al ratio 423 K for 24 h. As shown in Fig. 7, the reaction in

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


79

lyzed into glucose over the solid catalyst, and the


catalyst is not deactivated during the catalytic reaction.
3. 5.◎Comparison of AC – SO3H Catalyst with
Diluted Sulfuric Acid Catalysts
Figure 8 shows the changes in product yields during
cellulose hydrolysis using dilute acid of 0.01 mol・L-1
H2SO4 and AC _ SO3H catalyst at 423 K. The SO3H
functional groups bonded on AC_SO3H catalyst (50 mg)
in 5 mL corresponded to 0.0044 mmol・L-1 which was
lower than the 0.01 mol・L-1 of the dilute acid. At the
reaction time of 24 h, the dilute acid gave a similar glu-
cose yield to the AC_SO3H catalyst, but the resultant
solution became brown and contained large amounts of
water soluble by-products including formic, acetic, and
Reaction conditions; reaction time 24 h (closed symbol) or 3 h (open glycolic acids. These by-products are known inhibi-
symbol), catalyst 50 mg, cellulose 45 mg, distilled water 5 mL, agita- tors for further chemical and biochemical conversions
tion. of glucose into useful chemicals. The solid acid cata-
lysts with SO42- elution during reaction, such as sulfated
Fig. 6●Effect of Reaction Temperatures on Cellulose Hydrolysis
Using AC_SO3H Catalyst zirconia and Amberlyst 15, also showed relatively high
yields of water soluble by-products which would be due
to free SO42- ions. During the reaction within 24 h,
the yields of glucose increased linearly with reaction
time in both reactions. Under such reaction conditions
with low conversion, the AC _ SO3H catalyst always
showed high selectivity for glucose, whereas the dilute
acid showed high selectivity for by-products. When
the reaction time was longer than 24 h, the glucose
yield did not increase for either AC _ SO3H or dilute
acid. Insoluble milled cellulose seemed to partly con-
tain a robust structure resistant to hydrolysis over AC_
SO3H. The glucose yield significantly decreased in
the dilute acid for reaction times longer than 24 h.
Further reaction of glucose did not occur over the AC_
SO3H, compared with dilute acid. These results indi-
cated that AC_SO3H catalyst without SO42- elution had
excellent catalytic properties in contrast to dilute acid
(a) After 1st run with AC_SO3H catalyst, the catalyst was removed by for cellulose hydrolysis into glucose.
filtration, fresh cellulose was added the filtrate solution without solid 3. 6. Effects of Hydrothermal Pre-treatment of
catalyst and 2nd run was performed. (b) After 1st run with AC _ AC–SO3H Catalyst on Selective Hydrolysis of
SO3H catalyst, fresh cellulose was added the slurry solution including
solid catalyst and products. After 2nd run, fresh cellulose was added
Cellulose
again to the solution with catalyst, and 3rd run was performed. To clarify the effects of pre-treatment of the AC _
Reaction conditions were the same as in Fig. 1 SO3H catalyst (Entry 2 in Table 2) under hydrothermal
conditions at 473 K on the catalytic properties, sulfo-
Fig. 7 Recycled Catalyst Runs nated activated-carbon without hydrothermal treatment
was also examined. As shown in Entry 3, this material
the filtrate solution without the solid catalyst resulted in had SO3H functional groups of about 0.6 mmol・g-1 and
a marked decrease of the glucose yield similar to those surface area of 941 m2・g -1, both larger than those of
in the blank reaction (Fig. 5) and the reactions with AC_SO3H of Entry 2. The sulfonated activated-carbon
dilute formic acid at less than 1.0 mmol・L-1. However, without hydrothermal treatment (Entry 3) showed simi-
after the 1st run, fresh cellulose was added to the lar glucose yield to the AC _ SO3H catalyst, but also
resultant solution with the AC_SO3H catalyst, and then water soluble by-products yield of about 10 C-% and a
the 2nd reaction was carried out. The reaction was significant amount of SO42- elution after the reaction.
repeated once again (3rd reaction). The products in The water soluble by-products were not oligo-saccarides,
the 2nd and 3rd runs were similar to the 1st run, and the but may have been the derivatives of oligo-saccharides
glucose concentration doubled and tripled in the reac- and glucose, such as carboxylic acids. The hydro-
tor. These results indicated that the cellulose is hydro- thermal pre-treatment of the sulfonated catalyst has a

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


80

Reaction conditions; catalyst 50 mg, cellulose 45 mg, distilled water (or dilute acid) 5 mL, agitation.

Fig. 8●Changes in Product Yields during Cellulose Hydrolysis Using Dilute Acid of 0.01 M H2SO4 (a) and
AC_SO3H Catalyst (b) at 423 K

Table 2 Characterizations and Catalytic Properties for Cellulose Conversion

Product yields [C-%]a) SO42- elutionb) S contentc)


Entry Catalysts
Total WSOCs a)
Glucose C1-C2 acids [mmol・g-1] [mmol・g-1]

1 Activated carbon 7.2 6.4 0.8 <0.03 0.02


2 AC_SO3H 42.8 40.5 1.9 <0.03 0.44
3 AC_SO3H without hydrothermal treatment 52.8 41.4 2.4 1.1 0.58
4 Amberlyst 15 32.7 25.5 0.7 1.7 1.7
5 Sulfated ZrO2 38.4 14.2 3.1 14.1 1.2
6 0.01 M H2SO4c) 61.8 38.7 6.1 10 —
Reaction conditions; reaction at 423 K for 24 h. Catalyst 50 mg, cellulose 45 mg, distilled water (diluted sulfuric acid) 5 mL.
a) Yields of products and total water soluble organic compounds (WSOCs) were determined by the HPLC and TOC analyzers, respec-
tively, and shown as carbon % based on moles of carbon, determined by CHNS analyzer, in cellulose.
b) Concentration of SO42- ions in resultant solutions after the reactions were determined by ion-chromatography.
c) S contents were determined by CHNS analyzer.

powerful effect for preventing the removal of SO3H and 5, also had relatively high yields of water soluble
functional groups during the hydrothermal reaction. by-products, which would be due to the eluted SO42-
An ion-exchange resin with SO3H groups (Entry 4) ions.
showed significant catalytic activity for glucose forma- Consequently, this chemical process to combine
tion, but also about 8 C-% of by-products and a signifi- mildly hydrothermal conditions and stable acid cata-
cant amount of SO42- elution as high as the untreated lysts, such as the AC _ SO3H catalyst, is efficient to
AC_SO3H catalyst (Entry 3). The ion-exchange resin selectively hydrolyze cellulose into glucose. The use
became dark brown after the reaction, which was due to of solid acid catalysts without suitable pre-treatment
the lower thermal stability. Sulfated zirconia (Entry 5) require scrupulous attention to elution of active sites,
also showed catalytic activity for cellulose conversion such as sulfo groups. The bond strength between sulfo
into glucose. However, the resultant solution was groups and activated carbon may depend on the binding
brown and contained large amounts of water soluble location of the activated carbon. The hydrothermal
by-products. Furthermore, the sulfated zirconia was pre-treatment would remove SO3H groups with relatively
decomposed during the hydrothermal reaction, which weakly binding with the activated carbon. On the other
resulted in 14.1 mmol・L -1 SO42- ions in the resultant hand, the acid strength of SO3H groups also depends on
solution. the binding location.
Dilute acid of 0.01 mol・L-1 H2SO4 (Entry 6) showed 3. 7. Selective Hydrolysis of Starch over AC–SO3H
similar glucose yield to the AC_SO3H catalyst (Entry 2), Catalyst
but the resultant solution was brown and contained In reactions of cellulose using solid catalysts, the true
large amounts of water soluble by-products including conversion of cellulose is difficult to determine because
formic, acetic, and glycolic acids. These carboxylic unreacted cellulose residues cannot be completely sepa-
acids are known inhibitors for further conversion of glu- rated from the solid catalysts and insoluble by-products.
cose into useful chemicals. The solid acid catalysts Starch contains α-glycosidic bonds of D-glucose, and
leading to SO42- elution during reaction, in Entries 3, 4, is a soluble polysaccharide under hydrothermal condi-

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


81

Reaction conditions; reaction time 24 h (a), reaction temperature 393 K (b), catalyst 50 mg, starch
45 mg, distilled water 5 mL, agitation.

Fig. 9●Effect of Reaction Temperature (a) and Reaction Time (b) on Starch Hydrolysis Using AC _
SO3H Catalyst

tions. The AC_SO3H catalyst in the hydrolysis of starch of polysaccharides such as starch and cellulose into
showed selective glucose production of higher than monosaccharides such as glucose and for the oxidation
90 % yield (Fig. 9). The amounts of total carbon of of monosaccharides into sugar acids are likely to be
water soluble organic compounds was always over 96 developed. As is well known, polysaccharides can be
C-% of the charged starch in the reaction-temperature converted into monosaccharides by homogeneous acid-
region of 373-423 K for 24 h. This result suggests that catalyzed reactions using sulfuric acid. However, the
most products from the hydrolysis of polysaccharides use of sulfuric acid results in large amounts of acid
under such reaction conditions using the AC_SO3H cat- waste and energy consumption in the separation pro-
alyst are present in the aqueous phase. Few products cess. Solid acid catalysts can also be used for the
are found in the gas phases or on the solid catalysts. hydrolysis of polysaccharides with low environmental
In this study, the conversion of cellulose was estimated impact as discussed above. Although the noble metal-
to be almost equal to the yield of WSOCs. In the reac- solid acid catalysts, such as Pt/zeolites and Pt/sulfated-
tion using the AC _ SO3H catalyst at 423 K for 24 h zirconia, have bifunctional catalysis effects for the
(Entry 2 in Table 1), the cellulose conversion was esti- dehydroisomerization of butane into isobutene45),46) and
mated to be 43 %. The insoluble cellulose treated by the isomerization of alkanes47),48) and so on, these con-
ball milling in this study probably included about a half ventional catalysts are easily collapsed and/or dissolved
of its structure resistant to hydrolysis over the AC _ in hot water with low pH values attributed to the organic
SO3H catalyst. In addition, this result suggested that acids produced. As discussed above, we achieved the
the AC _SO3H catalyst selectively hydrolyzes soluble selective hydrolysis of cellulose using the AC_SO3H
polysaccharides into monosaccharides. catalyst34),35). Carbon materials are highly stable in
hot and acidic water. AC_SO3H is expected to be a
4. Direct Production of Gluconic Acid from suitable support for acid catalysis, because the activated
Polysaccharides Using a Bifunctional Pt/AC – carbon provides high surface area and high thermal sta-
SO3H Catalyst bility for the impregnation method to prepare noble
metal fine particles, and the AC_SO3H provides strong
D-Gluconic acid is an important industrial product, acidity and water tolerance for the hydrolysis of saccha-
used as an intermediate in the food industry, in pharma- rides in water35),44).
ceutical applications, and as a water-soluble cleansing 4. 1. Characterization of the Pt/AC–SO3H Catalyst
agent38). Recent developments have shown the poten- The characterization data of the catalysts are summa-
tial of inorganic heterogeneous catalysts for oxidizing rized in Table 3. The platinum content of Pt/AC and
monosaccharides with oxygen or air39)~44). However, Pt/AC_SO3H were 4.2 wt% and 3.9 wt%, respectively,
most natural sac charide s are pol ysacchari des. or about 0.2 mmol・g -1. The platinum content of Pt/
Therefore, a one-pot synthesis of sugar acids from poly- AC _SO3H catalyst was almost the same as that of its
saccharides would be extremely important in a sustain- precursor Pt/AC, which indicated that platinum species
able society. Bifunctional catalysts for the hydrolysis were little removed during the sulfonation treatment.

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


82

Table 3 Characterization Data of the Used Catalysts


a)
BET Acidb) S contentc) Pt contentd) Pt particle sizee)
[m2・g-1] [mmol・g-1] [mmol・g-1] [wt%] [nm]
AC 1243 0.24 0.0 — —
AC_SO3H 806 0.69 0.44 — —
Pt/AC 1202 n.d. 0.0 4.2 3.3
Pt/AC_SO3H 226 0.57 0.26 3.9 4.7
a) Determined by nitrogen adsorption. b) Determined by titration. c) Determined by CHNS analyzer.
d) Determined by ICP. e) Estimated by powder XRD.

Reaction conditions; starch 45 mg, water 5.0 mL, a) catalyst 50 mg.


b) mixed catalyst 100 mg (consisting of 50 mg of Pt/AC and 50 mg of
Fig. 10●XRD Patterns of Activated Carbon (a), AC_SO3H (b), Pt/ AC_SO3H).
AC (c), and Pt/AC_SO3H (d)
Fig. 11 Reactions of Starch at 393 K for 24 h

As shown in Fig. 10, XRD patterns of these platinum


catalysts show diffraction peaks of metallic platinum catalyst formed almost no glucose or oligosaccharides
which indicated that the platinum particles were mainly but formed the amounts of water soluble organic com-
in the metallic state. The platinum particle sizes pounds (WSOCs) corresponding with the starting
increased from 3.3 nm in Pt/AC to 4.7 nm in Pt/AC_ starch, based on carbon %. The main component of the
SO3H, base on the XRD findings. The S content of Pt/ WSOCs was unreacted starch. The AC catalyst had
AC_SO3H was 0.26 mmol・g-1, as determined by CHNS acidic surface functional groups, such as carboxylic
elemental analysis, which was comparable but less than acid groups, but showed low catalytic activity for the
the 0.44 mmol・g-1 of AC_SO3H. The specific surface starch hydrolysis. The AC catalyst formed about 1
area of Pt/AC _ SO3H was 226 m2・g -1. This surface C-% yield of glucose and 31 C-% of other water solu-
area was much higher than those of sulfonated carbon- ble organic compounds which were mainly unreacted
nanotube (CNT)49), sulfonated CNT supported plati- starch. The other 68 C-% disappeared from the water
num51), and sulfonated carbon31), but lower than that of phase. As shown in Table 4, the C and H chemical
the Pt/AC precursor. The specific surface area of AC_ compositions of the AC treated under hydrothermal
SO3H was also significantly less than that of AC. The conditions without starch was almost the same as that
surface area was measured by the BET method without of fresh AC. In contrast, the C/H ratio of the AC cata-
the heating pre-treatment. The sulfonation treatments lyst after the starch reaction was lower than that of the
resulted in decreased surface area, which might be due fresh AC. The decrease in C/H ratio corresponded to
to the increase of adsorbed water with more acidic sur- the adsorption of about 75 C-% of starch on the AC.
face functional groups on the sulfonated catalysts and The other 68 C-% was probably adsorbed on the AC.
the decrease of porosity. These findings show that Pt/ In contrast, the AC_SO3H catalyst formed glucose in
AC_SO3H with strong acidic sulfo groups, platinum 69 C-% yield and oligosaccharides, such as maltose and
fine particles, and high surface area was prepared by the maltotoriose, in 29 C-% yield, but almost no water sol-
impregnation and sulfonation method. uble by-products. As shown in Fig. 12 (a), the glu-
4. 2. Catalytic Conversion of Starch cose yields increased with longer reaction time over the
The reaction results at 393 K for 24 h are summa- AC_SO3H catalyst, and the glucose yield was over 90
rized in Fig. 11. After the reactions, all solutions C-% and the yield of WSOCs was about 95 C-% after
were clear and colorless. A blank reaction without 70 h. The AC _ SO3H catalyst selectively converted

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


83

Table 4 CHN Measurements of the AC before and after the Starch Reaction

C [wt%] H [wt%] Treatments


AC 68 3.7 After starch reaction at 393 K for 24 h
AC 87 1.8 After hydrothermal treatment at 393 K for 24 h
AC 87 1.8 Before both treatments

Reaction conditions; starch 45 mg, water 5.0 mL, and catalyst 50 mg.

Fig. 12●Changes in Product Yields during Reaction of Starch at 393 K over AC_SO3H (a) and Pt/AC_SO3H (b)
Catalysts

Reaction conditions; starch 45 mg and water 5.0 mL.

Fig. 13●Effects of the Amounts of AC_SO3H (a) and Pt/AC_SO3H (b) Catalysts on the Reactions of Starch
at 393 K for 24 h

starch into glucose, and adsorption of glucose on the a main product was gluconic acid in 40 C-% yield.
AC_SO3H catalyst was negligible. The molar ratio of Minor amounts of degradation products, such as acetic
produced glucose to sulfo groups in the AC_SO3H was acid and formic acid, were also formed. We carried
about 10, indicating that the sulfo groups acted as a cat- out the catalytic reactions with various amounts of cata-
alyst for the hydrolysis of starch. lysts. As shown in Fig. 13 (b), the yield of gluconic
As shown in Fig. 11, the Pt/AC_SO3H catalyst also acid increased linearly with higher amount of catalysts
gave high yields of the hydrolysis products, indicating up to 100 mg over the Pt/AC_SO3H catalyst, like the
that the Pt/AC _ SO3H catalyst had sulfo groups to yield of glucose over the AC _SO3H catalyst (Fig. 13
hydrolyze starch, like the AC_SO3H catalyst. However, (a)). The platinum particles were the active sites for

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


84

Reaction conditions; starch 45 mg, water 5.0 mL, and initial catalyst Reaction conditions; saccharides 45 mg, water 5.0 mL, and catalyst
50 mg. 50 mg.

Fig. 14●Recycled Catalyst Runs of the Reaction of Starch at 393 K Fig. 15●Catalytic Conversions of Starch, Pullulan, Maltose, and
for 20 h over Pt/AC_SO3H Catalyst Cellobiose at 393 K for 24 h over Pt/AC_SO3H Catalyst

glucose oxidation into gluconic acid because the cata- Pt/AC_SO3H catalyst were nearly neutral at about 6 and
lysts without platinum formed no gluconic acid. After about 3, respectively. The decrease in pH value was
reaction, the used Pt/AC_SO3H catalyst was character- mainly due to the production of gluconic acid. The fil-
ized. The amount of platinum in the used Pt/AC _ trate solution after the reaction using the Pt/AC_SO3H
SO3H was 4.0 wt% determined by ICP, and the average catalyst contained almost no sulfuric ion as detected by
platinum particle size was estimated to be 4.5 nm by ion chromatography. In addition, fresh starch was
XRD, which were almost the same as before the reac- introduced into the filtrate solution and then the reaction
tion. In addition, no leaching of platinum from Pt/ in the filtrate solution without catalyst was carried out
AC_SO3H catalysts was observed in the resultant solu- at 393 K for 24 h, but the starch was not hydrolyzed.
tion by ICP. The acid properties evaluated by the titra- These results clarified that the gluconic acid was pro-
tion method were also not changed by the reactions duced from starch by the one-pot process using the
with starch. The catalytic active sites, such as Pt parti- heterogeneous bifunctional Pt/AC_SO3H catalyst.
cles and sulfo groups, remained stable during the reac- On the other hand, the yield of gluconic acid was
tion in hot aqueous solution, because of the hydro- constant at 40 C-% over 24 h, possibly because oxygen
thermal pre-treatment of the Pt/AC _SO3H catalyst at was consumed during the oxidation reaction in the
473 K. batch reactor. After reaction for 40 h, the reactor was
Figure 12 (b) shows the changes in product yields cooled to room temperature and opened to introduce
during starch hydrolysis using the Pt/AC_SO3H catalyst fresh air. Further reaction was carried out at 393 K for
at 393 K. Although the yields of oligosaccharides, another 24 h. As shown in Fig. 3b, the yield of glu-
glucose, and gluconic acid increased linearly with conic acid increased to about 60 C-%. These results
longer reaction time within 9 h, the yield of oligo- suggest that a continuous flow of air in the reactor will
saccharides decreased with reaction time longer than increase the gluconic acid yield.
9 h, and the yield of glucose decreased with reaction 4. 3.◎C a t a l y t i c C o n v e r s i o n o f V a r i o u s
time longer than 18 h. In contrast, gluconic acid was Polysaccharides
sequentially produced and became the main product at The reactions of cellobiose, maltose, and pullulan
24 h. Molar ratios of gluconic acid to total S atoms were also carried out over the Pt/AC_SO3H catalyst at
and total Pt atoms in the catalyst were about 8 and 9, 393 K. The results are summarized in Fig. 15. The
respectively, indicating that the sulfo groups and plati- reaction products from pullulan, which is a poly-
num particles in the catalyst accelerated the hydrolysis saccharide of glucose with α-glycoside bonds and is
of starch into glucose and the oxidation of glucose into soluble in water at room temperature, were almost same
gluconic acid. The catalyst was separated by filtration, as those of starch. The reaction products of maltose
and then repeatedly used. Although a small amount of were glucose and gluconic acid. The yield of gluconic
the catalyst was lost in each run, gluconic acid and glu- acid was similar to those in the reactions of starch and
cose were formed as the main products even in the third pullulan. The product yields from cellobiose were
run with little slowing of formation rate (Fig. 14). almost same as those from maltose, indicating that
The pH values before and after starch reaction over gluconic acid is also obtained directly from oligo-

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


85

saccharides with β-1,4-glycoside bonds over the Pt/AC_ thermal reactions, Prof. M. Ikehara in Kochi Univ. for
SO3H catalyst. Consequently, Pt/AC _SO3H has bi- CHNS analysis, Prof. A. Usui in Kochi Univ. for SEM
functional catalysis for the hydrolysis and air oxidation observations, and the Catalysis Society of Japan for ref-
of various poly saccharides, such as cellobiose and erence catalysts.
starch, into gluconic acid. Referencese
4. 4. Comparison of Pt/AC–SO3H Catalyst and
Mixed Catalyst of AC–SO3H with Pt/AC 1) Huber, G. W., Iborra, S., Corma, A., Chem. Rev., 106, 4044
(2006).
The Pt/AC_SO3H catalyst (50 mg) was compared to 2) Klemm, D., Heublein, B., Fink, H., Bohn, A., Angew. Chem.,
the mixed catalyst of AC _ SO3H (50 mg) with Pt/AC Int. Ed., 44, 3358 (2005).
(50 mg). As shown in Fig. 11, the total amount of the 3) Farrell, A. E., Plevin, R. J., Turner, B. T., Jones, A. D., O’Hare,
hydrolysis products, such as oligosaccharides, glucose, M., Kammen, D. M., Science, 311, 506 (2006).
and gluconic acid, over the mixed catalyst was signifi- 4) Fan, L. T., Gharpuray, M. M., Lee, Y. H., “Cellulose
Hydrolysis,” Springer, Berlin (1987).
cantly smaller than that over the Pt/AC_SO3H catalyst. 5) Zhang, Y. P., Lynd, L. R., Biotechnol. Bioeng., 88, 797 (2004).
The mixed catalyst formed glucose in 43 C-% yield, 6) Ragauskas, A. J., Williams, C. K., Davison, B. H., Britovsek,
and gluconic acid in 11 C-% yield, whereas, the Pt/AC_ G., Cairney, J., Eckert, C. A., Frederick, W. J., Hallett, J. P.,
SO3H catalyst gave gluconic acid in 40 C-% yield. Leak, D. J., Liotta, C. L., Mielenz, J. R., Murphy, R., Templer,
The Pt/AC_SO3H catalyst showed higher activity than R., Tschaplinski, T., Science, 311, 484 (2006).
7) Davda, R. R., Dumesic, J. A., Chem. Commun., 36 (2004).
the mixed catalyst because adsorbed starch was easily 8) Davda, R. R., Shabaker, J. W., Huber, G. W., Cortright, R. D.,
desorbed after the hydrolysis of starch into sugars on Dumesic, J. A., Appl. Catal. B: Environment, 56, 171 (2005).
the Pt/AC_SO3H catalyst, as well as the AC_SO3H cata- 9) Mok, W. S., Antal, M. J., Varhergyi, G., Ind. Eng. Chem. Res.,
lyst. In contrast, adsorbed starch remained on the sur- 31, 94 (1992).
face of Pt/AC in the mixed catalyst, which led to de- 10) Faith, W. L., Ind. Eng. Chem., 37, 9 (1945).
11) Torget, R. W., Kim, J. S., Lee, Y. Y., Ind. Eng. Chem. Res., 39,
activation of the active platinum sites. If the conversion 2817 (2000).
of starch is carried out in a two-step reaction of hydro- 12) Bergius, F., Ind. Eng. Chem., 29, 247 (1937).
lysis of starch over AC_SO3H and oxidation of glucose 13) Higgins, F. J., Ho, G. E., Agric. Wastes, 4, 97 (1982).
over Pt/AC, unreacted polysaccharides and oligo- 14) Rorrer, G. L., Mohring, W. R., Hawley, M. C., Energy & Fuels,
saccharides might persist in the resultant solution of the 2, 556 (1988).
15) Sasaki, M., Fang, Z., Fukushima, Y., Adschiri, T., Arai, K., Ind.
first step and lead to the deactivation of Pt/AC in the Eng. Chem. Res., 39, 2883 (2000).
second step. 16) Sasaki, M., Adschiri, T., Arai, K., AIChE J., 50, 192 (2004).
17) Saka, S., Ueno, T., Cellulose, 6, 177 (1999).
5. Conclusions 18) Swatloski, P. R., Spear, S. K., Holbrey, J. D., Rogers, R. D., J.
Am. Chem. Soc., 124, 4974 (2002).
19) Li, C., Wang, Q., Zhao, Z. K., Green Chem., 10, 177 (2008).
This study describes our new environmentally friendly 20) Rinaldi, R., Meine, N., vom Stein, J., Palkovits, R., Schuth, F.,
chemical process to selectively hydrolyze cellulose into ChemSusChem, 3, 266 (2010).
glucose using sulfonated activated-carbon catalyst 21) Zhao, H., Kwak, J. H., Wang, Y., Franz, J. A., White, J. M.,
under hydrothermal conditions. The catalytic hydro- Holladay, J. E., Energy & Fuels, 20, 807 (2006).
thermal reactions using hydrothermally stable AC _ 22) V y ve r, S . V. , G e b o e r s , J . , J a c o b s , P. A . , S e l s , B . F. ,
ChemCatChem, 3, 82 (2011).
SO3H catalyst resulted in high glucose yields of about 23) Fukuoka, A., Dhepe, P. L., Angew. Chem., Int. Ed., 45, 5161
40 C-%, significant TON values of 15 or higher, and (2006).
almost no SO42- elution, which clearly indicates the 24) Yan, N., Zhao, C., Luo, C., Dyson, P. J., Liu, H., Kou, Y., J. Am.
heterogeneously catalytic hydrolysis of insoluble cellu- Chem. Soc., 128, 8714 (2006).
lose into glucose. In addition, the eluted SO42- ions 25) Luo, C., Wang, S., Liu, H., Angew. Chem., Int. Ed., 46, 7636
(2007).
from catalysts lead to reduced waste and catalytic de- 26) Cortright, R. D., Davda, R. R., Dumesic, J. A., Nature, 418,
activation, and increased water soluble by-products. 964 (2002).
This catalytic hydrothermal process using solid acid 27) Huber, G. W., Shabaker, J. W., Dumesic, J. A., Science, 300,
catalysts opens new opportunities for the efficient use 2075 (2003).
of cellulose resources as a chemical feedstock. The 28) Abbadi, A., Gotlieb, K. F., van Bekkum, H., Starch, 50, 23
(1998).
new bifunctional Pt/AC_SO3H catalyst was prepared by 29) Dhepe, P. L., Ohashi, M., Inagaki, S., Ichikawa, M., Fukuoka,
the impregnation and sulfonation method. The cata- A., Catal. Lett., 102, 163 (2005).
lyst was highly water tolerant and had catalytic proper- 30) Hara, M., Yoshida, T., Takagaki, A., Takata, T., Kondo, J. N.,
ties for the hydrolysis of polysaccharides and sequential Domen, K., Hayashi, S., Angew. Chem., Int. Ed., 43, 2955
air oxidation into gluconic acid in a one-pot process (2004).
31) Toda, M., Takagaki, A., Okumura, M., Kondo, J. N., Hayashi,
under hot water conditions. S., Domen, K., Hara, M., Nature, 438, 178 (2005).
32) Okumura, M., Takagaki, A., Toda, M., Kondo, J. N., Domen, K.,
Acknowledgments Tatsumi, T., Hara, M., Hayashi, S., Chem. Mater., 18, 3039
I thank Prof. Yanagisawa in Kochi Univ. for hydro- (2006).

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012


86

33) Zong, M. H., Duan, Z. Q., Lou, W. Y., Smith, T. J., Wu, H., 42) Ishida, T., Kinoshita, N., Okatsu, H., Akita, T., Takei, T.,
Green Chem., 9, 434 (2007). Haruta, M., Angew. Chem., Int. Ed., 47, 9265 (2008).
34) Onda, A., Ochi, T., Yanagaisawa, K., Green Chem., 10 1033 43) Abbadi, A., van Bekkum, H., J. Mol. Catal. A, 97, 111 (1995).
(2008). 44) Onda, A., Ochi, T., Kajiyoshi, K., Yanagisawa, K., Appl. Catal.
35) Onda, A., Ochi, T., Yanagaisawa, K., Top. Catal., 52, 801 A: General, 343, 49 (2008).
(2009). 45) Pirngruber, G. D., Seshan, K., Lercher, J. A., J. Catal., 186,
36) Onda, A., Ochi, T., Yanagaisawa, K., Catal. Commun., 12, 421 188 (1999).
(2011). 46) Komatsu, T., Ikenaga, H., J. Catal., 241, 426 (2006).
37) Tsubouchi, N., Xu, C., Ohtsuka, Y., Energy & Fuels, 17, 1119 47) Ebitani, K., Konishi, J., Hattori, H., J. Catal., 130, 257 (1991).
(2003). 48) Iglesia, E., Soled, S. T., Kramer, G. M., J. Catal., 144, 238
38) Datta, R., “Encyclopedia of Chemical Technology,” Vol. 13, (1993).
4th ed., Wiley, New York (1995). 49) Wang, H. J., Yu, H., Peng, F., Lv, P., Electrochem. Commun., 8,
39) Besson, M., Gallezot, P., Catal. Today, 7, 127 (2000). 499 (2006).
40) Biella, S., Prati, L., Rossi, M., J. Catal., 206, 242 (2002). 50) Peng, F., Zhang, L., Wang, H., Lv, P., Yu, H., Carbon, 43, 2397
41) Mirescu, A., Prüße, U., Catal. Commun., 7, 11 (2006). (2005).

要   旨

スルホン化活性炭を用いた触媒水熱法によるセルロースなどの多糖類から単糖への選択的加水分解

恩田 歩武

高知大学理学部附属水熱化学実験所,780-8520 高知市曙町2-5-1

比較的温和な水熱反応と固体触媒反応を組み合わせる方法に したのは,水熱反応場で安定であり,強酸性のスルホ基を持ち,
よりセルロースからグルコースを得るプロセスは,セルロース 単糖ではなく多糖を吸着しやすい活性炭表面を有するためであ
系バイオマスを利用する持続型社会の実現において重要な技術 る。また,そのスルホン化活性炭触媒に貴金属の白金微粒子を
の一つとして期待される。著者らは,H 型ゼオライトや硫酸基 担持した二元機能触媒(Pt/AC _ SO3H)は,活性炭に含侵法で
およびスルホ基を有するものなどを固体触媒に用いて,β-1,4- 白金微粒子を担持し,それをスルホン化することにより調製し
グリコシド結合をもつセルロースに対して 150 ℃ 付近の温度 た。Pt/AC _ SO3H 触媒を用いたワンポット反応により,水溶媒
で 触 媒 水 熱 反 応 を 行 っ た と こ ろ, ス ル ホ ン 化 活 性 炭(AC _ 中 120 ℃ 空気雰囲気において,デンプンやセロビオースから
SO3H)触媒が高いグルコース収率を示すことを見出した。こ グルコン酸を得た。
の水熱前処理したスルホン化活性炭触媒が優れた触媒特性を示

J. Jpn. Petrol. Inst., Vol. 55, No. 2, 2012

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