Selective Hydrolysis of Cellulose and Polysaccharides Into Sugars by Catalytic Hydrothermal Method Using Sulfonated Activated-Carbon
Selective Hydrolysis of Cellulose and Polysaccharides Into Sugars by Catalytic Hydrothermal Method Using Sulfonated Activated-Carbon
Selective Hydrolysis of Cellulose and Polysaccharides Into Sugars by Catalytic Hydrothermal Method Using Sulfonated Activated-Carbon
[Review Paper]
Ayumu ONDA*
Research Laboratory of Hydrothermal Chemistry, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi 780-8520, JAPAN
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
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
Scheme 2 Catalytic Conversion of Starch into Gluconic Acid over Pt/AC_SO3H Catalyst
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
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-
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.
Table 4 CHN Measurements of the AC before and after the Starch Reaction
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
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
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-
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).
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