One pot direct catalytic conversion of cellulose to hydrocarbon by decarbonation using Pt/H-beta zeolite catalyst at low temperature

Article abstract of DOI:10.1007/s10562-013-0992-8

We investigated one pot direct catalytic conversion of cellulose to light hydrocarbon selectively at low temperature in the presence of Pt and solid-acid zeolite catalysts. Results revealed that Pt/H-beta zeolite catalyst prepared by ion exchange enabled

Full text of DOI:10.1007/s10562-013-0992-8

Catal Lett (2013) 143:418–423
DOI 10.1007/s10562-013-0992-8
One Pot Direct Catalytic Conversion of Cellulose to Hydrocarbon
by Decarbonation Using Pt/H-beta Zeolite Catalyst at Low
Temperature
Yuki Kato Yasushi Sekine
•
Received: 23 January 2013 / Accepted: 6 March 2013 / Published online: 14 March 2013
Ó Springer Science+Business Media New York 2013
Abstract We investigated one pot direct catalytic con-
version of cellulose to light hydrocarbon selectively at low
temperature in the presence of Pt and solid-acid zeolite
catalysts. Results revealed that Pt/H-beta zeolite catalyst
prepared by ion exchange enabled selective production of
C and C hydrocarbons.
Better safety, a lower environmental burden, lower cost,
and single-step processing are required. Some processes
use solid catalysts to solve these problems for cellulose
conversion. At present, various solid catalysts are under
investigation to convert cellulose into glucose [8–10],
chemical precursors [11–13], and fuel [14–16]. Fukuoka
et al. [17] developed Pt-supported or Ru-supported catalyst
to convert cellulose into monosaccharide.
3
4
Keywords One pot conversion Á Cellulose Á Beta zeolite Á
Biomass Á Solid acid catalyst Á Low temperature reaction
In this paper, we examined one pot conversion of cel-
lulose to light hydrocarbons including C and C , which are
3
4
important feedstocks for petrochemistry, by decarbonation
using zeolite catalysts at low temperatures around 443 K
using water as a medium. We applied a high Si/Al ratio
proton form zeolite, which functions as a solid acid catalyst
even in water [18].
1
Introduction
Renewable resources (sunlight, solar heat, water energy, wind
energy, biomass, etc.) are attracting increasing attention as
substitutes for fossil resources. Among them, biomass offers
some advantages as a ubiquitous feedstock. Major uses of
cellulose biomass have remained limited to paper, recycled
fiber, cellulose acetate, and cellulose nitrate because of the
difficulty of cleavage of b-glycoside bonds in cellulose. To
expand cellulose biomass use, a multi-step process of cellu-
lose conversion is proposed. Concentrated sulfuric acid [1, 2],
dilute sulfuric acid [3], cellulase [2, 4, 5], and supercritical
water [6, 7] are useful for hydrolysis of cellulose to glucose in
the first step. In each way, various problems exist, including
corrosion of equipment, distillation of products, higher cost,
low reaction rate, and higher temperature and pressure. Glu-
cose is converted into chemical precursors and fuel in the
second step through fermentation.
2 Experimental
2.1 Catalyst Preparation
Various zeolites were used for this study: H-*BEA (beta)
zeolites were prepared using the dried gel conversion
method with a preparation method described elsewhere
[19]. The as-made *BEA was calcined at 813 K for 8 h
-
1
under 100 mL min of air to obtain Na-*BEA zeolite.
Na-*BEA zeolite was ion-exchanged with 1 N-NH NO
4
3
(Kanto Chemical Co. Inc.) solution containing 40 times of
?
NH4 to the mass of Al and kept at 353 K for 1 h except
some experiments. After ion exchange, zeolite was filtered
and washed with distilled water. This operation was repe-
ated three times and dried at 383 K overnight to obtain
Y. Kato Á Y. Sekine (&)
Department of Applied Chemistry, School of Advanced Science
and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku,
Tokyo 169-8555, Japan
NH -*BEA zeolite. The sample was calcined at 813 K for
4
-
1
8
h under 100 mL min
of air to obtain H-*BEA(25)
e-mail: ysekine@waseda.jp
zeolite, its SiO /Al O ratio was 25.
2 3
2
1
23

One Pot Direct Catalytic Conversion of Cellulose to Hydrocarbon
419
3
Metal-supported catalysts were prepared by impregna-
tion or ion exchange. For impregnation, the following
supports were used: H-*BEA(25), H-*BEA(150) (JRC-Z-
HB150), H-MOR(10.2) (Tosoh Corp.), H-MOR(90) (JRC-
Z-HM90), H-FER(18) (Tosoh), H-USY(14) (Tosoh),
H-ZSM-5(38) (Tosoh), and c-Al O (JRC-ALO-8). The
2.0 % mixture gas was adsorbed for 0.49 cm (STP) per
dose. The CO amount was detected using a TCD.
2.3 Catalytic Experiments
All experiments were performed in a batchwise autoclave
(inner volume: 30 mL, made of stainless SUS316). The
reaction condition was as follows: distilled water/cellulose/
zeolite (/M/c-Al O ) = 20 mL/0.25 g/0.25 g (/0.25 g), reac-
2
3
number in parentheses after the name of zeolite denotes its
SiO /Al O ratio. For loading active metal, Pt, Pd, Co, Cu,
2 2 3
Ni, or Fe was supported on c-Al O or H-zeolite. The
2
3
2 3
loading amount was 3 mol% for c-Al O or 1.0 wt% for
tion temperature = 423, 443 or 463 K, reaction time = 1, 3
or 5 h, stirring rate = 600 rpm. Cellulose was pre-treated
using a planetary mill (Pulverisette 6 classic line; Fritsch
GmbH) to produce fine particles using 14 grinding balls of
10 mm / diameter, rotation speed was 600 rpm for 30 min.
The catalyst was pre-treated in the reactor by 10 % H2
gas at 773 K. After a passivation of the catalyst by diluted
air, cellulose, distilled water and catalyst were charged in
the autoclave, and the autoclave was deaerated by nitrogen
2
3
H-zeolite. Only for Pt/H-*BEA(25) was the loading
amount changed to 0.10, 1.0 and 5.0 wt%. The following
reagents were used as metal precursors: tetra ammine
platinum (II) nitrate (Soekawa Chemical Co. Ltd.), palla-
dium (II) acetate (Kanto Chemical), cobalt (II) nitrate
hexahydrate (Kanto Chemical), copper (II) nitrate trihy-
drate (Kanto Chemical), nickel (II) nitrate hexahydrate
(
Kanto Chemical), iron (III) nitrate non-hydrate (Kanto
-
1
Chemical). Acetone was used as a solvent to prepare
Pd-supported catalysts. The support was mixed with ace-
tone for 1 h. Then a solution of palladium (II) acetate was
added to this mixture. The slurry was aged for 2 h. Then
the solvent was evaporated under heating and stirring and
powder was obtained. Distilled water was used as a solvent
to prepare the other supported catalysts, which were
otherwise prepared similarly to the Pd-supported catalyst.
After the obtained powder was dried at 383 K overnight, it
was calcined at 773 K for 3 h. The designation ‘‘IM’’ for
the catalyst denotes that it was prepared using an impreg-
nation method.
of 100 mL min for 5 min at atmospheric pressure. After
the deaeration, the reaction was conducted with continuous
stirring (600 rpm). The reaction starting time was deter-
mined at when the reaction temperature reached at a preset
temperature. After the reaction, the reactor was cooled with
water for 30 min. Gaseous and liquid products were ana-
lyzed qualitatively and quantitatively using a GC–MS
(GCMS-QP2010; Shimadzu Corp.), GC-FID (GC-2010,
GC-8A; Shimadzu Corp.), and GC-TCD (GC-8A; Shima-
dzu Corp.). In gaseous products, hydrogen, CO, CO , and
2
C –C hydrocarbons were detected for major products.
1
6
Acetone, furan, and 2-methylfuran were detected for minor
products. In liquid products, furfural, 5-hydroxy methyl
furfural (5-HMF) and levulinic acid were detected for major
products and acetone, butanone, pentanone were detected
for minor products. Cellulose consumption was calculated
by the sum of these all products based on carbon atom.
Another series of Pt/H-*BEA catalyst was prepared by ion
exchange and 0.10, 1.0, and 5.0 wt% Pt were supported on
NH -*BEA(25). Tetraammineplatinum (II) nitrate (Soeka-
4
wa Chemical Co. Ltd.) was used as the precursor. The
ion-exchanged zeolite was dried at 383 K overnight, and
-
1
calcined at 813 K for 8 h under 100 mL min of air to
obtain Pt/H-*BEA(25). The designation‘‘IE’’for the catalyst
denotes that it was prepared using ion exchange method.
3 Results and Discussion
2
.2 Characterization of Catalyst
3.1 Nature of Prepared Catalysts
The structures of zeolite and supported platinum were
determined using powder X-ray diffraction (XRD, RINT-
Before reaction experiments, we investigated the nature of
prepared catalysts using XRD, ICP, and CO adsorption to
elucidate the crystalline structure, exact amount of metal
loading, and metallic surface area. Powder XRD patterns
for each Pt/H-*BEA(25) catalyst applied in this research
showed a fine *BEA (beta zeolite) structure (see supporting
2
100, Cu Ka radiation; Rigaku Corp.).
A platinum loading amount over the support was deter-
mined using inductively coupled plasma (ICP, SPECTRO-
CIRO-CCD; Rigaku Corp.).
0
The metallic surface area of supported metal was mea-
sured for adsorption using CO pulse adsorption (Bel Cat;
Bel Japan Inc.). All samples were heated at a rate of
information). Pt peaks, 2h = 39.9°, 46.3°, 67.5°, 81.3°,
were observed on Pt/H-*BEA(25) exceed 1.0 wt% Pt
loading, but these peaks were very broad because of their
small particle size. The Pt loading amount was measured
using ICP, and the exact amounts of Pt weight for 0.10, 1.0,
5.0 wt% Pt/H-*BEA(25) were, respectively 0.11, 1.2,
-
1
1
0 K min up to 773 K and were kept for 1 h with H2
flow for pretreatment. After cooling to 323 K, the sample
was purged with He flow for 1 min, afterwards, CO/He
123

4
20
Y. Kato, Y. Sekine
4
.8 wt% by impregnation and 0.13, 1.0, and 1.9 wt% by
hydrocarbons. Next we investigated the effect of zeolite
structure, including different pore sizes, acid strengths and
acid amounts using various zeolites with 1 wt% Pt impreg-
nation. The reaction conditions were the following: distilled
water/cellulose/1 wt% Pt/H-zeolite = 20 mL/0.25 g/0.25 g,
applied zeolites were; H-*BEA(25) (homemade as above
mentioned), H-*BEA(150), H-USY(14), H-MOR(10.2),
H-MOR(90), H-ZSM-5(38), and H-FER(18), reaction tem-
perature was 443 K, reaction time was 3 h.
ion exchange. The metallic surface area of the catalyst was
measured using CO adsorption, and their values for 0.10,
1
.0, 5.0 wt% Pt/H-*BEA(25) prepared by impregnation
and ion exchange were 0.49, 0.68, 2.57, and 0.18, 1.23,
2
-1
.24 m g , respectively. The metallic surface areas were
1
almost identical between 1.0 wt% Pt/H-*BEA(25)IE and
1
3
.9 wt% Pt/H-*BEA(25)IE.
.2 Effects of Various Metal Catalysts
Table 2 shows cellulose consumption, amounts of prod-
ucts and selectivity to C and C hydrocarbons over various
3
4
First, we investigated the catalytic activity of various
metals on the reaction. To elucidate the catalytic nature of
various metals, we applied a physical mixture of metal
loaded alumina and H-*BEA zeolite to avoid sensitive
preparation. The reaction condition was as follows: dis-
tilled water/cellulose/H-*BEA(25)/M/c-Al O = 20 mL/
1.0 wt% Pt/H-zeolite. Cellulose consumptions were in the
following order: Pt/H-FER(18) \ Pt/H-MOR(90) \ Pt/H-
ZSM-5(38)\Pt/H-MOR(10.2) \Pt/H-*BEA(150) \Pt/H-
*BEA(25) \Pt/H-USY(14). This trend suggested that
H-zeolite which had large-pore and lower Si/Al ratio had
higher activity for the hydrolysis of cellulose, because cel-
lulose-derived products such as glucose, were able to diffuse
into these zeolite pores, and access acid sites and Pt metallic
sites easily in and on large pore zeolite. Netrabukkana et al.
[20] reported that glucose, which had 0.86 nm kinetic
diameter diffused into Y-zeolite, which had large pore sys-
tem. C and C hydrocarbons were produced selectively in
2
3
0
.25 g/0.25 g/0.25 g (M = Pt, Pd, Co, Cu, Ni, or Fe),
reaction temperature was 443 K, reaction time was 3 h.
Table 1 presents cellulose consumption, amounts of
products and selectivity to C and C hydrocarbons over
3
4
various catalysts. Cellulose consumptions showed close
values between over c-Al O and no catalyst, and between
2
3
3
4
over H-*BEA(25) and H-*BEA(25) ? c-Al O . Therefore,
products over zeolites with a large pore system: H-*BEA,
H-USY, and H-MOR. The selectivity to C and C hydro-
2
3
c-Al O is thought to have little or no activity for hydrolysis
2
3
3
4
of cellulose. On the other hand H-*BEA zeolite promoted
the hydrolysis of cellulose. Cellulose consumption was no
great distinction among H-*BEA(25) ? M/Al O catalysts
carbons was related to the inner pore reaction of glucose-
derived products. All liquiform products were produced less
degree and gaseous products were produced much over Pt/H-
*BEA(25) and Pt/H-USY(14) compared to other catalysts.
These two zeolites, H-*BEA(25) and H-USY(14) seemed to
be good candidates for the reaction, and we can control the
catalytic property only for H-*BEA (i.e. USY is a commer-
cial dealuminated zeolite), so we applied H-*BEA(25) as a
solid acid in further investigations.
2
3
except for H-*BEA(25) ? Pt/c-Al O . Gaseous products
2
3
were observed over Pt, Pd, Ni/c-Al O , which suggests that
2
3
cellulose-derived products were able to be cracked to gas-
eous product over these metal-supported catalysts. C and
3
C hydrocarbons were produced selectively in products
4
over only H-*BEA(25) ? Pt/c-Al O and its selectivity
2
3
was 46.8 % (carbon based). Pt catalyst was known to have
high activity for several petrochemical processes. In our
reaction system, results suggested that cellulose-derived
products were able to be converted to C and C hydro-
3.4 Effect of Pt Supported State
To elucidate the interaction between Pt metal and H-*BEA
zeolite, we conducted the following experiments using
various catalyst systems. The reaction condition was as
follows: distilled water/cellulose/zeolite catalyst (?M/c-
Al O catalyst) = 20 mL/0.25 g/0.25 g (?0.25 g), catalyst
3
4
carbons by the synergetic activities of Pt and H-*BEA,
including decarbonation, dehydrogenation, and cracking/
hydrogenolysis. Moreover, the formation amounts of
liquiform products were smaller over H-*BEA(25) ?
Pt/c-Al O compared to other catalyst system. Generally,
2
3
was H-*BEA(25) ? Pt/c-Al O , Pt/c-Al O , Pt/H-*BEA
2
3
2
3
2 3
furfural is produced from pentose, 5-HMF is produced from
hexose, and levulinic acid is produced from 5-HMF. These
intermediate products, hexose, pentose, furfural, 5-HMF,
and levulinic acid, were converted into C and C hydro-
(25)IM (IM denoted prepared by an impregnation method)
or Pt/H-*BEA(25)IE (IE denotes prepared by an ion
exchange method), planned loading amount of Pt was
5.0 wt% to each support. The exact loading amount of Pt
was described in the previous Sect. 3.1. The reaction
temperature was 443 K. The reaction time was 3 h.
3
4
carbons by decarbonation over H-*BEA ? Pt catalyst.
3
.3 Effect of Zeolite Structure
Table 3 shows cellulose consumption, amounts of prod-
ucts and selectivity to C and C hydrocarbons over various
3
4
In the previous section, we found that a combination of Pt and
zeolite enabled effective conversion of cellulose to C and C
combination catalysts. Cellulose consumptions over these
catalyst systems were in a following order; H-*BEA(25)
3
4
1
23

One Pot Direct Catalytic Conversion of Cellulose to Hydrocarbon
421
Table 1 Cellulose consumption, amounts of products and selectivity to C
3
and C
4
hydrocarbons over H-*BEA(25) and various M/c-Al
2 3
O
Catalyst
Cellulose
consumption/
carbon (lmol)
Product amount/carbon (lmol)
Selectivity to
C
3
and C (%)
4
Gaseous
Liquiform
CO ? CO
2
C
1
? C
2
C
3
? C
4
C
5?
Furfural 5-HMF Levulinic
acid
None
61.79
341.15
82.45
0.00
0.00
0.00
0.00
0.00
0.00
17.15
4.13
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00 279.49
0.00 77.89
0.00 173.16
61.79
0.00
27.36
4.56
0.00
34.31
0.00
0.00
0.00
0.00
0.00
46.84
3.71
0.00
0.00
0.00
0.00
H-*BEA(25)
c-Al
H-*BEA(25) ? c-Al
H-*BEA(25) ? Pt/c-Al
2
O
3
0.00
2
O
3
310.15
483.67
315.50
389.40
216.02
288.60
365.99
0.00
82.19
9.84
54.80
6.48
2
O
3
191.55
171.26
0.00
226.57
11.71
0.00
23.42
0.00
8.67
H-*BEA(25) ? Pd/c-Al
H-*BEA(25) ? Co/c-Al
H-*BEA(25) ? Cu/c-Al
2
O
3
96.22
15.12
97.52
30.68
80.80
85.87
17.06
25.06
18.66
43.79
24.33
2
2
O
O
3
3
0.00 266.81
0.00 166.69
0.00 137.07
0.00 255.78
0.00
0.00
H-*BEA(25) ? Ni/c-Al
H-*BEA(25) ? Fe/c-Al
2
O
3
26.94
0.00
0.00
2
O
3
0.00
Table 2 Cellulose consumption, amounts of products and selectivity to C
3
and C
4
hydrocarbons over various 1 wt% Pt/H-Zeolite
Catalyst
Cellulose consumption/ Product amount/carbon (lmol)
Selectivity to
and C (%)
carbon (lmol)
C
3
4
Gaseous
Liquiform
CO ? CO
2
C
1
? C
2
C
3
? C
4
C5? Furfural 5-HMF Levulinic acid
Pt/H-*BEA(25)
280.06
129.89
71.39
206.05
77.22
25.51
99.01
56.98
19.84
2.66
76.97
21.93
126.57
52.92
15.03
30.09
29.88
1.74
22.61
13.22
21.28
14.32
16.46
12.87
6.71
15.79
13.64
0.00
27.48
8.97
Pt/H-*BEA(150) 244.54
Pt/H-USY(14) 414.59
Pt/H-MOR(10.2) 234.10
Pt/H-MOR(90) 171.35
Pt/H-ZSM-5(38) 177.10
Pt/H-FER(18) 114.38
0.82 112.83
51.87
7.33
4.07
0.95
0.59
6.13
4.42
11.71
79.22
99.99
4.97
30.53
22.61
8.77
0.00
1.38
15.98
12.37
0.00
17.81
23.08
16.99
26.13
0.00
0.00
?
Pt/c-Al O \ Pt/H-*BEA(25)IM \ Pt/c-Al O \ Pt/H-
Various Pt/H-*BEA(25) prepared by impregnation or ion
exchange were used, and the planned loading amounts of
Pt were 0.1, 1.0, 5.0 wt%, respectively. The exact amount
of Pt loading was described in the previous sec. 3.1. The
reaction conditions were as follows: distilled water/cel-
lulose/Pt/H-*BEA(25)IM or IE = 20 mL/0.25 g/0.25 g.
The reaction temperature was 443 K; the reaction time
was 3 h.
2
3
2 3
*
BEA(25)IE. Gaseous products were produced more over
Pt/H-*BEA(25)IE despite lower Pt loading because of the
preparation method. The selectivity to C and C hydrocarbons
3
4
was 37.7 % on Pt/H-*BEA(25)IE catalyst, and the yield of
C ? C was 423 C-lmol, the highest value among all the
3
4
catalysts. The result was considered that glucose-derived
light products were produced by the synergetic effect
between Pt and Brønsted acid site because highly dispersive
Pt was located on H-*BEA by the ion-exchange method. The
Pt/H-zeolite prepared by ion exchange is known to be higher
dispersion of Pt than that by impregnation. Cellulose was
converted into C and C hydrocarbons selectively over the
Table 4 presents cellulose consumption, amounts of
products and selectivity to C and C hydrocarbons over
3
4
various Pt/H-*BEA(25). The gas amount was increased
relative to Pt loading prepared using each method. Fur-
thermore, cellulose was converted into more gaseous
products over Pt/H-*BEA prepared by the ion-exchange
method. These results showed that the effective Pt surface
was increased because Pt was supported for high disper-
sion and loaded selectively by the ion-exchange. Conse-
quently, results suggest that glucose-derived liquiform
intermediates were converted to C and C hydrocarbons
3
4
catalyst including both H-*BEA and Pt. Over Pt/c-Al O ,
cellulose was converted mainly into CO, CO , C , and C .
2
2
3
2
1
3
.5 Effect of Pt Loading Method and Amount
To optimize the Pt/H-*BEA catalyst, we examined the
effect of the Pt loading amount and loading method.
3
4
with the increase of Pt loading.
123

4
22
Y. Kato, Y. Sekine
Table 3 Cellulose consumption, amounts of products and selectivity to C
3
and C
4
hydrocarbons over various combinations of Pt and H-*BEA
Selectivity
Catalyst
Cellulose
consumption/
carbon (lmol)
Product amount/carbon (lmol)
to C
3
and C
Gaseous
Liquiform
4
(%)
CO ?CO
2
C
1
? C
2
C
3
? C
4
C
5?
Furfural 5-HMF Levulinic
acid
H-*BEA(25) ? 5.4 wt%
Pt/c-Al
483.67
191.55
17.15
226.57
23.42
8.67
9.84
6.48
46.84
2 3
O
5
4
1
.4 wt% Pt/c-Al
2
O
3
632.30
567.43
468.66
228.23
554.01
78.49
47.87
84.26
193.38
423.31
0.89
0.00
8.71
0.00
24.88
4.55
0.00
0.78
0.00
13.33
34.08
37.66
.8 wt% Pt/H-*BEA(25)IM
.9 wt% Pt/H-*BEA(25)IE
63.58
1124.13
108.32
22.86 11.08
Table 4 Cellulose consumption, amounts of products and selectivity to C
impregnation and ion exchange
3
and C
4
hydrocarbons over various Pt/H-*BEA(25) prepared by
Selectivity to
Loading
method
Pt
loading
Cellulose
consumption/
carbon (lmol)
Product amount/carbon (lmol)
3 4
C and C (%)
Gaseous
Liquiform
(wt%)
CO ? CO
2
C
1
? C
2
C
3
? C
4
C
5?
Furfural 5-HMF
Levulinic
acid
Not loading
–
341.15
321.68
280.06
567.43
179.00
448.15
1124.13
0.00
26.90
0.00
0.00
0.00
0.00
0.00 279.49
0.00 191.36
27.36
49.56
13.22
24.88
56.48
9.97
34.31
53.86
15.79
0.78
0.00
0.00
Impregnation 0.11
1
4
.2
.8
129.89
228.23
0.00
19.84
47.87
0.00
76.97
193.38
0.00
1.74
63.58
0.00
22.61
8.71
27.48
34.08
0.00
Ion exchange 0.13
46.02
17.13
11.08
76.51
4.00
1
1
.0
.9
209.91
554.01
32.43
108.32
169.59
423.31
5.12
37.84
37.66
22.86
4.55
0.00
3 4
Table 5 Effect of reaction temperature and reaction time on cellulose consumption, amounts of products and selectivity to C and C
hydrocarbons over 1 wt% Pt/H-*BEA(25) prepared by ion exchange
Temp.(K) Time Cellulose
h) consumption/carbon
lmol)
Product amount/carbon (lmol)
Selectivity to C
3
(
4
and C (%)
Gaseous
Liquiform
(
CO ? CO
2
C
1
? C
2
C
3
? C
4
C
5?
Furfural 5-HMF
Levulinic
acid
4
4
4
4
23
43
43
63
3
1
3
3
100.38
116.66
448.15
1473.82
37.73
38.66
8.14
7.04
48.30
30.85
0.61
5.60
0.00
4.60
0.00
0.00
48.11
26.45
37.84
12.82
0.43 35.08
5.12 17.13
11.93 18.10
209.91
421.16
32.43
83.74
169.59
189.02
9.97
4.00
113.35
636.52
3
.6 Influence of Reaction Time and Temperature
effect of reaction temperature, the reaction time was fixed
to 3 h. The temperatures were 423, 443, or 463 K.
Table 5 presents cellulose consumption, amounts of
products and selectivity to C and C hydrocarbons with
To elucidate the reaction path and effect of reaction tem-
perature, we conducted several reactions under different
reaction times and temperatures. The reaction condition
was as follows: distilled water/cellulose/1.0 wt% Pt/H-
3
4
various reaction conditions over 1.0 wt% Pt/H-*BEA(25).
For the reaction time, cellulose consumption was 116.7
C-lmol at 1 h, and this increased to 448.2 C-lmol at 3 h.
This result indicated that the hydrolysis of non-crystalline
cellulose was not so fast reaction, and residual non-
*
BEA(25)IE = 20 mL/0.25 g/0.25 g. To evaluate the
reaction path, the reaction temperature was fixed at 443 K
and the reaction time was changed. For evaluating the
1
23

One Pot Direct Catalytic Conversion of Cellulose to Hydrocarbon
423
crystalline cellulose was hydrolyzed from 1 h to 3 h. The
gas amount also increased by 3 h. Regarding effects of
reaction temperature, both cellulose consumption and the
gas amount increased relative to increasing temperature
thanks to the increased reaction rate. Although the gas
to the synergetic effect of Pt metallic site and acid site in
*BEA zeolite, which has a large pore system and effective
acidity.
amount was the highest at 463 K, selectivity to C and C4
3
References
hydrocarbons were not high because cellulose-derived
products were polymerized or that C and C hydrocarbons
3
4
1
2
3
4
. Camacho F, Gonzalez-Tello P, Jurado E, Robles A (1996) J
Chem Tech Biotechnol 67:350
. Millet MA, Baker AJ, Satter LD (1976) Biotechnol Bioeng Symp
5:193
. Schell DJ, Farmer J, Newman M, McMillan JD (2003) Appl
Biochem Biotechnol 105:69
. Himmel ME, Ruth MF, Wymans CE (1999) Curr Opin Bio-
technol 10:358
5. Mandels M, Kostick J, Parizek R (1971) Polym Sci C 36:445
were converted into lighter products. Only the yield of
levulinic acid was increased in liquiform products. If this
reason was the influence of increasing temperature, then
the other two products would also be increased. However,
the yields of furfural and 5-HMF were not increased.
Consequently, it was inferred that furfural and 5-HMF
were cracked or polymerized easily, and levulinic acid was
not. The selectivity to C and C hydrocarbons was high at
6
. Sasaki M, Kabyemela B, Malaluan R, Hirose S, Takeda N,
Adschiri T, Arai K (1998) J Supercrit Fluids 13:261
. Adschiri T, Hirose S, Malaluan R, Arai K (1993) J Chem Eng Jpn
3
4
lower temperature, but the rate of hydrolysis of cellulose
was low at lower temperature.
7
2
6:676
8
9
. Onda A, Ochi A, Yanagisawa K (2009) Top Catal 52:801
. Hegner J, Pereira KC, DeBoef B, Lucht BL (2010) Tetrahedron
Lett 51:2356
4
Conclusion
1
0. Van de Vyver S, Peng L, Geboers J, Schepers H, Clippel F,
Gommes CJ, Goderis B, Jacobs PA, Sels BF (2010) Green Chem
12:1560
We found that cellulose could be converted selectively and
directly into C and C hydrocarbons over Pt/H-*BEA
1
1
1. Kobayashi H, Matsuhashi H, Komanoya T, Hara K, Fukuoka A
(
3
4
2011) Chem Commun 47:2366
2. Su Y, Brown HM, Huang X, Zhou X, Amonette JE, Zhang ZC
(2009) Appl Catal A 361:117
(
beta) catalyst even at 443 K. Other catalyst systems did
not enable conversion of cellulose into C and C hydro-
3
4
carbons selectively. Using H-*BEA and H-*Y which had
three-dimensional structure and large pore system as a
support, gaseous products were produced in large amounts.
As for the metal loading method, ion exchange was more
effective than impregnation. Increasing Pt loading amount
brought increasing gaseous products including C and C
13. Ji N, Zhang T, Zheng M, Wang A, Wang H, Wang X, Chen JG
2008) Angew Chem 120:8638
(
1
1
4. Davda RR, Dumesic JA (2004) Chem Commun 0:36
5. Serrano-Ruiz JC, Braden DJ, West RM, Dumesic JA (2010) Appl
Catal B 100:184
16. Murata K, Liu Y, Inaba M, Takahara I (2010) Catal Lett 140:8
1
1
1
7. Fukuoka A, Dhepe PL (2006) Angew Chem Int Ed 45:5161
8. Namba S, Hosonuma N, Yashima T (1981) J Catal 72:16
9. Sekine Y, Ichikawa Y, Tajima Y, Nakabayashi K, Matsukata M,
Kikuchi E (2012) J Jpn Petrol Inst 55(5):299
3
4
hydrocarbons. Selective production of C and C hydrocar-
3
4
bons was observed only on the optimized conditions,
.0 wt% Pt loading, H-*BEA(25) zeolite, 443 K reaction
temperature, and longer reaction time. This was attributable
1
20. Netrabukkana R, Lourvanij K, Rorrer FL (1996) Ind Eng Chem
Res 35:458
123