Hydrocracking of biomass-derived materials into alkanes in the presence of platinum-based catalyst and hydrogen

Article abstract of DOI:10.1007/s10562-010-0396-y

Renewable green C2-C9 alkanes can be directly produced by Pt/H-ZSM-5-catalyzed hydrocracking of biomass-derived materials, no pre-treated or pre-treated by alcohol. The pre-treatment of cellulose in 1-hexanol at 623 K, followed by hydrocracking catalyzed

Full text of DOI:10.1007/s10562-010-0396-y

Catal Lett (2010) 140:8–13
DOI 10.1007/s10562-010-0396-y
Hydrocracking of Biomass-Derived Materials into Alkanes
in the Presence of Platinum-Based Catalyst and Hydrogen
Kazuhisa Murata
Isao Takahara
•
Yanyong Liu
•
Megumu Inaba
•
Received: 9 May 2010 / Accepted: 7 June 2010 / Published online: 18 August 2010
Ó Springer Science+Business Media, LLC 2010
Abstract Renewable green C2–C9 alkanes can be
directly produced by Pt/H-ZSM-5-catalyzed hydrocracking
of biomass-derived materials, no pre-treated or pre-treated
by alcohol. The pre-treatment of cellulose in 1-hexanol at
problems. In general, gasification and fermentation are
used for biomass conversion. Gasification needs very high
temperature of 900–1,000 °C and subsequent liquefaction
processes of biogas such as Fischer–Tropsch reaction and
methanol synthesis are required for obtaining liquid fuel.
Fermentation proceeds at mild conditions, but slow pro-
ductivity, pretreatment of biomass and fermentation wastes
are still problem to be solved.
6
23 K, followed by hydrocracking catalyzed by Pt/H-
ZSM-5(23) at 673 K, produced C2–C9 alkanes in as high
as 89% yields with CH /COx yields of only 6%. The
4
reaction pathway involves lowering of molecular weight of
cellulose materials, producing, probably, oxygenates
intermediates such as mono-saccharide and disaccharide,
which are further efficiently converted to alkane products
by successive hydrocracking and condensation, catalyzed
by Pt/H-ZSM-5.
Pyrolysis is one of a thermochemical process that is an
efficient way of converting biomass into gases, liquids, and
char at temperature as relatively low as 573–873 K. Of
these products, we are interested in liquids for fuels as well
as chemicals. To our knowledge, most pyrolysis process is
performed under inert gas conditions. But in these cases,
pyrolysis reactor design, reaction parameters (temperature,
heating rate, residence time, pressure, and catalyst), and
biomass type and characteristics (particle size, shape, and
structure) have strong effects on the yield and properties of
the products formed [2]. Also, since obtained liquids con-
tain 40–45 wt% of oxygen as organic compounds such as
phenol derivatives, additional hydrotreating process is
required for deoxygenation.
Keywords Pt/H-ZSM-5 Á Hydrocracking Á
Alcohol pre-treatment Á C2–C9 alkanes
1
Introduction
Due to the advantages of being CO neutral, having low
2
sulfur content, and being easy to transport, renewable
biomass resources will become more important in the
future as alternatives to fossil fuels. In addition, 240 mil-
lion tons of biomass wastes such as the lignocellulosics are
generated annually in Japan, of which 65 million tons are
not used effectively [1]. Therefore, technology that can
convert them to valuable liquid fuels and chemicals will be
important for solving our energy and environmental
Fluid catalytic cracking (FCC) is the most widely used
process for the conversion of vacuum gas oil (VGO) [3]. In
this process, no additional hydrogen is required and aro-
matics are major products. The conversion of carbohy-
drates and lignin over H-ZSM-5 catalysts has been reported
and major products are coke, CO, aromatics, and CO2 [4,
5]. Hydrotreating of bio-oil and lignin using Co–Mo and
Ni–Mo catalysts produced C7–C11 alkylbenzenes C5–C11
branched alkanes, but hydrocracking of cellulose and wood
has not been reported [6, 7].
K. Murata (&) Á Y. Liu Á M. Inaba Á I. Takahara
National Institute of Advanced Industrial Science and
Technology, AIST Tsukuba Central 5, 1-1-1, Higashi,
Tsukuba, Ibaraki 305-8565, Japan
Hence, in this work, an attempt was made to investigate
the effect of hydrogen on the pyrolysis product yield, in
which liquid and, partly, gaseous alkanes are expected to
e-mail: kazu-murata@aist.go.jp
1
23

Hydrocracking of Biomass-Derived Materials into Alkanes
9
be major products. As biomass materials, cellulose and
wood flour are used. The present study also included
comparison of yields of C2–C9 alkanes with and without
alcohol pretreatment, prior to hydrocracking.
Q column for FID and Porapak Q and MS 5A columns for
the TCD were used. Liquid products were extracted with
10 mL of tetradecane (C14) and organic phase was ana-
lysed by FID GC, where SE-30 column was used. TCD
analysis was performed using N internal standard, while,
2
for FID analysis, hexacosane (C26) was used as internal
standard. The each carbon selectivity is defined as the
moles of carbon in each product divided by the total carbon
in the feed. The amount of total carbon soluble in water
liquid phase was estimated by elemental analysis and the
amount of carbon deposit over the catalyst surface was
analysed by thermo-gravimetric analysis under air
conditions.
2
Experimental
Cellulose and organosolv lignin were obtained from
Aldrich Chemicals. Wood tip samples such as eucalyptus,
cedar, and Douglas fir used in this study were given from
Oji paper Co. Ltd. Pyroligneous acid (Wood vinegar) was
purchased from Kishu-Sin-Binchotan Co. The wood vine-
gar contains AcOH, ethylene glycol, glycerol, methanol
and acetone, as ascertained by GC-FID analysis. Elemental
analysis of the vinegar shows 4.31 wt% of carbon and 10.2
wt% of hydrogen. The wood vinegar was used without any
pretreatment. Elemental analysis of organosolv lignin was
C (44.12%), H (45.90%), and O (9.98%) [8]. These wood
tips were sieved to obtain the average particle size of ca.
3 Results and Discussion
The hydrocracking reactions of wood vinegar were carried
out at 573 K for 12 h.
Table 1 summarizes a detail of hydrocarbons and CO
and CO products (Abbreviated as CO ). At 603 K over
1
mm. Microporous materials such as H-ZSM-5 and USY
2
x
were provided by Zeolyst and Tosoh Co. Ltds. The Si/Al
ration of these zeolites were given in the table and also, the
Si/Al ratio of silica–alumina was 2.2. Pt(NH ) Cl ÁH O
Pt/H-ZSM-5(23), 100% yield was achieved from organic
oxygenates contained in wood vinegar and ca. 50% of C1
and C2 alkanes were formed, probably from C1/C2 oxy-
genates such as methanol and AcOH. As other products,
3
4
2
2
and NH ReO were purchased from Soekawa Chemicals,
4
4
Japan. The Pt/zeolite catalyst used in this study was pre-
pared by impregnating zeolite support with Pt(NH3)4
Cl ÁH O, followed by drying at 373 K and calcination for
C3–C4, C5? and CO were detected, in which C5? would
x
be formed by condensation of carbon species. Lower
conversions and (C1 ? C2) selectivities were obtained
over USY(6.3) and SiO2-Al2O3 than those of H-ZSM-
5(23), indicating less sufficient hydrocracking ability than
that of H-ZSM-5 support. Thus, in the presence of Pt/H-
ZSM-5 catalyst, lower hydrocarbons were mainly formed
by hydrocracking of wood vinegar.
2
2
5
h at 773 K. Pt–Re/zeolite was prepared by impregnation
of zeolite with Pt(NH ) Cl ÁH O followed by drying at
3
4
2
2
3
73 K and calcination for 5 h at 773 K. The concentrations
of platinum metal were 1 wt% [9].
Hydrocracking experiments were carried out using a
3
00-cm autoclave-type reactor. In a one-pot reaction, the
1
Next, a direct hydrocracking of cellulose was examined.
catalyst (1.0 g) was introduced into the autoclave and
The yield into (alkanes ? CO ) was 42.1%, which is sum
x
pretreated by reduction with 2 MPa of H at 473 K for 5 h.
2
of gaseous and liquid products. The selectivity to C2–C9
After the reduction, 1 g of cellulose (or wood vinegar) was
hydrocarbons was 29.7%, while CO selectivity was 40.9%
x
introduced with 9 g of H O and the autoclave was pres-
2
with 18.9% of C10? alkanes and 10.6% of CH , as shown
4
surized with 6.5 MPa of H /N gas mixture (H /N = 91/9
2
in Table 2.
2
2
2
vol.%). The reaction was carried out at 573–673 K for 12 h
with vigorous stirring by using shaking-type furnace. In a
two-step reaction, cellulose or wood flour (1 g) and solvent
In the presence of catalyst, both the yield and selectivity
into alkanes were increased and CO selectivity decreased.
x
For Pt/USY(6.3), the conversion was 97.2% and C2–C9
selectivity was 38.4% with 18.5% of C10? selectivity and
31% of CO with 12% of CH . The amount of carbon
(
10 mL) such as 1-hexanol were introduced into the auto-
clave and pretreated with 2 MPa of Ar at 623 K for 2 h.
After cooling down, gas was removed. Then, the solvent
was roughly distilled away in vacuo and the obtained
slurry-like product was immediately returned to the auto-
x
4
deposited on catalyst surface was 2.8%, ascertained by
thermo-gravimetric analysis. So, the carbon balance was
approximately 100%. When Pt/H-ZSM-5 catalysts were
used, C2–C9 selectivities were close to that of Pt/USY(6.3),
while CH selectivities were higher and CO selectivities
clave with pre-reduced catalyst (1 g) and H O (9 g), fol-
2
lowed by re-pressurization with 6.5 MPa of H /N gas
2
2
4
x
mixture. The reaction was performed at 673 K and 12 h.
After one- or two-step reaction, the gaseous and liquid
products were collected and analyzed by off-line FID and
TCD gas chromatographies. For gaseous products, Porapak
were lower than that of Pt/USY(6.3). Also, total alkane
selectivities were 77.9% for Pt/H-ZSM-5(23) and 88.6% for
Pt/H-ZSM-5(30), while the cellulose conversions were
decreased to 89.1 and 69.7%. Then, the reaction was carried
123

1
0
K. Murata et al.
Table 1 Hydrocracking of wood vinegar
a
Support
Yield into
(
Carbon selectivity (%)
alkanes ? CO
c
x
)
d
Residue (%)
CH (%)
4
C2 (%)
C3–C4 (%)
CO (%)
x
(
%)
H-ZSM-5
H-ZSM-5
USY
74.7
21.8
22.5
5.27
4.55
25.3
28.4
14.5
0
8.66
14.6
13.4
29.8
23.2
10.3
56.0
65.6
21.0
24.3
10.7
0
b
100
48.1
17.9
2 2 3
SiO –Al O
Conditions: 1 wt% Pt/support, 1.0 g; wood vinegar, 9 mL; T = 573 K; 12 h; P = 6.5 MPa; H
for 4 h
/N
2 2
= 9/1. Pretreatment at 473 K and 2 MPa of H
2
a
H-ZSM-5 (23) and USY (6.3) were used
b
6
03 K
c
Yield = (sum of C-containing products)/carbon initially added * 100
d
x
Residue selectivity = 100 - sum of ((C1 - C4) and CO selectivities)
Table 2 Hydrocracking of cellulose under hydrogen conditions
g
Catalyst
Temp. (K)
Yield into
alkanes ? CO
Carbon selectivity (%)
(
x
)
h
f
CH4
C2–C4
C5–C9
C10–C20
C21?
Oxy
COx
(
%)
None
a
Pt /H-ZSM-5 (23)
a
Pt /H-ZSM-5 (30)
673
673
673
673
42.1
89.1
69.7
97.2
51.8
64.7
10.6
17.6
28.7
12.0
14.5
18.9
21.8
19.0
20.6
18.6
34.9
10.8
17.5
18.6
17.8
58.2
40.9
16.4
18.7
21.0
14.5
1.09
7.99
2.47
2.22
1.21
3.96
1.76
1.75
0
40.9
22.1
11.4
31.0
0
c
c
0.00
0
a
Pt /USY (6.3)
c
0
b
PtRe /H-ZSM-5 (23)
b
PtRe /H-ZSM-5 (23)
c
c
d
573
0.04
e
543
3.67
O 9 g, 12 h, H /N
16.7
0
Reaction conditions: Catalyst 1.0 g, Cellulose 1 g, H
a
Pt: 1 wt%
2
2
2
= 85/15 (vol.%), 6.5 MPa. Catalyst pretreatment: see Table 1
b
Pt 1 wt%, Re 2 wt%
c
Si/Al
2
d
e
f
Catalyst: 0.2 g
2
Catalyst: 0.2 g, H O: 50 g, 2 h
Yield = [(sum of C atoms in all products)/(total C atoms of cellulose introduced)] 9 100
Carbon selectivity = (moles products 9 number of carbon atoms in products)/(total moles of carbon atoms in products) 9 100
MeOH ? EtOH ? PrOH ? BuOH ? EG ? PG
g
h
out at 573 K using Pt–Re/H-ZSM-5(23), which was effec-
tive for hydrocracking of triglycerides [3]. The selectivity to
successfully decomposed and liquefied in any supercritical
alcohol and many kinds of oxygenates such as acetic acid
and saccharides were formed.
C2–C9 alkanes was as high as 76.8% with no CO forma-
x
tion, but the yield into alkanes and CO decreased to 51.8%.
x
First, organosolv-lignin commercially available from
Aldrich Chemicals was pretreated. After 12 h-reaction at
673 K, gaseous and liquid products were analysed. As
Also, at 543 K, the conversion and C2–C9 selectivities
were 64.7 and 75.8% and other hydrocarbons and oxygen-
ates were also detected. Thus, Pt-based catalysts were found
to be effective for a direct hydrocracking of cellulose
without any pretreatment.
shown in Table 3, alkanes and CO were formed. Oxygen-
x
containing products such as phenol, guaiacol were not
detected by GC analysis.
Then, in order to improve carbon efficiencies into
C2–C9 alkanes by reducing CH and CO even at 673
The yield into (alkanes ? CO ) was affected by alcohols
x
and the order of the yield was EtOH % 1-propanol [
1-hexanol [ 1-butanol. For 1-propanol, C2–C4 alkanes
(50.1%) and C5–C9 alkanes (35.3%) were mainly formed
with small amounts of other alkanes and CH (3.27%)/CO
4
x
K-reaction, biomass-derived materials were pretreated with
C2–C6 alcohols such as 1-hexanol, prior to hydrocracking.
Saka [1] has already reported that woody biomass can be
4
x
1
23

Hydrocracking of Biomass-Derived Materials into Alkanes
11
Table 3 Pretreatment with alcohol in hydrocracking of organosolv lignin
a
Alcohol
Yield into
x
alkanes ? CO ) (%)
Carbon selectivity (%)
(
CH
4
C2–C4
C5–C9
C10–C20
C21?
CO
x
EtOH
100
100
8.34
3.27
2.46
3.56
32.5
50.1
52.9
41.6
44.7
35.3
37.9
45.8
6.88
7.72
4.12
5.41
0.62
0.39
0.46
1.20
6.93
3.26
2.16
2.38
1
1
1
-Propanol
-Butanol
-Hexanol
74.2
88.2
Pretreatment: alcohol (10 mL) ? organosolv lignin (1 g), Ar (2 MPa), 623 K, 2 h. Reaction conditions: pre-reduced 1 wt% Pt/H-ZSM-5 (23)
(
2 2 2
1 g) and H O (9 g), 673 K, 12 h, H /N = 85/15 (vol.%), 6.5 MPa
a
The yield and carbon selectivity: see Table 2
(
3.26%). For other alcohols, C2–C4 and C5–C9 alkanes
lignin-like structure and, therefore, the lignin could dis-
solve even in ethanol and propanol. On the contrary, wood
flour has much complex structures and it contains not only
lignin, but also cellulose and hemicellulose structures.
Therefore, alcohols with longer alkyl chain, probably,
could be favorable for dissolving wood-like materials with
higher molecular weight [1].
were also predominantly formed. Thus, pre-treatment by
alcohol prior to hydrocracking was found to be effective
for hydrocracking of organosolv-lignin to give C2–C9
alkanes.
Second, our interest is cellulose. As already mentioned
in Table 2, a direct hydrocracking of cellulose produced
large amount of CO and CH with total selectivity of
For 1-hexanol pre-treatment, the selectivity to higher
carbon number compounds (C10?) was 4.86%, much
lower than that from direct hydrocracking (C10? = 20.9%),
indicating that pre-treatment by alcohol may cause slightly
preventing condensation reactions, but the condensation
could still occur. Generally, it is well-known that zeolites
would catalyze condensation of ethylene and ethanol to
form propylene and butanes wit higher alkanes at 673–
873 K [10]. So, even at high pressure conditions of
hydrogen at 673 K, these condensations, probably, occur.
For two-step reaction using 1-hexanol, effects of catalyst
support were examined, where Pt content was 1 wt%. The
x
4
3
9.7%, even in the presence of Pt/H-ZSM-5(23) catalyst.
By pretreatment with alcohols, CH and CO formations
4
x
were dramatically reduced to approximately 1–4% selec-
tivities, as shown in Table 4. The order of the yield into
alkanes and CO were 1-pentanol % 1-hexanol [ 1-pro-
panol[1-butanol. For 1-hexanol, C2–C4 alkanes (42.1%)
and C5–C9 alkanes (47.0%) were mainly formed with
x
4
.86% of higher alkanes and CH (3.10%)/CO (2.88%).
4 x
For 1-butanol and 1-propanol, the selectivities to C2–C4
alkanes increased to 52.3 and 79.0%, while C5–C9 selec-
tivities decreased to 38.5 and 15.7%. In these cases, the
order of the kind of alcohol in pre-treatment of cellulose is
found to be different from that of organosolv-lignin, as
shown in Tables 3 and 4. Organosolv-lignin contains only
order of the yield into alkanes and CO were H-ZSM-5(23)
x
[USY(5.3)[Y(5.1), in which the number in parenthesis
denotes Si/Al2 ratio. On the contrary, CH4 and COx
Table 4 Pretreatment with alcohol in cellulose hydrocracking
b
Catalyst support
Alcohol
Yield into
(
Carbon selectivity (%)
x
alkanes ? CO ) (%)
CH
4
C2–C4
C5–C9
C10–C20
C21?
CO
x
a
H-ZSM-5 (23)
None
89.1
81.3
77.4
17.6
1.77
21.8
79.0
52.3
37.0
42.1
30.4
22.2
17.4
15.7
38.5
45.9
47.0
28.9
33.8
18.7
1.11
3.60
10.1
4.43
22.9
13.8
2.22
0.04
0.23
0.49
0.43
1.29
1.70
22.2
2.37
H-ZSM-5 (23)
H-ZSM-5 (23)
H-ZSM-5 (23)
H-ZSM-5 (23)
USY (5.3)
1-Propanol
1-Butanol
1-Pentanol
1-Hexanol
1-Hexanol
1-Hexanol
1.75
3.27
3.10
7.23
8.03
3.65
3.23
2.88
9.20
100
100
84.4
72.2
Y (5.1)
20.5
2
Pretreatment: alcohol (10 mL) ? cellulose (1 g), Ar (2 MPa), 623 K, 2 h. Reaction conditions: 1 wt% Pt/support (1 g) and H O (9 g), 673 K, 12
h, H /N
2
2
= 85/15 (vol.%), 6.5 MPa
a
Si/Al
2
ratio
b
The yield and carbon selectivity: see Table 2
123

1
2
K. Murata et al.
Table 5 Pretreatment with alcohol in hydrocracking of wood flour
d
Wood
Yield into
(
Carbon selectivity (%)
x
alkanes ? CO ) (%)
CH
4
C2–C4
C5–C9
C10–C20
C21?
CO
x
a
Eucalyptus
Eucalyptus
Eucalyptus
Eucalyptus
76.3
33.4
16.2
15.8
25.4
20.4
42.6
38.3
37.1
37.4
29.5
11.7
46.8
40.4
37.3
49.2
9.88
4.34
5.74
14.4
19.5
10.0
1.64
2.85
0.54
0.77
1.32
0.10
17.4
44.9
a, b
100
100
2.59
1.69
c
2.57
3.10
1.80
3.62
1.71
1.39
Japanese cedar (Hita)
Douglas fir
92.4
80.5
2
Pretreatment: 1-hexanol (10 mL) ? wood flour (1 g), Ar (2 MPa), 623 K, 2 h. Reaction conditions: 1 wt% Pt/H-ZSM-5 (23) (1 g) and H O
(
2 2
9 g), 673 K, 12 h, H /N = 85/15 (vol.%), 6.5 MPa
a
No pre-treatment with 1-hexanol
Reaction time is 1 h
b
c
d
Pretreatment temperature: 543 K
The yield and carbon selectivity: see Table 2
selectivities were in the order: Y(5.1) [ USY(5.3) [ H-
ZSM-5 (23). Thus, the product selectivity would be asso-
ciated with solid acid properties of catalyst supports,
although further study is now in progress.
except for C21? selectivity. Figure 1 shows alkane product
distributions in the 1- and 12 h-reactions. As the reaction
proceeds, the yield of each alkane product increased, indi-
cating that hydrocracking with deoxygenation of wood
structure was found to be major reactions, but condensation
could still occur under these conditions.
Third, alcohol pretreatment and successive hydrocrack-
ing of wood flour was carried out. As wood flour, Euca-
lyptus, Japanese cedar (Hita), and Douglas fir were used. As
in the case of cellulose, a direct hydrocracking of Eucalyptus
produced large amount of CO and CH with total selectivity
By pretreatment with alcohols, CH and CO formations
4
x
were dramatically reduced to approximately 2–4% selec-
tivities. The order of the yield into alkanes and CO was
x
x
4
of 35.4%, even in the presence of Pt/H-ZSM-5 (23) catalyst
Eucalyptus [ Japanese cedar (Hita) [ Douglas fir. For
Eucalyptus, C2–C4 alkanes (42.6%) and C5–C9 alkanes
(46.8%) were mainly formed with 6.28% of higher alkanes
and CH4 (2.59%)/COx (1.69%). Pretreatment at 543 K
resulted in slight decreases in C2–C4 and C5–C9 selec-
tivities, but increase in C10–C20 selectivity. For Japanese
cedar (Hita) and Douglas fir, the selectivities to C2–C4
alkanes slightly decreased to 37.1 and 37.4%, while C5–C9
selectivities were 37.3 and 49.2%.
and the yield into (alkanes and CO ) were 76.3% after 12 h-
x
reaction, as shown in Table 5. At 1 h-reaction of direct
hydrocracking, the yield decreased to 33.4% and each
alkane selectivity was lower than those after 12 h-reaction,
Postulated scheme of decomposition pathway is shown in
Fig. 2, where cellulose is chosen as a typical starting
materials. By a direct hydrocracking of cellulose, C2–C9
alkanes and CH /CO are produced in 35 and 35% yields.
4
x
Alcohol pretreatment could lead to lowering of molecular
weight, by producing intermediates of, for example, mono-
saccharide and disaccharide [1], which are further converted
to mainly C2–C9 alkanes by successive hydrocracking and
condensation. By pretreatment using 1-hexanol, C2–C9
yields are dramatically increased to 89%, while CH /CO
4
x
yields are reduced to only 6%. These findings suggest that
the alcohol treatment of various cellulosic materials prior to
catalytic hydrocracking can be extremely effective for
improving selective formation of C2–C9 hydrocarbon,
being useful for chemicals and liquid fuels without using
fossil resources.
Fig. 1 Product distributions in direct hydrocracking of Eucalyptus.
Eucalyptus(1 g), Cat.: 1 wt% Pt/H-ZSM-5 (23) (1.0 g), H
.5 MPa, H O (9 g), 673 K
2 2
/N = 9/1,
6
2
1
23

Hydrocracking of Biomass-Derived Materials into Alkanes
13
were formed in 35 and 35% yields, respectively. Combi-
nation of alcohol pre-treatment and Pt/H-ZSM-5-catalyzed
hydrocracking was also effective for organosolv-lignin and
wood flour. In Eucalyptus, C2–C9 alkanes yields were
89.4%. The reaction pathway involves lowering of
molecular weight of cellulose materials, producing, prob-
ably, oxygenates intermediates such as mono-saccharide
and disaccharide, which are further efficiently converted to
alkane products by successive hydrocracking and conden-
sation, catalyzed by Pt/H-ZSM-5. Co-feeding process of
fossil-based heavy residue and biomass-based resources
into chemicals and fuels would be feasible for a larger
industrial scale, because biomass resources are much
smaller scale than the fossil resources.
Fig. 2 Postulated scheme of cellulose hydrocracking
References
4
Conclusion
1
2
. Ishikawa Y, Saka S (2001) Cellulose 8:189–195
. Bridgwater AV (1999) J Anal Appl Pyrolysis 51:3
Pt/H-ZSM5 catalysts, which were active for glycerol
reforming into propane and hydrotreating of triglycerides,
were found to be active for hydrocracking of biomass-
derived materials to form C2–C9 alkanes directly. Fur-
thermore, by pre-treatment of these materials by alcohol
such as 1-hexanol, prior to the hydrocracking, C2–C9
alkanes yields were found to be extremely improved. The
pre-treatment of cellulose in 1-hexanol at 623 K, followed
by hydrocracking catalyzed by Pt/H-ZSM-5(23) at 673 K,
3. Biswas J, Maxwell IE (1990) Appl Catal 63:197
4
5
. Chen NY, Degnan JTF (1986) Chemtech 16:506
. Thring RW, Katikaneni SPR, Bakhshi NN (2000) Fuel Process
Technol 62:17
6. Laurent E, Delmon B (1994) J Catal 146:281
7. Piskorz J, Majerski P, Radlein D, Scott DS (1989) Energy Fuels
3
:723
8
. Yokoyama C, Nishi K, Nakajima A, Seino K (1998) Sekiyu
Gakkaishi 41(4):243
9. Murata K, Liu Y, Inaba M, Takahara I (2010) Energy Fuels
24:2404
0. Oikawa H, Shibata Y, Inazu K, Iwase Y, Murai K, Hyodo S,
Kobayashi G, Baba T (2006) Appl Catal A Gen 312:181
1
produced C2–C9 alkanes in 89% yields with CH /COx
4
yields of only 6%, whereas, by direct hydrocracking of
cellulose at 673 K, C2–C9 alkanes and CH /CO yields
4
x
123