Energy Conversion and Management 77 (2014) 262–268

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Energy Conversion and Management

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Production of liquid alkanes by controlling reactivity of sorbitol

hydrogenation with a Ni/HZSM-5 catalyst in water
Qing Zhang, Tiejun Wang ⇑, Ying Xu, Qi Zhang, Longlong Ma ⇑
Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

a r t i c l e i n f o a b s t r a c t

Article history: Liquid fuels derived from renewable biomass are of great importance on the potential substitution for
Received 21 April 2013 diminishing fossil fuels. The conversion of sorbitol (a product of biomass-derived glucose hydrogenation)
Accepted 11 September 2013 into liquid alkanes such as pentane and hexane over the Ni/HZSM-5 catalysts with or without MCM-41
addition was investigated in the presence of hydrogen in water medium. The production distribution of
sorbitol hydrogenation can be controlled by adjusting the acidity of the catalyst. The scission of C–C bond
Keywords: in the sorbitol molecule into light C1–C4 alkanes was mainly carried out over Ni/HZSM-5 containing
Liquid alkane
strong Brønsted acid sites, while C–O bond scission into heavier alkanes was dominated over the catalysts
Sorbitol
Ni/HZSM-5 catalyst
added by MCM-41 containing weak Lewis acid sites. The sorbitol conversion and total liquid alkanes
MCM-41 selectivity were found to be 67.1% and 98.7% over 2%Ni/HZSM-5 modified by 40 wt% of MCM-41, whereas
Characterization the corresponding value was 40% and 35.6% over 2%Ni/HZSM-5 in the absence of MCM-41. The effect of
MCM-41 on the structure, acidity, and reducibility of Ni/HZSM-5 was investigated by using XRD, Py-IR, IR,
and H2-TPR. Meanwhile, the resistance of carbon deposition over the catalyst modified by MCM-41 was
studied by using TG–DSC technique. MCM-41 was found to have a positive interaction with HZSM-5 on
the modulation of its structure properties and acidity, accompanying by the improvement on the
reducibility of the catalyst. In addition, MCM-41 can distinctly decrease carbon deposition on the catalyst
surface. These roles can favor the selective hydrodeoxygenation of C–O bond in the sorbitol molecule to
generate liquid alkanes.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Liquid transportation fuels for modern society are mostly
derived from diminishing fossil fuel sources such as petroleum
and coal due to much higher consumption rate than that of natural
regeneration generally taken about millions of years [1,2].
Moreover, a large amount of CO2 and soot can be formed during
the utilization of these fossil fuels by combustion. Notably, the
production of liquid transportation fuels from petroleum requires
complicated chemical refining processes and therefore large
amount of waste residues was inevitable. These should be
responsible for growing global warming and grave environmental
pollution problems. However, the production of liquid fuels
derived from biomass resources has been considered to be
environmentally benign because of its neatness and less CO2
emission [3,4]. In addition, biomass is the only renewable source
of organic carbon on the earth [5,6], and has a wide application
in the production of liquid biofuels (e.g., methanol, ethanol or
bio-oils) [7–10,3,11,12] due to its abundance of raw materials
and relatively simple operation processes. Recently, particular
⇑ Corresponding authors. Tel.: +86 20 8705 7751; fax: +86 20 8705 7789.
E-mail addresses: wangtj@ms.giec.ac.cn (T. Wang), mall@ms.giec.ac.cn (L. Ma).
interest has been attracted on creating new liquid fuel mainly
composed of liquid alkanes ranging from C5 to C6 by aqueous phase
reforming of biomass-derived sugars or sugar alcohols such as sor-
bitol [13–17], wherein a key challenge was present on the hydro-
deoxygenation of these biomass-derived species. In the process, a
bifunctional metal–acid catalyst (e.g., Pt/SiO2–Al2O3) was used to
fulfill the scission of C–O bonds in the oxygenated molecules on
the acid centers and followed by successive hydrogenation and
reforming into liquid alkanes (C5–C6) on the metal centers. And it
should be noted that the scission of C–C bond occurred to a great
extent on the Pt metal sites to generate the undesirable byproducts
such as lighter alkanes (C1–C4) under the reaction condition of
245 °C and 2.93 MPa, and thereby caused a decrease in the forma-
tion of liquid hydrocarbons [17].
In this regard, supported Ni/HZSM-5 catalysts were developed
to take the place of those noble ones, but HZSM-5 zeolite showed
stronger Brønsted acidity, leading to the heavier formation of coke
and poor stability under severe hydrothermal conditions of
aqueous phase reforming [18,19]. It has been stated that acid
amount of HZSM-5 can be adjusted by dealumination of the frame-
work Al of the catalyst under different calcination temperature,
which facilitates aqueous phase processing of sorbitol conversion
to liquid alkanes [18]. In addition, the framework Al of HZSM-5

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 Q. Zhang et al. / Energy Conversion and Management 77 (2014) 262–268
can be substituted by nonpolar Si groups in a certain extent and
thus would result in the acid modulation of the zeolite. MCM-41
mesoporous silica, firstly reported in 1992, has been confirmed
to adjust the amount of Brønsted acidity of other zeolite such as
MCM-22 because of its containing Lewis acidic sites [20]. Further-
more, such MCM-41 materials were widely used in catalysis owing
to their high hydrothermal stability, large surface area and control-
lable mesoporous diameter [21,22]. MCM-41 was also found to
improve effectively the adsorption capacity of the Ni/HZSM-5
catalyst and adjust the acidity of the catalyst and thereby facilitate
sorbitol conversion to alkanes [23].
Here, to better understand the catalytic behavior and promoting
effect of MCM-41 for sorbitol hydrogenation in water, meanwhile,
to evaluate the potential application of the resulted catalyst in the
substitution of fossil fuels with new liquid fuels from biomass, the
selected catalysts were characterized by X-ray powder diffraction
(XRD) and H2 temperature-programmed reduction (H2-TPR) on
the structure properties and reducibility. The variation in the acid
distribution of the catalyst was also investigated by infrared spec-
troscopy using pyridine as probe molecule (Py-IR) and infrared
spectroscopy (IR) to distinguish the scission of C–C or C–O bond
in the sorbitol molecule during the reaction. In addition, thermo-
gravimetric analysis measurements (TG–DSC) of the used catalysts
were adopted to investigate the behavior of carbon deposited on
the catalyst surface.
2. Experimental
2.1. Catalyst preparation
The catalyst used in this work was prepared by the incipient
wetness impregnation method. Prior to the preparation, appropri-
ate amount of HZSM-5 (80–100 mesh, Si/Al atomic ratio of 38) was
separately blended with different amounts of pure silica MCM-41
(100–120 mesh) in batches in deionized water at room tempera-
ture for 3 h under the stirring speed of 300 r min1, followed by
drying in air at 110 °C for 12 h, and the dried samples were cal-
cined at 500 °C for 6 h, then the resulting HZSM-5 composite pre-
cursors were formed and simply denoted as HZSM-5(x), where x
refers to the weight percent of MCM-41 in the corresponding
HZSM-5 composite and equals to 30, 40, 50 and 60, respectively.
Subsequently, appropriate amount of each abovementioned
HZSM-5 composite precursor was impregnated solely in an aque-
ous solution of nickel nitrate at room temperature for 12 h, dried
in air at 110 °C overnight, and thereafter calcined at 500 °C for
4 h, the resulting catalysts were denoted as 2%Ni/HZSM-5(30),
2%Ni/HZSM-5(40), 2%Ni/HZSM-5(50), and 2%Ni/HZSM-5(60),
respectively. For comparison, pure HZSM-5 and MCM-41 were also
used to prepare 2%Ni/HZSM-5 and 2%Ni/MCM-41 catalysts accord-
ing to the aforementioned process, respectively. HZSM-5 and pure
silica MCM-41 were supplied by Nankai University catalyst Co.,
Ltd., (Tianjin, China), and Ni(NO3)26H2O (AR, 99.9%) was bought
from Tianjin Fucheng Reagents (Tianjin, China). All of the catalysts
were reduced by a flow of H2 (30 ml min1) at 500 °C for 3 h before
reaction.
2.2. Catalyst characterization
X-ray powder diffraction (XRD) analysis was carried out on a
Panalytical X’pert PRO diffractometer using Cu Ka (k = 0.154 nm)
radiation at 40 kV and 30 mA. For the wide-angle XRD, the 2h an-
gles were scanned from 5 to 80° with a step of 0.016°, whereas
for the small-angle XRD, the 2h angles were scanned from 0.5° to
8° with a step of 0.02°.
263
Infrared spectra of pyridine adsorption (Py-IR) were recorded
on a Thermo Nicolet Nexus FT-IR spectrometer equipped with a
liquid nitrogen cooled MCT detector. The samples were pressed
into a self-supported wafer and treated at 400 °C in an in situ IR cell
for 0.5 h followed by cooling to 50 or 100 °C under vacuum to re-
cord the background spectra of the cell and the catalyst wafer. Sub-
sequently, the samples were exposed to pyridine vapor for 10 min
and then vacuum evacuated at the same temperature in order to
remove physical adsorbed pyridine. The spectra were recorded in
the range of 1700–1400 cm1 with 32 scans and a resolution of
4 cm1.
Infrared spectra (FT-IR) were collected on the abovementioned
Thermo Nicolet Nexus FT-IR spectrometer. The samples were
pressed into a self-supported wafer at room temperature using
KBr and treated at 100 °C in an in situ IR cell for 0.5 h under vacuum
and then cooled down to room temperature. The spectra were
recorded in the range of 3000–4000 cm1 with 32 scans and a res-
olution of 4 cm1.
H2 temperature-programmed reduction (H2-TPR) was carried
out on a self-made instrument. Typically, in order to remove the
surface contaminants, 50 mg of the sample loaded in a quartz reac-
tor was firstly pretreated at 350 °C in a pure N2 stream for 1 h. After
cooling to room temperature, a flow of 5%H2/N2 (25 ml min1) was
introduced into the sample, and the temperature was raised to
750 °C at a heating rate of 10 °Cmin1. The H2 consumption was
monitored with a thermal conductivity detector (TCD) equipped
with a 5A molecular sieve column to remove H2O from the effluent
gas.
Thermal analysis curves (TG–DSC) of the catalysts were ob-
tained by STA409PC from 40 °C to 900 °C at the heating rate of
15 °Cmin1 under air condition.
2.3. Catalytic activity test
The activity test of the catalyst was carried out in a batch-type
autoclave reactor with a capacity of 250 ml. Typically, 9.1 g of sor-
bitol and 3.0 g of the reduced catalyst were filled in the reactor
with 150 ml of deionized water per run. The reactor was purged
in advance with H2 for three times so as to remove oxygen con-
tained in the reactor, and then the reaction was performed at
240 °C and 4.0 MPa for 1 h under the stirring speed of 200 r min1.
The effluent products were measured via a wet flowmeter and ana-
lyzed by a Shimadzu GC-2010 gas chromatograph (SE-30 capillary
column, 30 m  0.32 mm  0.32 lm) equipped with a flame ioni-
zation detector (FID). The conversion and alkane selectivity were
measured by the definition formulas listed below:
Sorbitolm  Sorbitolresidue
Sorbitol conversion % ¼  100 ð1Þ
Sorbitolm
i  nCi
Alkane selectivity % ¼ P6  100 ð2Þ
i¼1 i  nC i
In the formulas (2), i is the carbon atom numbers for alkanes; Ci
is the alkane which contains carbon atom numbers of i.
3. Results and discussion
3.1. Structural changes in the support
Fig. 1 displays the XRD patterns of HZSM-5 samples added with
different amount of MCM-41. Sharp diffraction peaks appearing at
2h = 7.9°, 8.9° and 22–25° were observed over the bare HZSM-5
sample, indicating the highly crystalline structure of HZSM-5
[24]. However, the intensities of these characteristic diffraction
peaks decrease significantly as the amount of MCM-41 added up
264 Q. Zhang et al. / Energy Conversion and Management 77 (2014) 262–268
Fig. 1. XRD patterns of the HZSM-5 samples with different amounts of MCM-41
addition by wide angle scanning.
to 60 wt%. This implies that the framework Al in HZSM-5 may be
substituted partially by Si species in pure silica MCM-41. It was
also noticeable that the characteristic diffraction peaks of HZSM-
5 still occurred during the process of MCM-41 addition. For the
MCM-41 sample, a broad diffraction peak appearing at 2h = 20–
30° associating with SiO2 was also observed. Seen from the pat-
terns of small angle XRD of samples (Fig. 2), an intense diffraction
peak at 2h = 2.3° can be detected over pure silica MCM-41, which
can be associated with (1 0 0) reflection, and two other weak peaks
at 2h = 3.8° and 4.6°, respectively, which can be attributed to the
corresponding higher order (1 1 0) and (2 0 0) reflections, indicating
a typical well-ordered hexagonal structure of MCM-41 [25]. The
typical XRD diffraction peak of MCM-41 at 2h = 2.3° occurs over
Fig. 2. XRD patterns of the HZSM-5 samples with different amounts of MCM-41
addition by small angle scanning.
HZSM-5(30), indicating that the framework Al of HZSM-5 could
be partially substituted by Si species when a certain amount of
pure silica MCM-41 was added. Moreover, the intensities of these
three (1 0 0), (1 1 0) and (2 0 0) reflections generally increased with
the increasing amount of MCM-41 addition in the range of 30–
60 wt%. The unit cell parameters of HZSM-5 with different amount
of MCM-41 addition are listed in Table 1. Interestingly, the remark-
able decrease in the intensity of the (1 0 0) reflection peak can be
observed in HZSM-5(40) in comparison with that in HZSM-5(30),
indicating that a stronger interaction between HZSM-5 and
MCM-41 occurred when 40% of MCM-41 was incorporated in
HZSM-5. Thus, it can be speculated the optimal molecular struc-
ture was obtained in the HZSM-5(40) due to its smaller value of
unit cell parameter a0. This effect may play an important role in
the improvement of the stability or activity of the resulting
catalyst.
3.2. Acidity modulation in the support
The acidity of HZSM-5 with different amounts of MCM-41 addi-
tion was measured by Py-IR spectroscopy and the results are
shown in Fig. 3. IR bands at 1450, 1595 and 1612 cm1 were ob-
served over HZSM-5, which can be attributed to the adsorption
of pyridine coordinated on Lewis acid sites [26]. IR bands near at
1545 and 1637 cm1 are associated with pyridine adsorption on
Brønsted acid sites, which are generally assigned to the framework
Al. In addition, the band at 1490 cm1 is ascribed to the vibration of
the pyridine ring on Brønsted and Lewis acid sites [27,28]. How-
ever, pure silica MCM-41 exhibits only two strong bands at 1446
and 1595 cm1 and a weak band at 1490 cm1 after pyridine
chemsorption, indicating that Brønsted acid sites can be negligible
and Lewis acid sites are the dominant acid centers in MCM-41 due
to the absence of the framework Al. Interestingly, the intensity of
Brønsted acid sites in HZSM-5 decreased sharply when small
amount of MCM-41 was added to HZSM-5, such as 30 wt%, while
that of Lewis acid sites increased distinctly. Meanwhile, the band
arising from Lewis acid sites at 1450 cm1 shifted to 1446 cm1,
indicating that there occurs an interaction between HZSM-5 and
MCM-41 added and therefore causes the increase in the amount
of pyridine adsorbed due to the increase in the intensity of these
sites. Generally, hydrodeoxygenation of C–O in the sorbitol mole-
cule was mainly carried out on the weak acid sites, while the
strong acid ones were used for C–C breakage to generate lighter al-
kanes by successive hydrogenation. Thus, the appropriate amount
of total acid sites and Lewis acid sites can easily result in the pro-
duction of liquid alkanes from sorbitol hydrogenation on the Ni/
HZSM-5 composites. This is proven by the results of activity tests
and Py-IR over 2%Ni/HZSM-5(40). In addition, the intensity of Le-
wis acid sites decreased gradually with the amount of MCM-41
added beyond 40 wt%, implying that an optimum proportion
Table 1
The unit cell parameters of HZSM-5 with different amount of MCM-41 addition.
Samples d100 (nm) d110 (nm) d200 (nm) a0a
b
HZSM-5 – – – –
HZSM-5(30) 3.93 2.29 1.97 4.53
HZSM-5(40) 3.84 2.24 1.96 4.43
HZSM-5(50) 3.88 2.28 1.97 4.48
HZSM-5(60) 3.93 2.29 1.96 4.53
MCM-41 3.96 3.91 2.00 4.57
a
d100 Calculated by formula 2d sin h = nk and the unit cell parameter a0 calcu-
p
lated by formula a0 = 2d100/ 3.
b
Since no diffraction peak at 2h = 0.5–6.0° over pure HZSM-5 from small angle
XRD, the corresponding unit cell parameters were not calculated.
 Q. Zhang et al. / Energy Conversion and Management 77 (2014) 262–268
Fig. 3. Infrared spectra of pyridine on HZSM-5 with different amounts of MCM-41
addition at the desorption temperature of 100 °C.
between HZSM-5 and MCM-41 may exist in the framework of the
HZSM-5 composites.
To investigate the strength of Lewis acid sites estimated by the
stability of chemisorbed pyridine on HZSM-5(40), IR spectra after
evacuation at various temperatures were collected under the dif-
ferent temperature and the results are shown in Fig. 4. It is clear
that the intensity of IR bands at 1446 and 1595 cm1 decreased
significantly with the increasing evacuation temperature in the
range of 50–200 °C. Moreover, IR band at 1595 cm1 disappeared
when the evacuation temperature was elevated to 250 °C, follow-
ing by a broaden peak occurred near 1612 cm1, indicating that
the HZSM-5(40) sample still contains a certain amount of Lewis
acid sites under higher temperature. This also is the evidence that
the resulting catalyst prepared from HZSM-5(40) exhibits higher
catalytic activity for C–O hydrodeoxygenation in the sorbitol mol-
ecule by aqueous phase processing under the harsh hydrothermal
reaction condition. However, the intensities of the peaks of Lewis
acid sites were quite low as evacuation temperature further
Fig. 4. Infrared spectra of pyridine on HZSM-5(40) at the desorption temperature
ranging from 50 to 400 °C.
265
increased up to 400 °C, indicating that pyridine interacts weakly
with these Lewis acid sites under high temperature and results
in the negligible acidity.
Additionally, FTIR spectroscopy was adopted to further investi-
gate the variety of surface hydroxyl groups between MCM-41 and
HZSM-5, and the spectra collected at room temperature in the
vibration band rang of 3000–4000 cm1 (O–H stretching region)
are presented in Fig. 5. The band at 3618 cm1 was observed over
bare HZSM-5, which can be assigned to the stretching vibration of
surface Al–OH groups in the HZSM-5 framework [29]. For the
MCM-41 sample, one band at about 3727 cm1 was detected dis-
tinctly, which can be associated with terminal Si–OH groups [30].
Notably, Al–OH groups in HZSM-5 are generally recognized as
strong Brønsted acid sites, while those Si–OH groups are weak Le-
wis acid sites. As an appropriate amount of MCM-41 was added to
HZSM-5 (e.g., 30 wt%), the initial band at 3618 cm1 in HZSM-5
disappeared completely, and a new band at 3733 cm1 occurred.
In addition, the intensity of this peak increased with increasing
amount of MCM-41 addition in the range of 30–60 wt%, implying
a visible increase in the amount of surface hydroxyl groups. Com-
pared to MCM-41, the peak shift from 3727 cm1 to 3733 cm1
indicates that an interaction between MCM-41 and HZSM-5 exists
and that Al–OH groups in HZSM-5 can be substituted partially by Si
species and then formed Si–OH, Si–O–Si or Si–OH–Al groups after
calcined at 500 °C for 3 h, accompanying by the adjustment of the
types and amount of acidic sites of HZSM-5 and subsequently
resulting in the easy formation of heavier liquid alkanes from sor-
bitol hydrogenation.
3.3. Hydrogen reducibility of the catalyst
Fig. 6 shows the H2-TPR profiles of 2%Ni/HZSM-5 with different
amount of MCM-41 addition. Two reduction peaks can be detected
over 2%Ni/HZSM-5, one at 349 °C ascribed to the reduction of
superficial NiO, and the other at higher temperature (426 °C)
attributed to the reduction of bulk NiO [31], which were both low-
er than those over 10%Ni/HZSM-5 reported in our previous study
[18], indicating that Ni species are much easily reduced by
hydrogen under the lower level of nickel loading due to its better
Fig. 5. IR spectra of HZSM-5 with different amounts of MCM-41 addition collected
at 3000–4000 cm1.
266 Q. Zhang et al. / Energy Conversion and Management 77 (2014) 262–268
Fig. 6. H2-TPR profiles of 2%Ni/HZSM-5 with different amounts of MCM-41
addition.
dispersion on the surface of HZSM-5. Compared to 2%Ni/HZSM-5,
higher temperature of the reduction peak of NiO was observed
over 2% Ni/MCM-41, and the temperature of both reduction peaks
was found to be around 408 and 637 °C, respectively, suggesting a
stronger interaction between NiO and MCM-41 due to its higher
surface area and bigger adsorption capacity demonstrated by N2
physical adsorption in our previous study [23]. Moreover, a shift
to higher temperature of the reduction peak of NiO can be also
found over 2%Ni/HZSM-5 with small amount of MCM-41 addition.
The temperature of both reduction peaks was shifted to higher
temperature by 13 and 82 °C, respectively when the amount of
MCM-41 was added in the range from 30 to 40 wt%, indicating that
appropriate amount of MCM-41 can significantly promote the
interaction between NiO and the support. Interestingly, the tem-
perature of the reduction of superficial NiO was found to be around
398 °C over 2%Ni/HZSM-5(50), while that of the reduction of bulk
NiO maintained unchanged, which was shifted to 534 °C when
the amount of MCM-41 was added up to 60 wt%. This indicates
that NiO species are relatively difficult to be reduced under higher
amount of MCM-41 added. This is also the evidence that the reduc-
tion of NiO species was carried out initially from the superficial
phase.
3.4. Sorbitol hydrogenation
Fig. 7 shows the catalytic performance of 2%Ni/HZSM-5 cata-
lysts with different amounts of MCM-41 addition for sorbitol
hydrogenation. It can be seen that 2%Ni/HZSM-5 exhibited a low
catalytic activity of sorbitol hydrogenation with sorbitol conver-
sion of 40%, and the selectivity of liquid alkanes (pentane and hex-
ane) was only 35.6%, wherein a larger amount of lighter alkanes
(C1–C4) was formed with the total selectivity of 64.4%, indicating
that the scission of C–C bond was carried out to a great extent
on the surface of HZSM-5 due to its strong acidity, which has been
demonstrated by Zhang et al. [18]. Meanwhile, a lower conversion
of sorbitol was found to be 16.3% over 2%Ni/MCM-41, implying
that the hydrogenation of C–O or C–C bond was difficult to accom-
plish on the pure silica MCM-41 containing only weak acidic sites,
but the selectivity of pentane and hexane was both higher than
those over 2%Ni/HZSM-5, accompanying by a clear decrease in
Fig. 7. Catalytic performance of various 2%Ni/HZSM-5 catalysts for sorbitol
hydrogenation. Ni/HZSM-5(40)’ was referred to the used Ni/HZSM-5(40) catalyst
after one recycling.
the selectivity of lighter alkanes. Interestingly, the product of sor-
bitol hydrogenation was completely dominated by hexane with
the selectivity of 91.4% when 30 wt% of MCM-41 was added to
the catalyst, although the sorbitol conversion was relatively un-
changed in the process. In addition, 2%Ni/HZSM-5(40) exhibited
the maximum activity with 67.1% of sorbitol conversion and
98.7% of liquid alkanes selectivity and then decreased as a function
of MCM-41 addition in the range of 40–60 wt%, wherein the selec-
tivity of hexane maintained at 90–94%, which was higher than
those obtained on the Pt-based catalysts [13,17]. Notably, the cat-
alytic performance for the reaction on the used 2%Ni/HZSM-5(40)
catalyst was found to be a bit less than that on the fresh one. These
mean that proper amount of MCM-41 addition to 2%Ni/HZSM-5
can enhance remarkably sorbitol to convert into heavier liquid
alkanes (C5–C6), and thus a promoting effect of MCM-41 can be
deduced on the product selectivity, which may be due to a positive
interaction between HZSM-5 and MCM-41 based on the
abovementioned results of characterization techniques.
3.5. Carbon deposition resistance of the catalyst
In order to explore the carbon deposition behavior of the used
Ni/HZSM-5 and Ni/HZSM-5(40) catalyst, the samples were investi-
gated by using TG technique, and TG–DSC curves are shown in
Fig. 8. As seen from Fig. 8a, the used Ni/HZSM-5 catalyst had a seri-
ous weight loss of 27%, which was found to be much higher than
that for the used Ni/HZSM-5(40) catalyst with a value of 8%. More-
over, two exothermic peaks were observed from Fig. 8b over these
two catalysts, indicating that two types of different carbon species
deposited on the catalyst surface. The peak at the region of 200–
400 °C can be attributed to the combustion of the amorphous car-
bon, while the one at the region of 400–650 °C can be associated
with graphitic species [32]. In addition, the heat release of two
peaks over the used Ni/HZSM-5 catalyst was both much higher
than that over the Ni/HZSM-5(40) catalyst, especially the peak at
high temperature. This means that carbon deposition on the for-
mer was more serious than the latter, that is, 40 wt% of MCM-41
embedded into HZSM-5 can greatly restrain the formation of car-
bon deposition on the surface of the catalyst. Notably, no obvious
change can be detected on the exothermic peak value over these
two used catalysts, suggesting that MCM-41 added does not affect
 Q. Zhang et al. / Energy Conversion and Management 77 (2014) 262–268
Fig. 8. Thermal analysis curves of the used Ni/HZSM-5 and Ni/HZSM-5(40) catalyst: (a) TG and (b) DSC.
the types of carbon species while only decreases their generation
amount. Moreover, the adjustment of Brønsted acid concentration
in Ni/HZSM-5 by 40 wt% of MCM-41 addition based on the above-
mentioned results of Py-IR should be responsible for the decrease
of carbon deposition on the catalyst surface. Thus, it can be specu-
lated that graphitic species formed during the reaction may be one
of main factors of deactivation for Ni/HZSM-5 due to its difficult
transformation and covering the active sites and blocking HZSM-
5 channels.
4. Conclusions
Liquid alkanes such as C5–C6 alkanes can be selectively pro-
duced from sorbitol hydrogenation via modifying the structure of
the Ni/HZSM-5 catalyst and its types of acidic sites in water med-
ium in the present study. An appropriate amount of MCM-41 addi-
tion to the 2%Ni/HZSM-5 catalyst was found to significantly
enhance the activity of the catalyst for sorbitol hydrogenation into
C5–C6 alkanes. The catalyst containing 40 wt% MCM-41 exhibited
the maximal sorbitol conversion of 67.1% and the liquid alkane
selectivity of 98.7%. As the amount of MCM-41 addition was fur-
ther increased to 60 wt%, the sorbitol conversion decreased dis-
tinctly to 41.8%, whereas the hexane selectivity maintained at
about 90%, indicating that MCM-41 added favors the scission of
C–O bond in the sorbitol molecule.
The characterization results of XRD, IR and Py-IR techniques
showed that the addition of 40 wt% MCM-41 to Ni/HZSM-5 would
result in the optimum structural properties and visible increase in
the amount of Lewis acid sites of the catalyst, which favor the scis-
sion of C–O in the sorbitol molecule into heavier C5–C6 alkanes by
successive hydrogenation in water. The results of H2-TPR analysis
revealed that a strong interaction between Ni species and the sup-
port existed over the Ni/HZSM-5 catalyst contained appropriate
amount of MCM-41. Meanwhile, TG–DSC experiments displayed
that MCM-41 added can greatly restrain carbon deposition on
the surface of the Ni/HZSM-5 catalyst under the harsh hydrother-
mal condition. These roles might give some insights for better
understanding the catalytic behavior of MCM-41 on the catalyst
for sorbitol hydrogenation, and it however should be noted that
the structure of the catalyst may be changed in water medium.
Detailed studies are still required to design and improve a more
267
robust catalyst for biomass conversion by adding some stabilizers
or promoters in the future.
Acknowledgements
This Project is supported by National Natural Science Founda-
tion of China (Nos. 21206162 and 51006110) and National Key
Basic Research Program 973 Project founded by MOST of China
(No. 2012CB215304) and Key Program of Chinese Academy of
Sciences (No. KGZD-EW-304-2) and National Technology Research
Project (No. 2012AA101806).
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