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9th International Conference on Applied Energy, ICAE2017, 21-24 August 2017, Cardiff, UK

Catalytic pyrolysis of sugarcane bagasse over cerium (rare earth)

The 15th International Symposium on District Heating and Cooling
loaded HZSM-5 zeolite
Assessingaa,the
Vekes Balasundram feasibility
Norazana Ibrahimof a,*, using the heat demand-outdoor
a, a
Rafiziana Md. Kasmania, Mohd. Kamaruddin
temperature function
Abd. Hamid bb
, Ruzinahfor
Ishaacc,long-term district
Hasrinah Hasbullah dd
heat demand
, Roshafima forecast
Rasit Ali
a
aClean
Clean andand Efficient
Efficient Energy Research
Research Group,
a,b,c
Energy Group, Faculty
a
Faculty of
of Chemical
Chemicala and
and Energy
Energy Engineering,
b
Engineering, Universiti
Universiti Teknologi
c Malaysia
Teknologi Malaysia (UTM),
(UTM), 81310
c UTM
81310 UTM
I. Andrić *, A. Pina , P. Ferrão , J. Fournier ., B. Lacarrière , O. Le Corre
Johor
Johor Bahru,
Bahru, Johor,
Johor, Malaysia.
Malaysia.
bb
a
Faculty
Faculty of
of Chemical
Chemical & & Natural
Natural Resources
Resources Engineering,
Engineering, Universiti
Universiti Malaysia
Malaysia Pahang,
Pahang, 26300,
26300, Gambang,
Gambang, Pahang,
Pahang, Malaysia.
Malaysia.
IN+
cc Center for
Faculty Innovation, Energy
Technology and Policy ResearchTeknologi
- InstitutoMalaysia
Superior(UTM),
Técnico,81310
Av. Rovisco Pais Bahru,
1, 1049-001 Lisbon, Portugal
Faculty of
of Chemical
Chemical and
andb Energy Engineering,
Engineering, Universiti
Universiti Teknologi Malaysia (UTM), 81310 UTM
UTM Johor
Johor Bahru, Johor,
Johor, Malaysia.
Malaysia.
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
c
Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France

Abstract
Abstract
Abstractobjective of the present work is to investigate the influence of catalyst to biomass ratio (C:B) on pyrolysis sugarcane
The
The main
main objective of the present work is to investigate the influence of catalyst to biomass ratio (C:B) on pyrolysis sugarcane
bagasse
bagasse over cerium loaded Hydrogen exchanged Zeolite Socony Mobil-5 (HZSM-5, Si/Al =
= 23)
23) catalyst via in-situ fixed
fixed bed
Districtover
reactor. HZSM-5
cerium
heating loaded are
networks
catalyst
Hydrogen
was commonly
used as
exchanged
addressed
aa support
Zeolite
with
Socony
in 1the
wt.% of
Mobil-5
literature
Ce as
as
(HZSM-5,
one Si/Aleffective
of theloaded
promoter most via
catalyst via for
solutions
incipient wetness
in-situ
decreasing bed
impregnation the
reactor. HZSM-5 catalyst was used as support with 1 wt.% of Ce as promoter loaded via incipient
greenhouse gas emissions from the building sector. These systems require high investments which are returned through the heat wetness impregnation
method.
method. The
The topyrolysis
pyrolysis oil
oil (PO)
(PO) yield
yield and
and coke
coke yield
yield were significantly affected by
by the use ofof Ce/HZSM-5 at
at various C:B ratio
sales. Due the changed climate conditions and were significantly
building renovationaffected
policies, the
heatusedemand
Ce/HZSM-5
in the future various
couldC:B ratio
decrease,
than
than the
the none
none catalytic
catalytic pyrolysis,
pyrolysis, in
in which
which generating
generating low
low PO
PO yields
yields (50.0
(50.0 wt.%).
wt.%). The
The increasing
increasing Ce/HZSM-5
Ce/HZSM-5 loading
loading has
has an
an
prolongingeffect
additional the investment
with return
respect to period.
PO and coke yields. Among the tested C:B ratio, a catalyst to biomass ratio of 1:1 has
additional effect with respect to PO and coke yields. Among the tested C:B ratio, a catalyst to biomass
The main scope of this paper is to assess the feasibility of using the heat demand – outdoor temperature function for heat demand ratio of 1:1 has
demonstrated
demonstrated to be
be potential candidates in
in the catalytic pyrolysis
pyrolysis of SB into
into aaashigher yield of condensable pyrolysis oil
oilofwith
forecast. Thetodistrictpotential candidates
of Alvalade, located the
in catalytic
Lisbon (Portugal), ofwas
SB used higher
a caseyield of The
study. condensable
district ispyrolysis
consisted with
665
lower
lower coke
coke contents.
contents.
© buildings
2017 The that vary in
Authors. both construction
Published by Elsevier period
Ltd. and typology. Three weather scenarios (low, medium, high) and three district
©renovation
2017 The Authors.
scenariosPublished by Elsevier
were developed Ltd. intermediate, deep). To estimate the error, obtained heat demand values were
(shallow,
© 2017 The under
Peer-review Authors. Published
responsibility by
of Elsevier
the Ltd. committee of the 9th International Conference on Applied Energy.
scientific
Peer-review
Peer-review under
under
compared with responsibility
responsibility
results of the scientific
of the scientific
from a dynamic heat demandcommittee
model,of
committee of the
the 9th
9th International
previously International
developed and Conference
validatedon
Conference byApplied
on Applied Energy.
Energy.
the authors.
The results showedbagasse;
Keywords: that when onlypyrolysis;
weather change is considered, theoils;
margin of error could be acceptable for some applications
Keywords: Sugarcane
Sugarcane bagasse; Catalytic
Catalytic pyrolysis; Zeolites;
Zeolites; Cerium;
Cerium; Pyrolysis
Pyrolysis oils; Coke
Coke contents
contents
(the error in annual demand was lower than 20% for all weather scenarios considered). However, after introducing renovation
scenarios, the error value increased up to 59.5% (depending on the weather and renovation scenarios combination considered).
The value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the
decrease in the number of heating hours of 22-139h during the heating season (depending on the combination of weather and
renovation scenarios considered). On the other hand, function intercept increased for 7.8-12.7% per decade (depending on the
coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and
improve the accuracy of heat demand estimations.

© 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and
*
* Corresponding
Corresponding author.
Cooling. author. Tel.:
Tel.: +607-553-5495;
+607-553-5495; fax:
fax: +607-558-1463.
+607-558-1463.
E-mail
E-mail address:
address: norazana@utm.my
norazana@utm.my
Keywords: Heat demand; Forecast; Climate change
1876-6102 ©
1876-6102 © 2017
2017 The
The Authors.
Authors. Published
Published by
by Elsevier
Elsevier Ltd.
Ltd.
Peer-review
Peer-review under
under responsibility
responsibility of
of the
the scientific
scientific committee
committee of
of the
the 9th
9th International
International Conference
Conference on
on Applied
Applied Energy.
Energy.

1876-6102 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.
10.1016/j.egypro.2017.12.129
802 Vekes Balasundram et al. / Energy Procedia 142 (2017) 801–808
2 Author name / Energy Procedia 00 (2017) 000–000

1. Introduction

Biomass is considered as one of the renewable energy sources with the highest potential to contribute to the
energy needs of modern society [1]. Due to the extensive agricultural activities in various countries, agricultural
wastes contribute significantly to the yearly global yield of biomass [1, 2]. Thus, thermochemical conversion or
pyrolysis of biomass has potential to generate usable forms of energy such as liquid oil (pyrolysis oil), gas (pyrolytic
gases) and solid (char). Since pyrolysis oil could yield in the range of 60 – 70 wt.% of total products, thus it becomes
as target product from biomass pyrolysis [3]. Consequently, generated raw pyrolysis oil comprises of highly
oxygenated compounds such as phenols, esters, ethers, alcohols, aldehydes, ketones, furans, acids and sugars [1-3].
Hence, the presence of mentioned compounds leads to undesired physicochemical properties such as high viscosity,
corrosive, low heating value and thermally unstable. Regardless of these shortcomings, it has some favourable
properties, such as less toxicity, good lubricity and greater biodegradation than the petroleum fuels [4]. Therefore, it
is necessary to upgrade raw pyrolysis oil in order to improve its physicochemical properties. For this reason,
catalytic pyrolysis would be a passport for biomass pyrolysis to extent its applications as gasoline enhancers in the
petrochemical industry. Currently, the zeolite type catalyst specifically HZSM-5 catalyst has gained attention in
biomass pyrolysis research area to convert oxygenates in pyrolysis oil into aromatics [5]. Moreover, the HZSM-5
catalyst is rich in acid sites that enhance the cleavage of C-O and formation of C-C bonds [6]. The acid sites of
HZSM-5 convert oxygenates in pyrolysis vapour into aromatics through multiple reactions such as dehydration,
decarboxylation, decarbonylation, oligomerization, alkylation, isomerization and finally aromatization [5, 6].
Additionally, the presence of acid sites in catalyst plays a major role in the formation of aromatics and coke build
up on the catalyst. Therefore, the catalyst should be designed at optimized acidity in order to achieve higher
aromatics yield, while reducing the possibility deactivation of the catalyst by coke. The deactivation is occurred due
to the deposition of carbonaceous materials (coke) on catalyst surface during catalytic pyrolysis, in which limits the
diffusion of oxygenates to enter and exit as aromatics along with the pore passage [7]. Currently, most literature is
available on the modification of transition metal into HZSM-5 zeolite in order to improve the selectivity of aromatics
and simultaneously reduce coke formation [3-7]. Transition metals modified HZSM-5 zeolite shows good
performance over aromatic selectivity but some metals are considered as cost ineffective and thermally unstable [6,
7]. Among transition metals, nickel (Ni) is reported as selective toward aromatics formation in pyrolysis oil and also
inexpensive metals for catalytic pyrolysis biomass [7, 8]. For example, Iliopoulou et al. (2012) [7] reported that the
pyrolysis of beech wood over Ni/HZSM-5 has higher aromatic yields of 8 % in pyrolysis oil than HZSM-5 (6 %) [8].
Conversely, they also reported catalytic pyrolysis over Ni/HZSM-5 generates higher coke residues of 27.03 wt.%
than that of HZSM-5 (25.7 wt.%). Hence, the finding of a suitable catalyst in catalytic pyrolysis of biomass towards
higher aromatics selectivity and lower coke formation is still in the research area.
Interestingly, rare earth element has the ability on the inhibition of coke build up, thus a higher concentration of
acid sites could be sustained that improves the activity and hydrothermal stability of catalyst [9]. For example, a
study by Xu et al. (2014) [10] suggested that the addition of rare earth element specifically cerium (Ce) in catalyst
could gradually reduce coke depositions and prolong its lifetime. A similar study by Balasundram et al. (2017) [11]
found that cerium was loaded in catalyst due to its high redox property that improves the volatiles of biomass
pyrolysis. In the meantime, it is important to realize that the greater number of active acid sites in the rare earth
element modified HZSM-5 could enhance the cracking of oxygenated compounds and hydrogen atom transfer
reaction [12]. In addition, the influence of rare earth element on HZSM-5 and the overall performance towards
catalytic cracking of biomass pyrolysis are still lacking in the literature. For this reason, cerium is loaded on HZSM-
5 as a bi-functional catalyst for catalytic pyrolysis of sugarcane bagasse is further investigated in this study. To the
best of our knowledge, the comprehensive study on the effect of rare earth element (Ce) modified on HZSM-5 in
catalytic pyrolysis of sugarcane bagasse is lacking in the literature. Thus, in this work, the catalytic performance of
Ce/HZSM-5 was evaluated on the pyrolysis of sugarcane bagasse in a fixed bed reactor. The influence of catalyst to
biomass ratio (C:B) as a function of pyrolysis oils yield and coke contents was discussed.
 Vekes Balasundram et al. / Energy Procedia 142 (2017) 801–808 803
Author name / Energy Procedia 00 (2017) 000–000 3

2. Materials and methods

2.1. Biomass preparation and characterization

In this study, sugarcane bagasse (SB) sample was selected as pyrolysis feedstock. First, the SB sample was
collected as wastes (left over after extraction of sugarcane juice) from the local market in Johor, Malaysia. The
samples were dried under sunlight. Then, the dried samples were ground and sieved to obtain particle size (dp) of
less than 0.5 mm. Later, the samples were allowed for pre-treatment of drying at 105 °C in a microwave oven for
about 24 hours until the weight remained constant. The samples were kept in a desiccator to minimize the absorption
of moisture from surrounding humidity.
The prepared SB samples were then characterized to obtain the ultimate, proximate and high heating value
(HHV). The ultimate analysis was carried out using an elemental analyser (Vario MICRO Cube, Germany) to
determine the amount of carbon (C), hydrogen (H), nitrogen (N) and sulphur (S) according to ASTM D-4239. Then,
the oxygen content was calculated by difference. Proximate analysis of SB sample was analysed via
Thermogravimetric Analyzer (TGA/SDTA851, METTLER TOLEDO, USA) according to ASTM D-3172. The
proximate analysis is used to determine the amount of volatile matter (VM), moisture content (MC) and ash content
(AC) in the samples. The fixed carbon (FC) content was then determined by difference. In order to avoid confusion
and to give a good representation of the fuel, the proximate and ultimate analyses are reported on a dry basis by
weight percent (d.b. wt.%). Finally, high heating value (HHV) of SB sample was determined by bomb calorimeter.

2.2. Catalyst preparation and characterization

The solid powder of zeolite ZSM-5 (Si/Al = 23) in ammonium form (NH 4+) was purchased from Alfa Aesar,
while Cerium(III)Nitrate Hexahydrate [Ce(NO3)3.6H2O] (Purity = 99.5%) was purchased from ACROS Organics.
First, the ZSM-5 (NH4+) in ammonium form was converted into the protonic form (H +) of zeolite (HZSM-5) by
calcined at a temperature of 600 °C for 4 hours in the static air (ramp rate = 5 °C/min). The calcination was done in
laboratory muffle furnace. Next, the impregnation of cerium (Ce) (1 wt.%) was achieved on HZSM-5 via incipient
wetness impregnation (IWI) method. After that, the chemicals were mixed in a beaker with 80 mL of deionized
water (DIW). The solution was well mixed and stirred using magnetic stirrer hot plate at a fixed temperature of 80
°C for 4 hours. Next, the formed paste was dried in a microwave oven at a temperature of 105 °C at about 12 hours
to remove DIW. Then, the formed solid catalyst was calcined in a muffle furnace at 600 °C for 4 hours (ramp rate, 5
°C/min). Finally, a mortar and pestle were used to crush the solid catalyst. The characterizations on prepared
catalysts were performed to investigate its physicochemical properties.
The characterizations on synthesized catalysts were performed to investigate its physicochemical properties. X-
ray diffraction (XRD) (Rigaku SmartLab X-ray diffractometer, Japan) was employed to measure the crystalline
structure of the synthesized catalyst. The catalyst sample was irradiated using Cu Kα radiation with a wavelength (λ)
of 0.15406 nm at a tube voltage of 40 kV and tube current of 40 mA. The sample scanning was carried out over a 2θ
range from 3° to 100° with a scanning rate of 5 °C/min. Brunauer Emmett Teller (BET) specific surface area and
porosity texture of catalyst were determined by nitrogen (N 2) physisorption at – 196 °C using an automatic gas
adsorption analyser (ThermoScientific, Waltham, MA, USA). Prior to measurement, the catalyst samples were
degassed under vacuum at 300 °C for about 6 hours to remove adsorbed compounds. The specific surface area and
pore diameter of catalyst were computed according to the Brunauer-Emmett-Teller (BET) method. The pore volume
of catalyst was calculated based on Barrett-Joyner-Halenda (BJH) method. Pore volume was estimated at a relative
pressure (P/P0 = 0.995). Scanning electron microscopy (SEM, CARL-ZEISS) was used to investigate the
morphology structure of the catalyst. The catalyst was placed in a high-resolution coater and coated with
platinum/palladium (Pt/Pd). The accelerating voltage was set to 7 kV with the working distance of 8 – 8.5 mm in a
vacuum condition. A high-resolution SEM (CARL-ZEISS) was produced various signals contain information about
the catalyst’s surface topography and composition.
For coke analysis, Thermogravimetric Analyzer TGA/SDTA851 (METTLER TOLEDO, USA) was employed to
measure the amount of coke formed on the catalyst. At the end of pyrolysis, about 5 mg of spent catalyst was heated
804 Vekes Balasundram et al. / Energy Procedia 142 (2017) 801–808
4 Author name / Energy Procedia 00 (2017) 000–000

in TGA from 25 °C to 700 °C at a constant heating rate of 10 °C/min under nitrogen (N2) atmosphere at a fixed flow
rate of 150 mL/min. The sample was then maintained at the final temperature (700 °C) for about 10 minutes.

2.3. Experimental setup

In-situ fixed bed pyrolysis reactor (lab-scale) was used to conduct the experiments of in-situ catalytic pyrolysis of
bagasse as shown in Fig. 1. The setup consists of a reactor (including fixed bed reactor), tubular furnace (as a
heater), condenser system, gas bag and nitrogen (N2) source as an inert gas. Prior to the experiment, 2g of SB
sample and synthesized catalyst were well mixed before loading into fixed bed at a various catalyst to biomass ratio
(C:B) of 0.5:1, 1:1, 1.5:1 and 2:1 by mass percent. All the outlet and inlet fittings were tightened to prevent any form
of leakage during an experimental run. An inert atmosphere was created inside the reactor by purging nitrogen (N 2)
stream flowing downstream at a rate of 50 mL/min. The atmospheric pressure (1 atm) was maintained throughout
the experiment. The tubular furnace was heated up to desired reaction temperature. The experiments were conducted
at a temperature of 500 °C by setting the electrical control panel. A thermocouple was inserted into the tubular
furnace to measure the actual temperature of the reactor from time to time as safety precautions. The generated
volatile products in the reactor were purged downward by a nitrogen stream and flow into the condenser (filtering
flask). The condensation system was set up by immersing filtering flask into an ice bath at a temperature range of 10
– 20 °C. The volatiles undergoes condensation to produce liquid pyrolysis oil. Condensed pyrolysis oil was then
collected and further analysed for the presence of chemical compounds. Meanwhile, the incondensable vapours were
collected using the gas bag. After the experiment complete, the reactor was dissembled and content left in the
reactor were separated. In order to make experimental results objective, each test was repeated at least three times
and average data values were utilized.

Fig. 1. Schematic diagram of in-situ fixed bed pyrolysis set-up

3. Results and discussions

3.1. Biomass characterization

The prepared sugarcane bagasse (SB) sample was characterized to obtain the ultimate, proximate and high
heating value (HHV). From the ultimate analysis, it is observed that the SB has high carbon elements (44.32 wt.%)
and oxygen elements (48.87 wt.%). However, high oxygen contents in biomass could lead to the formation of
oxygenated liquid pyrolysis oil. Meanwhile, hydrogen, nitrogen and sulphur are in small amounts of 6.04 wt.%, 0.53
 Vekes Balasundram et al. / Energy Procedia 142 (2017) 801–808 805
Author name / Energy Procedia 00 (2017) 000–000 5

wt.% and 0.24 wt.%, respectively. In general, high content of carbon and hydrogen with low oxygen in biomass is
preferred in order to obtain aromatic liquid products. Apart from that, the proximate analysis shows that SB has
higher volatile matter of 73.50 wt.% and fixed carbon contents of 19.17 wt.%, Therefore, SB could possibly
produce a higher yield of pyrolysis oil. Meanwhile, it is observed that SB has low ash (2.34 wt.%) and moisture
contents (4.99 wt.%). In addition, the biomass of lower ash and moisture contents is highly preferable as pyrolysis
feedstock [13]. Lastly, high heating value (HHV) of SB is 18.60 MJ/kg that could maximize the combustion
efficiency of pyrolysis oil when come to use as transportation fuel.

3.2. Catalyst characterization

The phase purity and crystallinity of the Ce/HZSM-5 were determined by X-ray diffraction (XRD) technique as
shown in Fig. 2. The main XRD peaks of Ce/HZSM-5 zeolite were presented at 2θ of 7.88°, 8.76°, 23.06° and
23.32°, of which are in the XRD peak range of HZSM-5 (2θ = 7° – 9° and 23° – 25°) as reported in previous
literature [8]. The similar XRD peak range after metal loading on HZSM-5 shows that the metal oxides may present
either as amorphous or well dispersed small particles in the external HZSM-5 surface. Thus, it can be concluded that
the addition of cerium by IWI method did not change the framework of HZSM-5. The morphologies Ce/HZSM-5
catalyst is presented in Fig. 3. It was observed that Ce/HZSM-5 appeared in agglomeration that possibly due to the
interconnection of small particles. However, the distributions of cerium particles could not be observed at this
magnification due to they were presented in a small amount. This was well consistent with XRD patterns. The
textural properties such as BET surface area, total pore volume, and average pore size was reported to be 385.15
m2/g, 0.2086 cm3/g, and 1.83 nm respectively. The nitrogen adsorption isotherm for catalyst sample is
corresponding to a type I in the Brunauer classification as shown in Fig. 4. In detail, the catalyst showed a steep
increase of the adsorbed volume of nitrogen at low relative pressure (P/P o) of less than 10-5 followed by a gradual
increase, thus indicating that the adsorption occurred mainly on micropores.
Intensity (a.u.)

0 20 40 60 80 100
2θ (°)

Fig. 2. XRD pattern of Ce/HZSM-5 catalyst

806 Vekes Balasundram et al. / Energy Procedia 142 (2017) 801–808
6 Author name / Energy Procedia 00 (2017) 000–000

Fig. 3. SEM image of Ce/HZSM-5 catalyst

250
Volume adsorbed (cc/g)

200

150

100

50

0
0 0.2 0.4 0.6 0.8 1
P/Po

Fig. 4. Nitrogen adsorption isotherm of Ce/HZSM-5 catalyst

3.3. Catalyst to biomass ratio

These experiments studied the effect of catalyst to biomass ratio (C:B) of catalytic pyrolysis of sugarcane bagasse
over Ce/HZSM-5 catalyst as a function of pyrolysis oil (PO) yield and coke contents on the spent catalyst as shown
in Fig. 5. The overall mass balance calculation was employed to calculate the condensed pyrolysis oil (PO),
pyrolysis gas (PG) and pyrolysis char (PC) yield. Meanwhile, TGA analysis on the spent catalyst was used to
measure the coke contents for each experiment. For comparison, none catalytic sample has been conducted to
compare the yield of PO. It is observed that the pyrolysis of sugarcane bagasse (SB) has the lowest yield of PO at
50.0 wt.% than that of catalytic samples. Interestingly, the highest yield of pyrolysis gas and char is observed for
none catalytic sample. Meanwhile, the presence of Ce/HZSM-5 catalyst at a various catalyst to biomass ratio (C:B)
shows significant differences in PO yield varying from 58.0 to 68.0 wt.%. Hence, Ce/HZSM-5 has a beneficial
effect on cracking lignocellulosic biomass into higher PO yields. This possibly due to the exposure of pyrolysis
vapours on balanced active acid sites of Ce/HZSM-5 catalyst during pyrolysis that able to degrade into condensable
pyrolysis oil. Similarly, pyrolysis gas (PG) or also known as incondensable gaseous yields decreased in the range of
18.0 – 23.0 wt.% with the addition of the catalyst.
At the same time, PC yields of catalytic samples decreased with increasing catalyst loading. This might be due to
the redox property of cerium that reduces the re-adsorption of pyrolysis vapours for secondary cracking into solid
char. In other words, cerium as a promoter in catalyst framework could inhibit the rapid coking on the surface of the
 Vekes Balasundram et al. / Energy Procedia 142 (2017) 801–808 807
Author name / Energy Procedia 00 (2017) 000–000 7

catalyst and more active acid sites that are still available for reaction to take place. This observation was supported
by Liu (2012) [14] that the presence of cerium improves the dispersion of the active acid site in the catalyst. In
general, during catalytic pyrolysis, the oxygenated pyrolysis vapours undergo deoxygenation reaction such as
dehydration, decarbonylation and decarboxylation for removal of oxygenates via water molecules (H2O) and
incondensable gaseous (CO and CO2). Meanwhile, in the present study, the high PO yields and low PG yields could
be concluded that Ce/HZSM-5 catalyst might have a higher tendency in cracking oxygenated pyrolysis vapours via
oligomerization, isomerization, and aromatization into condensable PO instead deoxygenation reaction.
In the meantime, the presence of acid sites in catalyst plays a major role in both formations of pyrolysis oil and
coke build up on catalyst [5-7]. From the coke analysis, it observed that at a catalyst to biomass ratio of 1:1, a lower
amount of coke was build up during pyrolysis. Conversely, although at higher catalyst loading ratio (1.5 and 2)
produce higher PO yield, however, it generates higher and similar amount of coke than at C:B ratio of 1:1. In detail,
at a higher catalyst loading, more active acid sites of catalyst are available during pyrolysis of biomass. This
explains that before condensation, the pyrolysis vapour was highly exposed to a high number of active acid sites, in
which repeatedly polymerized into coke on the surface of the catalyst. The formed coke could block the pore
passage of catalyst and inhibit the reaction to occur that finally led to the catalyst deactivation. These are in a good
agreement with the literature reported on the rapid deactivation of the catalyst by coking [8].
This result concludes that the further catalyst loading increases the PO yield but failed to reduce coke content
during biomass pyrolysis. Hence, a catalyst to biomass ratio (C:B) of 1:1 work best in achieving higher PO yield and
lower coke contents from catalytic pyrolysis of SB over Ce/HZSM-5 catalyst. On one hand, the chemistry of
oxygenates conversion into aromatics in PO could be demonstrated via gas chromatography mass spectrometer
(GC/MS) analysis. However, GC/MS analysis of PO did not perform in this study. In future works, the C:B ratio
will be further increased to 3:1, to identify the pattern of PO yields and coke contents at higher catalyst loading ratio.
100
Pyrolysis Oil (PO)
Pyrolysis Gas (PG)
80 Pyrolysis Char (PC)
Coke 68.0
Yield (wt. %)

60.0 62.0
60 58.0
50.0

40
29.0
23.0 21.0
21.0 22.0
20 18.0
14.9 16.1
12.9 10.8
4.1 2.9 3.2 3.2
0
None 0.5 1 1.5 2
Catalyst to Biomass ratio (C:B)

Fig. 5. Catalytic and none catalytic pyrolysis products yield

4. Conclusion

In-situ catalytic pyrolysis of sugarcane bagasse over Ce/HZSM-5 zeolite was successfully conducted to study the
effect of catalyst to biomass ratio (C:B) with respect to pyrolysis oil (PO) yields and coke contents during pyrolysis.
The results reveal a significant improvement in the yield of PO over catalytic pyrolysis compared to none catalytic
pyrolysis. From this study, it is suggested that Ce/HZSM-5 catalyst work best at a catalyst to biomass ratio of 1:1 in
producing higher PO yield with lower coke contents. In future, it is suggested that the obtained PO should further
analysis to identify valuable chemical compounds that could be used as gasoline enhancers in the petrochemical
industry. Apart from that, an appropriate catalyst loading could simultaneously improve the desirable pyrolysis oil
808 Vekes Balasundram et al. / Energy Procedia 142 (2017) 801–808
8 Author name / Energy Procedia 00 (2017) 000–000

yield and reduce coke yield. Hence, lower coke content on catalyst could extend the lifetime of catalyst in which
could be used more than one cycle and eventually reduce catalyst cost. However, other parameters such as pyrolysis
reaction temperature, cerium loading content on HZSM-5, and higher catalyst to biomass ratio should be performed
in order to gain a better understanding of the chemistry of catalytic pyrolysis of sugarcane bagasse over Ce/HZSM-5
catalyst.

Acknowledgements

The authors would like to acknowledge the financial support by Universiti Teknologi Malaysia and Ministry of
Higher Education (MOHE) of Malaysia (R.J130000.7842.4F654, Q.J130000.2546.14H48, and
Q.J130000.2642.05J10).

References

[1] Galadima, A., Muraza, O. In situ fast pyrolysis of biomass with zeolite catalysts for bioaromatics/gasoline production: A review.
Energy Conversion and Management 2015; 105:338-354. http://dx.doi.org/10.1016/j.enconman.2015.07.078.
[2] Alias, N., Ibrahim, N., Hamid, M. K. A., Hasbullah, H., Ali, R. R., Kasmani, Md. R. Investigation of oil palm wastes’ pyrolysis by
thermogravimetric analyzer for potential biofuel production. Energy Procedia 2015; 75:78-83.
http://dx.doi.org/10.1016/j.egypro.2015.07.141.
[3] Alias, N., Ibrahim, N., Hamid, M. K. A. Pyrolysis of empty fruit bunch by thermogravimetric analysi. Energy Procedia 2014; 61:2532-3536.
http://dx.doi.org/10.1016/j.egypro.2014.12.039
[4] Zhang, L., Liu, R., Yin, R., Mei, Y. Upgrading of bio-oil from biomass fast pyrolysis in China: A review. Renewable and Sustainable Energy
Reviews 2013; 24:66-72. http://dx.doi.org/10.1016/j.rser.2013.03.027.
[5] Rezaei, P. S., Shafaghat, H., Daud, W. M. A. W. Production of green aromatics and olefins by catalytic cracking of oxygenate compounds
derived from biomass pyrolysis: A review. Applied Catalysis A: General 2014; 469:490-511.
http://dx.doi.org/10.1016/j.apcata.2013.09.036.
[6] Shen, D., Jin, W., Hu, J., Xiao, R., Luo, K. An overview on fast pyrolysis of the main constituents in lignocellulosic biomass to valued-added
chemicals: Structures, pathways and interactions. Renewable and Sustainable Energy Review 2015; 51:761-774.
http://dx.doi.org/10.1016/j.rser.2015.06.054.
[7] Iliopoulou, E. F., Stefanidis, S. D., Kalogiannis, K. G., Delimitis, A., Lappas, A. A., Triantafyllidis, K. S. Catalytic upgrading of biomass
pyrolysis vapors using transition metal-modifies ZSM-5 zeolite. Applied Catalysis B: Environmental 2012; 127:281-290.
http://dx.doi.org/10.1016/j.apcatb.2012.08.030.
[8] Vichaphund, S., Aht-ong, D., Sricharoenchaikul, V., Atong, D. Catalytic upgrading pyrolysis vapors Jatropha waste using metal promoted
ZSM-5 catalysts: An analytical PY-GC/MS. Renewable Energy 2014; 65:70-77. http://dx.doi.org/10.1016/j.renene.2013.07.016.
[9] Momayez, F., Darian, J. T., Sendesi, S. M. T. Synthesis of zirconium and cerium over HZSM-5 catalysts for light olefins production
from naphtha. Journal of Analytical and Applied Pyrolysis 2015; 112:135-40. http://dx.doi.org/10.1016/j.jaap.2015.02.006.
[10] Xu, Y., Zheng, X., Yu, H., Hu, X. Hydrothermal liquefaction of Chlorella pyrenoidisa for bio-oil production over Ce/HZSM-5. Bioresource
Technology 2014; 156:1-5. http://dx.doi.org/10.1016/j.biortech.2014.01.010.
[11] Balasundram, V., Ibrahim, N., Kasmani, R. Md., Hamid, M. K. A, Isha, R., Hasrinah, H., Ali, R. R. (2017). Thermogravimetric catalytic
pyrolysis and kinetic studies of coconut copra and rice husk for possible maximum production of pyrolysis oil. Journal of Cleaner
Production, 167, 218-228. http://dx.doi.org/10.1016/j.jclepro.2017.08.173.
[12] Shackleford, A., Masak, T., Fu, Q., Smith, G. M., Yilmaz, B., BASF Corporation, Culp, R. D., Gawecki, P., Shell Global Solutions.
An alternative to rare earth elements in FCC catalysts – the use of Phinesse at Shell Sarnia. Hydrogen Engineering 2015; 20(9):50-56.
[13] Ibrahim, N., Dam-Johansen, K., Jensen, P. A., 2012. PhD Thesis: Bio-Oil from Flash Pyrolysis of Agricultural Residues. Technical
University of Denmark (DTU), Department of Chemical Engineering. ISBN: 978-87-92481-86-3.
[14] Liu, J., Fan, K., Tian, W., Liu, C., Rong, L. Hydroprocessing of Jatropha oil over NiMoCe/Al2O3 catalyst. International Journal of
Hydrogen Energy 2012; 37:17731 – 17737. http://dx.doi.org/10.1016/j.ijhydene.2012.09.020.