Materials Chemistry and Physics 213 (2018) 548e555

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Pt-promoted sulfated zirconia as catalyst for hydrocracking of LDPE

plastic waste into liquid fuels
Maisari Utami, Karna Wijaya*, Wega Trisunaryanti
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Bulaksumur, Yogyakarta, 55281, Indonesia

h i g h l i g h t s

Hydrocracking of LDPE plastic waste into liquid fuels over Pt/SZ has been studied.

Modification of ZrO2 using H2SO4 and Pt increased the physico-chemical properties.

A larger concentration of Pt on SZ led to enhance the activity and selectivity.

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

Article history: The conversion of LDPE plastic waste into liquid fuels over commercial zirconia nanopowder (ZrO2) with
Received 4 May 2017 a fixed amount of sulfate and different amounts of Pt was systematically studied. The aims of this
Received in revised form research were focused on the preparation of Pt-promoted sulfated zirconia (Pt/SZ) and study the effect of
12 January 2018
different concentrations of Pt on SZ for hydrocracking reaction of LDPE plastic waste. The SZ was pre-
Accepted 20 March 2018
pared by dispersing ZrO2 in H2SO4 solution. The obtained SZ was refluxed in aqueous solutions of PtCl4
Available online 20 March 2018
(0.5, 1.0 and 1.5 wt% Pt). The catalyst samples were calcined and followed by H2 reduction to produce Pt1/
SZ, Pt2/SZ and Pt3/SZ. The catalysts were characterized by FTIR, XRD, GSA, TEM, SEM-EDS and EDXRF. A
Keywords:
Platinum
larger concentration of Pt on SZ led to increase the activity and selectivity for catalytic hydrocracking of
Sulfated zirconia LDPE plastic waste. The liquid yields were analyzed by GC-MS. This study found that the hydrocracking
LDPE plastic waste process was carried out effectively at 250  C. The hydrocracking reaction of LDPE plastic waste over Pt3/
Liquid fuels SZ produced the highest gasoline-range fuels conversion, reached 67.51 wt%. The liquid yield consisted of
hydrocarbon compounds with atom chain of C5-C20 indicated fuel chemical structures, such as paraffins,
olefins, isoparaffins, naphthenes and aromatics.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction (ZrO2) [5,6]. The ZrO2 is an important material as catalyst or support

Hydrocracking is a process to convert a larger hydrocarbon
molecules into smaller molecules by simultaneous or sequential
carbon bond breaking and hydrogenation. It is not only commonly
applied for petroleum refining, but also one of the promising
method to recycle plastic wastes. In recent years, some in-
vestigations concerning the use of solid acid catalysts for degra-
dation of LDPE plastic waste into fuel oils have been reported. These
catalysts have been selected due to their excellent activity,
selectivity and stability [1e4].
The type of catalyst that has attracted a significant amount of
interest in the catalytic reaction is metal oxides, such as zirconia
* Corresponding author.
E-mail address: karnawijaya@ugm.ac.id (K. Wijaya).
in industry because of its high thermal stability, high ionic con-
ductivity and low thermal conduction [5e11]. The nature of acidity
on ZrO2 can be improved by coating the surface with an acid so-
lution, such as H2SO4 to form sulfated zirconia (SZ) [12,13]. The
modification of ZrO2 using sulfate is known to be well-suited for
catalyzing several reactions, e.g., isomerization, esterification and
hydrocracking reactions [14e17]. The sulfate ion can stabilize the
crystal phase of ZrO2 at room temperature. The activation process
of ZrO2 is one method to increase the reactivity of catalyst based on
the nature of active sites, Brønsted and Lewis acid sites [18]. It is
generally accepted that the acid strength and catalytic properties of
SZ are strongly influenced by the method of preparation, the nature
of starting material, the type of sulfation agent and thermal treat-
ment [19,20].
The phase of SZ depends on the crystallinity properties of ZrO2

https://doi.org/10.1016/j.matchemphys.2018.03.055
0254-0584/© 2018 Elsevier B.V. All rights reserved.
 M. Utami et al. / Materials Chemistry and Physics 213 (2018) 548e555
as the starting material [21]. The obtained SZ will be tetragonal if it
is synthesized from the amorphous precursor, but if the precursor
is entirely or partly monoclinic which has higher crystallinity and
stability, the SZ will be monoclinic as well [22]. The calcination is
the variable that affects the acidity distribution belonging to the
high-symmetry crystal phases [23]. Moderate calcination temper-
atures are required for the formation of active sites, whereas high
calcination temperatures lead to the loss of sulfate [19].
In spite of SZ shows high acid strength, the catalytic activity of
SZ has been reported to exhibit sharp decrease when in contact
with hydrocarbons at high temperature. It causes deactivation by
the formation of coke deposits on the catalyst surface and loss of
acidity or active sites. Hence, the catalytic activity is significantly
reduced and the lifetime is shortened [24]. The deactivation of SZ
can be overcome by modifying it with noble metals, like platinum
[19]. The addition of Pt as a promoter and hydrogen as a carrier gas
in hydrocracking reaction is necessary to enhance the activity at
low temperature and improve the stability of SZ [25e27]. Fo €ttinger
et al. [28] reported that Pt/SZ is a bifunctional metal-acid catalyst
with Pt acts as the metallic function and the acid function is from
the interaction of hydrogen dissociated on Pt with sulfate species.
The role of Pt promotion on SZ is suggested to enhance the acidity
of SZ [29e32]. Ebitani et al. [29] have explained that hydrogen
molecule dissociates into H atoms on Pt sites and spills over to SZ,
where the conversion of an H atom to Hþ occurs by releasing an
electron to Lewis acid sites. The Hþ is then proposed to act as the
acid sites for catalytic reactions [33].
This present research is focused on the preparation and physico-
chemical characterization of Pt/SZ and study the effect of different
concentrations of Pt on SZ for hydrocracking reaction of LDPE
plastic waste into liquid fuels. The results of this work will be
beneficial to the development of bifunctional metal-acid catalysts
that possess the key role in chemical industries.
2. Materials and methods
2.1. Materials
The commercial zirconium dioxide nanopowder (ZrO2
60e70 nm, purity 99.9%) was supplied by Hongwu International
Group Ltd and tetrachloroplatinum (PtCl4, purity 99.9%) was
provided by Zibo Jiashitai Chemical Technology Co., Limited. The
sulfuric acid solution (H2SO4 98%) and ammonium hydroxide so-
lution (NH4OH 25%) were obtained from Merck. All chemicals were
analytical grade and used without further treatment. The low
density polyethylene (LDPE) plastics were collected from the
household waste. Hydrogen gas (H2) was supplied by PT. Samator
Gas Industri.
2.2. Methods
2.2.1. Preparation of SZ
The sulfated zirconia was prepared by wetness impregnation of
ZrO2 and H2SO4. The calculated amount of 0.8 M H2SO4 solution and
ZrO2 were stirred at room temperature for 24 h. The samples were
dried in an oven at 100  C for 24 h and calcined at 600  C for 4 h
[20]. The obtained sulfated zirconia was labeled as SZ.
2.2.2. Pt impregnation on SZ
The prepared SZ was refluxed with 0.5, 1.0 and 1.5 wt% Pt using
aqueous solutions of PtCl4 at 90  C for 4 h. The obtained materials
were dried in an oven at 100  C for 24 h. The catalyst samples were
calcined at 600  C for 4 h, followed by reducing of Pt4þ to Pt0 under
H2 gas stream (20 mL/min) at 400  C for 3 h. The obtained catalysts
549
were donated by Pt1/SZ, Pt2/SZ and Pt3/SZ. The functional groups
of the material were identified by Fourier transform infrared
spectrometer (FTIR, Shimadzu Prestige-21). The acidity of catalyst
was determined by studying ammonia sorption using the gravi-
metric method, followed by FTIR analysis. The crystalline structures
were characterized by X-ray diffractometer (XRD, Rigaku Multi-
flex). The textural properties of catalyst were measured by gas
sorption analyzer (GSA, Quantachrome NOVA 1200e). The
morphology of the investigated material was characterized by
transmission electron microscope (TEM, JEOL JEM-1400). The sur-
face topography and elemental analysis of the test sample were
estimated by scanning electron microscope (SEM, JEOL JSM-6510)
with energy dispersive spectrometer (EDS, JED-2300 Analysis Sta-
tion). The concentration of Pt on SZ was determined by energy
dispersive X-ray fluorescence spectrometer (EDXRF, PANalytical
MiniPal 4).
2.2.3. Hydrocracking process
The collected LDPE plastics were washed, dried and cut into
small pieces. The plastics were vaporized in a pyrolysis reactor at
300e400  C for 3e4 h and condensed into liquid fraction. The hy-
drocracking processes were carried out under H2 gas stream
(20 mL/min) in hydrocracking microreactor as flow reactor system
(Fig. 1) with feed/catalyst ratio of 100 for 1 h of reaction time. The
activity and selectivity tests were operated at various temperatures,
i.e., 250, 300 and 350  C with various catalysts, i.e., ZrO2, SZ, Pt1/SZ,
Pt2/SZ and Pt3/SZ to obtain the optimum conditions for hydro-
cracking reaction of LDPE plastic waste. The liquid yields were
analyzed by gas chromatograph-mass spectrometer (GC-MS, Shi-
madzu QP 2010S).
3. Results and discussion
3.1. Fourier transform infrared spectroscopy (FTIR)
The FTIR spectra of ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ in the
400-4000 cm1 region are depicted in Fig. 2. The FTIR spectra upon
the loading of SZ by different amounts of Pt show the same vi-
brations as ZrO2 and SZ at 424-741 cm1 which are corresponded to
ZreOeZr bond [18]. The bands around 3449 and 1636 cm1 are
attributed to stretching and bending frequencies of OeH from
adsorbed water, respectively [12,24]. Moreover, upon the loading of
SZ by different amounts of Pt, the FTIR spectra have the same OeH
€ttinger et al. [23] specified the assignment of the
vibrations [24]. Fo
broad band in the range of 3400 cm1 is ascribed to bridged hy-
droxyl groups between two or three Zr atoms. All bands in the
range between 995 and 1404 cm1 belong to the sulfate region. The
bands at 995-1157 cm1 are ascribed to symmetric and asymmetric
vibrations of SeO and S]O, while the band at 1404 cm1 is cor-
responded to stretching modes for S]O of adsorbed SO3 molecules
[24].
3.2. Acid properties
The total amount of acidity has determined by using ammonia
base vapor as the adsorbate. Table 1 shows the amounts of acidity
on ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ. Total acidity is increased by
the addition of H2SO4, in coincidence with an increase of the
amounts of acid sites and sulfur surface density of the support that
have been pointed out as the main causes of acidity [9,20]. The
sulfation process properly takes place before calcination step to
increase the catalytic properties and provide an active catalyst [12].
The activation through acid treatment and modification using
supported metal will increase the acidity of catalysts. It can be seen
550 M. Utami et al. / Materials Chemistry and Physics 213 (2018) 548e555

Fig. 1. The schematic diagram of hydrocracking microreactor.

Fig. 2. FTIR spectra of ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ. Fig. 3. FTIR spectra of ammonia sorption over ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ.

Table 1 3.3. X-ray diffraction (XRD)

The acidity of catalyst.

Sample Acidity (mmol/g) The XRD patterns for ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ recor-
ZrO2 0.18 ded at 4e80 (2q) are presented in Fig. 4. The crystallinity of ZrO2
SZ 1.06 decreases as the addition of sulfate as well as Pt loading with
Pt1/SZ 10.75 different concentrations. Thus, this phenomenon indicates that
Pt2/SZ 11.05
sulfate and Pt have been successfully impregnated to ZrO2, whereby
Pt3/SZ 11.14
Pt is evenly dispersed and sulfate covers the catalyst surface. The
diffraction peaks appearing at 2q of 28.34 (d-111) and 31.64 (d111)
refer to the monoclinic crystal phase of ZrO2 [15]. The crystalline
that the metal loaded on SZ increases the acid amounts signifi- structure of catalysts is related not only to the calcination tem-
cantly compared to ZrO2 and SZ. It can be noticed that Pt3/SZ shows perature and activation process but also to the precursor, in
the highest acidity, reached 11.14 mmol/g. agreement with the work reported by Stichert and Schüth [22].
The types of active sites, Brønsted and Lewis acid sites, play an However, the diffraction peak of Pt is not detected because the
important role in determining the catalytic activity. The presence of impregnated metal concentration is relatively low [24].
both acid sites is confirmed by ammonia sorption via the use of FTIR The modification of ZrO2 using sulfate and Pt sufficiently in-
spectroscopy analysis. Fig. 3 presents the FTIR spectra of ammonia fluences the crystal phase of ZrO2. The appearance of a minor
sorption over ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ. Ammonia sorp- diffraction peak at 2q of 30.16 (d011) in the patterns of SZ indicates
tion over the samples on Brønsted acid sites forms ammonium ion the crystal phase transformed from monoclinic to metastable
with vibration band in the range of 1396e1404 cm1, while the tetragonal [20]. The mixture of monoclinic and metastable tetrag-
coordination bond of ammonia on Lewis acid sites yields the onal phases also observes after Pt impregnation. The ZrO2 has three
characteristic band at 1119 cm1 [34,35]. polymorphs: monoclinic (stable up to 1200  C), tetragonal (stable
 M. Utami et al. / Materials Chemistry and Physics 213 (2018) 548e555
Fig. 4. XRD patterns of ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ.
up to 1900  C) and cubic (stable above 1900  C). Also, above three
crystal phases, a metastable tetragonal phase is stable up to 650  C
[36]. The transformation of metastable tetragonal phase is due to
the thermal treatment and sulfation process [20]. The sulfate spe-
cies will be thermally crystallized, whereby it undergoes a phase
transformation and the phase being stabilized as a result of sulfate
incorporation [19]. The ZrO2 may exist in two crystal phases after
calcination at low temperatures (less than 800  C): a metastable
tetragonal phase and the thermodynamically favored monoclinic
phase [37]. The utilization of ZrO2 as a catalyst involves only three
crystal phases: monoclinic, tetragonal and metastable tetragonal
[36].
The average crystal size (D) for each sample can be estimated by
using Scherrer equation: D ¼ K l=bcosq; where D is the mean
crystal diameter (nm), K is Scherrer constant (0.89), l is the X-ray
wavelength, b is the observed angular width at half maximum in-
tensity of the peak and q is Bragg's angle. The crystal sizes of
samples are cited in Table 2. It demonstrates that the crystal size of
catalyst increases with the addition of sulfate [20]. The catalysts
containing Pt exhibit smaller crystal sizes than SZ. Moreover, a
higher amount of Pt is gradually decreased the crystal size of
catalyst.
3.4. Gas sorption analysis (GSA)
The BET isothermal nitrogen (N2) adsorption-desorption
method has been used to estimate the specific surface area of the
prepared catalyst. The BJH method has been applied for calculating
the average pore diameter of catalyst [24]. The specific surface area,
total pore volume and average pore diameter of catalyst are pre-
sented in Table 3. The specific surface area of SZ is much smaller
Table 2
The crystal size of catalyst.
Sample Crystal size (nm)
ZrO2 31.54
SZ 34.06
Pt1/SZ 32.80
Pt2/SZ 31.54
Pt3/SZ 31.53
551
than ZrO2. It seems likely that the interaction between ZrO2 and
sulfate tends to form agglomeration. The gradual increment in the
metal loading causes an increase of the specific surface area, total
pore volume and average pore diameter. The specific surface area of
Pt1/SZ amounts to 13.49 m2/g and increases gradually to 29.48 m2/
g for Pt3/SZ. Also, the total pore volume of Pt1/SZ increases from
0.05 cm3/g to reach 0.08 cm3/g for Pt3/SZ. Aboul-Gheit et al. [24]
reported that upon a larger concentration of Pt on SZ, the specific
surface area and total pore volume decreased gradually. It could be
attributed to the fact that Pt was deposited in the pores of catalyst.
However, the difference in our findings is probably due to an even
dispersion of Pt in the pores and on the surface of SZ. According to
the calculation of BJH desorption, the catalysts have mesopore type
(2e50 nm). A larger of pore diameter indicates the collapse of the
pores due to the inclusion of Pt.
3.5. Transmission electron microscopy (TEM)
TEM is suitable and powerful equipment to examine the
morphology of the sample. Fig. 5 shows the TEM micrographs of
ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ. The presence of sulfate over
ZrO2 leads to form agglomerates of semispherical nanosized par-
ticles, which can be attributed to heat treatment [18]. This obser-
vation seems to suggest that ZrO2 tends to aggregate much easier in
the presence of anionic surface species. In the loading of Pt, there is
no occurrence of visible metallic Pt aggregates. A larger concen-
tration of Pt on SZ leads to the formation of smaller and regular
particle size.
3.6. Scanning electron microscopy with energy dispersive
spectrometry (SEM-EDS)
SEM image shows the topography and surface morphology,
while EDS indicates the elements contained on the sample surface.
Fig. 6 shows the SEM images of ZrO2, SZ, Pt1/SZ, Pt2/SZ and Pt3/SZ.
Through the addition of sulfate, the presence of agglomerates of
particles with different size and disordered shape are obtained by
joining very small particles [12,19]. The particles of Pt cannot be
identified by SEM-EDS. However, the effect of Pt can be distin-
guished and described. In general, the abundance of smaller par-
ticles with regular size appears by the inclusion of Pt. Table 4 shows
the content of O, S and Zr over the samples. The enhancement of O
and S contents can be observed after sulfation process [20]. How-
ever, the addition of Pt leads to decrease the content of O and S. It
gives an indication that sulfate and Pt have modified ZrO2 well.
3.7. Energy dispersive X-ray fluorescence spectrometry (EDXRF)
The concentrations of Pt over Pt1/SZ, Pt2/SZ and Pt3/SZ samples
are shown in Table 5. It can then be seen that Pt content is strongly
affected by the dispersion of Pt on SZ. The reduction treatment
under H2 gas stream after calcination step is necessary to obtain
supported Pt0 particles and leads to the virtually complete disper-
sion of the noble metal [38]. The data show that Pt contents are
lower than the theoretical initial concentrations used due to the
competition of Pt in catalytic pores. Hence, the amounts of active
metals having weak interactions in the pore area of SZ tend to be
desorbed. It can be noticed that Pt1/SZ, Pt2/SZ and Pt3/SZ samples
contain only 0.35, 0.90 and 1.19 wt% Pt, respectively.
3.8. Hydrocracking experiments
This experiment has been performed a catalytic hydrocracking
of heavy oil obtained from pyrolysis step of the solid plastic waste
to further optimize the properties of the final hydrocarbon
552 M. Utami et al. / Materials Chemistry and Physics 213 (2018) 548e555

Table 3
The textural properties of catalyst.

Sample Specific surface area (m2/g) Total pore volume (cm3/g) Average pore diameter (nm)

ZrO2 22.05 0.08 3.49

SZ 12.49 0.05 3.82
Pt1/SZ 13.49 0.05 3.83
Pt2/SZ 20.23 0.06 3.84
Pt3/SZ 29.48 0.08 3.86

Fig. 5. TEM image of (a) ZrO2, (b) SZ, (c) Pt1/SZ, (d) Pt2/SZ and (e) Pt3/SZ.

Fig. 6. SEM image of (a) ZrO2, (b) SZ, (c) Pt1/SZ, (d) Pt2/SZ and (e) Pt3/SZ.

products. Fig. 7 illustrates the activity of Pt3/SZ in hydrocracking the gas, liquid and solid yields with no remaining residue. It can be
reaction of LDPE plastic waste at various temperatures, i.e., 250, 300 seen that the hydrocracking reaction over Pt3/SZ at 250  C results
and 350  C. The total conversion of 100 wt% has been produced by the highest proportion of liquid yield (74.60 wt%). Concerning
 M. Utami et al. / Materials Chemistry and Physics 213 (2018) 548e555 553

Table 4 Table 6
The element content on the catalyst surface. The selectivity of liquid yield from hydrocracking reaction of LDPE plastic waste over
various catalysts at 250  C.
Sample Element content (wt%)
Sample Yield (wt%)
O S Zr
Selectivity (wt%) Solid Gas
ZrO2 35.46 0.46 64.08
SZ 37.42 2.07 60.51 C5-C12 C13-C20
Pt1/SZ 24.02 0.74 75.24
Blank 30.82 9.38 e 59.80
Pt2/SZ 25.02 0.61 74.37
ZrO2 33.58 17.14 0.09 49.19
Pt3/SZ 24.40 0.26 75.34
SZ 42.95 14.97 0.35 41.73
Pt1/SZ 48.76 21.82 0.15 29.27
Pt2/SZ 64.22 6.93 0.16 28.69
Table 5 Pt3/SZ 67.51 7.09 0.15 25.25
The content of Pt on SZ.

Sample Pt content (wt%)

Pt1/SZ 0.35 catalyst surface [24]. This phenomenon appears in this study where
Pt2/SZ 0.90 SZ produces the highest amount of coke. However, the highest
Pt3/SZ 1.19
gasoline-range fuels conversion is shown by Pt3/SZ (67.51 wt%). The
acidity of catalyst is closely related to its catalytic activity for the
hydrocracking reaction. Thus, the desired conversion of liquid yield
in gasoline fraction also increases [4]. Based on the acidity test
result in Table 1, Pt3/SZ shows the highest acid amount compared
to Pt1/SZ and Pt2/SZ. Owing to their weaker acid properties, the
catalytic hydrocracking over Pt1/SZ and Pt2/SZ produces a lower
proportion of gasoline fraction (48.76 and 64.22 wt%, respectively).
The GC-MS analysis has been used to determine the proportion
of hydrocarbon compositions of liquid yield. Fig. 8 shows that the
compounds in gasoline fraction generated from the hydrocracking
reaction of LDPE plastic waste over Pt3/SZ at 250  C, almost
exclusively, to olefins, linear paraffins, isoparaffins and naphthenes,
with total composition of 56.36, 20.07, 14.60 and 6.81 wt%,
respectively. A small proportion of aromatics is also generated with
a composition of 0.70 wt%, while only 1.46 wt% indicates non-
hydrocarbon compounds. The presence of isoparaffins, aromatics
and naphthenes in the C5-C12 range is highly desirable and valuable
gasoline-range hydrocarbons. The liquid yield from hydrocracking
reaction of LDPE plastic waste produces a whole spectrum of hy-
drocarbons including paraffins, olefins, isoparaffins, naphthenes
and aromatics. However, not all of these hydrocarbons are suitable
for gasoline usage. Gasoline qualities are usually measured
Fig. 7. The product yields from hydrocracking reaction of LDPE plastic waste over Pt3/ regarding volatility and octane number of the hydrocarbons
SZ at various temperatures.

product yields, it is also be observed that the amount of coke

formed on the catalyst surface is very limited in all cases. The use of
higher temperature (350  C) supports the formation of gas yield
(82.67 wt%) and reduces the proportion of liquid yield which is
associated with a more intense cracking effect on the plastic feeds.
Moreover, the use of catalysts at 250  C leads to lower operating
conditions of the hydrocracking process that is responsible for an
increase the energy storage. It requires lower operating costs as
well [2,4].
The hydrocarbon products generated from the catalytic hydro-
cracking of LDPE plastic waste have been characterized for both
their carbon atom numbers and hydrocarbon types to evaluate the
extent of the hydrocracking reactions and determine their potential
application as liquid fuels or refinery feedstock [2]. Table 6 shows
the selectivity of liquid yield in gasoline fraction (C5-C12) and diesel
fraction (C13-C20). The overall hydrocracking reactions performed
suggest that gasoline fraction are higher than diesel fraction. In the
absence of catalyst, the conversion of LDPE plastic waste at 250  C
shows the highest formation of gas yield, while SZ produces the
highest amount of solid yield. It has been previously mentioned
Fig. 8. The compound composition of liquid yield in gasoline fraction from hydro-
that the use of SZ led to the formation of coke deposits on the cracking reaction of LDPE plastic waste over Pt3/SZ at 250  C.
554 M. Utami et al. / Materials Chemistry and Physics 213 (2018) 548e555
[39,40]. A close inspection of this result shows that without any
further treatment, the hydrocarbons have an insufficient applica-
tion as transportation fuels, but can be employed as refinery
feedstock for further cracking and reforming. Further investigations
on the catalytic studies are required to advance the field, particu-
larly to enhance the added value of fuels and minimize energy
consumption.
4. Conclusions
The preparation of Pt-promoted SZ catalysts was successfully
conducted as proved by characterization results as well as catalytic
activity and selectivity tests. The addition of Pt amounts on SZ was
extremely increased the acidity of catalysts and decreased the
crystallinity of ZrO2. It indicated that the relative amounts of active
sites were increased. The characterization using ammonia sorption
via the use of FTIR revealed that Pt3/SZ showed the highest acidity,
reached 11.14 mmol/g. The XRD analysis confirmed that SZ and Pt/
SZ samples exhibited the phase transformed from monoclinic to
metastable tetragonal. It could be noticed that the addition of
H2SO4 and Pt sufficiently influenced the crystal phase modification
of ZrO2. The GSA measurements revealed that a further increase of
Pt concentration caused an increase of the textural properties of
catalysts. Through the microscopic studies suggested that the
modification of SZ by a larger concentration of Pt was able to form
smaller and regular particle size. The analytical measurements
showed that Pt contents over the samples were lower than the
theoretical initial concentrations used. The result of hydrocracking
experiments clearly showed that gasoline-range fuels could be
produced from hydrocracking of LDPE plastic waste over Pt/SZ as
bifunctional metal-acid catalyst. The presence of higher concen-
tration of Pt on SZ enhanced the gasoline conversion with an in-
crease of the acid amounts. The hydrocracking reaction of LDPE
plastic waste over Pt3/SZ at 250  C effectively produced 74.60 wt%
of liquid yield, 0.15 wt% of solid yield and 25.25 wt% of gas yield.
From the liquid yield, it was estimated as much 67.51 wt% of gas-
oline range (C5-C12) and 7.09 wt% of diesel range (C13-C20). The
liquid yield consisted of hydrocarbon compounds that indicated
fuel chemical structures, such as paraffins, olefins, isoparaffins,
naphthenes and aromatics with atom chain of C5-C20.
Acknowledgements
The authors thank the Ministry of Research, Technology and
Higher Education, Republic of Indonesia for the fund through the
PMDSU Scholarships and Research Grants. We also thank the
Department of Chemistry of Universitas Gadjah Mada for chemical
analyses.
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