Chemical Engineering Journal 317 (2017) 800809

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Fe-, Ti-, Zr- and Al-pillared clays for efficient catalytic pyrolysis of mixed CrossMark
plastics
Kaixin Li a,b, Junxi Lei a, Guoan Yuan a, Piyarat Weerachanchai a, Jing-Yuan Wang a, Jun Zhao a,,
Yanhui Yang b,
a
Residues and Resource Reclamation Centre (R3C), Nanyang Environment and Water Research Institute, Nanyang Technological University, 1 Cleantech Loop, CleanTech
One, Singapore 637141, Singapore
b
School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637459, Singapore

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Transition metal-modified pillared

clays promote the pyrolysis of mixed Hydrogen Pillared clays
plastics.
 80.5% diesel fraction and 47.7 vol% for
H2 were observed in presence of BBBBKSmwffw
#
Fe-PILC.
 The high activity of Fe-PILC is due to Plastic waste
its moderate acidity and
nano-architecture.
 Two plausible pathways were
identified in the pyrolysis process.
 An efficient and novel strategy was
Morphology
developed for the plastic waste
treatment.

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

Article history: Catalytic pyrolysis of mixed plastics including high density polyethylene (HDPE), polystyrene (PS),
Received 3 October 2016 polypropylene (PP), and PET (polyethylene terephthalate) has been performed in presence of a series
Received in revised form 16 February 2017 of modified pillared clays (PILC) and Al-PILC. The catalysts were well characterized by BET, FTIR of pyr-
Accepted 20 February 2017
idine adsorption, XRD, SEM, TEM/EDX. The effect of different catalysts on the composition and amount of
Available online 22 February 2017
pyrolysis products including gas, liquid, and char residue was evaluated. With the introduction of Fe-PILC,
the yields of oil product were enhanced, suggesting that secondary over-cracking of primary pyrolytic
Keywords:
intermediate species was reduced in the presence of the catalyst. A high oil yield of 79.3 wt.% with excel-
Catalytic pyrolysis
Pillared clays
lent selectivity for diesel fraction (80.5%) and high yield of H2 gas (47.7 vol%) were obtained in the case of
Mixed plastics Fe-PILC. The superior catalytic performance of Fe-PILC is probably attributed to its moderate total acidity,
Feedstock recycling relatively high BET surface area, and uniformly dispersed iron oxide particles on montmorillonite sup-
port. Accordingly, with the clay catalyst, an efficient and environmentally friendly process can be devel-
oped to produce valuable products (e.g. diesel, hydrogen) through pyrolysis of plastic waste.
2017 Elsevier B.V. All rights reserved.

1. Introduction

Increasing demand of fossil fuel products has led to environ-

mental issues. One of the solutions to this problem is to convert
Corresponding authors. its waste products such as plastic wastes into useful hydrocarbon
E-mail addresses: Zhao0168@e.ntu.edu.sg (J. Zhao), yhyang@ntu.edu.sg
raw material for fuel oil production. In the past few years, research
(Y. Yang).

http://dx.doi.org/10.1016/j.cej.2017.02.113
1385-8947/ 2017 Elsevier B.V. All rights reserved.
 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809
on recycling of plastic wastes was receiving more and more atten-
tion [1]. Many techniques such as depolymerisation, thermal and
catalytic degradation for recycling of plastic were employed in
some industries. Pyrolysis is a sole thermal process which pro-
duces liquid and gaseous products containing a wide range of
hydrocarbons. This is resulted from random scission of the poly-
mer chains during thermal degradation in an inert environment.
As compared with sole thermal process, catalytic pyrolysis can sig-
nificantly control the product composition/distribution and dis-
plays several advantages [2,3], such as lower energy
consumption of the pyrolysis process, faster reaction and higher
selectivity for valuable chemical products.
Over the past two decades, lots of literatures were reported on
catalytic pyrolysis of plastic wastes. Many catalytic materials such
as homogeneous Lewis catalysts [4,5], acid or non-acid heteroge-
neous materials [69], commercial fluid catalytic cracking (FCC)
catalysts [10,11], metallic oxides [12,13] and zeolites [14,15] had
been tested. Most of these catalysts were used for pyrolysis of sin-
gle plastics or simple mixtures of plastics. Limited amount of stud-
ies was performed on catalytic pyrolysis of plastic waste or
complex mixtures containing polyvinyl chloride (PVC) or polyethy-
lene terephthalate (PET). This is because these polymers generate
oxygenated or chlorinated compounds which deactivate the cata-
lysts or degrade the fuel product. In fact, it is challenging to pro-
duce high quality fuel from mixed plastics using traditional
catalysts without modification. The development of catalyst tai-
lored for catalytic pyrolysis of mixed plastics with great efficiency
still remained an issue. The key features that allow a catalyst to be
tailored for a specific reaction are its adjustable acid strength and
textural structure. A suitable combination of physical structure
and catalytically active compound achievable through the modifi-
cation of catalysts would enable the wide application of these cat-
alysts in pyrolysis of a variety of feedstock.
Montmorillonite and their analogies (e.g. hectorite, beidellite,
and saponite) were used to crack polymers over the past few dec-
ades. They presented a high selectivity for the liquid product and a
low yield of coke deposited on the catalyst owing to their mild
acidity. In the recent years, pillared clays (PILC) had been mostly
reported as catalysts with an interlayered structure where differ-
ent moieties, such as metal oxides, could be intercalated in it to
improve their textural structure and acidity [1618]. However,
these catalysts only exhibited excellent regeneration capability
and catalytic performance for pyrolysis of single polymer such as
high density polyethylene (HDPE) and polypropylene (PP)
[16,19]. Further modifications of the pillared clays were required
in order to efficiently pyrolyse complex feedstock with multiple
plastic types. Recently, a series of mono/bimetallic ions modified
MCM-41 catalysts had been applied in catalytic pyrolysis of bio-
mass [20,21]. It was found that the Fe/Cu-Al-MCM-41 exhibited
higher catalytic activity than Al-MCM-41[21], which is a common
catalyst used to pyrolyse single plastics. Iliopoulou et al. developed
a series of transition metal-modified ZSM-5 catalysts and applied
them in the in situ upgrading of biomass pyrolysis vapours. As
compared with the parent ZSM-5, all the modified catalysts exhib-
ited enhanced production of aromatics and phenols and lower oxy-
gen content in the organic phase of bio-oil. This is probably due to
the formation of reduced transition metal phases that promotes
dehydrogenation and deoxygenation [22]. In addition, the incorpo-
ration of transition metals in the zeolites/MCM-41 was considered
to enhance the yield of fuel oil product and promote the produc-
tion of H2, due to the moderate acid strength and dehydrogenating
activity resulted from the metal active phase [21,2325]. The liter-
ature review inspired us to improve the catalytic performance of
pillared clay by modifying it via introduction of different metal
compounds into the inter-layered structure. Furthermore, pillared
801
clay was selected as it is more cost effective than zeolites and other
mesoporous catalyst when applied in industrial settings.
In this paper, catalytic pyrolysis of plastic mixture, instead of
single plastics (e.g. HDPE, PP or polystyrene (PS)), was investigated
using a series of modified pillared clay as catalysts. These clays
were loaded with different metallic compounds including Fe, Ti,
Zr. (designated as Fe-PILC, Ti-PILC, and Zr-PILC). So far, there was
no report on the application of these catalysts in the pyrolysis of
mixed plastics. Al-PILC (pillared clay), which were commonly used
in pyrolysis, were also employed in the study for comparison. The
study includes: (i) characterization of catalysts using BET, FTIR of
pyridine, XRD, SEM, and TEM/EDX, (ii) study on the effect of differ-
ent catalysts on the composition and yield of pyrolysis products
including gas, liquid, and char residue. A plausible pathway of
pyrolysis over the optimized PILC was also proposed.
2. Experimental
2.1. Materials
PET (Sigma-Aldrich, USA), HDPE (Alfa Aesar, USA), PP (Alfa
Aesar, USA), and PS (Alfa Aesar, USA) were commercially available.
The simulated mixed plastics wastes used in the experiments was
composed of 42 wt% HDPE, 35 wt% PP, 18 wt% PS, 5 wt% PET. This
proportion resembles the composition of real plastic waste as char-
acterized by National Environment Agency in Singapore. The char-
acterizations of plastic feedstock were showed in Table S1. As a
consequence of the high carbon and hydrogen content, the higher
heating value (HHV) of mixed plastics feedstock was as high as
44.9 MJ/mol. In addition, 3.19% ash and undetectable amount of
moisture were found in the mixed plastics.
Titanium(IV) chloride (99%, Sigma-Aldrich), Zirconium(IV)
oxychloride octahydrate (98%, Sigma-Aldrich), Iron(III) nitrate
nonahydrate (99%, Sigma-Aldrich), bentonite (Sigma-Aldrich),
and other chemicals are commercially available.
2.2. Catalyst preparation
Bentonite was used as raw material for the synthesis of Al-PILC,
Fe-PILC, Ti-PILC, Zr-PILC. After calcination at 773 K for 1 h, the ben-
tonite was characterized for comparison with Al-PILC, Fe-PILC, Ti-
PILC, Zr-PILC. The main exchangeable cations in bentonite and
the PILC catalysts were shown in the Table S2.
2.2.1. Al-PILC
Al-PILC was synthesized following a traditional intercalation
method [26,27]. Intercalated solution was prepared by mixing
sodium hydroxide solution with aluminium chloride solution at
an OH/Al molar ratio of 2:1 under stirring at 343 K for 1 h. After
intercalation, the intercalated solution was slowly added into a
2 wt% water suspension of bentonite at a ratio of 4 mmol Al3+/g
bentonite, followed by stirring for 20 h at room temperature to
attain equilibrium. Subsequently, the intercalated clay was washed
free of chloride ion by repeated centrifugation and dispersion in
deionized water. The washed clay was dried at 328 K for 8 h and
calcined at 773 K for 1 h.
2.2.2. Fe, Zr, Ti-PILC
These catalysts were synthesized via intercalation using
different polynuclear metal oxohydroxo cations as precursors.
The procedure presented here was a modified version of the proce-
dure described previously [2830]. The metal precursors for inter-
calation solution were Fe(NO3)3
9H2O, ZrOCl2
8H2O, and TiCl4 for
Fe-PILC, Zr-PILC, and Ti-PILC respectively. In the case of Fe-PILC
802 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809
and Ti-PILC, intercalation solution was prepared by slowly adding
metal precursor solution into the Na2CO3 solution and HCl solution
respectively under stirring at 298 K. On the other hand, in the case
of Zr-PILC, 0.1 mol/mL ZrOCl2
8H2O aqueous solution was used
directly as the intercalation solution. Subsequently, the intercala-
tion solution was slowly added into a 2 wt% water suspension of
bentonite at a ratio of 5 mmol metal ion/g bentonite for Fe-PILC
and Zr-PILC, and 6 mmol metal ion/g bentonite for Ti-PILC,
followed by stirring at 313 K for 1620 h (or shorter time under
sonication). The intercalated clay was subsequently washed by
repeated dispersion in deionized water and centrifugation,
followed by drying at 328 K for 8 h and calcination at 723 K for
1 h, at 773 K for 4 h and at 823 K for 3 h for Fe-PILC, Zr-PILC, and
Ti-PILC respectively. These synthesis conditions were optimized
in the preliminary study, some of them were shown in the support-
ing material.
2.3. Catalyst characterization
Finely ground catalysts (<1 mm) were prepared for the charac-
terization. Inductively coupled plasma optical emission spectrom-
eter (Optima 8300 ICP-OES, PerkinElmer) was used to measure the
metal loading of PILCs while Micrometrics ASAP 2010 nitrogen gas
adsorption analyzer was used to determine the textural properties
of PILCs at 77 K. The samples were degassed under vacuum at
150 C for 6 h before the measurements. Surface areas and pore
properties of the catalysts were estimated using the BET and BJH
equations except the micropore volumes which were determined
using the t-plot method. XRD patterns were collected on a
RigakuUltima IV diffractometer using Cu Ka radiation source at
40 kV and 20 mA with a scan rate of 0.5 degree/min at k of
1.54056 . The acidity was measured by means of the gas-phase
adsorption of pyridine (PY) and 2,6-dimethylpyridine (DMPY) at
different temperatures in the range of 473623 K [31,32]. Pulses
of 2 ll solution 1 mol/L of PY/DMPY (probe molecular) in cyclohex-
ane were injected into a N2 flow of 20 ml/min until the sample was
saturated. The characteristic adsorption peaks of the probe mole-
cule in the infrared spectra (IR) was observed after successive
injections and finally reached a constant intensity, indicating that
the sample was saturated with adsorbate. The amount of adsorbed
PY/DMPY (lmol/g of catalyst) was determined by the difference
between the injected amount of PY/DMPY and output of the PY/
DMPY which was collected by a gas bag and analysed by a gas
chromatograph (Agilent 7890B GC system, USA) equipped with
Agilent HP-5 column. Scanning electron microscope (SEM) images
were taken by a FE-SEM 7600F at 5 kV acceleration voltage. The
TEM images were taken by JEOL 2100F microscope with a ZrO/W
Schottky Field Emission Gun with an accelerating voltage of
200 kV. STEM image is using Annular Dark Field with EDAX Edx.
2.4. Catalytic test and product analysis
The pyrolysis experiments were carried out under a nitrogen
atmosphere in a laboratory scale installation as shown in Fig. 1,
which is similar to our previous study [33]. In a typical run, the cat-
alyst was mixed with the plastic sample in a proportion of 10 wt%
(the ratio of catalyst to plastic was constant for all the experiment).
The weight of each plastic sample was about 10 g per run. The sys-
tem was first heated at a rate of 40 K/min to 573 K and maintained
for 5 min. Subsequently, the temperature was increased to 773 K at
10 K/min, and kept for 30 min. The generated gas and oil vapour
was purged to the condenser which was cooled by running water.
The incondensable gas product was analysed by GC-TCD while the
condensable oil product was determined by GC-FID. The yield of oil
and wax, solid residue (exclusive of catalyst) as well as the gas
product were calculated in weight percentage with respect to the
plastic feedstock. The detailed analytical techniques for the compo-
sition and amount of pyrolysis products were presented in Sup-
porting Information.
3. Results and discussion
3.1. BET and XRD results
Table 1 showed the textural properties of the clay-based cata-
lysts. The BET surface areas of all the pillared catalysts were larger
than that of the parent material, bentonite. This result along with
the XRD data (d001) confirmed that the pillaring procedures for
these catalysts were effective [34]. However, the BET surface areas
of PILCs loaded with different transition metal (except Ti-PILC)
were lower than that of Al-PILC. This is mainly attributed to the
blockage of micropores by the transition metal phases formed
[22], which was also evidenced by the decrease of micropore vol-
ume in Fe-, Zr-, Ti-,PILCs. The exception for Ti-PILC is probably
due to the formation of supermicropores and large mesopores in
the catalyst [35]. The Fe-PILC, Ti-PILC, and Zr-PILC exhibited BET
surface area of 215, 280, 201 m2
g 1 and ESA surface area of 54.6,
125.9, 136.5 m2
g 1, respectively. These results indicated that con-
siderable external porosity was presented in the Zr-, Ti-PILCs. A
great portion of mesopores were incorporated into the textural
structure of Zr-PILC, Ti-PILC and Fe-PILC, as evidenced by the hys-
teresis loop and the type of isotherm which were shown in Fig. S1.
It was rational to infer that the intercalation of Zr, Ti and Fe species
in the matrix of pillared clay might produce significant mesoporos-
ity and reduce the microporosity as compared with the source
material. The high BET surface area resulted from the increased
mesoporosity is expected to favour multiple contacts of plastic
feedstock with the catalytically active centres and favour the pas-
sage of bulky pyrolytic product (such as olefins, cycloparaffin, and
aromatics) [36,37]. Overall, the pore architecture of the modified
PILCs depended on not only the pillaring process but also the nat-
ure of the incorporated transition metal, which was in agreement
with the result reported by Liu et al. [38]. In other words, irregular
pore distribution would be obtained when some specific metals
were introduced into the material with uniform arrangement of
pore size.
X-ray diffractograms (XRD) at the 2h angle from 1 to 60 for the
synthesized PILCs were measured to study their crystallinity, as
shown in Fig. 2. The XRD pattern of bentonite was also presented
for comparison. The basal spacing of d001 characteristic of the
ordering of the clay layers was presented in Table 1. The 0 0 1
reflection of bentonite presented a basal spacing of 11.9 . All the
other pillared clays presented the 0 0 1 reflection with basal spac-
ing larger than 11.9 , indicating that pillaring procedures for the
pillared clays was successful with resultant expansion of the inter-
layer distances [39]. This conclusion was in agreement with the
BET surface area result mentioned above. Two phases were identi-
fied in bentonite and its pillared samples. The peaks at 4, 20,
35 are attributed to the montmorillonite phase while the peaks
at 22 and 27 are ascribed to the quartz phase. The diffraction
peaks at 27.5 and 29.3 observed in the Bentonite was found to be
absent in the Al-PILC. In contrast, a small peak at 10.3 emerged,
indicating the existence of a fraction of non-pillared material
which had been previously noted by Molina et al. [40] and
Bouberka et al. [41]. In addition, the typical peak corresponding
to 0 0 1 reflection was very sharp, distinct and well-defined, indi-
cating a good crystallinity for this sample [42]. The introduction
of different transition metals instead of aluminium into the layered
clay resulted in significantly different XRD patterns. The peaks of
0 0 1 reflection became broad and the corresponding intensity
 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809 803

3
8 lllilllililiiiiyBii 5

XX c X7

aij
2

n
Mlliiiiiia
8

1
10 11 11
t
o

9
13

1- N 2 cylinder; 2-Gas valve; 3 - Flowmeter; 4-Furnace; 5-Tube reactor; 6- Reaction boat; 7-Plastic sample
and catalyst; 8-Thermocouple; 9-Controller; 10- Computer; 11- Condenser; 12-Gas bag; 13- Chiller

Fig. 1. Schematic diagram of the tubular pyrolysis reactor and the condensing unit.

Table 1
Textural properties of different catalysts.a

Catalyst SBETb SESAc VMPVc VTPVd d001

(m2
g 1
) (m2
g 1
) (cm3
g 1
) (cm3
g 1
) ()
Bentonite 34.6 22.3 0.0057 0.0908 11.9
Al-PILC 218 69.1 0.069 0.229 18.3
Fe-PILC 215 54.6 0.052 0.290 26.2
Zr-PILC 201 136.5 0.034 0.191 20.9
Ti-PILC 280 125.9 0.046 0.235 22.5
a
Nitrogen adsorption at 77 K.
b
Multi-point BET method.
c
External surface area and micropore volume was calculated from t-plot analysis.
d
Total pore volume at P/Po equal to 0.99.

decreased slightly for the modified PILCs as compared with the
source material (bentonite). This effect is attributed to the partial
disordering of the clay layer arrangement (non-parallel ordering
of the clay layers), which is resulted from the formation of the
delaminated structure after calcination [35]. The Zr-PILC, Ti-PILC,
and Fe-PILC retained the typical peaks attributable to montmoril-
lonite phase whereas the peaks of quartz phase became broad
and poor-defined. Fe-PILC exhibited a significantly large basal
spacing as compared with other pillared clays. The high gallery
height of Fe-PILC is probably attributed to the large size of polyca-
tions (15 30 ) formed by reaction of Na+ montmorillonite with
ferric nitrate under base-hydrolyzed conditions, which was previ-
ously reported by Rightor et al. and Pinnavaia et al. [4344]. We
prepared the iron pillared clays under heat treatment at 333 K
and 723 K respectively, using the optimum base-hydrolysis condi-
tion reported by Rightor et al. As could be seen from the XRD pat-
terns in Fig. S2, The d001 of Fe-PILC decreased from 29 to 26.2 as
the calcination temperature increased from 333 K to 723 K. This
behaviour is in good agreement with the results reported by
Rightor et al. [43]. The Ti-PILC and Zr-PILC also showed slightly lar-
ger basal spacings of 22.5 and 20.9 respectively as compared
with some previous results [36,45].The present results are
consistent with some studies [2830] reporting similar synthesis
methods. In brief, the XRD characterization results revealed that
all the clay-based catalysts were successfully pillared, as demon-
strated by the basal spacing of 0 0 1 reflection. After introduction
of different metal into the clay material, the catalysts still retained
some typical structural features. However, various factors, such as
restructure of the clay material caused by the intercalation of dif-
ferent metallic species and calcination temperature for the clay-
based catalysts greatly influenced the crystallization behaviour of
the modified PILCs hence resulted in atypical XRD patterns [39].
3.2. Acidity measurement
The acidity of the catalysts characterized by FTIR PY/2,6-DMPY
adsorption was presented in Table 2. It is generally accepted
[46,47] that DMPY is preferably adsorbed on Brnsted acid site,
rather than Lewis acid site, due to the steric hindrance caused by
the two methyl groups of DMPY, whereas PY is adsorbed on both
Brnsted and Lewis acid sites due to its sterically non-hindered
structure. Accordingly, the adsorbed DMPY was an indicator of
the Brnsted acidity while the adsorbed PY was an indicator of
the total acidity. Also, the FTIR spectra of pyridine adsorption for
some pillared catalysts were shown in Fig. S3. It could be clearly
seen that these pillared clays possessed both Brnsted and Lewis
acid sites, which are mainly attributed to the structural hydroxyl
group of montmorillonite and the metallic oxide pillars, respec-
tively [48]. It was reasonable to conjecture that Lewis acidity could
be measured by the difference between DMPY and PY adsorption.
As shown in Table 2, the PILCs showed comparable total acidity at
473 K. As the temperature increased, both the total acidity and the
Brnsted acidity gradually decreased. It was worth noting that
Brnsted acidity declined more dramatically than total acidity, as
evidenced by the adsorbed amount of DMPY and PY, implying that
the H-bonded amine (Brnsted acidity) was thermally less stable
than Lewis center coordinated amine (Lewis acidity) in the PILC
catalysts. This observation was also consistent with the previous
work by Kooli et al. [49]. Besides, the impregnation of different
metal oxides resulted in different acidity distribution for the cata-
lysts. The Brnsted acid sites of the Fe-, Ti-, Zr-PILC almost disap-
peared at the temperature of 623 K whereas Al-PILC still
possessed a considerable amount of Brnsted acid sites. All the
modified PILC presented comparable Brnsted acidity while the
Ti-PILC showed the highest Lewis acidity at 473 K. The high Lewis
804 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809

from nanometre to micron (Fig. S4a). The feature conferred it a

highly heterogeneous internal structure [50], resulting in the rela-
Ti-PILC Zr-PILC Fe-PILC tively high BET surface area. Intercalation of different metal oxide
Al-PILC pillars into the interlayer space of clays significantly affects the
Bentonite
morphology of clay (Figs. 3 and S4bc). The modified PILCs were
Quartz Montmorillonite found to be composed of randomly oriented flaky particles. It
was interesting to note that many grains uniformly spread over
the surface of the support in the case of Fe-PILC (Fig. 3a), implying
the good dispersion of these unknown particles. The size of indi-
001 Reflection vidual grains detectable at higher magnification was found to be
predominantly in the range of 100200 nm (Fig. 3b). It should be
noted that the uniformly dispersed particles might contribute to
its relatively higher BET surface area among the modified PILCs.
Some representative results from TEM observation were shown
in Fig. 4. The TEM images of PILCs showed different morphology.
The regular layer structure with enlarged interlayer distance was
observed in the Al-PILC (Fig. 4a). However, such regular structure
was found to partially collapse, leading to the overlap of clay layers
{
(see Fig. 4b, Zr-PILC as a representative). This typical TEM image
I was consistent with some results reported earlier [37,51]. The col-
lapse of interlayers induced a different porous structure which was
defined as house of cards structure [52,53]. However, uniquely, a
very uniformly distributed granular morphology was present in Fe-
PILC (Fig. 4c), which was consistent with its SEM image. The EDX
mapping for these separated grains were shown in Fig. 5. O was
selected as reference element. It could be seen that both O and
Fe showed similar distribution along the analysed region. All of
these results indicated that this disordered porous material most
likely consisted of iron oxides nanoparticles dispersed on the
montmorillonite support both externally and internally.

3.4. Effect of different catalysts on pyrolysis yield

I I I

1.5 10 20 30 40
2 theta degrees (o)
Fig. 2. XRD pattern of the clay-based catalysts.
acidity is possibly due to the nature of the pillared oxides, i.e. TiO2,
which could function as Lewis acidity centres. The order of the
total acidity for all the catalysts resulted to be: Fe-PILC < Zr-
PILC < Ti-PILC < Al-PILC. The characteristic acidic strength and
amount of acid sites for the modified PILC in the study were similar
to the previous reports [31,32,49]. In summary, the acidity distri-
bution for these clay-based catalysts was associated with the nat-
ure of the introduced metal, and the inherent structural hydroxyl
groups in the clay matrix.
3.3. SEM and TEM results
Fig. 3 showed the FE-SEM images of Fe-PILC (more images are
included in Fig. S4) Al-PILC was constituted by different irregular
shape of aggregates with different particle sizes, with size ranging
50
Table 3 showed the yields of solid residue, gases, as well as oil
products (in weight percentage, %) obtained in the pyrolysis and
catalytic pyrolysis of mixed plastics over different catalysts. Negli-
gible amount of solid residue was observed in all pyrolysis runs,
indicating the high conversion of the plastic feedstock under the
pyrolysis conditions. No significantly increased gas yield was
observed in the clay-catalysed pyrolysis as compared with that in
non-catalytic run, suggesting that there were no significant sec-
ondary over-cracking of the primary pyrolytic intermediates
caused by the clay-based catalysts owing to their moderate acidity
(shown in Table 2). Among these catalysts, Fe-PILC exhibited the
highest selectivity for the oil product, as denoted by the highest
oil yield (79.3%) and the lowest gas yield (18.0%). Al-PILC showed
the second highest oil yield among the pyrolysis runs. Zr-PILC
and Ti-PILC presented slightly lower oil yield as compared with
the non-catalytic run. This suggested that the over-cracking was
slightly promoted in the presence of these catalysts. The difference
of pyrolysis yield was probably due to their difference in acidity
and textural properties discussed in earlier sections. Interestingly,
neither Ti-PILC with the largest BET surface area nor Al-PILC with
the highest total acidity showed as satisfactory oil yield as that

Table 2
Surface acid properties of different catalysts.a

Temperature (K) lmol Pyridine/g catalyst lmol 2,6 DMPY/g catalyst

Al-PILC Fe-PILC Ti-PILC Zr-PILC Al-PILC Fe-PILC Ti-PILC Zr-PILC
473 382.7 336.2 373.5 338.1 203.4 145.2 126.8 150.2
523 343.6 238.2 309.1 263.4 183.7 81.6 91.2 101.1
573 254.2 179.3 242.3 198.5 112.3 43.8 48.9 56.7
623 163.5 113.2 165.5 122.6 49.1 9.3 10.2 13.5
a
pKa (Pyridine) = 5.1; pKa (2,6-DMP) = 6.7.
 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809 805

(a) (b)

Fig. 3. SEM micrographs of (a) Fe-PILC at 15,000 magnification and (b) Fe-PILC at 50,000 magnification.

(a) (b) (c)

Fig. 4. TEM images of (a) Al-PILC, (b)Zr-PILC, (c) Fe-PILC.

with Fe-PILC. This implies that a suitable combination of porous

structure and acidity of catalyst is needed to favour oil production
Table 3
from pyrolysis of mixed plastics. As mentioned above, the meso- The influence of different catalysts on the yield of pyrolytic products (wt.%).a
pores found in the modified clays are expected to favour the diffu-
Catalystb Oil product Gas product Residue
sion of bulky pyrolytic molecules. However, differences between
average pore diameter and size of pore opening can cause steric Thermal pyrolysis 67.6 31.1 1.30
Al-PILC 68.2 30.8 1.00
hindrance to the pyrolytic intermediates [37]. The pyrolytic inter-
Fe-PILC 79.3 18.0 2.70
mediates retained by steric hindrance will subsequently decom- Ti-PILC 62.8 34.2 3.00
pose into lighter products by the catalytic active sites. Fe-PILC Zr-PILC 62.1 36.7 1.10
exhibited the largest gallery height which may alleviate the steric a
Reaction conditions: 10 g of plastic mixture, N2 (200 mL/min), temperature
hindrance to some extent. In addition, the uniform morphology of programme: heating from room temperature to 300 C at 20 C/min, then hold for
Fe-PILC (as shown by SEM & TEM) is prone to generate pyrolytic 5 min, continuously heating from 300 C to 500 C at 10 C/min, hold for 30 min.
products with similar carbon distribution, which resulting in The conversion was 100% for all the pyrolysis runs using different catalysts.
b
higher selectivity of Fe-PILC for oil product over other pillared The mass ratio of catalyst to plastics (C/P) was 1:10.
clays.

200 .OkV X 400000 20.00nm

r1

, :Wmrn
Fig. 5. TEM image of Fe-PILC at 400,000 magnification (left) and its corresponding EDX mapping for Fe (middle) and O (right) elements.
806 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809

3.5. Effect of different catalysts on the composition and amount of oil of the chromatographic peaks. In comparison with the thermal
product run, the catalytic runs presented a larger amount of alkanes and
alkenes in the heavy hydrocarbon fractions (>C13) and a compara-
The distribution of the carbon number of the oil products were ble amount of aromatics in the light hydrocarbon fractions (C6
showed in Fig. 6, while the main components of the products and C13). Pyrolysis with Al-PILC produced a considerable amount of
their respective percentages were showed in Table 4. As could be light hydrocarbon fractions primarily composed of aromatic com-
seen in Fig. 6, in the non-catalytic run, the oil product composed pounds. The other PILCs also exhibited a similar aromatics distri-
of three comparable fractions (C6C12, C13C19 and C20C40), bution in the light hydrocarbon fractions. This result revealed
indicative of a relatively even distribution of carbon number as that the PILC catalysts favoured strong aromatization/abscission
compared with the catalytic runs. The high variability of carbon of aromatic ring from the PS molecule in the pyrolysis of mixed
number is attributed to the random scission of polymer chain plastics. Its worth noting that Ti-PILC and Fe-PILC displayed the
under the sole effect of thermal treatment. Since the fuels with a highest selectivity for the aromatic compounds in the light
relatively narrow carbon number range are preferred for applica- hydrocarbon fraction and heavy hydrocarbon fraction, respec-
tion in most engines, the oil product from non-catalytic run could tively. The increase of aromatics in light fraction (mainly benzene
not be readily used and requires further upgrading treatment. On and naphthalene) could be predominantly attributed to the arom-
the other hand, all the clay-based catalysts produced a significant atization/cyclization of hydrocarbons or abscission of aromatic ring
amount of C13C19 fraction. The concentrated carbon number dis- from PS and PET, while the increase of aromatics (mainly polycyclic
tribution corresponded well to the high oil yields shown in Table 3. aromatics) in the heavy fraction was predominantly attributed to
Since it is well-known that the hydrocarbons in the range of C13 the aromatization by the Brnsted sites of the catalyst [37] and
C19 are representative of diesel products, the modified PILC cata- subsequent dehydrogenation by the Lewis sites via a free radical
lysts could potentially be applied in the industry for diesel produc- mechanism [38]. The large gallery height and uniform particle dis-
tion from plastic wastes. Among the clay catalysts, Fe-PILC tribution of Fe-PILC may play a role in the increased production of
presented a particularly high selectivity for the C13C19 fraction polycyclic aromatics. The said textural properties could make the
and low selectivity for the C20C40 fraction. Since Fe-PILC exhib- Lewis acidic pillars more accessible to the bulky reactant, thereby
ited the lowest total acidity, it is reasonable to deduce that the high increase the occurrence of bimolecular reactions among the
diesel production is partially attributed to its milder acidity, which monoaromatic molecules. It is also worth mentioning that
is accompanied by less over-cracking of hydrocarbons. In terms of Fe-PILC exhibited considerable amounts of alkane and alkene in
yield and quality of oil products, Fe-PILC was found to display the heavy hydrocarbon fraction, which were the main constituents
advantages over other clay catalysts. of diesel fuel, demonstrating the good potential of Fe-PILC to be
The major constituents in the oil and wax products were listed used for the production of valuable diesel fuel from plastic waste.
in Table 4. They were identified by matching the peaks obtained In addition, it was found that the content of alkane was higher than
from GCMS against the NIST11 mass spectral library, while their that of alkene in the heavy hydrocarbon fraction obtained from all
respective quantities were calculated in term of percentage area the catalytic runs. As explained by Liu et al. [38], this could be due
to the alkanisation of the primary intermediates, which was
favoured by alumina silicate supported catalysts like clay.

80.5
80 C6-C12
C13-C19
3.6. Effect of different catalysts on the composition and amount of gas
71.4
70 C20-C40 product
65.3
62.3
60
The composition of gas products from non-catalytic and cat-
Percentage (%)

52.9
50 alytic runs were presented in Table 5. The pyrolysis gases were
composed of CO, CO2, H2 as well as a mixture of C1C5 gaseous
40
hydrocarbons. In non-catalytic run, a considerable content of car-
30 28.0 bon dioxide (CO2) and carbon monoxide (CO) were observed.
23.4 23.7
21.1 22.6 When the catalysts were introduced into pyrolysis, the amount
20
14.4 of CO2 increased significantly. The result was consistent with the
12.1
10 7.5 9.7
5.1
earlier findings which demonstrated an increased amount of CO2
in catalytic pyrolysis of plastics/biomass [48,50]. It was reported
0
No catalyst Al-PILC Fe-PILC Ti-PILC Zr-PILC that the increase of CO2 was related to the decarboxylation reac-
Catalyst type tions of PET which could be influenced by the acidic properties
(e.g. acid number, acid strength, and type of acidity) of catalysts
Fig. 6. Distribution of the oil products in terms of carbon number. in the process of pyrolysis. In addition, part of the CO2 could be

Table 4
Main components of the oil product determined by GCMS (% area).a

Catalyst Light hydrocarbons (C13) Heavy hydrocarbons (>C13)

Alkane Alkene Cycloparaffin Aromatics Alkane Alkene Cycloparaffin Aromatics
No catalyst 2.1% 8.2% 1.6% 14.1% 17.8% 25.4% 0.5% 11.3%
Al-PILC 1.5% 2.5% 2.3% 15.6% 41.5% 15.6% n.d. 14.1%
Fe-PILC 0.6% 1.8% 0.8% 11.0% 31.1% 21.2% n.d. 33.5%
Ti-PILC 2.2% 3.9% 1.8% 23.5% 49.6% 3.6% n.d. 4.0%
Zr-PILC 1.1% 3.76% 0.94% 14.8% 32.3% 25.5% n.d. 16.67%
Fe-PILCb 3.22% 1.79% n.d. n.d. 55.60% 30.5% 1.44% n.d.
a
n.d. indicates not detected.
b
The plastic feedstock is the mixture of HDPE and PP with the weight ratio of 6:5.
 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809 807

Table 5
Composition of the pyrolysis gas (mol%).

Catalyst H2 CH4 CO2 CO C2 gas C3 gas C4 gas C5 gas

No catalyst 6.1% 9.7% 9.0% 6.0% 18.7% 21.6% 10.2% 5.9%
Al-PILC 10.0% 6.8% 11.7% 13.5% 15.3% 20.5% 6.9% 3.2%
Fe-PILC 47.7% 5.1% 12.2% 9.1% 8.0% 9.6% 3.6% 1.6%
Ti-PILC 25.3% 14.7% 13.7% 2.8% 18.8% 24.0% 7.5% 1.4%
Zr-PILC 3.1% 11.5% 8.3% 2.2% 23.7% 29.7% 9.0% 9.5%
Fe-PILCa 25.2% 8.9% 3.1% 1.3% 15.0% 19.2% 8.0% 4.8%
a
The plastic feedstock is the mixture of HDPE and PP with the weight ratio of 6:5.

Table 6
HHV (MJ/kg), elemental composition (wt%) and moisture of the pyrolysis char.

Catalyst Moisture C H N Othersa H/C Ratio HHV

No catalyst 3.50 86.9 8.99 0.12 0.53 0.103 36.3
Al-PILC 5.11 74.2 17.7 0.16 2.87 0.238 42.9
Fe-PILC 0.89 92.1 4.00 0.06 3.00 0.044 36.8
Ti-PILC 2.29 88.7 6.03 0.07 2.96 0.068 37.6
Zr-PILC 3.08 89.4 4.52 0.11 2.93 0.051 38.0
b
Not detected
a
By difference

produced by stepwise reduction of metallic oxides to metallic iron Pathway A

through reactions between hydrocarbons and metallic oxides [50]. Fe- PILC
Among the catalysts tested in the present work, Fe-PILC showed
the highest H2 yield (47.7 vol%). This is possibly attributed to its cyclization
acidic nature and pore architecture that favours the production aromatization
of H2 in pyrolysis of mixed plastics. The reason behind was
explained in detail in Section 3.8.
#
PlPlPlPlPlFlPlMaffi
Finally, it was noticeable that the prepared Fe-PILC in our study
exhibited remarkable production of H2. Fe-PILC is inexpensive and dehydrogenation
environmentally friendly. Hence, it can be considered a potential
catalyst for the production of hydrogen in the pyrolysis of waste
plastics, as well as other solid wastes such as biomass, etc.
Metallic oxide cluster ( pillars )
Pathway B
3.7. Char residue analysis and regeneration of catalysts

The composition of the pyrolysis solids was presented in Table 6.
In both thermal and catalytic runs, low H/C ratio and negligible
nitrogen content were obtained. In particular, the modified clays
showed relatively high carbon content. This indicated that the char
from pyrolysis catalysed by the modified PILCs was substantially
upgraded, as opposed to the studies with ZSM-5 and red mud
reported by Lpez et al. [50]. On the other hand, the pyrolysis
solids in all cases were carbonaceous materials with negligible
amount of moisture and high HHV (3442 mJ/kg) that was compa-
rable with lignite and coke [54]. These properties of char indicated
that it could be a potential substitute for fossil fuels, carbon black
and pigment after being separated from catalyst.
The performance of the regenerated Fe-PILC in the pyrolysis of
mixed plastics was presented in Table S3. Fe-PILC somewhat
retained a similar performance as the fresh Fe-PILC even after
two regeneration cycles. Although the yield of oil product and
the selectivity for the diesel fraction and H2 were found to decrease
slightly, Fe-PILC is still considered effective after regeneration. It is
also worth mentioning that, in our study, there was no significant
detrimental effect to the catalyst caused by the oxygenated com-
pounds (eg. benzoic acid) generated from pyrolysis of PET.
3.8. Reaction pathway for the production of H2
A series of possible reactions (e.g. isomerization, b-scission,
hydrogen transfer, oligomerization) had been proposed in the
pyrolysis process. In this paper, a plausible reaction pathway for
Scheme 1. A plausible reaction pathway over Fe-PILC for hydrogen production.
theH2 production over Fe-PILC (as a model catalyst) was proposed
according to the abovementioned results (as shown in Scheme 1).
There were two major reaction pathways in this process: i) Cycliza-
tion/aromatization of pyrolytic intermediates that results in the
formation of cycloparaffin, aromatics, and hydrogen (denoted as
Pathway A); ii) Cracking reaction which is randomly followed by
the alkanisation/deep dehydrogenation, resulting in the formation
of aliphatic compounds (eg. alkane, alkene), hydrogen as well as
pyrolysis gases (Pathway B). Some evidences for elucidating the
pathways could be obtained by correlating the composition of
pyrolysis gas (see Table 5) with the main component in the pyrol-
ysis oil (see Table 4). According to Table 4, a considerable amount
of both aromatics and alkene were obtained in the liquid product
in the case of Fe-PILC. Hence, it was reasonable to conjecture that
both Pathway A and Pathway B were responsible for the high yield
of hydrogen (47.7 vol%) over Fe-PILC. In order to get insight into
the hydrogen production by these two pathways, a parallel exper-
iment was conducted under the same experimental conditions,
using the mixture of HDPE and PP as feedstock. Interestingly, a
negligible amount of aromatics was observed and the amount of
hydrogen decreased significantly. This indicated that (i) the hydro-
gen production favoured by Fe-PILC was found to follow Pathway A
predominantly, and (ii) the considerable amount of aromatics
obtained in mixed plastics pyrolysis mainly originated from the
aromatic fragments of PS and PET.
808 K. Li et al. / Chemical Engineering Journal 317 (2017) 800809
4. Conclusion
A series of pillared clay intercalated with different metals (Ti,
Fe, Zr) were synthesized, characterized and employed in the pyrol-
ysis of mixed plastics consisting of PP, HDPE, PS and PET. The BET
and XRD characterizations of all the catalysts revealed their
respective characteristic textural properties, which depended on
not only the pillaring process but also the nature of the incorpo-
rated transition metal. The FTIR of pyridine adsorption analyses
revealed that all the modified PILCs exhibited two types of acid
site, which were attributed to the structural hydroxyl group of
montmorillonite and the metallic oxide pillars, respectively. Col-
lectively, the inherent structural hydroxyl groups in the clay
matrix and different nature of metals bestowed different acidity
distribution on the modified PILCs. SEM and TEM provided an
insight into the morphology of different catalysts. In the case of
Fe-PILC, a uniformly distributed granular structure was observed.
Owing to a suitable combination of acidity and textural properties,
Fe-PILC was found to produce a large amount of diesel fraction in
the oil product and a great amount of H2 in the gas product. The
reason behind was illustrated by a proposed pathway in pyrolysis.
Further research work could be conducted to explore the possibil-
ities to widen the application of modified pillared clay catalyst in
recycling of a variety of municipal solid waste.
Acknowledgements
We acknowledge the financial support from the National Envi-
ronment Agency of Singapore under the Environment Technology
Research Program (ETRP grant No: 1202-109).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2017.02.113.
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