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Catalytic pyrolysis of LDPE plastic wastes over mortar cement catalyst

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Advanced Materials Research Vols. 931-932 (2014) pp 47-51
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.931-932.47

Catalytic pyrolysis of LDPE plastic wastes over mortar cement catalyst

Veeranuch Srakeaw1,a*, Siriporn Yodjai1,b and Unalome Wetwatana2,c
1
Department of Chemistry, Faculty of Science, Chandrankeam Ratjabhat University, Thailand
2
Chemical and Process Engineering, Sirindhorn International Thai-German Graduate School of
Engineering , King Mongkut’s University of Technology North Bangkok, Thailand
a
veeranuch2004@gmail.com, bmirageyui.sy@gmail.com, cunalomew@kmutnb.ac.th
Keywords: mortar cement catalyst, pyrolysis, plastic wastes

Abstract. A CaO based catalyst synthesized from mortar previously used in construction was
chosen for pyrolysis of LDPE plastic waste. The samples were calcined at temperatures of 500 and
800 °C for comparison purpose. After calcination, two mixed oxides were obtained, denoted as
catalyst A and B. The chemical composition of the metal oxide catalysts and the liquid products of
the pyrolysis were characterized by X-ray Fluorescence (XRF) and Simulated Distillation - Gas
Chromatography (SD-GC), respectively. The XRF analysis indicated that the catalyst, reformed
from the mortar cement, consisted of CaO, silica (silicon dioxide, SiO2) and alumina (aluminium
(III) oxide, Al2O3) as the main constituents, though, the composition of each compound differed
because of the influence of calcination temperature. Catalyst A had 41.96% of CaO, 4.27% of
Al2O3 and 30.82% of SiO2 when the catalyst B had 37.04% of CaO, 2.38% of Al2O3 and 37.31% of
SiO2. The amount of CaO in the catalyst B was found to be less in catalyst A. The catalyst A gave
higher percentage yield of naphtha oil (48±1.14%v/v), compared to catalyst B (21±1.26%v/v). The
performance of this catalyst (A) towards the pyrolysis of plastic wastes was compared to
commercial grade ZSM-5 and FCC catalysts. It was found that the catalyst A, CaO based catalyst,
reformed from the mortar cement, gave the highest yield of naphtha oil (48±1.14%v/v) compared to
ZSM-5 (26±1.52%v/v) and FCC (16±1.09%v/v). The optimum operating temperature for the
pyrolysis was found at 410 °C (in the temperature range 370 °C to 450 °C) and the optimum
catalyst (A) composition was 0.3 %w/w of mortar cement catalyst in LDPE. This optimum
condition gave 86.67± 0 %w/w of liquid, 12.49± 0.24 %w/w of gas and 0.84± 0.24 %w/w of solid.
The catalyst A showed the best performance amongst all the catalysts towards the pyrolysis process
of plastic wastes.
1. Introduction
The total plastic wastes volume in 2011 was reported to be 1.84 million tons/day in
Thailand. [1]. The plastic wastes are forecast to grow to around 2.6 million tons/years by 2016.
Currently, plastic wastes are disposed of by combustion, landfill, recycle, reuse and pyrolysis. In
Thailand, less than 500 million tons/years of municipal plastic waste was reused and recycled in
2011, 61% of it was openly dumped, 37% went to landfilling and 2% was used in municipal
incineration projects.
Pyrolysis is the thermochemical decomposition of organic materials at high temperature
without oxygen. The pyrolysis can be carried out with or without catalyst. Plastic wastes were
reported to be pyrolysed to liquid fuels under high ranges of temperature (350 °C to 400 °C) [2]
over various catalysts such as Y-zeolite or zeolite ZSM-5 catalyst [3], CaC2 catalyst [4], CaO [5],
HZSM-5 [6]. The catalyst properties (pore size, acidity, basicity and types) and reaction parameters
(operating temperature, retention time and quantity of the catalyst) are reported to influence the
types the liquid hydrocarbon compounds produced [7].
Zeolite Socony Mobil (ZSM-5) was reported to be a promising catalyst for plastic wastes
conversion to fuels [3, 8-9]. Fluid Catalytic Cracking (FCC) catalyst is also well-known for
petroleum production processes. The FCC catalyst basically has the same chemical formula as the
ZSM-5 but with different composition, 40.17 % wt SiO2, 46.15 %wt Al2O3, 0.22 %wt Na2O and
0.35 %wt CaO [10]. From previous work [10], the yield of naphtha oil produced via the pyrolysis of
LDPE over the FCC catalyst was reported to be relatively low [10] (16±1.09%v/v). Recent work by
Z. Tingyu and et al, have reported that the key compound that helps catalyzing the pyrolysis

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48 KKU International Engineering Conference

reaction is CaO [5]. In this work, mortar cement was chosen, as a CaCO3 rich-source, to be a raw
material for producing CaO catalyst substitute.
In this work, samples of mortar were removed from local buildings. This mortar is
composed of sand (SiO2, in quartz form), lime (CaCO3 and Ca(OH)2), and water. This research
focuses on use of waste mortar as a potential CaO based-catalyst for pyrolysis process of plastic
wastes to liquid hydrocarbons.
2. Materials and Methods
2.1 Materials
The CaO from mortar cement catalyst, prepared at the Laboratory of chemistry
department, Chandrakrasem Ratjabhat University was calcined at 500 and 800 °C and grounded.
The commercial grade ZSM-5 and FCC catalysts were supplied from Xusen, China. Some of ZSM-
5 and FCC properties are displayed in Table 1. 99.99% nitrogen gas was used as a carrier and
introduced to the reactor at 1 liter.min-1.

Table 1 Characteristics of the ZSM-5 and FCC catalysts

Catalyst property ZSM-5 FCC
Particle size (µm) ≤ 6 µm 0-40 µm (14.8%), 0-149 µm (85.2)
Pore size (nm) 2-3 -
Pore volume (ml/g) ≥ 0.17 0.34
Surface area (m2/g) ≥ 340 298
2.2 Methods
2.2.1 Pyrolysis reactor
The pyrolysis reactor’s design and fabrication were described elsewhere [10]. The electrical furnace
can produce a maximum temperature of 800 °C. The reactor was 322 mm in length and 20 mm in
diameter. Thermocouples were inserted into three different locations of the reactor as shown below.
2.2.2 Preparation and characterization of mortar catalyst
The mortar samples were calcined at 500 °C and 800 °C to give CaO
based catalysts named as catalyst A and B, respectively. The ground mortar catalysts chemical
composition and morphology were characterized by X-ray fluorescence (XRF) and Scanning
Electron Microscope (SEM) to investigate the catalyst’s chemical composition and morphology.
2.2.3 Determining optimum catalyst quantity and operating conditions for naptha yield?
30 g of low density polyethylene (LDPE) was used as feedstock and mixed with catalyst of weight
ratios at 0.1, 0.3, 0.5 and 1 %w/w. Nitrogen carrier gas was introduced into the reactor at 1 Liters
min-1. The reaction was carried out at temperatures of 370, 390, 410 and 450 °C under atmospheric
pressure for 3 hours. The liquid and condensable gaseous-products were collected in a glass vessel
in a cooling bath (containing 70% ethylene glycol) at -20 °C. The products were then analyzed by
Simulate Distillation-Gas Chromatography.
3. Results and discussions
3.1 Morphology and characteristic of mortar, ZSM-5 and FCC catalysts
The mortar generally consists of 1 part cement, 4 parts of rough sand, and 1.5 parts of lime and 10
liters of clean water [11]. 50 g of Mortar cement was calcined at 500 °C and 800 °C then pounded
to produce fine particles. The morphology of the particles were observed by SEM techniques and
shown in Figure 1. Figure 2 shows the SEM of catalyst calcined at 500 °C. The pore size of the
mortar was measured as 116.85 nm. The chemical composition of the prepared mortar catalysts
particles defined as catalysts A and B (calcined at 500 and 800 °C, respectively), were analyzed by
X-ray Fluorescence (XRF). The composition of the catalysts was tabulated in Table 2. Catalyst B
has less CaO than the catalyst A due to the decomposition of CaO which occurred at 800 °C [12].
The naphtha oil obtained from pyrolysis process catalysed by catalyst A gave a yield of
48±1.14%v/v. This is possibly because the polarity of the active site of calcium oxide can affect the
p-electron cloud’s stability of condensed aromatic compounds, and calcium oxide itself has an
active cracking site on both inner and outer surfaces [5]. The amount of CaO in catalyst A and B are
 Advanced Materials Research Vols. 931-932 49

quite similar, but the naphtha oil received from catalyst B was only 21±1.26%v/v. However, the
level of SO3 found in the catalyst B was quite high (11.15 %v/v). Therefore, it is possible that the
SO3 reacted with the CaO producing CaSO4 [13]. This obviously reduced the amount of the reactive
CaO resulting in less amount of the naphtha oil produced.

Fig. 1 Characteristic of mortar particles Fig. 2 Pore size of mortar catalyst at 500 °C
Table 2 Chemical Compositions of vary catalysts
Percent compositions Percent compositions
Compound Mortar Compound Mortar
ZSM-5 FCC ZSM-5 FCC
500 800 500 800
SiO2 30.82
° 37.31
° 96.23 40.1 MnO2 0.04
° 0.03
° 0 0
Al2O3 4.27 2.38 3.41 46.1 Fe2O3 2.15 1.64 0.14 0.74
CaO 41.96 37.04 0.04 5
0.35 ZnO 0.02 0 0 0
MgO 0.67 0 0 0 SrO 0.01 0.01 0 0
Na2O 0.29 0 0.05 0.22 ZrO2 0.01 0.01 0.003 0
P2O5 1.06 0 0 0.36 SnO2 0 0 0 0.04
SO3 1.63 11.15 0.04 2.61 La2O3 0 0 0 3.07
Cl 0.12 0 0.03 1.31 Ce2O3 0 0 0 4.33
K2O 2.16 0.43 0.03 0.38 TiO2 0.19 0.21 0.034 0.30

3.2 Condition of pyrolysis with mortar catalyst

Quantity of the liquid and gaseous products (by weights) produced via the
pyrolysis over catalyst A, at different weight of mortar cement, was categorized in Table 3 at 410
°C for 2 hours under N2 atmosphere. 0.3% weight of catalyst (catalyst to feed) was suitable for the
process as this condition produced the greatest amount of liquid and gas products. The less catalyst
used will help reducing cost of production and also reduce the contamination of the produced fuel
[14].

Table 3. Percent of products at vary percent weight of mortar cement catalyst at 410 °C for 2 hours
Plastic %weight Percent of products (by weights)
Type of catalyst
wastes of catalyst gas liquid solid
LDPE 0.1 50.81±2.26 48.44±2.12 0.75±0.01
A 0.3 12.49±0.24 86.67±0.00 0.84±0.24
0.5 57.24±3.21 42.22±3.21 0.54±0.10
1 8.83 ± 1.00 90.00±1.00 1.17±0.07

Table 4 shows the percentage of the liquid and gaseous products (by weights) produced through the
pyrolysis of LDPE over catalyst A, at different temperatures of pyrolysis. The reaction occurring
under 410 °C gave the greatest quantity of liquid product (86.67 ± 0.00%w/w) as the liquid
hydrocarbons started to be cracked to smaller molecules or lighter hydrocarbons [15]. At
temperatures higher than 410 °C, the amounts of liquid products were decreased as they were
converted to lighter hydrocarbons appearing in gas phase.
50 KKU International Engineering Conference

Table 4. Percent of products at vary temperature with mortar cement catalyst

Plastic Type of %weight of Pyrolysis temperature Percent of products (by weights)
waste catalyst catalyst (°C) gas liquid Solid
370 36.58±0.46 32.22±0.29 31.2±0.30
390 47.67±2.88 48.89±3.21 3.44±0.73
LDPE A 0.3 410 12.49±0.24 86.67±0.00 0.84±0.24
430 65.45±3.73 33.89±3.75 0.66±0.03
450 63.77±2.22 35.56±2.25 0.67±0.04
Table 5 shows the yield of liquid fuel obtained from pyrolysis process catalysed by catalyst
A was similar to the yield of liquid fuel with the catalyst B due to their similarity of the CaO
content. The quantity of CaO is believed to have a strong effect on the catalyst’s performance.

Table 5. Percent of products using catalyst A and B

Plastic Type of %weight Temperature Percent of products (by weights)
waste catalyst of catalyst (°C) gas liquid solid
LDPE Mortar 0.3 500 (A) 12.49 ± 0.24 86.67 ± 0 0.84 ± 0.24
cement 800 (B) 21.16 ± 1.00 77.77 ± 1.15 1.07 ± 0.17
Table 6 shows percent of products which were produced from pyrolysis over different types
of catalyst. Catalyst A showed the best performance towards the pyrolysis process amongst ZSM-5
and FCC because it has higher level of CaO. Also, the different degree of CaO level may affect the
catalyst’s alkalinity which possibly causes the difference in liquid product selectivity [16].

Table 6. Comparison of percent of products at 410 °C using various types of catalyst

Plastic Type of % weight Percent of products (by weights)
Waste Catalyst of catalyst Gas Liquid Solid
A 8.83 ± 1.00 90.00 ± 1 1.17 ± 0.07
LDPE ZSM-5 1 30.37 ± 4.08 66.73 ± 4.07 2.9 ± 1.22
FCC 20.73 ± 1.15 73.33 ± 5.42 5.94 ± 2.95
3.3 Characterization of liquid fuel
Table 7 shows compositions of liquid fuels in pyrolysis processes using FCC catalyst, ZSM-
5 catalyst and catalysts A and B. The catalyst A gave the highest yield of naphtha oil due to it
having the largest amount of CaO which effected on the numbers of the catalyst’s acid site. The
lack of acid sites caused lower performance of the catalyst. In general, the catalyst’s performance
depends on the amount of acid sites, pore size and shape of catalyst [6].

Table 7. Compositions of liquid fuels in pyrolysis processes using FCC catalyst, ZSM-5 catalyst
and catalysts A and B
Range of Percent of products (by volumes)
Fuel Type distillation Mortar
ZSM-5 FCC
temperature at 500 °C (A) at 800 °C (B)
naphtha < 200 °C 48±1.14 21±1.26 26±1.52 16±1.09
kerosene 200-250 °C 22±1.3 15±1.32 6.5±0.76 7±1.6
light gas oil 250-300 °C 14±0.54 19±1.02 20.5±0.5 22±2.03
heavy gas oil 300-370 °C 11±0.83 32±1.74 22±2.07 29±0.75
Residue > 370 °C 5± 1.48 13±0.74 25±1.5 26±1.72
(tar+catalyst)
The composition of the liquid product obtained from the pyrolysis process over catalyst A
was determined using SD-GC. The result agreed with table 7 confirming that the liquid product
from the process consists of naphtha oil, kerosene oil, light gas oil and heavy gas oil. Naphtha oil
was found to be the main compound of the liquid product.
 Advanced Materials Research Vols. 931-932 51

4. Summary
The optimum condition for pyrolysis of LDPE was found to be at 410 °C under
atmospheric pressure using 0.3% wt of the catalyst (to feed) produced from mortar calcined at 500
°C (named as catalyst A) giving 48±1.14% of naphtha oil. Catalyst A has higher quantity of CaO as
it was calcined at lower temperature (compared to Catalyst B, calcined at 800 °C). Catalyst A has
more CaO content compared with ZSM-5 and FCC. CaO caused reduction of the catalyst’s acidity,
therefore, reducing the ability of the catalyst to crack hydrocarbons. This inhibits conversion of
liquid product to gas product resulting in higher amount of naphtha oil.

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