Effects of Mgo-Zsm-23 Zeolite Catalyst On The Pyrolysis of Pet Bottle Waste
Effects of Mgo-Zsm-23 Zeolite Catalyst On The Pyrolysis of Pet Bottle Waste
Effects of Mgo-Zsm-23 Zeolite Catalyst On The Pyrolysis of Pet Bottle Waste
205–211, 2017
Research Article
Selected Paper from the 6th International Thai Institute of Chemical Engineering and Applied Science Conference (ITIChE2016)
Supak Tontisirin*
Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s University of Technology
North Bangkok, Bangkok, Thailand
Center of Eco-Materials and Cleaner Technology, King Mongkut’s University of Technology North Bangkok,
Bangkok, Thailand
Abstract
The pyrolysis reaction of poly(ethylene terephthalate) or PET bottle waste was conducted comparatively in
two cases: without catalyst and with MgO-ZSM-23 zeolite catalyst. The pyrolysis of PET was successfully
decomposed to the product of liquid/wax, char, and gas (major product). Applying MgO-ZSM-23 catalyst, the
product shows pronounced higher yield of gas (72.5 vs. 58.7 wt.%) and less yield of char solid (8 vs. 17.6 wt.%).
The gas product shows less yield of CO2 (75 vs. 98 wt.%) but gives higher hydrocarbon gas fractions of C1–C5
(25 vs. 2.1 wt.%). In liquid/wax products, the catalytic pyrolysis shifted the product spectrum from higher
molecular weight, e.g., biphenyl, terphenyl to benzene derivatives, predominantly in “benzoic acid”.
Please cite this article as: P. Kongsupapkul, K. Cheenkachorn and S. Tontisirin, “Effects of MgO-ZSM-23
zeolite catalyst on the pyrolysis of PET bottle waste,” KMUTNB Int J Appl Sci Technol, vol. 10, no. 3,
pp. 205–211, Jul.–Sep. 2017.
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P. Kongsupapkul et al., “Effects of MgO-ZSM-23 Zeolite Catalyst on the Pyrolysis of PET Bottle Waste.”
support because of its excellent acidity and shape Cooling water Gas product
selective properties. Its unique structure of one- TIC
ZSM-23 zeolite was synthesized with molar The pyrolysis experiments were conducted using 5L
composition of 110SiO2: 1.1Al2O3: 50C4H9N: 45 NaOH: batch reactor equipped with gas product condenser
18H2SO4: 5000H2O at 180°C for 2 days by rotational and sampling points as shown in Figure 1. The reactor
reactor. It was calcined at 580°C in N2 and hold at was heated by electrical furnace and the reaction
this temperature for 3 hr in O2. The calcined form temperature was measured in the pyrolysis zone. The
was converted to protonate form by ion-exchanging reactor was loaded with 300 g of shred of PET bottle
with 1 M NH4NO3 at 65°C for 4 times (each for 3 hr) waste (in non-catalytic test). The test was carried out at
and was calcined at 450°C for 3 hr MgO-ZSM-23 440°C with heating rate of 5°C/min. This temperature
catalyst (10 wt.% of MgO in zeolite) was prepared by was maintained for 1 hr. Then the gas product was
wet impregnation using solution of Mg(NO3)2∙6H2O collected in sample bags for each 15 min interval
in ethanol (10 ml ethanol/1 g zeolite). It was stirred until 60 min. The liquid/wax product was collected
for 6 hr at 40°C. The solvent was removed by rotary at one time in each test. In case of catalytic test,
evaporator and then the solid of MgO-ZSM-23 was 10 g MgO-ZSM-23 was placed on top of the PET
obtained. The solid was dried at 200°C overnight and bottle waste inside the reactor. The gas product
calcined at 450°C for 6 hr. (CO2) was analyzed by Gas Chromatograph with
Thermal Conductivity Detectors (GC-TCD) of Agilent
2.2 Characterizations 5973N with PoraPLOT Q column. Hydrocarbon gases
(C1–C5) were analyzed by Gas Chromatograph with
The materials were characterized by powder X-ray Flame Ionization Detector (GC-FID) of Agilent 6890N
diffraction (XRD, BRUKER AXS model D8 Advance, with PoraPLOT Q column. The result was calibrated
Germany) operated at 40 kV and 30 mA. The with the standard gases. The product from liquid/wax
measurement ran with angle from 5 to 50° of angle 2 was extracted by dichloromethane (0.017 g liquid/
theta with step size of 0.02° and scan speed of 1°/min. wax: 5.609 g CH2Cl2). It was analyzed by using Gas
The surface characteristics of the materials were recorded Chromatography coupled with Mass Spectrometry
using scanning electron microscope (FESEM, JEOL, (GC-MS) as a convenient method used in other studies
model JSM-7610, Japan) operated at 15 kV. The [12]. The GC-MS with FID detector and column type
chemical composition was determined by energy DB-1MS of Agilent 6890 and Agilent 5973 was used.
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KMUTNB Int J Appl Sci Technol, Vol. 10, No. 3, pp. 205–211, 2017
(a)
Intensity (a.u.)
(b)
5 10 15 20 25 30 35 40 45 50
Angle 2 Theta (degree)
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P. Kongsupapkul et al., “Effects of MgO-ZSM-23 Zeolite Catalyst on the Pyrolysis of PET Bottle Waste.”
Non-catalytic Catalytic and less CO2 (75 vs. 98 wt.%) comparing to non-
100 catalyst pyrolysis. These major hydrocarbon gas
products of C1–C5 can be useful as fuel or chemical
80
feed stocks for olefins and polymers production.
Mass yield (wt.%)
60
Table 1: Gas product yields obtained in non-catalytic
pyrolysis test
40
Products (wt.%)
Time (min)
20 CO2 C1 C2 C3 C4 C5
0–15 97.2 2.85 0.00 0.00 0.00 0.00
0 15–30 98.4 1.47 0.03 0.01 0.12 0.00
liquid / wax char gases
30–45 98.7 1.16 0.03 0.01 0.10 0.05
Figure 5: Product yields distribution obtained in the
45–60 97.5 1.77 0.04 0.02 0.67 0.00
pyrolysis tests.
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In non-catalytic case, the second predominant product Table 5: Top ten components extracted from liquid/wax
is a group of biphenyl derivatives, e.g., biphenyl- product from the pyrolysis tests
4-carboxylic acid and 9-fluorenone. For clarification, No. Non-catalytic Catalytic
Figure 6 and Table 5 present the GC-MS chromatograms Benzoic acid Benzoic acid
and molecular structures with index of top-ten products.
In summary, the results show catalytic pyrolysis using 1
MgO-ZSM-23 catalyst affected product distribution of 62.94 wt.% 63.58 wt.%
liquid/wax fraction by increasing benzoic acid and its Biphenyl 2-Propanoylbenzoic acid
derivatives (80 vs. 71.3 wt.%) but suppressing large
molecules of biphenyl, terphenyl, and their derivatives 2
(10.44 vs. 14.48 wt.%). The acid activity and shape
selectivity of the MgO-ZSM-23 zeolite catalyst could 4.54 wt.% 4.24 wt.%
play a role leading to cracking reaction in specific 4-Methylbenzoic acid 4-Methylbenzoic acid
pattern. Higher yield of gas product in the catalytic case 3
can support more intensive of the cracking reaction. 3.40 wt.% 3.91 wt.%
The main product of benzoic acid (ca. 63 wt.%) Allylquinol 1,1'-Biphenyl-4-carboxylic
is useful as industrial chemical. It can be used as acid
preservatives in food industry, constituent of Whitfield’s 4
ointment for treatment of fungal skin diseases. Moreover,
benzoic acid and some of its derivatives are also important 3.05 wt.% 3.62 wt.%
precursor for the synthesis of many organic substances N,N'-Dibenzoylhydrazine 4-Ethylbenzoic acid
[16], [17].
5
Table 4: Components extracted from liquid/wax product 2.63 wt.% 3.45 wt.%
from the pyrolysis tests 2-Propanoylbenzoic acid Biphenyl
Non-catalytic Catalytic
Components 6
(wt.%) (wt.%)
1. Mono-benzene Ring
2.44 wt.% 3.01 wt.%
Benzaldehyde 0 0.29
4-Carboxybenzoic acid
Phenol 0.39 0.38 ethyl ester
m-Terphenyl
Methyl Phenyl Ketone 0.44 0.84
Benzeneacetic Acid 0.56 1.40 7
Benzoic Acid 62.94 63.58
Benzoic Acid Derivatives 8.35 16.40 1.45 wt.%
Allylquinol 3.05 0 2.36 wt.%
Total 75.73 82.89 Tetrachloro-ethane 4-Vinylbenzoic acid
2. Di-benzene Ring
8
Biphenyl 4.54 3.01
Biphenyl Derivatives 7.76 6.66 1.45 wt.% 2.11 wt.%
Naphthalene Derivatives 0 0.41 1,1'-Biphenyl-4-carboxylic Benzeneacetic acid
Total 12.30 10.08 acid
3. Tri-benzene Ring 9
Terphenyl 2.18 0.77 1.40 wt.%
1.41 wt.%
Phenanthrene 0.46 0.14
9-Fluorenone 1-Ethenyl-3-nitrobenzene
Total 2.64 0.91
4. Long Chain 10
Hexadicanoic Acid 1.20 0.31
5. Others 8.13 5.81 1.25 wt.% 1.24 wt.%
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P. Kongsupapkul et al., “Effects of MgO-ZSM-23 Zeolite Catalyst on the Pyrolysis of PET Bottle Waste.”
Non-catalytic
1
2
5
8 6 7
3 4 10 9
Abundance
Catalytic
9 2 4
3 58 7
10
4 6 8 10 12 14 16 18 20 22 24 26 28
Retention time (min)
Figure 6: GC-MS chromatograms of the components extracted from liquid/wax product from the pyrolysis tests.
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