Effects of Mgo-Zsm-23 Zeolite Catalyst On The Pyrolysis of Pet Bottle Waste

Download as pdf or txt
Download as pdf or txt
You are on page 1of 8

KMUTNB Int J Appl Sci Technol, Vol. 10, No. 3, pp.

205–211, 2017

Research Article
Selected Paper from the 6th International Thai Institute of Chemical Engineering and Applied Science Conference (ITIChE2016)

Effects of MgO-ZSM-23 Zeolite Catalyst on the Pyrolysis of PET Bottle Waste

Pattra Kongsupapkul and Kraipat Cheenkachorn


Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s University of Technology
North Bangkok, Bangkok, Thailand

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

* Corresponding author. E-mail: supak.t@eng.kmutnb.ac.th DOI: 10.14416/j.ijast.2017.08.004


Received: 9 February 2017; Accepted: 10 March 2017; Published online: 15 August 2017
© 2017 King Mongkut’s University of Technology North Bangkok. All Rights Reserved.

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”.

Keywords: ZSM-23 zeolite, Catalytic pyrolysis, PET, Renewable energy, Fuel

1 Introduction terephthalic acid and oxygen-containing compounds,


e.g., aldehyde and ester with suppressed carbonaceous
The continuous demand of plastics causes the plastic residue [5]. Pyrolysis of several PET with and without
wastes accumulation in the landfill. This consumes a fillers in fluidized bed reactor gave major solid yield of
lot of spaces and results in environmental problem. The aromatic hydrocarbons, 38–49 wt.% of gases yield, and
recovery of plastic wastes to fuel by pyrolysis process 5–40 wt.% of carbonaceous residue, which is strongly
has great potential since to avoid negative effects and depends on the pyrolysis temperature [6]. Both works
provide the new source of energy [1]. Certain types of used virgin PET plastic from the companies. In this
plastic, e.g., PP, PE, PS can be pyrolysed to different work, PET plastic from used drinking water bottles
product spectrum [2]–[4]. For pure poly(ethylene was applied in the pyrolysis tests. Moreover applying
terephthalate) or PET plastic which is abundant waste catalytic pyrolysis of PET plastic could be interesting
as water drinking bottles and not biodegradable, its and no work has been reported for this type of catalyst.
pyrolysis data is quite a few. The pyrolysis products Therefore this research will contribute the effects of
of gas and solid were reported in different operating MgO-ZSM-23 catalyst to the pyrolysis of pure PET
conditions. Pyrolysis in steam atmosphere yielded bottle waste. ZSM-23 zeolite was selected as catalyst

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.

205
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

dimensional 10-member-ring window enhances the TI

isomerization degree of long chain hydrocarbon. This


Condenser
could maximize the octane number and improve Separator
Pyrolyzer
cold flow property of the pyrolysis product. ZSM-23 PET waste
Liquid product
was first synthesized by Plank et al. [7]. This shape
Water tank Feed pump water
selective zeolite is active catalyst in hydroconversion
of n-dodecane [8], isodewaxing process for lowering Figure 1: Process flow diagram of the pyrolysis.
pour points of lubricants and diesel fuels [9], and
catalytic cracking of mixed C4 alkene [10]. The dispersive X-ray spectroscope (EDS, Oxford Instrument,
incorporation of MgO can modify the acidity of the X-MAX). The textural properties of the materials
catalyst by increasing of weak Lewis acid site. This were determined by adsorption and desorption of N2 at
can avoid the excessive cracking and reduce undesired –196°C (BELSORP-max). Prior to determination of an
coke of the reaction [11]. adsorption isotherm, samples were pretreated at 250°C
for 12 hr (BELSORP-flow). The specific surface area
2 Experimental was calculated using the BET method and micropore
volume was determined by the t-plot analysis.
2.1 Synthesis and preparation of MgO-ZSM-23
catalyst 2.3 Pyrolysis experiments

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.

206
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)

Figure 2: XRD patterns of as-synthesized ZSM-23 (a)


and calcined ZSM-23 (b).

3 Results and Discussions

3.1 Catalyst characterizations

The XRD patterns of as-synthesized and calcined


ZSM-23 zeolite are shown in Figure 2 (a) and (b). The
peak positions at 2 theta around 8.26, 19.80, 21.08,
22.98, 26.10 and 35.66° are resembled to those of
the reference of MTT framework [13]. This shows
the pure phase of ZSM-23 zeolite. The calcined form Figure 3: Scanning electron micrographs of ZSM-23
shows relatively higher intensity of the main peaks in zeolite with different magnifications at 1000x (a) and
range of 2 theta between 5–23°. After calcination at 5000x (b).
high temperature to remove the organic template in the
100
pore, the well preserved framework is still recognized.
The morphology of zeolite ZSM-23 is shown
Adsorbed Volume at STP (cm³/g)

in Figure 3 (a) and (b) with different magnifications. 80


Its crystal exhibits needle shape with approximately
6 μm long and 1.2 μm width. The needle crystals are
60
intertwined and clustered.
The N 2 adsorption/desorption isotherms of
calcined ZSM-23 are presented in Figure 4. The 40
isotherm shows characteristic of type II isotherm. This
isotherm is attributed to monolayer adsorption at low 20
relative pressure around 0.05 and multilayer adsorption
after this point [14]. The micropore filling effect
0
was observed at low relative pressure. This material
0 0.2 0.4 0.6 0.8 1
possesses BET specific surface area of 193 m2/g, total
p/p0
pore volume of 0.15 cm3/g, and micropore volume of
0.067 cm3/g. The elementary analysis shows calcined Figure 4: Nitrogen adsorption and desorption isotherms
ZSM-23 has Si/Al molar ratio of 50 which is similar of calcined ZSM-23. Closed and open symbols denote
to the Si/Al ratio of the synthesis gel. adsorption and desorption, respectively.

207
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.

3.2 Pyrolysis test Table 2: Gas product yields obtained in catalytic


pyrolysis test
The product yields from the pyrolysis of PET bottle Products (wt.%)
Time (min)
waste are shown in Figure 5. There are mainly three CO2 C1 C2 C3 C4 C5
types of products (1) liquid/wax (2) char, and (3) non- 0–15 11.6 73.2 0.84 0.71 1.77 11.8
condensable gases. Yellow liquid/wax occurred mostly 15–30 96.3 3.12 0.03 0.53 0.00 0.00
out of the reactor, along the condenser and outlet. Char
30–45 94.1 4.00 0.00 1.72 0.00 0.18
or carbonaceous residue occurred mostly inside the
45–60 98.0 1.66 0.01 0.30 0.00 0.00
reactor. The gas fraction is the main product in both non-
catalytic and catalytic pyrolysis. Applying MgO-ZSM-23
catalyst, it obviously increases gas yield (72.5 vs. 58.7 Table 3: Average gas product yields obtained in the
wt.%) and suppresses char product (8 vs. 17.6 wt.%). pyrolysis tests
Products (wt.%)
Condition
3.2.1 Pyrolysis gases CO2 C1 C2 C3 C4 C5
Non-catalytic 98.0 1.81 0.03 0.01 0.22 0.01
The gas product component obtained in non- Catalytic 75.0 20.5 0.22 0.82 0.44 3.00
catalytic pyrolysis by reaction time is presented in
Table 1. CO2 is the major product with yield ca. 97–98
wt.%. The second product is methane (C1) ca. 1.2–2.9 3.2.2 Pyrolysis liquid/wax
wt.%. Other hydrocarbon gases (C2–C5) were slightly
detected. Table 2 shows gas product in catalytic The components extracted from liquid/wax product
pyrolysis. Contrastly, after 15 min, C1 is the major using dichloromethane (CH2Cl2) in both non-catalytic
product with high yield of 73.2 wt.%. C5 is the and catalytic cases were summarized in groups as
secondary product of 11.8 wt.%. CO2 shows relative low shown in Table 4. They are complex product spectrum
amount of 11.6 wt.%. C2–C4 occurred at relatively higher of mainly aromatics with mono-, di-, and tri-benzene
at this time. This indicates C1 and other hydrocarbon rings. This could be influenced by its parent plastic
gases C2–C5 occurred predominantly at the early stage component which was derived from terephthalic
of the pyrolysis. CO2 product dominated at later stage acid and ethylene glycol [15]. The main product in
of the reaction. Table 3 summarizes the average values both cases is benzoic acid which is as high as ca.
of gas products in one hour. In both cases, CO2 and 63 wt.% in each of their product distributions. In
C1 are the main and secondary products, respectively. catalytic case, the second predominant product is
Applying MgO-ZSM-23 catalyst, the gas product gave benzoic acid derivatives, e.g., 2-propanoylbenzoic
more hydrocarbon gases of C1–C5 (25 vs. 2.1 wt.%) acid, 4-methylbenzoic acid, and 4-ethylbenzoic acid.

208
KMUTNB Int J Appl Sci Technol, Vol. 10, No. 3, pp. 205–211, 2017

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.%

209
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.

4 Conclusions of KMUTNB for master degree research fund. The


authors would like to convey special appreciation to
The pyrolysis of PET bottle waste was decomposed the academic committee of The 6th International Thai
into three types of products: liquid/wax, char, and gas Institute of Chemical Engineering and Applied Science
(major product). Comparing to non-catalytic pyrolysis, Conference (ITIChE2016) for providing the opportunity
the MgO-ZSM-23 zeolite catalyst affected product for this work to be published in this journal.
distribution giving higher yield of gas and lower yield
of char product. In gas product, it gave lower yield References
of CO2 but higher hydrocarbon fraction of aliphatic
C1–C5. These hydrocarbon products can be utilized [1] S. D. A. Sharuddin, F. Abnisa, W. M. A. W. Daud,
as fuel and/or chemical feed stock for petrochemical and M. K. Aroua, “A review on pyrolysis of plastic
industries. In liquid/wax product, highest yield of wastes,” Energy Conversion and Management,
benzoic acid was obtained in both cases at about vol. 115, pp. 308–326, Feb. 2016.
63 wt.%. MgO-ZSM-23 catalyst can tailor the product [2] I. Ahmad, M. I. Khan, H. Khan, M. Ishag, R.
distribution by increasing yield of benzoic acid and Tariq, K. Gul, and W. Ahmad, “Pyrolysis study
its derivatives but suppressing larger molecules of of polypropylene and polyethylene into premium
biphenyl, terphenyl, and their derivatives. High amount oil products,” International Journal of Green
of benzoic acid and its derivatives can be potentially Energy, vol. 12, no. 7, pp. 663–671, 2015.
utilized as important feedstocks in various chemical [3] S. H. Ng, H. Hesham, M. Stanciulescu, and
industries. Y. Sugimoto, “Conversion of polyethylene to
transportation fuels through pyrolysis and catalytic
Acknowledgments cracking,” Energy Fuels, vol. 9, pp. 735–742,
1995.
The authors gratefully acknowledge the financial [4] A. Karaduman, “Pyrolysis of polystyrene plastic
support from faculty of engineering, King Mongkut’s wastes with some organic compounds for
University of Technology North Bangkok (KMUTNB) enhancing styrene yield,” Energy Resources,
(contract no. 56-12-02-34) and the graduate school vol. 24, no. 7, pp. 667–674, 2002.

210
KMUTNB Int J Appl Sci Technol, Vol. 10, No. 3, pp. 205–211, 2017

[5] T. Masuda, Y. Miwa, A. Tamagawa, S. R. Mukai, Coronado, J. Cejka, and D. P. Serrano, “Lamellar
K. Hashimoto, and Y. Ikeda, “Degradation of and pillared ZSM-5 zeolites modified with MgO
waste poly(ethylene terephthalate) in a steam and ZnO for catalytic fast-pyrolysis of eucalyptus
atmosphere to recover terephthalic acid and woodchips,” Catalysis Today, vol. 277, part 1,
to minimize carbonaceous residue,” Polymer pp. 171–181, Nov. 2016.
Degradation and Stability, vol. 58, pp. 315–320, [12] R. Yeetsorn, S. Tungkamani, and S. Yoshikazu,
Jun. 1997. “Potential activity evaluation of CoMo/Al2O3-
[6] T. Yoshioka, G. Grause, C. Eger, W. Kaminsky, TiO 2 catalysts for hydrodesulfurization of
and A. Okuwaki, “Pyrolysis of poly(ethylene coprocessing bio-oil,” KMUTNB Int J Appl Sci
terephthalate) in a fluidized bed plant,” Polymer Technol, vol. 7, no. 4, pp. 35–45, Sep. 2014.
Degradation and Stability, vol. 86, pp. 499–504, [13] M. M. J. Treacy and J. B. Higgins, Collection of
Jun. 2004. Simulated XRD Powder Patterns for Zeolites,
[7] C. J. Plank, E. J. Rosinski, and M. K. Rubin, Amsterdam, Netherlands: Elsevier, 2007, pp. 298–
“Crystalline zeolite ZSM-23 and synthesis,” U.S. 299.
Patent 4 076 842, Feb 28, 1978. [14] M. Thommes, K. Kaneko, A. V. Neimark, J. P.
[8] S. Ernst, G. T. Kokotailo, R. Kumar, and J. Olivier, F. Rodriguez.-Reinoso, J. Rouquerol,
Weitkamp, “Shape selective catalysis in zeolites and K. S. W. Sing, “Physisorption of gases with
ZSM-22 and ZSM-23 influence of pore shapes special reference to the evaluation of surface area
on reaction selectivities,” in Proceedings 9th and pore size distribution,” Pure and Applied
International Congress on Catalysis, 1988, pp. 388– Chemistry, vol. 89, no. 9–10, pp. 1051–1069,
395. 2015.
[9] D. N. Gerasimov, V. V. Fadeev, A. N. Loginova, [15] F. Welle, “Twenty years of PET bottle to bottle
and S. V. Lysenko, “Catalysts based on zeolite recycling-an overview,” Resources Conservation
ZSM-23 for isodewaxing of a lubricant stock,” and Recycling, vol. 55, pp. 865–875, 2011.
Catalysis in Industry, vol. 5, pp. 123–132, Apr. [16] T. Maki and K. Takeda, “Benzoic acid and
2013. derivatives,” in Ullmann’s Encyclopedia of
[10] B. Wang, Q. Gao, J. Gao, D. Ji, X. Wang, and Industrial Chemistry, Weinheim: Wiley-VCH
J. Suo, “Synthesis, characterization and catalytic Verlag GmbH & Co. KGaA, 2000.
C4 alkene cracking properties of zeolite ZSM- [17] A. Renzetti, H. Nakazawa, and C.-J. Li, “Rhodium-
23,” Applied Catalysis, vol. 274, pp. 167–172, catalysed tandem dehydrogenative coupling-
2004. Michael addition: direct synthesis of phthalides
[11] J. Fermoso, H. Hernando, P. Jana, I. Moreno, from benzoic acids and alkenes,” RSC Advances,
J. Prech, C. Ochoa-Hernandez, P. Pizarro, J.M. vol. 6, pp. 40626–40630, 2016.

211

You might also like