Thermal and catalytic pyrolysis of a synthetic mixture representative of packaging plastics residue

doi:10.1007/s11705-019-1875-3

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (2) : 288-303 https://doi.org/10.1007/s11705-019-1875-3

RESEARCH ARTICLE

Thermal and catalytic pyrolysis of a synthetic mixture representative of packaging plastics residue

Simona Colantonio¹, Lorenzo Cafiero¹, Doina De Angelis¹, Nicolò M. Ippolito², Riccardo Tuffi¹(

), Stefano Vecchio Ciprioti³

¹. Department for Sustainability, ENEA—Casaccia Research Center, Rome 00123, Italy
². Department of Chemical, Materials and Environmental Engineering, Sapienza University of Rome, Rome 00184, Italy
³. Department of SBAI, Sapienza University of Rome, Rome 00161, Italy

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Abstract

A synthetic mixture of real waste packaging plastics representative of the residue from a material recovery facility (plasmix) was submitted to thermal and catalytic pyrolysis. Preliminary thermogravimetry experiments coupled with Fourier transform infrared spectroscopy were performed to evaluate the effects of the catalysts on the polymers’ degradation temperatures and to determine the main compounds produced during pyrolysis. The thermal and catalytic experiments were conducted at 370°C, 450°C and 650°C using a bench scale reactor. The oil, gas, and char yields were analyzed and the compositions of the reaction products were compared. The primary aim of this study was to understand the effects of zeolitic hydrogen ultra stable zeolite Y (HUSY) and hydrogen zeolite socony mobil-5 (HZSM5) catalysts with high silica content on the pyrolysis process and the products’ quality. Thermogravimetry showed that HUSY significantly reduces the degradation temperature of all the polymers—particularly the polyolefines. HZSM5 had a significant effect on the degradation of polyethylene due to its smaller pore size. Mass balance showed that oil is always the main product of pyrolysis, regardless of the process conditions. However, all pyrolysis runs performed at 370°C were incomplete. The use of either zeolites resulted in a decrease in the heavy oil fraction and the prevention of wax formation. HUSY has the best performance in terms of the total monoaromatic yield (29 wt-% at 450°C), while HZSM5 promoted the production of gases (41 wt-% at 650°C). Plasmix is a potential input material for pyrolysis that is positively affected by the presence of the two tested zeolites. A more effective separation of polyethylene terephthalate during the selection process could lead to higher quality pyrolysis products.

Keywords packaging plastics waste plasmix pyrolysis zeolite catalyst degradation temperature

Corresponding Author(s): Riccardo Tuffi

Just Accepted Date: 22 October 2019 Online First Date: 09 December 2019 Issue Date: 24 March 2020

Cite this article:

Simona Colantonio,Lorenzo Cafiero,Doina De Angelis, et al. Thermal and catalytic pyrolysis of a synthetic mixture representative of packaging plastics residue[J]. Front. Chem. Sci. Eng., 2020, 14(2): 288-303.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1875-3
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I2/288

Tab.1 Elemental analysis, proximate analysis, and LHV of CPCPW2 [⁵,²⁵]

Tab.2 Zeolites characteristics (supplier data)

Fig.1 System and operating conditions of pyrolysis experiments: a. N₂ cylinder, b. upstream flowmeter, c. manometer, d. electric furnace, e. reactor containing the plastic sample or the plastic sample and the catalyst, f. flasks for collection of the condensed products (the second one works basically as a filter), g. cold trap, h. furnace section at constant temperature, i. freezing mixture trap, l. downstream flowmeter, m. gas sample bag.

Fig.2 Comparison of DTG curves of single polymers with CPCPW2 (with TG curves in the inner plot) at a heating rate of 10 °C?min^–1 in a N₂ atmosphere, both with and without catalyst. (a) PE film, (b) PP, (c) PS, (d) PET, (e) CPCPW2.

Tab.3 Identification of vapor the species evolved during the thermal degradation of CPCPW2 at the DTG peak temperature on the basis of the best match percentages between the FTIR spectra of the unknown vapor species and those selected from the database available from the FTIR instrument software

Fig.3 FTIR spectra of the vapor products evolved at (a) 447°C, 477°C (DTG peak) and 507°C for degradation of PE film without catalyst; (b) 265°C (first DTG peak), 350°C and 394°C (second DTG peak) for degradation of PE film with HUSY; (c) 395°C, 425°C (DTG peak) and 455°C for degradation of PE film with HZSM5.

Fig.4 FTIR spectra of the vapor products evolved at: (a) 381°C, 411°C (DTG peak), and 441°C for degradation of PS without a catalyst; (b) 228°C (first DTG peak), 316°C and 404°C (second DTG peak) for degradation of PS with HUSY; (c) 391°C, 421°C (DTG peak), and 451°C for degradation of PS with HZSM5.

Fig.5 FTIR spectra of the vapor products evolved at (a) 418°C (first DTG peak), 440°C and 461°C (second DTG peak) for degradation of CPCPW2 without catalyst; (b) 289°C (first DTG peak), 342°C and 395°C (second DTG peak) for degradation of CPCPW2 with HUSY; (c) 418°C (first DTG peak), 435°C and 452°C (second DTG peak) for degradation of CPCPW2 with HZSM5.

Tab.4 Product yields by thermal and catalytic pyrolysis of CPCPW2

Tab.5 Fractions of interest of the light oil/wax from thermal and catalytic pyrolysis at 450°C of CPCPW2 determined by GC-MS (relative area≥0.1% and similarity≥85%)

Fig.6 Yield percentages of benzene, toluene, ethylbenzene meta, para xylene, and styrene and of their sum with respect to the weight of CPCPW2 pyrolyzed under different conditions.

Tab.6 Gas composition and LHV of the gaseous mixtures produced during thermal and catalytic pyrolysis of CPCPW2 at 450°C and 650°C

Tab.7 Elemental analysis and LHV of char from thermal pyrolysis of CPCPW2 at 450°C and 650°C

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