Browsing by Author "Eimontas, Justas"

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Co-pyrolysis of Baltic wheat straw and low-density polyethylene bags and its kinetic and thermodynamic behaviour
(Elsevier B.V., 2024-06) Yousef, Samy; Eimontas, Justas; Meile, Kristine; Stri ¯ ugas, Nerijus; Abdelnaby, Mohammed Ali
Wheat cultivation represents about 42 % of the total cereal cultivation area in the Baltic Sea region, generating huge amounts of wheat straw (WS) that needs to be optimally managed. In this context, this research aims to investigate the extent of using pyrolysis process in WS valorization. The experiments were performed using a thermogravimetric (TG) analyzer on WS and its mixtures with low-density polyethylene (LDPE) bags at different mixing ratios (1:1, 1:2, 1:3, 1:4). The released TG vapours were monitored using TG-Fourier transform infrared spectroscopy (TG-FTIR) and chromatography-mass spectrometry (GC-MS). The thermochemical activation energy (Ea) were studied by Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, Friedman, and Vyazovkin models. The pyrolysis results showed that WS and LDPE could be completely decomposed as a single reaction up to 600 °C and 520 °C, respectively. Aromatic-carbonyl and CO2 were the main FTIR functional group for WS vapour versus -CH2- for LEDP vapour. The GC/MS analysis of WS showed various compounds such as sec-Butylamine (11.88 %), acetic acid (10.68 %), etc., while LDPE showed many compounds without specific trend even when the heating rate was changed. While the co-pyrolysis results showed that WS/LDPE could be decomposed individually in two successive reactions at 335 °C (WS) and 495 °C (LDPE). These results were confirmed by FTIR and GC/MS which showed that the functional groups and chemical compounds of vapour generated at these decomposition zones have similar characteristics to those obtained from pyrolysis of WS and LDPE. Finally, kinetic analysis showed that WS-Baltic (227–250 kJ/mol) is more complex compared to WS-Asian (163–217 kJ/mol) due to its higher ash content. While Ea of WS/LDPE was increases upto 274–291 kJ/mol (1:1), 266–297 kJ/mol (2:1), 268–289 kJ/mol (3:1), and 278–299 kJ/mol (1:4). Also, the enthalpy, and Gibbs free energy coefficients of WS were increased by mixing (1:1) up to 272 J/mol K, while its entropy does not change much by mixing (367 J/mol K). Accordingly, the co-pyrolysis process is a key technology in valorization of WS and convert into value-added chemicals and a sustainable energy source.
Co-pyrolysis of waste wind turbine blades and biomass and their kinetic analysis using artificial neural network
(Elsevier B.V, 2024-04) Yousef, Samy; Eimontas, Justas; Stri ¯ ugas, Nerijus; Abdelnaby, Mohammed Ali
This research aims to study co-pyrolysis of waste wind turbine blades (WTB) and biomass using a thermogravimetric (TG) analyser at various heating rates (10, 20, and 30 °C/min). The experiments were performed on WTB consisting of a glass fibre/unsaturated polyester resin (UPR) and woody biomass (WBs) at different mixing ratios (1:1, 2:1, 3:1 w/w). The effect of a mixing ratio and a heating rate on composition of vapours released from the co-pyrolysis process was observed using TG-FTIR and GC-MS. Also, the co-pyrolysis kinetic and thermodynamic behaviour of the WTB/WBs mixtures was studied. Meanwhile, the experimental TG curves were mathematically simulated using the Distributed activation energy method and the Independent parallel reactions, while unknown curves were predicted using an artificial neural network (ANN) model. The differential thermogravimetric results showed high compatibility between WTB and WBs (1:1 and 2:1) with a single decomposition peak, which is indicates that both feedstocks were degraded as a single-step reaction. While the higher mixing rate (3:1) revealed double decomposition peaks, indicating that the mixture undergoes two sequential decomposition reactions and several competing reactions occur simultaneously, which increases the complexity of the decomposition process. Meanwhile, the GC-MS results showed that the mixture of WTB/WBs (1:1) could significantly reduce the styrene (the main toxic compound of UPR) from 62% (in neat WTB) to 7 % at 30 °C/min. Also, presence of other aromatic hydrocarbons (benzoic acid, 2-Methoxy-4-vinylphenol, etc.) was observed in the mixture samples as a result of styrene cracking. Finally, the kinetic model-free isoconversional results showed that Ea was estimated at 275–383 kJ/mol (WBs) and 196–286 kJ/mol (WTB/WBs). Accordingly, co-pyrolysis of WTB with WBs is highly recommended to valorise WTB and eliminate their toxic styrene compound
Effect of aluminum leaching pretreatment on catalytic pyrolysis of metallised food packaging plastics and its linear and nonlinear kinetic behaviour
(Elsevier, 2022-07-05) Yousef, Samy; Eimontas, Justas; Striūgas, Nerijus; Abdelnaby, Mohammed Ali
This research aims to study the effect of aluminum (Al) leaching pre-treatment on the catalytic pyrolysis of metallised food packaging plastics waste (MFPW). The experiments started with removal of Al from MFPW using leaching process to prepare Al-free mixed plastic waste (MPW). The catalytic pyrolysis of MPW over ZSM-5 zeolite catalyst was carried out using thermogravimetric (TG) analysis coupled with FTIR, while GC–MS was used to observe the compounds of the volatile products. The catalytic pyrolysis kinetic behaviour of MPW was studied using the linear and nonlinear isoconversional approaches. The elemental and proximate results showed that MPW is very rich in carbon elements (79 %) and volatile content (99 %). The TG results showed that MPW and ZSM/MPW were fully decomposed in the range of 376–496 °C without any presence of char. Based on TG-FTIR analysis, methane and carboxylic acid residue were the main groups of the synthesized volatile products, whereas nitrous oxide, 1-Butanol, 1-Propene, acetic acid, and formic acid were the major GC compounds. In case of ZSM/MPW, carbon dioxide and acetic acid were the major GC compounds at 5–25 °C/min, triphenylphosphine oxide and Phosphine oxide at 30 °C/min. The kinetic analysis showed that when the activation energies are located in the range 287–297 kJ/mol (MPW) and 153–187 kJ/mol (ZSM/MPW) and KAS, Vyazovkin, and Cai methods are the most suitable models to study pyrolysis kinetic of MPW with R2 > 89. Based on that, leaching and catalytic pyrolysis processes are a highly suggested technol- ogy that can be used to convert MFPW into high-added energy and chemical products.
Phenol and benzoic acid recovery from end-of-life of polysulfone ultrafiltration membranes and its thermochemical kinetic behaviour
(Taylor and Francis Ltd., 2023-05) Yousef, Samy; Eimontas, Justas; Striūgas, Nerijus; Mohamed, Alaa; Praspaliauskas, Marius; Abdelnaby, Mohammed Ali
The remarkable properties of polysulfone (PSF) membranes have contributed to their use in many ultrafiltration applications. Meanwhile, this huge usage of PSF films and its short service life have generated a huge amount of waste PSF films that need to be managed carefully. Within this framework, this is the first research specifically developed to valorize the end-of-life of PSF membranes and convert them into high-value chemical and energy products using pyrolysis treatment. The treatment was performed using a thermogravimetric analyzer (TGA), while the structure and abundance of the phenol and benzoic acid compounds in the generated vapor were determined using Fourier-transform infrared (FTIR) spectroscopy and Gas chromatography-mass spectrometry (GC- MS). Thermogravimetric recorded data at different conditions (5–30°C/min) was subjected to linear and nonlinear models including KAS, FWO, Friedman, Vyazovkin, and Cai to assess the pyrolytic kinetic behavior of PSF films. The films showed higher content of volatile matter (57%), lower NOx emissions (0.321%), and a little bit more SOX emission (6.909%). The GC-MS showed that the pyrolytic gaseous products are rich in phenol (24.3%) and benzoic acid (52.4%) compounds and the highest abundance was achieved at 30°C/min. Whereas activation energies were estimated in the range of 193–240 kJ/mol based on linear kinetic criteria versus 161–163 kJ/mol in the case of nonlinear models, where R2 values (>0.91) indicated perfection. Also, distributed activation energy and independent parallel reaction kinetic models showed a good fit with the TGA-DTG experimental data with the minimum deviation. The study con- firmed the potential of pyrolysis treatment in converting wasted PSF films into a new source for the recovery of phenolic and benzoic acid. ARTICLE HISTORY Received 20 March 2023 Revised 27 April 2023 Accepted 2 May 2023
Pyrolysis behaviour of ultrafiltration polymer composite membranes (PSF/ PET): Kinetic, thermodynamic, prediction modelling using artificial neural network and volatile product analysis
(Elsevier B.V, 2024-04) Yousef, Samy; Eimontas, Justas; Striugas, Nerijus; Mohamed, Alaa; Abdelnaby, Mohammed Ali
This study aims to explore the feasibility of managing ultrafiltration polymer composite membranes (UPCM) waste and converting it into valuable chemicals and energy products using a pyrolysis process. The thermal decomposition experiments were performed on polysulfone (PSF)/polyethylene terephthalate (PET) membranes using thermogravimetric analysis (TG). The vapors generated during the thermochemical process were analyzed under different heating rate conditions using TG-FTIR and GC/MS. In addition, the kinetic and thermodynamic parameters of the pyrolysis process were determined using conventional modeling methods and artificial neural network (ANN) method. The results demonstrated that the PSF/PET feedstock exhibits ahigh volatile matter content (77 % wt.%), which can be completely decomposed up to 600 °C by 79 wt%. While TG-FTIR analysis showed that the released vapors contained aromatic groups and benzoic acid (89.21 wt% at 15˚C/min) as the main GC/MS compound. Moreover, the kinetic analysis demonstrated complete decomposition of the membranes at a lower activation energy (151 kJ/mol). Meanwhile, the ANN model exhibited high performance in predicting the degradation stages of PSF/PET membranes under unknown heating conditions. This approach shows potential for modeling the thermal decomposition of ultrafiltration composite membranes more broadly.
Pyrolysis Kinetic Behavior and Thermodynamic Analysis of PET Nonwoven Fabric
(MDPI AG, 2023-09) Yousef, Samy; Eimontas, Justas; Striugas, Nerijus; Mohamed, Alaa; Abdelnaby, Mohammed Ali
This research aims to maximize polyethylene terephthalate (PET) nonwoven fabric waste and make it as a new source for benzoic acid extraction using a pyrolysis process. The treatment was performed using a thermogravimetric analyzer (TGA) and released products were characterized using FTIR spectroscopy and gas chromatography–mass spectrometry (GC–MS). The pyrolysis kinetic and thermodynamic behavior of PET fabric was also studied and simulated using different linear and nonlinear models. The results show that the PET fabric is very rich in volatile matter (80 wt.%) and can completely degrade under 490 ◦C with a weight loss of 84%. Meanwhile, the generated vapor was rich in the carbonylic C=O functional group (FTIR), and the GC–MS analysis concluded that benzoic acid was the major compound with an abundance of 75% that was achieved at the lowest heating rate (5 ◦C/min). The linear kinetic results showed that PET samples had an activation energy in the ranges of 193–256 kJ/mol (linear models) and ~161 kJ/mol (nonlinear models). The thermodynamic parameters, including enthalpy, Gibbs free energy, and entropy, were estimated in the ranges of 149–250 kJ/mol, 153–232 kJ/mol, and 256–356 J/mol K, respectively. Accordingly, pyrolysis treatment can be used to extract benzoic acid from PET fabric waste with a 134% increase in the benzoic acid abundance that can be recovered from PET bottle plastic waste.
Recovery of phenol and acetic acid from glass fibre reinforced thermoplastic resin using catalytic pyrolysis process on ZSM-5 zeolite catalyst and its kinetic behaviour
(Elsevier, 2022-07-16) Yousef, Samy; Kiminaitė, Ieva; Eimontas, Justas; Striūgas, Nerijus; Abdelnaby, Mohammed Ali
Glass fibre-reinforced thermoplastic (GFRP) is the composite material of choice for engineers to improve their design, save expenses, and achieve sustainability goals, what leads to generation of a big quantity of GFRP waste (during production or as an end-life-product) that needs to be disposed of safely. In order to valorise GFRP waste, this research aims to recover phenol and acetic acid as high-added value chemical and energy products from the millions of tons of GFRP waste produced annually during the catalytic pyrolysis process. The experiments were performed on glass fibre-reinforced poly(methyl methacrylate)-PMMA (GF/PM) as a common and commercial thermoplastic resin in five stages. In the first stage, the thermal decomposition of the milled feedstock over different percentages of ZSM-5 zeolite catalyst to feedstock in the ranges 0.5-5 wt.% (w/w) was performed using TGA. The generated volatile products from TGA were analysed using TG-FTIR and GC/MS in the second and third stages, respectively. The fourth stage was used to study the kinetic behaviour of catalytic pyrolysis of the feedstock with different catalysts and at different heating conditions using isoconversional models. In the last stage, the experimental thermal decomposition curves were simulated numerically. The results showed that ZSM/GF/PM can decompose significantly in the ranges 320-460 ˚C. Meanwhile, 2 wt.% of catalyst-to-GF/PM ratio was sufficient to recover more than 48% of phenol, 23% of acetic acid, 19% carbon dioxide compounds at 30˚C/min with high intensity of aromatic benzene. Also, this batch gave a higher kinetic complexity in terms of activation energy in the ranges 100-200 kJ/mol (linear models) and 230-440 kJ/mol (nonlinear models). These results confirm that involvement of 2 wt.% ZSM-5 zeolite catalyst in the pyrolysis of GF/PM has a big impact on the formulated volatile components and their potential upscaling.
Synthesis of benzoic acid from catalytic co-pyrolysis of waste wind turbine blades and biomass and their kinetic analysis
(Elsevier B.V., 2024-08) Yousef, Samy; Eimontas, Justas; Striugas, Nerijus; Abdelnaby, Mohammed Ali
This work aims to study the catalytic co-pyrolysis of waste wind turbine blades (WTB: consists of fiberglass/unsaturated polyester resin) and woody biomass (WB) over ZSM-5 and Y-type zeolite catalysts for the production of benzoic acid. The experiments were performed on an equal combination of WTB and WB (WTB/WB) and a fixed amount of catalyst (50 wt%) using a thermogravimetric (TG) analyser at 10, 20 and 30 °C/min. The evolved products from the catalytic co-pyrolysis process were recognized using TG-FTIR and GC/MS. The kinetic and thermodynamic characteristics of catalytic co-pyrolysis was studied using various linear and nonlinear approaches. Also, the decomposition curves were predicted mathematically using an artificial neural network algorithm. The results revealed that the mixture was decomposed in the presence of both catalysts in the form of dual decomposition peaks at 361–374 °C and 428–443 °C, respectively. Based on TG-FTIR results, the C[dbnd]O stretching and carbon dioxide clusters were their main functional groups. While the GC-MS analysis revealed that the released vapours were completely free of toxic styrene (the main compound of resin) and the catalytic co-pyrolysis treatment succeeded in converting it into highly abundant benzoic acid, especially at 10 °C/ min, with an estimated 71.4 % (ZSM-5) and 64 % (Y-type). Whereas the activation energy was estimated at 262–295 kJ/mol (ZSM-5) and 319–357 kJ/mol (Y-type) with almost similar reaction complexity when compared to the case of absence of catalysts. Finally, the developed ANN algorithm showed high efficiency in predicting TG decomposition zones for both WTB/WB mixtures over zeolite catalysts with R2 more than 0.99. These results demonstrate that WB and zeolite catalysts can be used for upgrading the pyrolysis oil of WTB and eliminate its toxic styrene and convert it into benzoic acid and other aromatic hydrocarbons compounds (such as benzene, alanine, and 2-Propanamine).
Synthesis of value-added aromatic chemicals from catalytic pyrolysis of waste wind turbine blades and their kinetic analysis using artificial neural network
(Elsevier, 2024-01) Yousef, Samy; Eimontas, Justas; Striugas, Nerijus; Abdelnaby, Mohammed Ali
This research aims to convert the resin fraction of waste wind turbine blades (WTB) into value-added aromatic chemicals using catalytic pyrolysis. The catalytic study on WTB made of glass fibre/unsaturated polyester resin (UPR) was performed on two different types of zeolite catalysts (ZSM-5 and Y-type) using a thermogravimetric (TG) analyser. The effect of catalyst and heating rate on the abundance and composition of the synthesised aromatic chemicals was observed using TG-FTIR and GC/MS. The kinetics and thermodynamic behaviour of catalytic pyrolysis of WTB was also studied using traditional modelling techniques (KAS, FWO, Friedman, Vyazovkin, and Cai) and an artificial neural network (ANN). TG-FTIR results showed that the gases released from the catalytic process were very rich in aromatic groups, while GC/MS analysis revealed that benzene, toluene, and ethylbenzene (BTE) were the main constituents of the synthesised aromatic chemicals with abundance estimated at 36% (ZSM-5 at 10◦C/min) and 64% (Y-type at 15◦C/min) accompanied by a significant reduction in styrene formation up to 16.2% (main toxic element in the UPR). Besides, it contributed to reduction of the activation energy of the reaction up to 126 KJ/mol (ZSM-5) and 100 KJ/mol (Y-type). The trained ANN model also showed high performance in predicting the thermal decomposition zones of WTB at unknown heating rates with R2 close to 1. Accordingly, the use of catalytic pyrolysis of WTB over a Y-type zeolite catalyst is highly recommended for decomposition of UPR to aromatic chemicals BTE and reduction of styrene in the produced fuel.