Synergistic Effects and Mechanistic Insights into the Co-Hydropyrolysis of Chilean Oak and Polyethylene: Unlocking the Potential of Biomass-Plastic Valorisation.

This study employed a hydrogen atmosphere in an analytical reactor to investigate the thermochemical transformation of Chilean Oak (ChO) and polyethylene. Thermogravimetric assays and compositional analyses of the evolved gaseous chemicals provided valuable insights regarding the synergistic effects during the co-hydropyrolysis of biomass and plastics. A systematic experimental design approach assessed the contributions of different variables, revealing the significant influence of the biomass/plastic ratio and hydrogen pressure. Analysis of the gas phase composition showed that co-hydropyrolysis with LDPE resulted in lower levels of alcohols, ketones, phenols, and oxygenated compounds. ChO exhibited an average oxygenated compound content of 70.13%, while LDPE and HDPE had 5.9% and 1.4%, respectively. Experimental assays under specific conditions reduced ketones and phenols to 2-3%. Including a hydrogen atmosphere during co-hydropyrolysis contributes to enhanced reaction kinetics and reduced formation of oxygenated compounds, indicating its beneficial role in improving reactions and diminishing the production of undesired by-products. Synergistic effects were observed, with reductions of up to 350% for HDPE and 200% for LDPE compared to the expected values, achieving higher synergistic coefficients with HDPE. The proposed reaction mechanism provides a comprehensive understanding of the simultaneous decomposition of biomass and polyethylene polymer chains, forming valuable bio-oil products and demonstrating the how the hydrogen atmosphere modulates and influences the reaction pathways and product distribution. For this reason, the co-hydropyrolysis of biomass-plastic blends is a technique with great potential to achieve lower levels of oxygenated compounds, which should be further explored in subsequent studies to address scalability and efficiency at pilot and industrial levels.

Dataset from analytical pyrolysis assays for converting waste tires into valuable chemicals in the presence of noble-metal catalysts.

About 25.7 million tons of waste tires (WT) are discarded each year worldwide causing important environmental, and health problems. This waste is difficult to manage and dispose due to its huge rate of generation and its extremely slow biodegradation. Therefore, many efforts are being made to valorise WTs into a series of marketable products under a circular economy framework. In the attempt to convert WT into higher-value products, thermochemical decomposition by pyrolysis has emerged as a promising process [1]. The pyrolysis is a thermochemical transformation (under an oxygen-depleted atmosphere) of the tire´s polymeric constituents: natural rubber (NR), styrene-butadiene rubber (SBR), and butadiene rubber (BR) into three major fractions. These fractions are a gas (10-35%, TPG) which is usually used as a heat source (50 MJ kg-1), a solid consisting mainly of recovered carbon black (12-45%, rCB), and a liquid fraction (35-65%, TPO) containing a complex mixture of organic compounds. Among the high-value compounds that can be found in the TPO are D,L-limonene, isoprene, benzene, toluene, mixed-xylene, ethylbenzene, styrene, p-cymene, and some polycyclic aromatic hydrocarbons. This mixture is commonly used as a diesel substitute and owing to its complex composition it rarely is seen as a source for more valuable products. To overcome such a complexity, and selectively produce specific chemical identities, different types of catalysts have been used [2,3]. Herein, we provide a dataset from a systematic study about catalytic pyrolysis of WT for selectively producing benzene, toluene, and xylenes (BTX) and p-cymene on noble metals (Pd, Pt, Au) supported on titanate nanotubes (NT-Ti). The comprehensive analysis of this data was recently published, thus, the analytical techniques, experimental conditions and dataset are given in the present paper as a complement to that publication [1]. The reaction was evaluated in an analytical pyrolysis unit consisting in a micropyrolizer coupled to a mass spectrometer (Py-GC/MS) operating at temperatures between 400 and 450 °C in a fast pyrolysis regime (12 s). The effectivity of catalysts was measured in terms of selectivity to monoaromatics as BTX and p-cymene, under non-catalytic and for catalytic pyrolysis conditions. Moreover, the reaction was conducted on individual rubbers (Polyisoprene, Polybutadiene, and Styrene-Butadiene) and DL-limonene, to get deep insights into the transformation behaviour and reaction pathways. Therefore, the reader will find a data-in-brief paper containing some characterizations of the WTs used for the investigation, along with a complete dataset of Py-GC/MS results. Finally, the original files for the interpretation of the MS results are also provided, so that the reader can easily use this information to further expand the study to their own interest (industrial or scientific).

Waste tires pyrolysis kinetics and reaction mechanisms explained by TGA and Py-GC/MS under kinetically-controlled regime.

The fast pyrolysis of waste tires (WTs) is studied by quasi-isothermal thermogravimetric (TGA) analysis, kinetic modelling and an analytical pyrolyzer coupled with gas chromatography/mass spectrometry (Py-GC/MS). The TGA demonstrated that the WTs pyrolysis is ruled by devolatilization/condensation and depropagation reactions, up to 482 °C. At higher temperatures, the cyclization and aromatization of primary products take place to form mostly monoaromatics. Py-GC/MS experiments were performed under kinetic regime according to the thermal map established by the ratio between Biot́s (31.25) and Py-numbers (7.7⋅106). Limonene (51%) and isoprene (20.5%) were the major compounds detected at temperatures below 435 °C, while above 600 °C limonene was converted to mono-aromatics (SBTX = 28.7%). The approach to equilibrium of Diels-Alder reaction demonstrated that there is an equilibrium-ruled behavior between isoprene and limonene, particularly at T > 600 °C. The Ea values calculated by the Starinks model ranged from 101.5 to 176.7 kJ/mol, while for model-based kinetics it was 152.7 kJ/kmol. The integration of TGA, kinetic modelling and Py-GC/MS provided insights into pyrolysis reaction mechanism.