Prediction of Thermogravimetric Data in the Thermal Recycling of e-waste Using Machine Learning Techniques: A Data-driven Approach.

The release of bromine-free hydrocarbons and gases is a major challenge faced in the thermal recycling of e-waste due to the corrosive effects of produced HBr. Metal oxides such as Fe2O3 (hematite) are excellent debrominating agents, and they are copyrolyzed along with tetrabromophenol (TBP), a lesser used brominated flame retardant that is a constituent of printed circuit boards in electronic equipment. The pyrolytic (N2) and oxidative (O2) decomposition of TBP with Fe2O3 has been previously investigated with thermogravimetric analysis (TGA) at four different heating rates of 5, 10, 15, and 20 °C/min, and the mass loss data between room temperature and 800 °C were reported. The objective of our paper is to study the effectiveness of machine learning (ML) techniques to reproduce these TGA data so that the use of the instrument can be eliminated to enhance the potential of online monitoring of copyrolysis in e-waste treatment. This will reduce experimental and human errors as well as improve process time significantly. TGA data are both nonlinear and multidimensional, and hence, nonlinear regression techniques such as random forest (RF) and gradient boosting regression (GBR) showed the highest prediction accuracies of 0.999 and lowest prediction errors among all the ML models employed in this work. The large data sets allowed us to explore three different scenarios of model training and validation, where the number of training samples were varied from 10,000 to 40,000 for both TBP and TBP + hematite samples under N2 (pyrolysis) and O2 (combustion) environments. The novelty of our study is that ML techniques have not been employed for the copyrolysis of these compounds, while the significance is the excellent potential of enhanced online monitoring of e-waste treatment and extension to other characterization techniques such as spectroscopy and chromatography. Lastly, e-waste recycling could greatly benefit from ML applications since it has the potential to reduce total and operational costs and improve overall process time and efficiency, thereby encouraging more treatment plants to adopt these techniques, resulting in reducing the increasing environmental footprint of e-waste.

Combating toxic emissions from thermal recycling of polymeric fractions laden with novel brominated flame retardants (NBFRs) in e-waste: an in-situ approach using Ca(OH)2.

Legacy brominated flame retardants (BFRs) in printed circuit boards are gradually being replaced by novel BFRs (NBFRs). Safe disposal and recycling of polymeric constituents in the polymeric fractions of e-waste necessitate the removal of their toxic and corrosive bromine content. This is currently acquired through thermal recycling operations involving the pyrolysis of BFRs-containing materials with metal oxides. Nonetheless, the debromination capacity toward NBFRs is yet to be established. Thus, this study aims to address these two crucial gaps in the current knowledge pertaining to the plausible formation of brominated toxicants from the thermal decomposition of NBFRs and their thermal recycling potential. Herein, we investigate the pyrolysis of a mixture of 2,4,6-tribromophenol (TBP), allyl 2,4,6-tribromophenyl ether (ATE) and Tetrabromobisphenol A-bis (2,3-dibromo propyl ether) (TBBPA-DBPE) in the presence of acrylonitrile butadiene styrene (ABS) polymers at various loads. To demonstrate a viable debromination route, pyrolysis of NBFRs-ABS mixture with Ca(OH)2 was also investigated. The latter is a potent debromination agent for legacy BFRs. Upon pyrolysis with Ca(OH)2, the bromine content in the collected oil was reduced up to 80.49% between 25-500 °C. Products of the co-pyrolysis process generally feature non-brominated aromatic and aliphatic compounds; a finding that indicates an effective thermal recycling approach. As evident by IC measurements, no HBr emission could be detected when Ca(OH)2 is added to the mixture. As XRD patterns show, Ca(OH)2 is partially converted into CaBr2. DFT calculations provide pathways for the observed surface debromination characterized by surface-assisted fission of aromatic C-Br bonds and the formation of CaBr sites. Outcomes reported herein are instrumental to designing and operating a thermal recycling facility of polymeric materials contaminated with high loads of bromine, i.e., most notably during scenarios encountered in the thermal recycling of e-waste.

Prediction of Thermogravimetric Data in Bromine Captured from Brominated Flame Retardants (BFRs) in e-Waste Treatment Using Machine Learning Approaches.

The principal objective in the treatment of e-waste is to capture the bromine released from the brominated flame retardants (BFRs) added to the polymeric constituents of printed circuits boards (PCBs) and to produce pure bromine-free hydrocarbons. Metal oxides such as calcium hydroxide (Ca(OH)2) have been shown to exhibit high debromination capacity when added to BFRs in e-waste and capturing the released HBr. Tetrabromobisphenol A (TBBA) is the most commonly utilized model compound as a representative for BFRs. Our coauthors had previously studied the pyrolytic and oxidative decomposition of the TBBA:Ca(OH)2 mixture at four different heating rates, 5, 10, 15, and 20 °C/min, using a thermogravimetric (TGA) analyzer and reported the mass loss data between room temperature and 800 °C. However, in the current work, we applied different machine learning (ML) and chemometric techniques involving regression models to predict the TGA data at different heating rates. The motivation of this work was to reproduce the TGA data with high accuracy in order to eliminate the physical need of the instrument itself, so that this could save significant experimental time involving sample preparation and subsequently minimizing human errors. The novelty of our work lies in the application of ML techniques to predict the TGA data from e-waste pyrolysis since this has not been conducted previously. The significance of our work lies in the fact that e-waste is ever increasing, and predicting the mass loss curves faster will enable better compositional analysis of the e-waste samples in the industry. Three ML models were employed in our work, namely Linear, random forest (RF), and support vector regression (SVR), out of which the RF method exhibited the highest coefficient of determination (R2) of 0.999 and least error of prediction as estimated by the root mean squared error (RMSEP) at all 4 heating rates for both pyrolysis and oxidation conditions. An 80:20 split was used for calibration and validation data sets. Furthermore, for showing versatility and robustness of the best-predicting RF model, it was also trained using all the data points in the lower heating rates of 5 and 10 °C/min and predicted on all the data points for the higher heating rates of 15 and 20 °C/min to again obtain a high R2 of 0.999. The excellent performance of the RF model showed that ML techniques can be used to eliminate the physical use of TGA equipment, thus saving experimental time and potential human errors, and can further be applied in other real-time e-waste recycling scenarios.

Degradation of tetrabromobisphenol A (TBBA) with calcium hydroxide: a thermo-kinetic analysis.

Thermal treatment of bromine-contaminated polymers (i.e., as in e-waste) with metal oxides is currently deployed as a mainstream strategy in recycling and resources recovery from these objects. The underlying aim is to capture the bromine content and to produce pure bromine-free hydrocarbons. Bromine originates from the added brominated flame retardants (BFRs) to the polymeric fractions in printed circuits boards, where tetrabromobisphenol A (TBBA) is the most utilized BFR. Among notable deployed metal oxides is calcium hydroxide, i.e., Ca(OH)2 that often displays high debromination capacity. Comprehending thermo-kinetic parameters that account for the BFRs:Ca(OH)2 interaction is instrumental to optimize the operation at an industrial scale. Herein, we report comprehensive kinetics and thermodynamics studies into the pyrolytic and oxidative decomposition of a TBBA:Ca(OH)2 mixture at four different heating rates, 5, 10, 15, and 20 °C min-1, carried out using a thermogravimetric analyser. Fourier Transform Infrared Spectroscopy (FTIR) and a carbon, hydrogen, nitrogen, and sulphur (CHNS) elemental analyser established the vibrations of the molecules and carbon content of the sample. From the thermogravimetric analyser (TGA) data, the kinetic and thermodynamic parameters were evaluated using iso-conversional methods (KAS, FWO, and Starink), which were further validated by the Coats-Redfern method. The computed activation energies for the pyrolytic decomposition of pure TBBA and its mixture with Ca(OH)2 reside in the narrow ranges of 111.7-112.1 kJ mol-1 and 62.8-63.4 kJ mol-1, respectively (considering the various models). Obtained negative ΔS values suggest the formation of stable products. The synergic effects of the blend exhibited positive values in the low-temperature ranges (200-300 °C) due to the emission of HBr from TBBA and the solid-liquid bromination process occurring between TBBA and Ca(OH)2. From a practical point of view, data provided herein are useful in efforts that aim to fine-tune operational conditions encountered in real recycling scenarios, i.e., in co-pyrolysis of e-waste with Ca(OH)2 in rotary kilns.

Co-pyrolysis of polyethylene with products from thermal decomposition of brominated flame retardants.

Co-pyrolysis of brominated flame retardants (BFRs) with polymeric materials prevails in scenarios pertinent to thermal recycling of bromine-laden objects; most notably the non-metallic fraction in e-waste. Hydro-dehalogenation of aromatic compounds in a hydrogen-donating medium constitutes a key step in refining pyrolysis oil of BFRs. Chemical reactions underpinning this process are poorly understood. Herein, we utilize accurate density functional theory (DFT) calculations to report thermo-kinetic parameters for the reaction of solid polyethylene, PE, (as a surrogate model for aliphatic polymers) with prime products sourced from thermal decomposition of BFRs, namely, HBr, bromophenols; benzene, and phenyl radical. Facile abstraction of an ethylenic H by Br atoms is expected to contribute to the formation of abundant HBr concentrations in practical systems. Likewise, a relatively low energy barrier for aromatic Br atom abstraction from a 2-bromophenol molecule by an alkyl radical site, concurs with the reported noticeable hydro-debromination capacity of PE. Pathways entailing a PE-induced bromination of a phenoxy radical should be hindered in view of high energy barrier for a Br transfer into the para position of the phenoxy radical. Adsorption of a phenoxy radical onto a Cu(Br) site substituted at the PE chain affords the commonly discussed PBDD/Fs precursor of a surface-bounded bromophenolate adduct. Such scenario arises due to the heterogeneous integration of metals into the bromine-rich carbon matrix in primitive recycling of e-waste and their open burning.

Formation of phenoxy-type Environmental Persistent Free Radicals (EPFRs) from dissociative adsorption of phenol on Cu/Fe and their partial oxides.

The interplay of phenolic molecules with 3d transition metals, such as Fe and Cu, and their oxide surfaces, provide important fingerprints for environmental burdens associated with thermal recycling of e-waste and subsequent generation of notorious dioxins compounds and phenoxy-type Environmental Persistent Free Radicals (EPFRs). DRIFTS and EPR measurements established a strong interaction of the phenol molecule with transition metal oxides via synthesis of phenolic- and catecholic-type EPFRs intermediates. In this contribution, we comparatively examined the dissociative adsorption of a phenol molecule, as the simplest model for phenolic-type compounds, on Cu and Fe surfaces and their partially oxidized configurations through accurate density functional theory (DFT) studies. The underlying aim is to elucidate the specific underpinning mechanism forming phenoxy- or phenolate-type EFPRs. Simulated results show that, the phenol molecule undergoes fission of its hydroxyl's O-H bond via accessible activation energies. These values are lower by 46.5-74.1% when compared with the analogous gas phase value. Physisorbed molecules of phenol incur very low binding energies in the range of -2.1 to -5.5 over clean Cu/Fe and their oxides surfaces. Molecular attributes based on charge transfer and geometrical features are in accord with the very weak interaction in physisorbed states. Thermo-kinetic parameters established over the temperature region of 300 and 1000 K, exhibit a lower activation energy for scission of phenolic's O-H bonds over the oxide surfaces in reference to their pure surfaces (24.7 and 43.0 kcal mol-1vs 38.4 and 47.0 kcal mol-1).

Recycling of zincite (ZnO) via uptake of hydrogen halides.

Hydrogen halides (HCl/HBr) represent major halogen fragments from the thermal decomposition of halogen laden materials, most notably PVC and brominated flame retardants (BFRs). Co-pyrolysis of halogen-containing solid waste with metal oxides is currently deployed as a mainstream strategy to treat halogen content as well as to recycle the valuable metallic fraction embedded in electric arc furnace dust (EAFD) and e-waste. However, designing an industrial-scale recycling facility necessitates accurate knowledge on mechanistic and thermo-kinetic parameters dictating the interaction between metal oxides and hydrogen halides. In this contribution, we investigate chemical interplay between HCl/HBr and zincite surfaces as a representative model for structures of zinc oxides in EAFD by using different sets of functionals, unit cell size and energy cut-off. In the first elementary step, dissociative adsorption of the HCl/HBr molecules affords oxyhalide structures (Cl/Br-Zn, H-O) via modest activation barriers. Conversion of the oxyhalide structure into zinc halides occurs through two subsequent steps, further dissociative adsorption of HCl/Br over the same surface Zn atom as well as the release of a H2O molecule. Evaporation (or desorption of zinc halide molecules) signifies a bottleneck for the overall halogenation of ZnO. Our simplified kinetic model on the HCl + ZnO system concurs very well with experimentally reported TGA weight loss profiles on two grounds: accumulation of oxyhalides until ∼700 K and desorption of ZnCl2 at higher temperatures. The thermo-kinetic and mechanistic aspects reported herein could be useful in the pursuit of a design of a large-scale catalytic upgrading unit that operates to extract valuable zinc loads from EAFD.

Thermal Recycling of Brominated Flame Retardants with Fe2O3.

Plastics containing brominated flame retardants (BFRs) constitute the major fraction of nonmetallic content in e-waste. Co-pyrolysis of BFRs with hematite (Fe2O3) represents a viable option for the thermal recycling of BFRs. Consensus of experimental findings confirms the excellent bromine fixation ability of Fe2O3 and the subsequent formation of iron bromides. This contribution provides a comprehensive mechanistic account of the primary reactions between a cluster model of Fe2O3 and major bromine-bearing products from the decomposition of tetrabromobisphenol A (TBBA), the most commonly deployed BFR. We estimate the thermo-kinetic parameters for interactions of Fe2O3 with HBr, brominated alkanes and alkenes, bromobenzene, and bromophenol. Dissociative addition of HBr at a Fe-O bond proceeds through a trivial barrier of 8.2 kcal/mol with fitted parameters in the Arrhenius equation of k(T) = 7.96 × 10(11) exp(-6400/RT) s(-1). The facile and irreversible nature for HBr addition to Fe2O3 accords with the experimentally reported 90% reduction in HBr emission when Fe2O3 interacts with TBBA pyrolysates. A detailed kinetic analysis indicates that, transformation of Fe2O3 into iron bromides and oxybromides occurs via successive addition of HBr to Fe(Br)-O(H) entities. Elimination of a water molecule proceeds through an intramolecular H transfer. A direct elimination one-step mechanism operates in the dehydrohalogenation of bromoethane into ethene over Fe2O3. Dissociative decomposition and direct elimination channels assume comparable reaction rates in formation of acetylene from vinyl bromide. Results from this study provide an atomic-based insight into a promising thermal recycling route of e-waste.