Chemical Recycling of Mixed Polyolefin Post-Consumer Plastic Waste Sorting Residues (MPO323)-Auto-Catalytic Reforming and Decontamination with Pyrolysis Char as an Active Material.

Mixed plastic packaging waste sorting residue (MPO323) was treated by thermal pyrolysis to utilize pyrolysis oil and char. The pyrolysis oil was found to contain aromatic and aliphatic hydrocarbons. The chlorine and bromine contents were as high as 40,000 mg/kg and 200 mg/kg, respectively. Additionally, other elements like sulfur, phosphorous, iron, aluminum, and lead were detected, which can be interpreted as impurities relating to the utilization of oils for chemical recycling. The pyrolysis char showed high contents of potentially active species like silicon, calcium, aluminum, iron, and others. To enhance the content of aromatic hydrocarbons and to reduce the level of contaminants, pyrolysis oil was reformed with the corresponding pyrolysis char to act as an active material in a fixed bed. The temperature of the reactor and the flow rate of the pyrolysis oil feed were varied to gain insights on the cracking and reforming reactions, as well as on performance with regard to decontamination.

Household mixed plastic waste derived adsorbents for CO2 capture: A feasibility study.

The feasibility of producing activated carbon (AC) from real Household Mixed Plastic Waste (HMPW) comprising of LDPE, HDPE, PP, PS, and PET for carbon capture via direct carbonisation followed by microwave-assisted or conventional thermally assisted chemical activation was investigated. A microwave-assisted activation procedure was adopted to assess the impact on the CO2 capture capacity of the resulting AC using both a lower temperature (400 °C vs. 700 °C) and a shorter duration (5 vs. 120 mins) than that required for conventional activation. The results obtained showed that the AC yield was 71 and 78% for the conventional and microwave-assisted samples, respectively. Microwave activation consumed five-fold less energy (0.19 kWh) than the conventional activation (0.98 kWh). Thermal stability results indicated total weight loss of 10.0 and 8.3 wt%, respectively, for conventional and microwave-activated samples over the temperature range of 25-1000 °C, with ACs from both activation routes displaying a type 1 nitrogen isotherm. The dynamic CO2 uptake capacity at 1 bar and 25 °C was 1.53 mmol/g, with maximum equilibrium uptake ranging between 1.32 and 2.39 mmol/g at temperatures (0-50 °C) and 1 bar for the conventionally activated AC. The analogous microwave-activated sample showed a higher dynamic CO2 uptake of 1.62 mmol/g and equilibrium uptake in the range 1.58-2.88 mmol/g under equivalent conditions. The results therefore indicate that microwave activation results in enhanced carbon capture potential. To the best of our knowledge, this is the first-time microwave heating has been employed to convert household mixed plastic wastes directly into ACs for carbon capture applications. This report therefore demonstrates that the management of mixed plastics could lead to the development of a circular economy through the conversion of waste into value-added materials.

Unlocking a Sustainable Future for Plastics: A Chemical-Enzymatic Pathway for Efficient Conversion of Mixed Waste to MHET and Energy-Saving PET Recycling.

The heterogeneous monomers obtained from plastic waste degradation are unfavorable for PET recondensation and high-value derivative synthesis. Herein, we developed an efficient chemical-enzymatic approach to convert mixed plastic wastes into homogeneous mono-2-hydroxyethyl terephthalate (MHET) without downstream purification, benefiting from three discovered BHETases (KbEst, KbHyd, and BrevEst) in nature. Towards the mixed plastic waste, integrating the chemical K2CO3-driven glycolysis process with the BHETase depolymerization technique resulted in an MHET yield of up to 98.26 % in 40 h. Remarkably, BrevEst accomplished the highest BHET hydrolysis (~87 % efficiency in 12 h) for yielding analytical-grade MHET compared to seven state-of-the-art PET hydrolases (18 %-40 %). In an investigation combining quantum theoretical computations and experimental validations, we established a MHET-initiated PET repolymerization pathway. This shortcut approach with MHET promises to strengthen the valorization of mixed plastics, offering a substantially more efficient and energy-saving route for PET recycling.

Exploring the potential of clay catalysts in catalytic pyrolysis of mixed plastic waste for fuel and energy recovery.

Developing low-cost and high-activity catalysts is one of the keys to promoting the catalytic pyrolysis of waste plastics to fuels for plastic recycling. This work studied the effect of clay as the catalyst on mixed plastic pyrolysis for fuel and energy recovery. Four kinds of clay, including nanoclay, montmorillonite, kaolin, and hydrotalcite, were used as catalysts for the pyrolysis of mixed plastic consisted of polyethylene terephthalate, polystyrene, polypropylene, low-density polyethylene, and high-density polyethylene. The product yield and distribution varied with different clay in pyrolysis. The highest yield of oil was 71.0 % when using montmorillonite as the catalyst. While the highest contents of gasoline range hydrocarbons and diesel range hydrocarbons in the oil were achieved when using kaolin and nanoclay, respectively as catalysts. For the gas products, the CO, C2H4, C2H6, C3H6, and C4H10 increased with decreased CO2 in the gaseous products when using clay as catalysts. In general, the mild acidity of clay catalyst was essential to improve the oil yields and the proportion of the gasoline or diesel range fuels in the catalytic pyrolysis of mixed plastic waste.

Comparative environmental and socioeconomic assessment on mixed plastic waste management: A Singapore case study.

Proper end-of-life (EOL) management of mixed plastic waste remains a global challenge in both developed and developing countries as disposed plastic circulating within the ecosystem continues to increase at unprecedented rates. Presently, plastic EOL pathways are largely designed based on prevailing geographical conditions and environmental regulations across different regions. Till date, no work has been reported on the environmental and socioeconomic assessment on EOL pathway focusing on mechanical recycling of mixed plastic waste into raw ingredients for construction materials. This paper presents a life cycle assessment to characterize the environmental and socioeconomic impacts of four different plastic EOL pathways using Singapore as a case study. The present study describes how Singapore can redesign its current waste-to-resource taxonomy and reiterates the need to maximize mechanical recycling throughput of mixed plastic waste so to alleviate the reliance on thermal energies for waste valorisation and improve the overall performance of current plastic EOL pathway.

Computational Exploration of Bio-Degradation Patterns of Various Plastic Types.

Plastic materials are recalcitrant in the open environment, surviving for longer without complete remediation. The current disposal methods of used plastic material are inefficient; consequently, plastic wastes are infiltrating the natural resources of the biosphere. The mixed composition of urban domestic waste with different plastic types makes them unfavorable for recycling; however, natural assimilation in situ is still an option to explore. In this research work, we have utilized previously published reports on the biodegradation of various plastics types and analyzed the pattern of microbial degradation. Our results demonstrate that the biodegradation of plastic material follows the chemical classification of plastic types based on their main molecular backbone. The clustering analysis of various plastic types based on their biodegradation reports has grouped them into two broad categories of C-C (non-hydrolyzable) and C-X (hydrolyzable). The C-C and C-X groups show a statistically significant difference in their biodegradation pattern at the genus level. The Bacilli class of bacteria is found to be reported more often in the C-C category, which is challenging to degrade compared to C-X. Genus enrichment analysis suggests that Pseudomonas and Bacillus from bacteria and Aspergillus and Penicillium from fungi are potential genera for the bioremediation of mixed plastic waste. The lack of uniformity in reporting the results of microbial degradation of plastic also needs to be addressed to enable productive growth in the field. Overall, the result points towards the feasibility of a microbial-based biodegradation solution for mixed plastic waste.

Pyrolysis of mixed plastic waste: Predicting the product yields.

The predictability of pyrolysis yields and product composition of mixed plastics has been studied. To do so, pyrolysis of virgin polymers (HDPE, LDPE, PP, PS and PET) and eight individual sorting categories from a real waste DKR-350 stream (PE rigid/film, PP rigid/film, PET, PS, multilayer flexibles, and clogged materials) was performed in a batch reactor at 500 °C at laboratory scale. The obtained oil/wax, gas, and solid yields and the composition of oil/wax of those individual feedstocks were used as input of a superposition model to predict the corresponding pyrolysis yields and oil/wax composition of mixed feeds, which were later compared with the experimentally measured product yields from the pyrolysis of those mixed streams. This linear model predicts the oil/wax yield of the mixed streams to a reasonable extent, with a maximum yield deviation (overestimation) of 8 percentage points. However, the presence of significant amounts of PET (above 33 wt%) in the mixed plastic streams negatively impacts the production of the condensable product and promotes the formation of solid products beyond the expected predicted values. Quantification of the type of carbon (aliphatic, aromatic and carbonyl) present in all the oil/wax products was done using 13C NMR spectroscopy. A linear model could also predict the aliphatic carbon yield in the condensable product from plastic waste streams with high accuracy (maximum yield difference of 6 percentage points). However, the aromatic carbon yield could not be predicted, probably due to the observed behavior of PET, which interacts with other polymers to promote solid product formation.

Effect of aluminum leaching pretreatment on catalytic pyrolysis of metallised food packaging plastics and its linear and nonlinear kinetic behaviour.

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 technology that can be used to convert MFPW into high-added energy and chemical products.

Holey and Wrinkled Flash Graphene from Mixed Plastic Waste.

High surface area varieties of graphene have captured significant attention, allowing for improved performance in a variety of applications. However, there are challenges facing the use of graphene in these applications since it is expensive and difficult to synthesize in bulk. Here, we leverage the capabilities of flash Joule heating to synthesize holey and wrinkled flash graphene (HWFG) in seconds from mixed plastic waste feedstocks, using in situ salt decomposition to produce and stabilize pore formation during the reaction. Surface areas as high as 874 m2 g-1 are obtained, with characteristics of micro-, meso-, and macroporosities. Raman spectroscopy confirms the wrinkled and turbostratic nature of the HWFG. We demonstrate HWFG applications in its use as a metal-free hydrogen evolution reaction electrocatalyst, with excellent stability, competitive overpotential, and Tafel slope; in a Li-metal battery anode allowing for stable and high discharge rates; and in a material with high gas adsorption. This represents an upcycle of mixed plastic waste, thereby affording a valuable route to address this pressing environmental pollutant concern.

Anchor peptides promote degradation of mixed plastics for recycling.

Resource stewardship and sustainable use of natural resources is mandatory for a circular plastic economy. The discovery of microbes and enzymes that can selectively degrade mixed-plastic waste enables to recycle plastics. Knowledge on how to achieve efficient and selective enzymatic plastic degradation is a key prerequisite for biocatalytic recycling of plastics. Wild-type natural polymer degrading enzymes such as cellulases pose often selective non-catalytic binding domains that facilitate a targeting and efficient degradation of polymeric substrates. Recently identified polyester hydrolases with synthetic polymer degrading activities, however, lack in general such selective domains. Inspired by nature, we herein report a protocol for the identification and engineering of anchor peptides which serve as non-catalytic binding domains specifically toward synthetic plastics. The identified anchor peptides hold the promise to be fused to known plastic degrading enzymes and thereby enhance the efficiency of biocatalytic plastic recycling processes.