Application of chemometric tools in the QSAR development of VOC removal in plastic waste recycling.

Deodorization and, in a broader sense, the removal of volatile organic compounds (VOCs) from plastic waste have become increasingly important in the field of plastic recycling, and various new decontamination techniques have been developed. Both in research and industrial practice, the selection of VOCs has been random or unsubstantiated, making it difficult to compare studies and assess decontamination processes objectively. Thus, this study proposes the use of Statistical Molecular Design (SMD) and Quantitative Structure - Activity Relationship (QSAR) as chemometric tools for the selection of representative VOCs, based on physicochemical properties. Various algorithms are used for SMD; hence, several frequently used D-Optimal Onion Design (DOOD) and Space-Filling (SF) algorithms were assessed. Hereby, it was validated that DOOD, by dividing the layers based on the equal-distance approach without so-called 'Adjacent Layer Bias', results in the most representative selection of VOCs. QSAR models that describe VOC removal by water-based washing of plastic waste as a function of molecular weight, polarizability, dipole moment and Hansen Solubility Parameters Distance were successfully established. An adjusted-R2 value of 0.77 ± 0.09 and a mean absolute error of 24.5 ± 4 % was obtained. Consequently, by measuring a representative selection of VOCs compiled using SMD, the removal of other unanalyzed VOCs was predicted on the basis of the QSAR. Another advantage of the proposed chemometric selection procedure is its flexibility. SMD allows to extend or modify the considered dataset according to the available analytical techniques, and to adjust the considered physicochemical properties according to the intended process.

Operational Framework to Quantify "Quality of Recycling" across Different Material Types.

Many pledges and laws are setting recycling targets without clearly defining quality of recycling. Striving to close this gap, this study presents an operational framework to quantify quality of recycling. The framework comprises three dimensions: the Virgin Displacement Potential (VDP); In-Use Stocks Lifetime (IUSL); and Environmental Impact (EI). The VDP indicates to what extent a secondary material can be used as a substitute for virgin material; the IUSL indicates how much of a certain material is still functional in society over a given time frame, and the EI is a measure of the environmental impact of a recycling process. The three dimensions are aggregated by plotting them in a distance-to-target graph. Two example calculations are included on poly(ethylene terephthalate) (PET) and glass. The results indicate that the recycling of bottle and container glass collected via a deposit-refund system has the lowest distance-to-target, at 1.05, and, thus, the highest quality of recycling. For PET bottles, the highest quality of recycling is achieved in closed-loop mechanical recycling of bottles (distance to optimal quality of 0.96). Furthermore, sensitivity analysis indicates that certain parameters, e.g., the collection rate for PET bottles, can reduce the distance-to-target to 0.75 when all bottles are collected for recycling.

Thermal pyrolysis of waste versus virgin polyolefin feedstocks: The role of pressure, temperature and waste composition.

Due to the complexity and diversity of polyolefinic plastic waste streams and the inherent non-selective nature of the pyrolysis chemistry, the chemical decomposition of plastic waste is still not fully understood. Accurate data of feedstock and products that also consider impurities is, in this context, quite scarce. Therefore this work focuses on the thermochemical recycling via pyrolysis of different virgin and contaminated waste-derived polyolefin feedstocks (i.e., low-density polyethylene (LDPE), polypropylene (PP) as main components), along with an investigation of the decomposition mechanisms based on the detailed composition of the pyrolysis oils. Crucial in this work is the detailed chemical analysis of the resulting pyrolysis oils by comprehensive two-dimensional gas chromatography (GC × GC) and ICP-OES, among others. Different feedstocks were pyrolyzed at a temperature range of 430-490 °C and at pressures between 0.1 and 2 bar in a continuous pilot-scale pyrolysis unit. At the lowest pressure, the pyrolysis oil yield of the studied polyolefins reached up to 95 wt%. The pyrolysis oil consists of primarily α-olefins (37-42 %) and n-paraffins (32-35 %) for LDPE pyrolysis, while isoolefins (mostly C9 and C15) and diolefins accounted for 84-91 % of the PP-based pyrolysis oils. The post-consumer waste feedstocks led to significantly less pyrolysis oil yields and more char formation compared to their virgin equivalents. It was found that plastic aging, polyvinyl chloride (PVC) (3 wt%), and metal contamination were the main causes of char formation during the pyrolysis of polyolefin waste (4.9 wt%).

Tracing the origin of VOCs in post-consumer plastic film bales.

Volatile organic compounds (VOCs), including odors, are still a key issue in plastic recycling, especially in case of flexible packaging. Therefore, this study presents a detailed qualitative and quantitative VOC analysis by applying gas chromatography on 17 categories of flexible plastic packaging that are manually sorted from bales of post-consumer flexible packaging (e.g., beverage shrink wrap, packaging for frozen food, packaging for dairy products, etc.). A total of 203 VOCs are identified on packaging used for food products, while only 142 VOCs are identified on packaging used for non-food products. Especially, more oxygenated compounds (e.g., fatty acids, esters, aldehydes) are identified on food packaging. With more than 65 VOCs, the highest number of VOCs is identified on packaging used for chilled convenience food and ready meals. The total concentration of 21 selected VOCs was also higher on packaging used for food products (totally 9187 µg/kg plastic) compared to packaging used for non-food packaging (totally 3741 µg/kg plastic). Hence, advanced sorting of household plastic packaging waste, e.g., via tracer-based sorting or watermarking, could open the door towards sorting on other properties than polymer type, such as mono- versus multi-material packaging, food versus non-food packaging or even their VOC profile, which might allow for tailoring washing procedures. Potential scenarios showed that sorting the categories with the lowest VOC load, which corresponds to half of the total mass of flexible packaging, could result in a VOC reduction of 56%. By producing less contaminated plastic film fractions and by tailoring washing processes recycled plastics can ultimately be used in a broader market segment.

Material flow analysis and recycling performance of an improved mechanical recycling process for post-consumer flexible plastics.

Increasing the recycling rates for post-consumer flexible plastics (PCFP) waste is imperative as PCFP is considered a difficult-to-recycle waste with only 17 % of PCFP effectively recycled in Europe. To tackle this pressing issue, improved mechanical recycling processes are being explored to increase the recycling rates of PCFP. One interesting option is the so-called quality recycling process (QRP) proposed by CEFLEX, which supplements more conventional mechanical recycling of PCFP with additional sorting, hot washing, improved extrusion, and deodorization. Material flow analysis (MFA) model is applied to assess the performance of QRP. Four performance indicators related to quantity (process yield and net recovery) and quality (polymer grade and transparency grade) are applied to measure the performance of three PCFP mechanical recycling scenarios. The results are compared against the conventional recycling of PCFP, showing that QRP has a similar process yield (64 % - 66 %) as conventional recycling (66 %). The net recovery indicator shows that in QRP higher recovery rates are achieved for transparent-monolayer PCFP (>90 %) compared to colored-multilayer PCFP (51 % - 91 %). The quality indicators (polymer and transparency grades) demonstrate that the regranulates from QRP have better quality compared to the conventional recycling. To validate the modeling approach, the modeled compositional data is compared with experimental compositional analyses of flakes and regranulates produced by pilot recycling lines. Main conclusions are: (i) although yields do not increase significantly, extra sorting and recycling produces better regranulates' quality (ii) performing a modular MFA gives insights into future recycling scenarios and helps in decision making.

Maximizing olefin production via steam cracking of distilled pyrolysis oils from difficult-to-recycle municipal plastic waste and marine litter.

Plastic waste is steadily polluting oceans and environments. Even if collected, most waste is still predominantly incinerated for energy recovery at the cost of CO2. Chemical recycling can contribute to the transition towards a circular economy with pyrolysis combined with steam cracking being the favored recycling option for the time being. However, today, the high variety and contamination of real waste remains the biggest challenge. This is especially relevant for waste fractions which are difficult or even impossible to recycle mechanically such as highly mixed municipal plastic waste or marine litter. In this work, we studied the detailed composition and the steam cracking performance of distilled pyrolysis oil fractions in the naphtha-range of two highly relevant waste fractions: mixed municipal plastic waste (MPW) considered unsuitable for mechanical recycling and marine litter (ML) collected from the sea bottom. Advanced analytical techniques including comprehensive two-dimensional gas chromatography (GC × GC) coupled with various detectors and inductively coupled plasma - mass spectrometry (ICP-MS) were applied to characterize the feedstocks and to understand how their properties affect the steam cracking performance. Both waste-derived naphtha fractions were rich in olefins and aromatics (~70% in MPW naphtha and ~51% in ML naphtha) next to traces of nitrogen, oxygen, chlorine and metals. ICP-MS analyses showed that sodium, potassium, silicon and iron were the most crucial metals that should be removed in further upgrading steps. Steam cracking of the waste-derived naphtha fractions resulted in lower light olefin yields compared to fossil naphtha used as benchmark, due to secondary reactions of aromatics and olefins. Coke formation of ML naphtha was slightly increased compared to fossil naphtha (+ ~50%), while that of MPW naphtha was more than ~180% higher. It was concluded that mild upgrading of the waste-derived naphtha fractions or dilution with fossil feedstocks is sufficient to provide feedstocks suitable for industrial steam cracking.

Critical advances and future opportunities in upcycling commodity polymers.

The vast majority of commodity plastics do not degrade and therefore they permanently pollute the environment. At present, less than 20% of post-consumer plastic waste in developed countries is recycled, predominately for energy recovery or repurposing as lower-value materials by mechanical recycling. Chemical recycling offers an opportunity to revert plastics back to monomers for repolymerization to virgin materials without altering the properties of the material or the economic value of the polymer. For plastic waste that is either cost prohibitive or infeasible to mechanically or chemically recycle, the nascent field of chemical upcycling promises to use chemical or engineering approaches to place plastic waste at the beginning of a new value chain. Here state-of-the-art methods are highlighted for upcycling plastic waste into value-added performance materials, fine chemicals and specialty polymers. By identifying common conceptual approaches, we critically discuss how the advantages and challenges of each approach contribute to the goal of realizing a sustainable plastics economy.

Assessing the feasibility of chemical recycling via steam cracking of untreated plastic waste pyrolysis oils: Feedstock impurities, product yields and coke formation.

Chemical recycling of plastic waste to base chemicals via pyrolysis and subsequent steam cracking of pyrolysis oils shows great potential to overcome the limitations in present means of plastic waste recycling. In this scenario, the largest concern is the feasibility. Are plastic waste pyrolysis products acceptable steam cracking feedstocks in terms of composition, product yields and coke formation? In this work, steam cracking of two post-consumer plastic waste pyrolysis oils blended with fossil naphtha was performed in a continuous bench-scale unit without prior treatment. Product yields and radiant coil coke formation were benchmarked to fossil naphtha as an industrial feedstock. Additionally, the plastic waste pyrolysis oils were thoroughly characterized. Analyses included two dimensional gas chromatography coupled to a flame ionization detector for the detailed hydrocarbon composition as well as specific analyses for heteroatoms, halogens and metals. It was found that both pyrolysis oils are rich in olefins (∼48 wt%) and that the main impurities are nitrogen, oxygen, chlorine, bromine, aluminum, calcium and sodium. Steam cracking of the plastic waste derived feedstocks led to ethylene yields of ∼23 wt% at a coil outlet temperature of 820 °C and ∼28 wt% at 850 °C, exceeding the ethylene yield of pure naphtha at both conditions (∼22 wt% and ∼27 wt%, respectively). High amounts of heavy products were formed when steam cracking both pyrolysis oils, respectively. Furthermore, a substantial coking tendency was observed for the more contaminated pyrolysis oil, indicating that next to unsaturated hydrocarbons, contaminants are a strong driver for coke formation.

Deodorization of post-consumer plastic waste fractions: A comparison of different washing media.

An important impediment to the acceptance of recyclates into a broader market is their unwanted odor after reprocessing. Different types of washing procedures are already in place, but fundamental insights into the deodorization efficiencies of different washing media are still relatively scarce. Therefore, in this study, the deodorization efficiencies of different types of plastics after washing with different media were determined via gas chromatography and mass spectrometry analysis. A total of 169 compounds subdivided into various chemical classes, such as alkanes, terpenes, and oxygenated compounds, were detected across all packaging types. Around 60 compounds were detected on plastic bottles, and around 40 were detected on trays and films. Owing to the differences in physicochemical properties of odor compounds, different deodorization efficiencies were obtained with different washing media. Water and caustic soda were significantly more efficient for poly(ethylene terephthalate) bottles with deodorization efficiencies up to 80%, whereas for polyethylene (PE) and polypropylene bottles, the washing media were relatively inefficient (around 30-40%). Adding a detergent or an organic solvent could increase deodorization efficiencies by up to 70-90% for these packaging types. A similar trend was observed for PE films having deodorization efficiencies in the range of 40-50% when washing with water or caustic soda and around 70-80% when a detergent was added. Polystyrene trays were most effectively deodorized with a detergent, achieving efficiencies up to 67%. Hence, this study shows that optimal washing processes should be tailored to specific packaging types to further improve deodorization and to eventually be able to meet ambitious European recycling targets.

Towards a Better Understanding of Delamination of Multilayer Flexible Packaging Films by Carboxylic Acids.

Recycling multilayer plastic packaging is challenging due to its intrinsic compositional heterogeneity. A promising route to increase recycling rates for these materials is delamination, which allows recycling the polymers separately. Yet, this process is not well understood on a fundamental level. This study aimed to obtain first principles-based insights of the delamination mechanism of multilayer flexible packaging film (MFPF) with carboxylic acids. Delamination of MFPFs was described through a model based on Fick's first law of diffusion and first-order dissolution kinetics of polyurethane adhesives. The model was experimentally tested on 5 different MFPFs at different temperatures (50-75 °C), formic acid concentrations (50-100 vol %), and solid/liquid (S/L) ratios (0.005, 0.025, and 0.12 g mL-1 ). Under the studied conditions the model proved to successfully estimate the delamination time of MFPF with the average Theil's Inequality Coefficient (TIC) value of 0.14. Essential for scaling-up delamination processes is the possibility to use high S/L ratios as the solubility of the adhesive is rarely limiting.

Development and application of a predictive modelling approach for household packaging waste flows in sorting facilities.

Household packaging waste sorting facilities consist of complex networks of processes to separate diverse waste streams. These facilities are a key first step to re-enter materials into the recycling chain. However, so far there are no general methods to predict the performance of such sorting facilities, i.e. how efficiently the heterogeneous packaging waste is sorted into fractions with value for further recycling. In this paper, a model of the material flow in a sorting facility is presented, which allows changing the incoming waste composition, split factors on the sorting units as well as the setup of the sorting facility. The performance of the sorting facility is judged based on the purity of the output material (grade) and the recovery of the input material. A validation of the model was performed via a case study on Belgian post-consumer packaging waste with a selection of typical waste items that can be found in this stream. Moreover, the model was used to predict the possible sorting qualities of future Belgian post-consumer packaging waste after an extension of the allowed waste packaging items in the waste stream. Finally, a sensitivity analysis was performed on the split factors, which are a key data source in the model. Overall, the developed model is flexible and able to predict the performance of packaging waste sorting facilities as well as support waste management and design for recycling decisions, including future design of packaging, to ensure proper sorting and separation.

Towards a better understanding of odor removal from post-consumer plastic film waste: A kinetic study on deodorization efficiencies with different washing media.

Mechanical recycling is to date the most commonly applied recycling technology. However, mechanical recycling of post-consumer plastics still faces many challenges, such as the presence of odorous constituents. Accordingly, recycling industry is looking for cost-effective solutions to improve the current washing efficiencies. However, scientific literature and basic understanding of deodorization processes are still scarce, which impedes efficient industrial optimization. Therefore, this study aims to obtain more fundamental insights in the deodorization mechanisms of plastic films in different washing media such as water, detergent, caustic soda, and ethyl acetate as organic solvent. The removal efficiencies of 19 odor components with a wide range of physicochemical properties were quantified via GC-MS analysis. The results revealed that deodorization depends on various factors such as temperature and physicochemical properties as polarity, volatility, and molecular weight of the odor components and the washing media. It was shown that polar washing media are less efficient compared to apolar media or media containing a detergent, achieving efficiencies of around 50% and 90%, respectively. The desorption processes can be accurately modeled by the isotherm model of Fritz-Schlunder in combination with a reversible first order kinetic model for the deodorization kinetics. Aspen Plus® process simulations of a water-based washing process reveal that at least 60% fresh water is needed to avoid saturation of the medium and undesired (re-)adsorption of odor components onto the plastics, which results in a substantial ecological footprint.

Detailed Analysis of the Composition of Selected Plastic Packaging Waste Products and Its Implications for Mechanical and Thermochemical Recycling.

Plastic packaging typically consists of a mixture of polymers and contains a whole range of components, such as paper, organic residue, halogens, and metals, which pose problems during recycling. Nevertheless, until today, limited detailed data are available on the full polymer composition of plastic packaging waste taking into account the separable packaging parts present in a certain waste stream, nor on their quantitative levels of (elemental) impurities. This paper therefore presents an unprecedented in-depth analysis of the polymer and elemental composition, including C, H, N, S, O, metals, and halogens, of commonly generated plastic packaging waste streams in European sorting facilities. Various analytical techniques are applied, including Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), polarized optical microscopy, ion chromatography, and inductively coupled plasma optical emission spectrometry (ICP-OES), on more than 100 different plastic packaging products, which are all separated into their different packaging subcomponents (e.g., a bottle into the bottle itself, the cap, and the label). Our results show that certain waste streams consist of mixtures of up to nine different polymers and contain various elements of the periodic table, in particular metals such as Ca, Al, Na, Zn, and Fe and halogens like Cl and F, occurring in concentrations between 1 and 3000 ppm. As discussed in the paper, both polymer and elemental impurities impede in many cases closed-loop recycling and require advanced pretreatment steps, increasing the overall recycling cost.

Challenges and opportunities of solvent-based additive extraction methods for plastic recycling.

Additives are ubiquitously used in plastics to improve their functionality. However, they are not always desirable in their 'second life' and are a major bottleneck for chemical recycling. Although research on extraction techniques for efficient removal of additives is increasing, it resembles much like uncharted territory due to the broad variety of additives, plastics and removal techniques. Today solvent-based additive extraction techniques, solid-liquid extraction and dissolution-precipitation, are considered to be the most promising techniques to remove additives. This review focuses on the assessment of these techniques by making a link between literature and physicochemical principles such as diffusion and Hansen solubility theory. From a technical point of view, dissolution-precipitation is preferred to remove a broad spectrum of additives because diffusion limitations affect the solid-liquid extraction recoveries. Novel techniques such as accelerated solvent extraction (ASE) are promising for finding the balance between these two processes. Because of limited studies on the economic and environmental feasibility of extraction methods, this review also includes a basic economic and environmental assessment of two extreme cases for the extraction of additives. According to this assessment, the feasibility of additives removal depends strongly on the type of additive and plastic and also on the extraction conditions. In the best-case scenario at least 70% of solvent recovery is required to extract plasticizers from polyvinyl chloride (PVC) via dissolution-precipitation with tetrahydrofuran (THF), while solid-liquid extraction of phenolic antioxidants and a fatty acid amide slip agents from polypropylene (PP) with dichloromethane (DCM) can be economically viable even without intensive solvent recovery.