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Latest Trends in Pyrolysis Gas Chromatography for Analytical and Applied Pyrolysis of Plastics

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Latest Trends in Pyrolysis Gas Chromatography for Analytical and Applied Pyrolysis of Plastics ANALYTICAL SCIENCES JANUARY 2021, VOL. 37 145 2021 © The Japan Society for Analytical Chemistry Reviews Latest Trends in Pyrolysis Gas Chromatography for Analytical and Applied Pyrolysis of Plastics Shogo KUMAGAI† and Toshiaki YOSHIOKA Graduate School of Environmental Studies, Tohoku University, 6-6-07 Aoba, Aramaki-aza, Aoba, Sendai 980–8579, Japan Pyrolysis is considered to be a promising method for polymer characterization (in the field of analytical pyrolysis) and for chemical feedstock recovery from plastic wastes (in the field of applied pyrolysis) because it can decompose any polymeric material into smaller molecules by applying heat alone in an inert atmosphere. Pyrolysis–gas chromatography (Py-GC) involves pyrolyzing polymeric materials in a micropyrolyzer and a subsequent direct GC analysis of pyrolyzates. Py-GC has immense potential for applications in the fields of both analytical and applied pyrolysis, as it allows for rapid and accurate analysis of pyrolyzates. This is beneficial for elucidating microstructure and composition of polymers and for a rapid screening of pyrolysis conditions for designing feedstock recycling processes. In this review, we examined the latest research trends in Py-GC applications for polymer characterization, analysis of plastics in the environment, and chemical feedstock recovery from plastics. Keywords Analytical pyrolysis, applied pyrolysis, gas chromatography, plastics (Received August 20, 2020; Accepted October 12, 2020; Advance Publication Released Online by J-STAGE October 23, 2020) 1 Latest Trends in Plastic Production and 4·1 Py-GC for feedstock recycling of plastics Waste Plastic Recycling 145 4·2 Tandem micro-reactor-GC for feedstock recycling 2 Pyrolysis–Gas Chromatography 146 of plastics 3 Py-GC for Analytical Pyrolysis 147 5 Conclusions and Perspective 155 3·1 Characterization of polymer structure 6 Abbreviations 155 3·2 Analysis of plastics in the environment 7 Acknowledgements 155 4 Py-GC for Applied Pyrolysis 150 8 References 155 combination with additives. Global plastic production has 1 Latest Trends in Plastic Production and Waste increased from 1.5 million tons (Mt) in 1950 to 359 Mt in 2018. Plastic Recycling Over the last ten years (2008 – 2018), plastic production has increased ∼1.5 times.1,2 In the domestic market, over 150 types Plastics are widely used in our daily life owing to their light of resins are being manufactured.3,4 Plastics are classified into weight and inexpensive features, as well as because of their thermoplastics and thermosetting types, according to the good processability and ease of functionalization through molecular structure or molding method, and into commodity Shogo KUMAGAI is currently an Assistant Toshiaki YOSHIOKA is currently a Professor of Graduate School of Professor of Graduate School of Environmental Studies, Tohoku University, Environmental Studies, Tohoku University, and an Editor of Journal of Analytical and and a Chief Editor of Journal of Material Applied Pyrolysis (Elsevier). His research Cycles and Waste Management (Springer). interests are development of pyrolysis His research interest is development of processes for chemical feedstock recovery chemical recycling processes for waste from waste plastics and biomass and plastics, which is his lifework for more analytical pyrolysis methods employing than 30 years. The latest activities and pyrolysis–gas chromatograph systems. updates of his laboratory are available at: The latest activities and updates are http://www.che.tohoku.ac.jp/~env/index-e. available at his researchmap: https:// html. researchmap.jp/7000012617/?lang=en. † To whom correspondence should be addressed. E-mail: [email protected] Anal. Sci., 2021, 37, 145–157 DOI:10.2116/analsci.20SAR04 146 ANALYTICAL SCIENCES JANUARY 2021, VOL. 37 Fig. 1 Schematic diagram of the different types of pyrolyzers currently used. (A) Filament type, (B) Currie-point type, and (C) micro-furnace type.21 Copyright (2020) with permission from Elsevier [License number: 4892761025099]. plastics, engineering plastics, and super engineering plastics, plastics by 2030. Global trends like the Sustainable Development according to their heat resistance and application. In general, Goals (SDGs)9 and circular economy10 have led to a recent rapid plastic products contain several additives, such as antioxidants, increase in demand for plastic recycling. In addition, a recent stabilizers, lubricants, antistatic agents, antifogging agents, focus on ocean plastic pollution11–16 and the decision by China to plasticizers, nucleating agents, antiblocking agents, flame ban waste plastic imports17 have had significant impacts on retardants, foaming agents, and fillers, to achieve the desired several industrial sectors around the world. Therefore, the performance. More than 230 types of additives have been development of technologies that can significantly increase the manufactured3,4 in Japan; therefore, there are uncountable amount of recycled plastic waste as well as to improve the combinations of resins and additives. The rapid and accurate quality of recycled products have recently been in high demand. analysis of plastic products, especially identification of the As described above, pyrolysis is a promising technology that polymer type, polymer composition and microstructure, the can meet the demands of both the polymer industry and the additive type, and changes in the polymer structure by plastic recycling industry. Pyrolysis involves the decomposition deterioration have of late been in high demand in the polymer of polymeric materials with low solubility, high molecular mass, industry. and low volatility into smaller molecules by the application of The constant growth of waste plastic generation is observed in heat alone in an inert atmosphere. Pyrolysis allows the the data of global primary plastic waste generation.5 According characterization of a polymer structure and composition based to a report published by the Ellen Macarthur Foundation, 78 Mt on the distribution of pyrolyzates. Particularly, plastic of plastic packaging materials were produced in 2013, of which pyrolyzates can be utilized as a monomer, fuel, or a valuable 40% was treated by landfilling, 32% was leaked into the chemical. To harness the immense potential of pyrolysis for a environment, 14% was incinerated for energy recovery, and only broad range of applications, a high-throughput technology to 14% was recycled.6 Plastic leaked into the environment leads to conduct pyrolysis is crucial. This review presents the latest soil and water pollution, thereby deteriorating the ecosystem. developments in pyrolysis–gas chromatography (Py-GC) In Japan, 8.9 Mt of waste plastics were generated in 2018, of applications for polymer characterization, analysis of plastics in which 84% was recycled or utilized as an energy source (23% in the environment, and chemical feedstock recovery from plastics. mechanical recycling, 4% in feedstock recycling, and 56% for energy recovery), and 16% was treated by incineration without energy recovery and landfilling.7 In Japan, the Fourth 2 Pyrolysis–Gas Chromatography Fundamental Plan for Establishing a Sound Material-Cycle Society (2018) proposed establishing the Resource Circulation Pyrolysis–gas chromatography (Py-GC) allows for the pyrolysis Strategy for Plastics, which was formulated in May 2019.8 The of polymeric materials in a micropyrolyzer, followed by GC strategy has sloganized “3R+Renewable”, which aims to analysis of the pyrolyzates. Capillary columns and mass promote the reduction, reuse, recycling, and use of bio-based spectrometer (MS) have been commonly employed for Py-GC, plastics. Several milestones were established as part of the whereas the detection system should be selected to suit the strategy: a 25% reduction in single-use plastics usage by 2030, purpose of pyrolyzate analysis. Prof. Tsuge developed an 60% reuse/recycling of plastic containers and packaging by innovative Py-GC method18 for the first in-depth microstructural 2030, complete utilization of waste plastics via reuse and analysis of polymers using analytical pyrolysis.19 He also recycling by 2035, and the introduction of ∼2 Mt of bio-based developed a vertical furnace-type pyrolyzer20 that greatly ANALYTICAL SCIENCES JANUARY 2021, VOL. 37 147 improves the reproducibility of the observed data by Py-GC. ionization detector (FID). They also suggested that the Currently, there are mainly three types of pyrolyzers,21 viz. copolymer microstructure can be inferred based on the trimer filament-type (Fig. 1(A)), Curie-point type (Fig. 1(B)), and distribution. Salinas et al.29 (Entry 18) pyrolyzed physical micro-furnace-type (Fig. 1(C)), which allow for rapid heating, mixtures of poly(acrylonitrile-co-1,3-butadiene-co-styrene)/ with accurate and broad temperature control. Basically, Py-GC polyamide 6 (ABS/PA6) (10 – 80 wt% ABS) by using Py-GC/ allows for the investigation of any polymers and additives MS and FID at 700°C and reported a good linearity between without any pretreatment, thus providing important caprolactam/main ABS pyrolyzates and the PA6 content in the compositional and structural information in a simple manner. blends. Ohtani et al. have extensively studied reactive-Py-GC Analytical pyrolysis enables elucidation of the chemical techniques, using tetramethylammonium hydroxide (TMAH) as composition and structure of materials in the fields of an organic alkali, for the structural characterization of environmental, biological, medical, forensic, cultural
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