Journal of Material Cycles and Waste Management

, Volume 20, Issue 1, pp 439–449 | Cite as

Alkaline hydrolysis of PVC-coated PET fibers for simultaneous recycling of PET and PVC

  • Shogo Kumagai
  • Suguru Hirahashi
  • Guido Grause
  • Tomohito Kameda
  • Hiroshi Toyoda
  • Toshiaki Yoshioka
ORIGINAL ARTICLE

Abstract

Polyvinyl chloride (PVC)-coated poly(ethylene terephthalate) (PET) woven fibers are one of the hardest-to-recycle polymeric materials. Herein we investigate the possibility of recycling both PVC and PET through alkaline hydrolysis of PET. The coated woven fabrics were treated with NaOH, hydrolyzing the PET fibers into water-soluble sodium terephthalate, while the PVC could be removed by filtration. The PET fibers were completely hydrolyzed between 120 and 180 °C in the presence of 1 M NaOH solution, quantitatively yielding terephthalic acid. A minimum PVC dechlorination rate of 1% was simultaneously achieved at 120 °C. Furthermore, no alkaline hydrolysis of the plasticizer contained in the PVC, di(2-ethylhexyl)phthalate, was observed. Thus, the possibility of simultaneously recycling PET and PVC from PVC-coated woven fabrics was demonstrated. Kinetic analyses of PET hydrolysis and PVC dechlorination revealed that the simultaneously occurring reaction processes did not affect the progress of each other. Thus, the absence of interactions between PET, PVC, or their degradation products enables the design of a simplified recycling process without considering the interactions between the materials derived from coated woven fabrics.

Keywords

Feedstock recycling Hydrolysis Kinetics PET PVC 

Supplementary material

10163_2017_614_MOESM1_ESM.doc (668 kb)
Supplementary material 1 (DOC 668 kb)

References

  1. 1.
    Toyoda H (2012) Recyclable coated fabric using kenaf fiber for architectural membrane structure applications. Fabr Archit 24:7–16Google Scholar
  2. 2.
    The Ministry of Land I, Transport and Tourism Order for Enforcement of the Building Standards Act, the provision of Article 39. http://law.e-gov.go.jp/htmldata/S25/S25SE338.html. Accessed 19 Apr 2017
  3. 3.
    Van Krevelen DW (1997) Part VII—introduction to comprehensive tables. In: Properties of polymers (Third, completely revised edition), pp 759–823Google Scholar
  4. 4.
    Fukushima M, Shioya M, Wakai K, Ibe H (2009) Toward maximizing the recycling rate in a sapporo waste plastics liquefaction plant. J Mater Cycles Waste Manage 11:11–18CrossRefGoogle Scholar
  5. 5.
    Fukushima M, Wu B, Ibe H, Wakai K, Sugiyama E, Abe H, Kitagawa K, Tsuruga S, Shimura K, Ono E (2010) Study on dechlorination technology for municipal waste plastics containing polyvinyl chloride and polyethylene terephthalate. J Mater Cycles Waste Manage 12:108–122CrossRefGoogle Scholar
  6. 6.
    Bhaskar T, Kaneko J, Muto A, Sakata Y, Jakab E, Matsui T, Uddin MA (2004) Pyrolysis studies of PP/PE/PS/PVC/HIPS-Br plastics mixed with PET and dehalogenation (Br, Cl) of the liquid products. J Anal Appl Pyrolysis 72:27–33CrossRefGoogle Scholar
  7. 7.
    Bhaskar T, Uddin MA, Kaneko J, Kusaba T, Matsui T, Muto A, Sakata Y, Murata K (2003) Liquefaction of mixed plastics containing PVC and dechlorination by calcium-based sorbent. Energy Fuels 17:75–80CrossRefGoogle Scholar
  8. 8.
    Born JGP, Mulder P, Louw R (1993) Fly ash mediated reactions of phenol and monochlorophenols: oxychlorination, deep oxidation, and condensation. Environ Sci Technol 27:1849–1863CrossRefGoogle Scholar
  9. 9.
    The European Council of Vinyl Manufacturers PVC recycling by application. http://www.pvc.org/en/p/pvc-recycling-by-application. Accessed 13 July 2016
  10. 10.
    Grause G, Hirahashi S, Toyoda H, Kameda T, Yoshioka T (2015) Solubility parameters for determining optimal solvents for separating PVC from PVC-coated PET fibers. J Mater Cycles Waste Manag 19:612–622CrossRefGoogle Scholar
  11. 11.
    Ravens DAS, Ward IM (1961) Chemical reactivity of polyethylene terephthalate. Hydrolysis and esterification reactions in the solid phase. Trans Faraday Soc 57:150CrossRefGoogle Scholar
  12. 12.
    Zimmerman H, Kim NT (1980) Investigations on thermal and hydrolytic degradation of poly(ethylene terephthalate). Polym Eng Sci 20:680–683CrossRefGoogle Scholar
  13. 13.
    Campanelli JR, Cooper DG, Kamal MR (1993) A kinetic study of the hydrolytic degradation of polyethylene terephthalate at high temperatures. J Appl Polym Sci 48:443–451CrossRefGoogle Scholar
  14. 14.
    Zope VS, Mishra S (2008) Kinetics of neutral hydrolytic depolymerization of PET (polyethylene terephthalate) waste at higher temperature and autogenious pressures. J Appl Polym Sci 110:2179–2183CrossRefGoogle Scholar
  15. 15.
    Ramsden MJ, Phillips JA (1996) Factors influencing the kinetics of the alkaline depolymerisation of poly(ethylene terephthalate). I: the effect of solvent. J Chem Technol Biotechnol 67:131–136CrossRefGoogle Scholar
  16. 16.
    Wan B-Z, Kao C-Y, Cheng W-H (2001) Kinetics of depolymerization of poly(ethylene terephthalate) in a potassium hydroxide solution. Ind Eng Chem Res 40:509–514CrossRefGoogle Scholar
  17. 17.
    Karayannidis GP, Chatziavgoustis AP, Achilias DS (2002) Poly(ethylene terephthalate) recycling and recovery of pure terephthalic acid by alkaline hydrolysis. Adv Polym Technol 21:250–259CrossRefGoogle Scholar
  18. 18.
    Kumar S, Guria C (2005) Alkaline hydrolysis of waste poly(ethylene terephthalate): a modified shrinking core model. J Macromol Sci Part A 42:237–251CrossRefGoogle Scholar
  19. 19.
    Yoshioka T, Okayama N, Okuwaki A (1998) Kinetics of hydrolysis of PET powder in nitric acid by a modified shrinking-core model. Ind Eng Chem Res 37:336–340CrossRefGoogle Scholar
  20. 20.
    Yoshioka T, Motoki T, Okuwaki A (2001) Kinetics of hydrolysis of poly(ethylene terephthalate) powder in sulfuric acid by a modified shrinking-core model. Ind Eng Chem Res 40:75–79CrossRefGoogle Scholar
  21. 21.
    Achilias DS, Karayannidis GP (2004) The chemical recycling of PET in the framework of sustainable development. Water Air Soil Pollut Focus 4:385–396CrossRefGoogle Scholar
  22. 22.
    Shin S-M, Watanabe S, Yoshioka T, Okuwaki A (1997) Dehydrochlorination behavior of agricultural PVC polymer films in alkaline solution at elevated temperatures. Nippon Kagaku Kaishi 1:64–68CrossRefGoogle Scholar
  23. 23.
    Shin SM, Jeon HS, Kim YH, Yoshioka T, Okuwaki A (2002) Plasticizer leaching from flexible PVC in low temperature caustic solution. Polym Degrad Stab 78:511–517CrossRefGoogle Scholar
  24. 24.
    Kumagai S, Grause G, Kameda T, Yoshioka T (2014) Simultaneous recovery of benzene-rich oil and metals by steam pyrolysis of metal-poly(ethylene terephthalate) composite waste. Environ Sci Technol 48:3430–3437CrossRefGoogle Scholar
  25. 25.
    Kumagai S, Hosaka T, Kameda T, Yoshioka T (2016) Pyrolysis and hydrolysis behaviors during steam pyrolysis of polyimide. J Anal Appl Pyrolysis 120:75–81CrossRefGoogle Scholar
  26. 26.
    Kumagai S, Morohoshi Y, Grause G, Kameda T, Yoshioka T (2015) Pyrolysis versus hydrolysis behavior during steam decomposition of polyesters using 18O-labeled steam. RSC Adv 5:61828–61837CrossRefGoogle Scholar
  27. 27.
    Hashimoto K, Suga S, Wakayama Y, Funazukuri T (2007) Hydrothermal dechlorination of PVC in the presence of ammonia. J Mater Sci 43:2457–2462CrossRefGoogle Scholar
  28. 28.
    Siddiqui MN, Achilias DS, Redhwi HH, Bikiaris DN, Katsogiannis K-AG, Karayannidis GP (2010) Hydrolytic depolymerization of PET in a microwave reactor. Macromol Mater Eng 295:575–584CrossRefGoogle Scholar
  29. 29.
    López-Fonseca R, González-Marcos MP, González-Velasco JR, Gutiérrez-Ortiz JI (2009) A kinetic study of the depolymerisation of poly(ethylene terephthalate) by phase transfer catalysed alkaline hydrolysis. J Chem Technol Biotechnol 84:92–99CrossRefGoogle Scholar
  30. 30.
    Ikenaga K (2008) Microwave-titanium oxide catalyzed chemical depolymerization of waste PET. Kagaku Kogyo 59:494–499Google Scholar
  31. 31.
    Roh H-D, Bae D (2000) Process for manufacturing terephthalic acid. US Patent (US 6075163 A)Google Scholar
  32. 32.
    Jr. GEB, O’Brien RC (1976) Method for recovering terephthalic acid ethylene glycol from polyester materials. US Patent (US 3952053 A)Google Scholar

Copyright information

© Springer Japan 2017

Authors and Affiliations

  • Shogo Kumagai
    • 1
  • Suguru Hirahashi
    • 1
  • Guido Grause
    • 1
  • Tomohito Kameda
    • 1
  • Hiroshi Toyoda
    • 2
  • Toshiaki Yoshioka
    • 1
  1. 1.Graduate School of Environmental StudiesTohoku UniversitySendaiJapan
  2. 2.Taiyo Kogyo CorporationHirakataJapan

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