Skip to main content
SpringerLink
Log in

Catalytic Glycolysis of Poly(ethylene terephthalate) Using Zinc and Cobalt Oxides Recycled from Spent Batteries

  • Original Paper
  • Published:
Waste and Biomass Valorization Aims and scope Submit manuscript

Abstract

The chemical recycling of polyethylene terephthalate (PET) to bis(2-hydroxyethyl) terephthalate (BHET) was studied using recycled metal oxides. Recovered zinc (RZnO) and cobalt (RCoO) oxides were obtained after a biohydrometallurgical process to recycle spent alkaline and lithium-ion batteries (LIBs), respectively. Besides, a mixed oxide (Co/RZnO) was prepared by mechanical milling of 2.5 wt% of RCoO on RZnO. The structural, textural, and acidity properties of the catalysts were analyzed by XRD, XANES, SEM, TEM, FT-IR, SBET and pyridine-TPD. The depolymerization of PET (from soft-drink bottles) was carried out with ethylene glycol (EG) at 196 °C for 2 h, using PET/catalyst and PET/EG ratios of 100:1 and 1:8, respectively. The yields of the BHET monomer in the presence of RZnO, RCoO and Co/RZnO as catalysts were 50%, 10% and 80%, respectively. The highest catalytic activity of Co/RZnO could be attributed to the presence of weak and strong acid sites, its overall higher concentration of acid sites and a synergetic effect between Co3O4 and ZnO. The obtained BHET was characterized by DSC, FT-IR, 1H NMR and 13C NMR analyses, which confirmed the purity and structure of the monomer. Metal oxides obtained using spent alkaline and lithium-ion batteries as raw materials could be used as catalysts for waste PET treatment and pure BHET monomer synthesis.

Graphic Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11.

Similar content being viewed by others

References

  1. Payán, L., Poyatos, M.T., Muñoz, L., La Rubia, M.D., Pacheco, R., Ramos, N.: Study of the influence of storage conditions on the quality and migration levels of antimony in polyethylene terephthalate-bottled water. Food Sci. Technol. Int. 23, 318–327 (2017). https://doi.org/10.1177/1082013217690300

    Article  Google Scholar 

  2. Khoonkari, M., Haghighi, A.H., Sefidbakht, Y., Shekoohi, K., Ghaderian, A.: Chemical recycling of PET wastes with different catalysts. Int. J. Polym. Sci. (2015). https://doi.org/10.1155/2015/124524

    Article  Google Scholar 

  3. Wang, H., Liu, Y., Li, Z., Zhang, X., Zhang, S., Zhang, Y.: Glycolysis of poly(ethylene terephthalate) catalyzed by ionic liquids. Eur. Polym. J. 45, 1535–1544 (2009). https://doi.org/10.1016/J.EURPOLYMJ.2009.01.025

    Article  Google Scholar 

  4. Viante, M.F., Zanela, T.M.P., Stoski, A., Muniz, E.C., Almeida, C.A.P.: Magnetic microspheres composite from poly(ethylene terephthalate) (PET) waste: synthesis and characterization. J. Clean. Prod. 198, 979–986 (2018). https://doi.org/10.1016/j.jclepro.2018.07.101

    Article  Google Scholar 

  5. Bartolome, L., Imran, M., Lee, K.G., Sangalang, A., Ahn, J.K., Kim, D.H.: Superparamagnetic γ-Fe2O3 nanoparticles as an easily recoverable catalyst for the chemical recycling of PET. Green Chem. 16, 279–286 (2014). https://doi.org/10.1039/c3gc41834k

    Article  Google Scholar 

  6. Fang, P., Liu, B., Xu, J., Zhou, Q., Zhang, S., Ma, J., Lu, X.: High-efficiency glycolysis of poly(ethylene terephthalate) by sandwich-structure polyoxometalate catalyst with two active sites. Polym. Degrad. Stab. 156, 22–31 (2018). https://doi.org/10.1016/j.polymdegradstab.2018.07.004

    Article  Google Scholar 

  7. Ho, L.N., Ngo, D.M., Cho, J., Jung, H.M.: Enhanced catalytic glycolysis conditions for chemical recycling of glycol-modified poly(ethylene terephthalate). Polym. Degrad. Stab. 155, 15–21 (2018). https://doi.org/10.1016/j.polymdegradstab.2018.07.003

    Article  Google Scholar 

  8. Eshaq, G., ElMetwally, A.E.: (Mg–Zn)–Al layered double hydroxide as a regenerable catalyst for the catalytic glycolysis of polyethylene terephthalate. J. Mol. Liq. 214, 1–6 (2016). https://doi.org/10.1016/j.molliq.2015.11.049

    Article  Google Scholar 

  9. Pingale, N.D., Shukla, S.R.: Short communication. Eur. Polym. J. 44, 4151–4156 (2008). https://doi.org/10.1016/j.eurpolymj.2008.09.019

    Article  Google Scholar 

  10. Shukla, S.R., Harad, A.M.: Glycolysis of polyethylene terephthalate waste fibers. J. Appl. Polym. Sci. 97, 513–517 (2005). https://doi.org/10.1002/app.21769

    Article  Google Scholar 

  11. Al-Sabagh, A., Yehia, F., Eshaq, G., Rabie, A., El Metwally, A.: Greener routes for recycling of polyethylene terephthalate. Egypt. J. Pet. 25, 53–64 (2015)

    Article  Google Scholar 

  12. Zhu, M., Li, S., Li, Z., Lu, X., Zhang, S.: Investigation of solid catalysts for glycolysis of polyethylene terephthalate. Chem. Eng. J. 185, 168–177 (2012)

    Article  Google Scholar 

  13. Imran, M., Kim, D.H., Al-Masry, W.A., Mahmood, A., Hassan, A., Haider, S., Ramay, S.M.: Manganese-, cobalt-, and zinc-based mixed-oxide spinels as novel catalysts for the chemical recycling of poly(ethylene terephthalate) via glycolysis. Polym. Degrad. Stab. 98, 904–915 (2013). https://doi.org/10.1016/j.polymdegradstab.2013.01.007

    Article  Google Scholar 

  14. Sardá, C., Escalante, G., García-Díaz, I., López, F.A., Fernández, P.: Luminescence and gas-sensing properties of ZnO obtained from the recycling of alkaline batteries. J. Mater. Sci. (2017). https://doi.org/10.1007/s10853-017-1667-4

    Article  Google Scholar 

  15. Nayaka, G.P., Pai, K.V., Santhosh, G., Manjanna, J.: Recovery of cobalt as cobalt oxalate from spent lithium ion batteries by using glycine as leaching agent. J. Environ. Chem. Eng. 4, 2378–2383 (2016). https://doi.org/10.1016/j.jece.2016.04.016

    Article  Google Scholar 

  16. Li, L., Dunn, J.B., Zhang, X.X., Gaines, L., Chen, R.J., Wu, F., Amine, K.: Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment. J. Power Sources. 233, 180–189 (2013). https://doi.org/10.1016/j.jpowsour.2012.12.089

    Article  Google Scholar 

  17. Hosono, H.: Recent progress in transparent oxide semiconductors: materials and device application. Thin Solid Films 515, 6000–6014 (2007). https://doi.org/10.1016/j.tsf.2006.12.125

    Article  Google Scholar 

  18. Becheri, A., Dürr, M., Lo Nostro, P., Baglioni, P.: Synthesis and characterization of zinc oxide nanoparticles: application to textiles as UV-absorbers. J. Nanoparticle Res. 10, 679–689 (2008). https://doi.org/10.1007/s11051-007-9318-3

    Article  Google Scholar 

  19. Beydoun, D., Amal, R., Low, G., McEvoy, S.: Role of nanoparticles in photocatalysis. J. Nanoparticle Res. 1, 439–458 (1999). https://doi.org/10.1023/A:1010044830871

    Article  Google Scholar 

  20. Gallegos, M.V., Aparicio, F., Peluso, M.A., Damonte, L.C., Sambeth, J.E.: Structural, optical and photocatalytic properties of zinc oxides obtained from spent alkaline batteries. Mater. Res. Bull. 103, 158–165 (2018). https://doi.org/10.1016/j.materresbull.2018.03.022

    Article  Google Scholar 

  21. Ahmad, W., Noor, T., Zeeshan, M.: Effect of synthesis route on catalytic properties and performance of Co3O4/TiO2 for carbon monoxide and hydrocarbon oxidation under real engine operating conditions. Catal. Commun. 89, 19–24 (2017). https://doi.org/10.1016/j.catcom.2016.10.012

    Article  Google Scholar 

  22. Chen, Z., Wang, S., Liu, W., Gao, X., Gao, D., Wang, M., Wang, S.: Morphology-dependent performance of Co3O4 via facile and controllable synthesis for methane combustion. Appl. Catal. A Gen. 525, 94–102 (2016). https://doi.org/10.1016/j.apcata.2016.07.009

    Article  Google Scholar 

  23. Ren, Z., Wu, Z., Song, W., Xiao, W., Guo, Y., Ding, J., Suib, S.L., Gao, P.-X.: Low temperature propane oxidation over Co3O4 based nano-array catalysts: Ni dopant effect, reaction mechanism and structural stability. Appl. Catal. B Environ. 180, 150–160 (2016). https://doi.org/10.1016/j.apcatb.2015.04.021

    Article  Google Scholar 

  24. Marcoccia, C.G., Peluso, M.A., Sambeth, J.E.: Synthesis, characterization and catalytic properties of cobalt oxide recovered from spent lithium-ion batteries. Mol. Catal. (2018). https://doi.org/10.1016/j.mcat.2018.10.018

    Article  Google Scholar 

  25. Falco, L.R., Martinez, A., Di Nanno, M., Thomas, H., Curutchet, G.: Study of a pilot plant study for the recovery of metals from spent alkaline and zinc-carbon batteries with biological sulphuric acid and polythionate production. Lat. Am. Appl. Res. 44, 123–129 (2014)

    Google Scholar 

  26. Gallegos, M.V., Falco, L.R., Peluso, M.A., Sambeth, J.E., Thomas, H.J.: Recovery of manganese oxides from spent alkaline and zinc-carbon batteries. An application as catalysts for VOCs elimination. Waste Manag. 33, 1483–1490 (2013). https://doi.org/10.1016/j.wasman.2013.03.006

    Article  Google Scholar 

  27. Bertero, M., García, J.R., Falco, M., Sedran, U.: Equilibrium FCC catalysts to improve liquid products from biomass pyrolysis. Renew. Energy 132, 11–18 (2019)

    Article  Google Scholar 

  28. García, M.A., Jiḿnez-Villacorta, F., Quesada, A., De La Venta, J., Carmona, N., Lorite, I., Llopis, J., Fernández, J.F.: Surface magnetism in ZnO/Co3O4 mixtures. J. Appl. Phys. 107, 1–6 (2010). https://doi.org/10.1063/1.3294649

    Article  Google Scholar 

  29. Rubio-Marcos, F., Calvino-Casilda, V., Bañares, M.A., Fernandez, J.F.: Novel hierarchical Co3O4/ZnO mixtures by dry nanodispersion and their catalytic application in the carbonylation of glycerol. J. Catal. 275, 288–293 (2010). https://doi.org/10.1016/j.jcat.2010.08.009

    Article  Google Scholar 

  30. Agawane, S.M., Nagarkar, J.M.: Synthesis of 5-substituted 1H-tetrazoles using a nano ZnO/Co3O4 catalyst. Catal. Sci. Technol. 2, 1324–1327 (2012). https://doi.org/10.1039/C2CY20094E

    Article  Google Scholar 

  31. Rakibuddin, M., Ananthakrishnan, R.: Novel nano coordination polymer based synthesis of porous ZnO hexagonal nanodisk for higher gas sorption and photocatalytic activities. Appl. Surf. Sci. 362, 265–273 (2016). https://doi.org/10.1016/j.apsusc.2015.11.206

    Article  Google Scholar 

  32. Liu, Z., Deng, J., Li, F.: Fabrication and photocatalysis of CuO/ZnO nano-composites via a new method. Mater. Sci. Eng. B. 150, 99–104 (2008). https://doi.org/10.1016/j.mseb.2008.04.002

    Article  Google Scholar 

  33. Rong, F., Zhao, J., Su, P., Yao, Y., Li, M., Yang, Q., Li, C.: Zinc–cobalt oxides as efficient water oxidation catalysts: the promotion effect of ZnO. J. Mater. Chem. A. 3, 4010–4017 (2015). https://doi.org/10.1039/C4TA06527A

    Article  Google Scholar 

  34. Martin-González, M.S., García, M.A., Lorite, I., Costa-Krämer, J.L., Rubio-Marcos, F., Carmona, N., Fernández, J.F.: A solid-state electrochemical reaction as the origin of magnetism at oxide nanoparticle interfaces. J. Electrochem. Soc. 157, E31–E35 (2010). https://doi.org/10.1149/1.3272638

    Article  Google Scholar 

  35. Na, C.W., Woo, H.-S., Kim, I.-D., Lee, J.-H.: Selective detection of NO2 and C2H5OH using a Co3O4-decorated ZnO nanowire network sensor. Chem. Commun. 47, 5148–5150 (2011). https://doi.org/10.1039/C0CC05256F

    Article  Google Scholar 

  36. Chen, C.-H.: Study of glycolysis of poly(ethylene terephthalate) recycled from postconsumer soft-drink bottles. III. Further investigation. J. Appl. Polym. Sci. 87, 2004–2010 (2003). https://doi.org/10.1002/app.11694

    Article  Google Scholar 

  37. Duque-Ingunza, I., López-Fonseca, R., de Rivas, B., Gutiérrez-Ortiz, J.I.: Process optimization for catalytic glycolysis of post-consumer PET wastes. J. Chem. Technol. Biotechnol. 89, 97–103 (2014). https://doi.org/10.1002/jctb.4101

    Article  Google Scholar 

  38. Xi, G., Lu, M., Sun, C.: Study on depolymerization of waste polyethylene terephthalate into monomer of bis(2-hydroxyethyl terephthalate). Polym. Degrad. Stab. 87, 117–120 (2005). https://doi.org/10.1016/j.polymdegradstab.2004.07.017

    Article  Google Scholar 

  39. López-Fonseca, R., Duque-Ingunza, I., de Rivas, B., Flores-Giraldo, L., Gutiérrez-Ortiz, J.I.: Kinetics of catalytic glycolysis of PET wastes with sodium carbonate. Chem. Eng. J. 168, 312–320 (2011). https://doi.org/10.1016/j.cej.2011.01.031

    Article  Google Scholar 

  40. Fu, C.-Y.Y., Chang, C.-L.L., Hsu, C.-S.S., Hwang, B.-H.H.: Electrostatic spray deposition of La08Sr02Co02Fe08O3 films. Mater. Chem. Phys. 91, 28–35 (2005). https://doi.org/10.1016/j.matchemphys.2004.10.041

    Article  Google Scholar 

Download references

Acknowledgements

The authors acknowledge the CONICET, CICPBA and UNLP (Argentina). We are thankful to P. Fetsis, and M. Theiller.

Author information

Authors and Affiliations

  1. Centro de Investigación Y Desarrollo en Ciencias Aplicadas “Dr. Jorge J. Ronco” (CINDECA) (UNLP, CONICET, CICPBA), 47 Nro. 257, 1900, La Plata, Argentina

    Cynthia A. Fuentes, María V. Gallegos, Jorge Sambeth & Miguel A. Peluso

  2. Instituto de Investigaciones en Catálisis y Petroquímica “Ing. José Miguel Parera” INCAPE (UNL-CONICET), Colectora Ruta Nac. 168 Km. 0, 3000, Santa Fe, Argentina

    Juan R. García

Authors
  1. Cynthia A. Fuentes
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. María V. Gallegos
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Juan R. García
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jorge Sambeth
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Miguel A. Peluso
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Miguel A. Peluso.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Fuentes, C.A., Gallegos, M.V., García, J.R. et al. Catalytic Glycolysis of Poly(ethylene terephthalate) Using Zinc and Cobalt Oxides Recycled from Spent Batteries. Waste Biomass Valor 11, 4991–5001 (2020). https://doi.org/10.1007/s12649-019-00807-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12649-019-00807-6

Keywords

Search

Navigation