Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene
During the production of polymer-grade propylene, different processes are used to purify this compound and ensure that it is of the highest quality. However, some impurities such as acetylene and methyl acetylene are difficult to remove, and some of these impurities may be present in the propylene u...
- Autores:
-
Hernández-Fernández, Joaquín
Vivas-Reyes, Ricardo
Toloza, Carlos A. T.
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2022
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/10841
- Acceso en línea:
- https://hdl.handle.net/11323/10841
https://repositorio.cuc.edu.co/
- Palabra clave:
- Acetylene
Methylacetylene
Ziegler natta
Polypropylene
Catalysts
Degradation
- Rights
- openAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
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dc.title.eng.fl_str_mv |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene |
title |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene |
spellingShingle |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene Acetylene Methylacetylene Ziegler natta Polypropylene Catalysts Degradation |
title_short |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene |
title_full |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene |
title_fullStr |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene |
title_full_unstemmed |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene |
title_sort |
Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropylene |
dc.creator.fl_str_mv |
Hernández-Fernández, Joaquín Vivas-Reyes, Ricardo Toloza, Carlos A. T. |
dc.contributor.author.none.fl_str_mv |
Hernández-Fernández, Joaquín Vivas-Reyes, Ricardo Toloza, Carlos A. T. |
dc.subject.proposal.eng.fl_str_mv |
Acetylene Methylacetylene Ziegler natta Polypropylene Catalysts Degradation |
topic |
Acetylene Methylacetylene Ziegler natta Polypropylene Catalysts Degradation |
description |
During the production of polymer-grade propylene, different processes are used to purify this compound and ensure that it is of the highest quality. However, some impurities such as acetylene and methyl acetylene are difficult to remove, and some of these impurities may be present in the propylene used to obtain polypropylene, which may have repercussions on the process. This study evaluates the impact of these acetylene and methyl acetylene impurities on the productivity of the polypropylene synthesis process and on the mechanical and thermal properties of the material obtained through the synthesis of eight samples with different concentrations of acetylene and eight samples with different concentrations of acetylene. We discovered that for the first concentrations of both acetylene (2 and 3 ppm) and methyl acetylene (0.03 and 0.1), the MFI, thermal recording, and mechanical properties of the resin were unaffected by the variation of the fluidity index, thermal degradation by TGA, and mechanical properties such as resistance to tension, bending, and impact. However, when the concentration exceeded 14 ppm for methyl acetylene and 12 ppm for acetylene, the resistance of this resin began to decrease linearly. Regarding production, this was affected by the first traces of acetylene and methyl acetylene progressively decreasing. |
publishDate |
2022 |
dc.date.issued.none.fl_str_mv |
2022-10-12 |
dc.date.accessioned.none.fl_str_mv |
2024-03-08T20:43:18Z |
dc.date.available.none.fl_str_mv |
2024-03-08T20:43:18Z |
dc.type.spa.fl_str_mv |
Artículo de revista |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
dc.type.content.spa.fl_str_mv |
Text |
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info:eu-repo/semantics/article |
dc.type.redcol.spa.fl_str_mv |
http://purl.org/redcol/resource_type/ART |
dc.type.version.spa.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.coarversion.spa.fl_str_mv |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
format |
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dc.identifier.citation.spa.fl_str_mv |
Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A.T. Experimental Study of the Impact of Trace Amounts of Acetylene and Methylacetylene on the Synthesis, Mechanical and Thermal Properties of Polypropylene. Int. J. Mol. Sci. 2022, 23, 12148. https://doi.org/10.3390/ijms232012148 |
dc.identifier.issn.spa.fl_str_mv |
1661-6596 |
dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/10841 |
dc.identifier.doi.none.fl_str_mv |
10.3390/ijms232012148 |
dc.identifier.eissn.spa.fl_str_mv |
1422-0067 |
dc.identifier.instname.spa.fl_str_mv |
Corporación Universidad de la Costa |
dc.identifier.reponame.spa.fl_str_mv |
REDICUC – Repositorio CUC |
dc.identifier.repourl.spa.fl_str_mv |
https://repositorio.cuc.edu.co/ |
identifier_str_mv |
Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A.T. Experimental Study of the Impact of Trace Amounts of Acetylene and Methylacetylene on the Synthesis, Mechanical and Thermal Properties of Polypropylene. Int. J. Mol. Sci. 2022, 23, 12148. https://doi.org/10.3390/ijms232012148 1661-6596 10.3390/ijms232012148 1422-0067 Corporación Universidad de la Costa REDICUC – Repositorio CUC |
url |
https://hdl.handle.net/11323/10841 https://repositorio.cuc.edu.co/ |
dc.language.iso.spa.fl_str_mv |
eng |
language |
eng |
dc.relation.ispartofjournal.spa.fl_str_mv |
International Journal of Molecular Sciences |
dc.relation.references.spa.fl_str_mv |
1. Davarnejad, R.; Azizi, J.; Bahari, S. A Look at the industrial production of olefins based on naphtha feed: A process study of a petrochemical unit. In Alkenes—Recent Advances, New Perspectives and Applications; Davarnejad, R., Ed.; IntechOpen: London, UK, 2021; ISBN 978-1-83969-535-3. 2. Gholami, Z.; Gholami, F.; Tišler, Z.; Vakili, M. A Review on the Production of Light Olefins Using Steam Cracking of Hydrocarbons. Energies 2021, 14, 8190. [CrossRef] 3. Bu, J.; Liu, Z.; Ma, W.; Zhang, L.; Wang, T.; Zhang, H.; Zhang, Q.; Feng, X.; Zhang, J. Selective Electrocatalytic Semihydrogenation of Acetylene Impurities for the Production of Polymer-Grade Ethylene. Nat. Catal. 2021, 4, 557–564. [CrossRef] 4. Pässler, P.; Hefner, W.; Buckl, K.; Meinass, H.; Meiswinkel, A.; Wernicke, H.-J.; Ebersberg, G.; Müller, R.; Bässler, J.; Behringer, H.; et al. Acetylene. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA, Ed.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2011; p. a01_097.pub4; ISBN 978-3-527-30673-2. 5. Kluczynski, P.; Jahjah, M.; Nähle, L.; Axner, O.; Belahsene, S.; Fischer, M.; Koeth, J.; Rouillard, Y.; Westberg, J.; Vicet, A.; et al. Detection of Acetylene Impurities in Ethylene and Polyethylene Manufacturing Processes Using Tunable Diode Laser Spectroscopy in the 3-Mm Range. Appl. Phys. B 2011, 105, 427. [CrossRef] 6. US4127594A—Selective Hydrogenation of Olefinic Impurities in Epichlorohydrin—Google Patents. Available online: https: //patents.google.com/patent/US4127594A/en (accessed on 1 September 2022). 7. Li, J.; Han, X.; Kang, X.; Chen, Y.; Xu, S.; Smith, G.L.; Tillotson, E.; Cheng, Y.; McCormick McPherson, L.J.; Teat, S.J.; et al. Purification of Propylene and Ethylene by a Robust Metal–Organic Framework Mediated by Host–Guest Interactions. Angew. Chem. 2021, 133, 15669–15675. [CrossRef] 8. Wu, W.; Shao, B.; Zhou, X. Dynamic Control of a Selective Hydrogenation Process with Undesired MAPD Impurities in the C3-Cut Streams. J. Taiwan Inst. Chem. Eng. 2015, 54, 28–36. [CrossRef] 9. Hernández-Fernández, J. Quantification of Oxygenates, Sulphides, Thiols and Permanent Gases in Propylene. A Multiple Linear Regression Model to Predict the Loss of Efficiency in Polypropylene Production on an Industrial Scale. J. Chromatogr. A 2020, 1628, 461478. [CrossRef] 10. Joaquin, H.-F.; Juan, L. Quantification of Poisons for Ziegler Natta Catalysts and Effects on the Production of Polypropylene by Gas Chromatographic with Simultaneous Detection: Pulsed Discharge Helium Ionization, Mass Spectrometry and Flame Ionization. J. Chromatogr. A 2020, 1614, 460736. [CrossRef] 11. Hernández-Fernández, J. Quantification of Arsine and Phosphine in Industrial Atmospheric Emissions in Spain and Colombia. Implementation of Modified Zeolites to Reduce the Environmental Impact of Emissions. Atmos. Pollut. Res. 2021, 12, 167–176. [CrossRef] 12. Hernández-Fernández, J.; López-Martínez, J. Experimental Study of the Auto-Catalytic Effect of Triethylaluminum and TiCl4 Residuals at the Onset of Non-Additive Polypropylene Degradation and Their Impact on Thermo-Oxidative Degradation and Pyrolysis. J. Anal. Appl. Pyrolysis 2021, 155, 105052. [CrossRef] 13. Plata, D.L.; Meshot, E.R.; Reddy, C.M.; Hart, A.J.; Gschwend, P.M. Multiple Alkynes React with Ethylene To Enhance Carbon Nanotube Synthesis, Suggesting a Polymerization-like Formation Mechanism. ACS Nano 2010, 4, 7185–7192. [CrossRef] 14. Chemical Recycling of Waste Plastics for New Materials Production|Nature Reviews Chemistry. Available online: https: //www.nature.com/articles/s41570-017-0046 (accessed on 1 September 2022). 15. Al-Salem, S.M.; Lettieri, P.; Baeyens, J. Recycling and Recovery Routes of Plastic Solid Waste (PSW): A Review. Waste Manag. 2009, 29, 2625–2643. [CrossRef] [PubMed] 16. Fernández, J.H.; Cano, H.; Guerra, Y.; Polo, E.P.; Ríos-Rojas, J.F.; Vivas-Reyes, R.; Oviedo, J. Identification and Quantification of Microplastics in Effluents of Wastewater Treatment Plant by Differential Scanning Calorimetry (DSC). Sustainability 2022, 14, 4920. [CrossRef] 17. Joaquin, H.-F.; Juan, L.-M. Autocatalytic Influence of Different Levels of Arsine on the Thermal Stability and Pyrolysis of Polypropylene. J. Anal. Appl. Pyrolysis 2022, 161, 105385. [CrossRef] 18. Danciu, T.; Beckman, E.J.; Hancu, D.; Cochran, R.N.; Grey, R.; Hajnik, D.M.; Jewson, J. Direct Synthesis of Propylene Oxide with CO2 as the Solvent. Angew. Chem. 2003, 115, 1172–1174. [CrossRef] 19. Hernández-Fernández, J.; Guerra, Y.; Puello-Polo, E.; Marquez, E. Effects of Different Concentrations of Arsine on the Synthesis and Final Properties of Polypropylene. Polymers 2022, 14, 3123. [CrossRef] 20. Cano, H.; Ríos-Rojas, J.F.; Hernández-Fernández, J.; Herrera, W.B.; Betancur, M.B.; De La Hoz Vélez, L.; González, L.A. Impact of Environmental Pollution in the Sustainability of Architectural Heritage: Case Study from Cartagena of India, Colombia. Sustainability 2021, 14, 189. [CrossRef] 21. Lu, Y.; Li, H.; Wang, J.; Liu, T.; Wu, K. Productivity Evaluation Model for Multi-Cluster Fractured Wells Based on Volumetric Source Method. Energy Rep. 2022, 8, 8467–8479. [CrossRef] 22. Choi, J.; Lee, S.Y. Process Analysis and Economic Evaluation for Poly(3-Hydroxybutyrate) Production by Fermentation. Bioprocess Eng. 1997, 17, 335. [CrossRef] 23. Catalytic Polymerization of Olefins and Acetylenes. Available online: https://www.eng.uc.edu/~{}beaucag/Classes/ IntrotoPolySci/Catalytic%20Polymerization%20of%20Olefins%20and%20Acetylenes.htm (accessed on 26 September 2022). 24. Trotu¸s, I.-T.; Zimmermann, T.; Schüth, F. Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited. Chem. Rev. 2014, 114, 1761–1782. [CrossRef] 25. Oblak, P.; Gonzalez-Gutierrez, J.; Zupanˇciˇc, B.; Aulova, A.; Emri, I. Processability and Mechanical Properties of Extensively Recycled High Density Polyethylene. Polym. Degrad. Stab. 2015, 114, 133–145. [CrossRef] 26. Aurrekoetxea, J.; Sarrionandia, M.A.; Urrutibeascoa, I.; Maspoch, M.L. Effects of Recycling on the Microstructure and the Mechanical Properties of Isotactic Polypropylene. J. Mater. Sci. 2001, 36, 2607–2613. [CrossRef] 27. Choudhary, K.D.; Nayyar, A.; Dasgupta, M.S. Effect of Compression Ratio on Combustion and Emission Characteristics of C.I. Engine Operated with Acetylene in Conjunction with Diesel Fuel. Fuel 2018, 214, 489–496. [CrossRef] 28. Tzoganakis, C.; Vlachopoulos, J.; Hamielec, A.E.; Shinozaki, D.M. Effect of Molecular Weight Distribution on the Rheological and Mechanical Properties of Polypropylene. Polym. Eng. Sci. 1989, 29, 390–396. [CrossRef] 29. Maldhure, A.V.; Ekhe, J.D.; Deenadayalan, E. Mechanical Properties of Polypropylene Blended with Esterified and Alkylated Lignin. J. Appl. Polym. Sci. 2012, 125, 1701–1712. [CrossRef] 30. Shubhra, Q.T.; Alam, A.; Quaiyyum, M.A. Mechanical Properties of Polypropylene Composites: A Review. J. Thermoplast. Compos. Mater. 2011, 26, 362–391. [CrossRef] 31. Fu, S.-Y.; Lauke, B.; Mäder, E.; Yue, C.-Y.; Hu, X. Tensile Properties of Short-Glass-Fiber- and Short-Carbon-Fiber-Reinforced Polypropylene Composites. Compos. Part Appl. Sci. Manuf. 2000, 31, 1117–1125. [CrossRef] 32. Salemane, M.G.; Luyt, A.S. Thermal and Mechanical Properties of Polypropylene–Wood Powder Composites. J. Appl. Polym. Sci. 2006, 100, 4173–4180. [CrossRef] 33. Davis, T.E.; Tobias, R.L.; Peterli, E.B. Thermal Degradation of Polypropylene. J. Polym. Sci. 1962, 56, 485–499. [CrossRef] 34. Fernández, J.H.; Guerra, Y.; Cano, H. Detection of Bisphenol A and Four Analogues in Atmospheric Emissions in Petrochemical Complexes Producing Polypropylene in South America. Molecules 2022, 27, 4832. [CrossRef] 35. Hernández-Fernández, J.; Lopez-Martinez, J.; Barceló, D. Development and Validation of a Methodology for Quantifying Partsper-Billion Levels of Arsine and Phosphine in Nitrogen, Hydrogen and Liquefied Petroleum Gas Using a Variable Pressure Sampler Coupled to Gas Chromatography-Mass Spectrometry. J. Chromatogr. A 2021, 1637, 461833. [CrossRef] 36. Alonso-Fariñas, B.; Gallego-Schmid, A.; Haro, P.; Azapagic, A. Environmental Assessment of Thermo-Chemical Processes for Bio-Ethylene Production in Comparison with Bio-Chemical and Fossil-Based Ethylene. J. Clean. Prod. 2018, 202, 817–829. [CrossRef] 37. Himmelmann, R.; Otterstaetter, R.; Franke, O.; Brand, S.; Wachsen, O.; Mestl, G.; Effenberger, F.; Klemm, E. Selective Oxidation of Ethanol to Ethylene Oxide with a Dual-Layer Concept. Catal. Commun. 2022, 167, 106424. [CrossRef] 38. Del Campo, A.; de Lucas-Gil, E.; Rubio-Marcos, F.; Arrieta, M.P.; Fernández-García, M.; Fernández, J.F.; Muñoz-Bonilla, A. Accelerated Disintegration of Compostable Ecovio Polymer by Using ZnO Particles as Filler. Polym. Degrad. Stab. 2021, 185, 109501. [CrossRef] 39. Karanjikar, S.R.; Lakade, S.S. Evaluation of Mechanical Properties of Polypropylene—Acrylonitrile Butadiene Styrene Blend Reinforced with Cowrie Shell [Cypraeidae] Powder. Mater. Today Proc. 2022, 50, 1644–1652. [CrossRef] 40. Venkatesan, K.; Bhaskar, G.B. Evaluation and Comparison of Mechanical Properties of Natural Fiber Abaca-Sisal Composite. Fibers Polym. 2020, 21, 1523–1534. [CrossRef] |
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© 2022 by the authors. Licensee MDPI, Basel, Switzerland |
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Atribución 4.0 Internacional (CC BY 4.0) |
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Atribución 4.0 Internacional (CC BY 4.0) © 2022 by the authors. Licensee MDPI, Basel, Switzerland https://creativecommons.org/licenses/by/4.0/ http://purl.org/coar/access_right/c_abf2 |
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Atribución 4.0 Internacional (CC BY 4.0)© 2022 by the authors. Licensee MDPI, Basel, Switzerlandhttps://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Hernández-Fernández, JoaquínVivas-Reyes, RicardoToloza, Carlos A. T.2024-03-08T20:43:18Z2024-03-08T20:43:18Z2022-10-12Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A.T. Experimental Study of the Impact of Trace Amounts of Acetylene and Methylacetylene on the Synthesis, Mechanical and Thermal Properties of Polypropylene. Int. J. Mol. Sci. 2022, 23, 12148. https://doi.org/10.3390/ijms2320121481661-6596https://hdl.handle.net/11323/1084110.3390/ijms2320121481422-0067Corporación Universidad de la CostaREDICUC – Repositorio CUChttps://repositorio.cuc.edu.co/During the production of polymer-grade propylene, different processes are used to purify this compound and ensure that it is of the highest quality. However, some impurities such as acetylene and methyl acetylene are difficult to remove, and some of these impurities may be present in the propylene used to obtain polypropylene, which may have repercussions on the process. This study evaluates the impact of these acetylene and methyl acetylene impurities on the productivity of the polypropylene synthesis process and on the mechanical and thermal properties of the material obtained through the synthesis of eight samples with different concentrations of acetylene and eight samples with different concentrations of acetylene. We discovered that for the first concentrations of both acetylene (2 and 3 ppm) and methyl acetylene (0.03 and 0.1), the MFI, thermal recording, and mechanical properties of the resin were unaffected by the variation of the fluidity index, thermal degradation by TGA, and mechanical properties such as resistance to tension, bending, and impact. However, when the concentration exceeded 14 ppm for methyl acetylene and 12 ppm for acetylene, the resistance of this resin began to decrease linearly. Regarding production, this was affected by the first traces of acetylene and methyl acetylene progressively decreasing.10 páginasapplication/pdfengMultidisciplinary Digital Publishing Institute (MDPI)Switzerlandhttps://www.mdpi.com/1422-0067/23/20/12148Experimental study of the impact of trace amounts of acetylene and methylacetylene on the synthesis, mechanical and thermal properties of polypropyleneArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85International Journal of Molecular Sciences1. Davarnejad, R.; Azizi, J.; Bahari, S. A Look at the industrial production of olefins based on naphtha feed: A process study of a petrochemical unit. In Alkenes—Recent Advances, New Perspectives and Applications; Davarnejad, R., Ed.; IntechOpen: London, UK, 2021; ISBN 978-1-83969-535-3.2. Gholami, Z.; Gholami, F.; Tišler, Z.; Vakili, M. A Review on the Production of Light Olefins Using Steam Cracking of Hydrocarbons. Energies 2021, 14, 8190. [CrossRef]3. Bu, J.; Liu, Z.; Ma, W.; Zhang, L.; Wang, T.; Zhang, H.; Zhang, Q.; Feng, X.; Zhang, J. Selective Electrocatalytic Semihydrogenation of Acetylene Impurities for the Production of Polymer-Grade Ethylene. Nat. Catal. 2021, 4, 557–564. [CrossRef]4. Pässler, P.; Hefner, W.; Buckl, K.; Meinass, H.; Meiswinkel, A.; Wernicke, H.-J.; Ebersberg, G.; Müller, R.; Bässler, J.; Behringer, H.; et al. Acetylene. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA, Ed.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2011; p. a01_097.pub4; ISBN 978-3-527-30673-2.5. Kluczynski, P.; Jahjah, M.; Nähle, L.; Axner, O.; Belahsene, S.; Fischer, M.; Koeth, J.; Rouillard, Y.; Westberg, J.; Vicet, A.; et al. Detection of Acetylene Impurities in Ethylene and Polyethylene Manufacturing Processes Using Tunable Diode Laser Spectroscopy in the 3-Mm Range. Appl. Phys. B 2011, 105, 427. [CrossRef]6. US4127594A—Selective Hydrogenation of Olefinic Impurities in Epichlorohydrin—Google Patents. Available online: https: //patents.google.com/patent/US4127594A/en (accessed on 1 September 2022).7. Li, J.; Han, X.; Kang, X.; Chen, Y.; Xu, S.; Smith, G.L.; Tillotson, E.; Cheng, Y.; McCormick McPherson, L.J.; Teat, S.J.; et al. Purification of Propylene and Ethylene by a Robust Metal–Organic Framework Mediated by Host–Guest Interactions. Angew. Chem. 2021, 133, 15669–15675. [CrossRef]8. Wu, W.; Shao, B.; Zhou, X. Dynamic Control of a Selective Hydrogenation Process with Undesired MAPD Impurities in the C3-Cut Streams. J. Taiwan Inst. Chem. Eng. 2015, 54, 28–36. [CrossRef]9. Hernández-Fernández, J. Quantification of Oxygenates, Sulphides, Thiols and Permanent Gases in Propylene. A Multiple Linear Regression Model to Predict the Loss of Efficiency in Polypropylene Production on an Industrial Scale. J. Chromatogr. A 2020, 1628, 461478. [CrossRef]10. Joaquin, H.-F.; Juan, L. Quantification of Poisons for Ziegler Natta Catalysts and Effects on the Production of Polypropylene by Gas Chromatographic with Simultaneous Detection: Pulsed Discharge Helium Ionization, Mass Spectrometry and Flame Ionization. J. Chromatogr. A 2020, 1614, 460736. [CrossRef]11. Hernández-Fernández, J. Quantification of Arsine and Phosphine in Industrial Atmospheric Emissions in Spain and Colombia. Implementation of Modified Zeolites to Reduce the Environmental Impact of Emissions. Atmos. Pollut. Res. 2021, 12, 167–176. [CrossRef]12. Hernández-Fernández, J.; López-Martínez, J. Experimental Study of the Auto-Catalytic Effect of Triethylaluminum and TiCl4 Residuals at the Onset of Non-Additive Polypropylene Degradation and Their Impact on Thermo-Oxidative Degradation and Pyrolysis. J. Anal. Appl. Pyrolysis 2021, 155, 105052. [CrossRef]13. Plata, D.L.; Meshot, E.R.; Reddy, C.M.; Hart, A.J.; Gschwend, P.M. Multiple Alkynes React with Ethylene To Enhance Carbon Nanotube Synthesis, Suggesting a Polymerization-like Formation Mechanism. ACS Nano 2010, 4, 7185–7192. [CrossRef]14. Chemical Recycling of Waste Plastics for New Materials Production|Nature Reviews Chemistry. Available online: https: //www.nature.com/articles/s41570-017-0046 (accessed on 1 September 2022).15. Al-Salem, S.M.; Lettieri, P.; Baeyens, J. Recycling and Recovery Routes of Plastic Solid Waste (PSW): A Review. Waste Manag. 2009, 29, 2625–2643. [CrossRef] [PubMed]16. Fernández, J.H.; Cano, H.; Guerra, Y.; Polo, E.P.; Ríos-Rojas, J.F.; Vivas-Reyes, R.; Oviedo, J. 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Licensee MDPI, Basel, Switzerlandopen.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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