Dechlorination of Polyvinyl Chloride via Solvothermal Treatment with Glycerol
Abstract
:1. Introduction
2. Materials and Methods
2.1. Dechlorination of PVC
2.2. Characterization
3. Results and Discussion
3.1. Dechlorination of PVC-P
3.2. Effect of PVC/Glycerol Mass Ratio on Dechlorination
3.3. Comparison with Commercially Available PVC-Sheets
3.4. Calorific Value of the Solid Product
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Poerschmann, J.; Weiner, B.; Woszidlo, S.; Koehler, R.; Kopinke, F.D. Hydrothermal carbonization of poly(vinyl chloride). Chemosphere 2015, 199, 682–689. [Google Scholar] [CrossRef]
- Yu, J.; Sun, L.; Ma, C.; Qiao, Y.; Yao, H. Thermal degradation of PVC: A review. Waste Manag. 2016, 48, 300–314. [Google Scholar] [CrossRef]
- López, A.; de Marco, I.; Caballero, B.M.; Laresgoiti, M.F.; Adrados, A. Dechlorination of fuels in pyrolysis of PVC containing plastic wastes. Fuel Process. Technol. 2011, 92, 253–260. [Google Scholar] [CrossRef]
- Yoshioka, T.; Akama, T.; Uchida, M.; Okuwaki, A. Analysis of two stages dehydrochlorination of poly(vinyl chloride) using TG-MS. Chem. Lett. 2000, 29, 322–323. [Google Scholar] [CrossRef]
- Yoshioka, T.; Saitoh, N.; Okuwaki, A. Temperature dependence on the activation energy of dechlorination in thermal degradation of polyvinylchloride. Chem. Lett. 2005, 34, 70–71. [Google Scholar] [CrossRef]
- Yuan, G.; Chen, D.; Yin, L.; Wang, Z.; Zhao, L.; Wang, J.Y. High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas-liquid fluidized bed reactor. Waste Manag. 2014, 34, 1045–1050. [Google Scholar] [CrossRef] [PubMed]
- Wu, J.; Chen, T.; Luo, X.; Han, D.; Wang, Z.; Wu, J. TG/FTIR analysis on co-pyrolysis behavior of PE, PVC and PS. Waste Manag. 2014, 34, 676–682. [Google Scholar] [CrossRef]
- Prawisudha, P.; Namioka, T.; Yoshikawa, K. Coal alternative fuel production from municipal solid wastes employing hydrothermal treatment. Appl. Energy 2012, 90, 298–304. [Google Scholar] [CrossRef]
- Takeshita, Y.; Kato, K.; Takahashi, K. Basic study on treatment of waste polyvinyl chloride plastics by hydrothermal decomposition in subcritical and supercritical regions. J. Supercrit. Fluids 2004, 31, 185–193. [Google Scholar] [CrossRef]
- Zhao, P.; Shen, Y.; Ge, S.; Chen, Z.; Yoshikawa, K. Clean solid biofuel production from high moisture content waste biomass employing hydrothermal treatment. Appl. Energy 2014, 131, 345–367. [Google Scholar] [CrossRef]
- Kuhlmann, B.; Arnett, E.M.; Siskin, M. Classical organic reactions in pure superheated water. J. Org. Chem. 1994, 59, 3098–3101. [Google Scholar] [CrossRef]
- Endo, K.; Emori, N. Dechlorination of poly(vinyl chloride) without anomalous units under high pressure and at high temperature in water. Polym. Degrad. Stabil. 2001, 74, 113–117. [Google Scholar] [CrossRef]
- Shin, S.-M.; Yoshioka, T.; Okuwaki, A. Dehydrochlorination behavior of flexible PVC pellets in NaOH solutions at elevated temperature. J. Appl. Polym. Sci. 1998, 67, 2171–2177. [Google Scholar] [CrossRef]
- Yoshinaga, T.; Yamaye, M.; Kito, T.; Ichiki, T.; Ogata, M.; Chen, J.; Fujino, H.; Tanimura, T.; Yamanobe, T. Alkaline dechlorination of poly(vinyl chloride) in organic solvents under mild conditions. Polym. Degrad. Stab. 2004, 86, 541–547. [Google Scholar] [CrossRef]
- Yoshioka, T.; Kameda, T.; Imai, S. Dechlorination of poly(vinylidene chloride) in NaOH/ethylene glycol as a function of NaOH concentration, temperature, and solvent. Polym. Degrad. Stab. 2008, 93, 1979–1984. [Google Scholar] [CrossRef]
- Huang, N.; Zhao, P.; Ghosh, S. Co-hydrothermal carbonization of polyvinyl chloride and moist biomass to remove chlorine and inorganics for clean fuel production. Appl. Energy 2019, 240, 882–892. [Google Scholar] [CrossRef]
- Shen, Y.; Yu, S.; Ge, S.; Chen, X.; Ge, X.; Chen, M. Hydrothermal carbonization of medical wastes and lignocellulosic biomass for solid fuel production from lab-scale to pilot-scale. Energy 2017, 118, 312–323. [Google Scholar] [CrossRef] [Green Version]
- Shen, Y. Dechlorination of poly(vinyl chloride) waste via hydrothermal carbonization with lignin for clean solid fuel. Ind. Eng. Chem. Res. 2016, 55, 11638–11644. [Google Scholar] [CrossRef]
- Yao, Z.; Ma, X. Characteristics of co-hydrothermal carbonization on polyvinyl chloride wastes with bamboo. Bioresour. Technol. 2018, 247, 302–309. [Google Scholar] [CrossRef]
- Kusakabe, K.; Steven, T.; Ong, J.Y.; Uemura, Y.; Ikenaga, K. Cohydrothermal carbonization of waste polyvinyl chloride and wood chip for dichlorination. W3S Web Conf. 2021, 287, 04008. [Google Scholar] [CrossRef]
- Kusakabe, K.; Steven, T.; Nagai, A.; Uemura, Y.; Ikenaga, K. Solvothermal carbonization of wood chips via the dechlorination of PVC in glycerol. J. Chem. Eng. Jpn. 2021, 54, 110–115. [Google Scholar] [CrossRef]
- Channiwala, S.A.; Parikh, P.P. A unified correlation for estimating HHV of solid, liquid and gaseous fuels. Fuel 2002, 81, 1051–1063. [Google Scholar] [CrossRef]
- Santacesaria, E.; Tesser, R.; Di Serio, M.; Casale, L.; Verde, D. New process for producing epichlorohydrin via glycerol chlorination. Ind. Eng. Chem. Res. 2010, 49, 964–970. [Google Scholar] [CrossRef]
- Iván, B.; Kennedy, J.P.; TKelen, T.; Tüdõs, F.; Nagy, T.T.; Turcsányi, B. Degradation of PVC’s obtained by controlled chemical dehydrochlorination. J. Polym. Sci. 1983, 21, 2177–2188. [Google Scholar]
Reaction Temperature (°C) | 200 | 220 | 240 |
---|---|---|---|
Decomposition ratio (wt%) | 61.1 | 63.3 | 64.9 |
Dechlorination yield (wt%) | 16.7 | 71.8 | 82.4 |
Chlorine fraction in solid residue (wt%) | 47.2 | 16.0 | 10.0 |
Sample | PVC-P | PVC-S | PVC-TS |
---|---|---|---|
C (%) | 38.4 | 48.4 | 44.6 |
H (%) | 4.8 | 7.1 | 6.4 |
O (%) | 0 | 8.9 | 5.2 |
Cl (%) | 56.8 | 35.6 | 43.8 |
Sample | Fraction of Additive (%) | Decomposition Ratio (%) | Dechlorination Yield (%) | ||||
---|---|---|---|---|---|---|---|
200 °C | 220 °C | 240 °C | 200 °C | 220 °C | 240 °C | ||
PVC-P | 0 | 61.1 | 63.3 | 64.9 | 16.7 | 71.8 | 82.4 |
PVC-TS | 22.9 | 65.2 | 64.2 | 66.9 | 25.0 | 33.4 | 82.9 |
PVC-S | 37.3 | 57.6 | 61.8 | 75.0 | 33.0 | 38.2 | 84.6 |
Sample (P/G (a)) | Temp. (%) | Weight Fraction (%) | H/C (mol/mol) | O/C (mol/mol) | Calorific Value (MJ/kg) | |||
---|---|---|---|---|---|---|---|---|
C | H | O | Cl | |||||
4:3 (b) | - | 36.78 | 6.23 | 22.39 | 29.59 | 2.03 | 0.46 | 17.9 |
4:3 | 200 | 41.4 | 5.48 | 5.51 | 47.6 | 1.59 | 0.045 | 20.3 |
4:3 | 220 | 73.0 | 7.058 | 4.0 | 15.9 | 1.16 | 0.019 | 33.4 |
4:3 | 240 | 79.3 | 7.34 | 2.66 | 10.7 | 1.11 | 0.011 | 36.1 |
2:3 (b) | - | 38.8 | 7.14 | 31.32 | 22.72 | 2.2 | 0.61 | 18.7 |
2:3 | 200 | 41.2 | 5.58 | 7.0 | 47.2 | 1.63 | 0.057 | 20.2 |
2:3 | 220 | 67.1 | 7.06 | 9.9 | 16.0 | 1.26 | 0.05 | 30.7 |
2:3 | 240 | 73.6 | 7.63 | 8.71 | 10.0 | 1.24 | 0.04 | 33.8 |
1:3 (b) | - | 38.93 | 7.73 | 39.15 | 14.2 | 2.38 | 0.75 | 18.7 |
1:3 | 200 | 40.9 | 5.51 | 7.72 | 46.4 | 1.62 | 0.064 | 20.0 |
1:3 | 220 | 54.5 | 6.45 | 13.0 | 26.1 | 1.42 | 0.0581 | 25.3 |
1:3 | 240 | 79.0 | 7.12 | 10.3 | 3.6 | 1.08 | 0.044 | 34.9 |
Sample | Temp. (%) | Weight Fraction (%) | H/C (mol/mol) | O/C (mol/mol) | Calorific Value (MJ/kg) | |||
---|---|---|---|---|---|---|---|---|
C | H | O | Cl | |||||
PVC-P (a) | - | 38.8 | 7.14 | 31.32 | 22.72 | 2.2 | 0.61 | 18.7 |
200 | 41.2 | 5.58 | 7.0 | 47.2 | 1.63 | 0.057 | 20.2 | |
220 | 67.1 | 7.06 | 9.9 | 16.0 | 1.26 | 0.05 | 30.7 | |
240 | 73.6 | 7.63 | 8.71 | 10.0 | 1.24 | 0.04 | 33.8 | |
PVC-TS (a) | - | 41.3 | 7.76 | 33.4 | 17.52 | 2.26 | 0.6 | 20.1 |
200 | 45.4 | 6.42 | 6.0 | 42.6 | 1.69 | 0.099 | 22.8 | |
220 | 48.4 | 6.41 | 6.39 | 37.8 | 1.59 | 0.099 | 23.8 | |
240 | 78.3 | 7.49 | 4.89 | 9.75 | 1.15 | 0.047 | 35.7 | |
PVC-S (a) | - | 42.82 | 8.04 | 34.88 | 14.24 | 2.25 | 0.61 | 20.8 |
200 | 44.4 | 6.35 | 10.8 | 38.0 | 1.72 | 0.182 | 21.9 | |
220 | 47.6 | 6.72 | 10.7 | 35.1 | 1.69 | 0.169 | 23.4 | |
240 | 79.1 | 7.7 | 6.52 | 8.7 | 1.17 | 0.062 | 36.0 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Kusakabe, K.; Nagai, A.; Leong, W.H.; Yamasaka, K.; Nakaaki, T.; Uemura, Y.; Ikenaga, K. Dechlorination of Polyvinyl Chloride via Solvothermal Treatment with Glycerol. Processes 2022, 10, 2047. https://doi.org/10.3390/pr10102047
Kusakabe K, Nagai A, Leong WH, Yamasaka K, Nakaaki T, Uemura Y, Ikenaga K. Dechlorination of Polyvinyl Chloride via Solvothermal Treatment with Glycerol. Processes. 2022; 10(10):2047. https://doi.org/10.3390/pr10102047
Chicago/Turabian StyleKusakabe, Katsuki, Anna Nagai, Wai Hong Leong, Kouki Yamasaka, Takuro Nakaaki, Yoshimitsu Uemura, and Kazutoshi Ikenaga. 2022. "Dechlorination of Polyvinyl Chloride via Solvothermal Treatment with Glycerol" Processes 10, no. 10: 2047. https://doi.org/10.3390/pr10102047