Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC
In this paper, we study the kinetics of polyvinyl chloride (PVC) decomposition using a combination of experimental and computational approaches. We develop a simplified kinetic model that contains only two steps: dehydrochlorination of PVC and further decomposition of the PVC residue. The model is c...
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| Veröffentlicht in: | ACS sustainable chemistry & engineering 2024-05, Vol.12 (19), p.7402-7413 |
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| creator | Wu, Jiayang Papanikolaou, Konstantinos G. Cheng, Feng Addison, Bennett Cuthbertson, Amy A. Mavrikakis, Manos Huber, George W. |
| description | In this paper, we study the kinetics of polyvinyl chloride (PVC) decomposition using a combination of experimental and computational approaches. We develop a simplified kinetic model that contains only two steps: dehydrochlorination of PVC and further decomposition of the PVC residue. The model is consistent with density functional theory (DFT) calculations and experimental data. Dehydrochlorination is an autocatalytic reaction that starts with a tertiary chloride (Cl) and generates hydrogen chloride (HCl) and benzene as the main products. Benzene and HCl formation rates showed similar trends, indicating that HCl likely catalyzes a homolytic carbon–carbon (C–C) bond cleavage, which gives rise to benzene and an aliphatic fragment. We characterized the structure of dehydrochlorinated PVC (PVC residue) by using thermal gravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). FTIR and NMR results indicate that the PVC residue contains 20% quaternary carbon content, indicating a high concentration of cross-linked molecules. We predict that the most probable structure in the cross-linked centers of the PVC residue is cyclohexadiene, which is supported by DFT calculations, FTIR, and NMR. |
| doi_str_mv | 10.1021/acssuschemeng.4c00564 |
| format | Article |
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National Energy Research Scientific Computing Center (NERSC)</creatorcontrib><description>In this paper, we study the kinetics of polyvinyl chloride (PVC) decomposition using a combination of experimental and computational approaches. We develop a simplified kinetic model that contains only two steps: dehydrochlorination of PVC and further decomposition of the PVC residue. The model is consistent with density functional theory (DFT) calculations and experimental data. Dehydrochlorination is an autocatalytic reaction that starts with a tertiary chloride (Cl) and generates hydrogen chloride (HCl) and benzene as the main products. Benzene and HCl formation rates showed similar trends, indicating that HCl likely catalyzes a homolytic carbon–carbon (C–C) bond cleavage, which gives rise to benzene and an aliphatic fragment. We characterized the structure of dehydrochlorinated PVC (PVC residue) by using thermal gravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). FTIR and NMR results indicate that the PVC residue contains 20% quaternary carbon content, indicating a high concentration of cross-linked molecules. We predict that the most probable structure in the cross-linked centers of the PVC residue is cyclohexadiene, which is supported by DFT calculations, FTIR, and NMR.</description><identifier>ISSN: 2168-0485</identifier><identifier>EISSN: 2168-0485</identifier><identifier>DOI: 10.1021/acssuschemeng.4c00564</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>benzene ; carbon ; chlorides ; crosslinking ; density functional theory ; DFT calculations ; Fourier transform infrared spectroscopy ; green chemistry ; homolytic cleavage ; hydrochloric acid ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; kinetic model ; kinetics ; nuclear magnetic resonance spectroscopy ; plastic pyrolysis ; poly(vinyl chloride) ; PVC dehydrochlorination ; pyrolysis ; thermogravimetry</subject><ispartof>ACS sustainable chemistry & engineering, 2024-05, Vol.12 (19), p.7402-7413</ispartof><rights>2024 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-a303t-d1104c4be5118688b69eed7cee08919173d3a9684796e4645900b8271caddddf3</cites><orcidid>0000-0002-5293-5356 ; 0000-0002-5948-7955 ; 0000-0002-7838-6893 ; 0000000252935356 ; 0000000259487955 ; 0000000278386893</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acssuschemeng.4c00564$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acssuschemeng.4c00564$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/2352421$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Wu, Jiayang</creatorcontrib><creatorcontrib>Papanikolaou, Konstantinos G.</creatorcontrib><creatorcontrib>Cheng, Feng</creatorcontrib><creatorcontrib>Addison, Bennett</creatorcontrib><creatorcontrib>Cuthbertson, Amy A.</creatorcontrib><creatorcontrib>Mavrikakis, Manos</creatorcontrib><creatorcontrib>Huber, George W.</creatorcontrib><creatorcontrib>National Renewable Energy Laboratory (NREL), Golden, CO (United States)</creatorcontrib><creatorcontrib>Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)</creatorcontrib><title>Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC</title><title>ACS sustainable chemistry & engineering</title><addtitle>ACS Sustainable Chem. Eng</addtitle><description>In this paper, we study the kinetics of polyvinyl chloride (PVC) decomposition using a combination of experimental and computational approaches. We develop a simplified kinetic model that contains only two steps: dehydrochlorination of PVC and further decomposition of the PVC residue. The model is consistent with density functional theory (DFT) calculations and experimental data. Dehydrochlorination is an autocatalytic reaction that starts with a tertiary chloride (Cl) and generates hydrogen chloride (HCl) and benzene as the main products. Benzene and HCl formation rates showed similar trends, indicating that HCl likely catalyzes a homolytic carbon–carbon (C–C) bond cleavage, which gives rise to benzene and an aliphatic fragment. We characterized the structure of dehydrochlorinated PVC (PVC residue) by using thermal gravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). FTIR and NMR results indicate that the PVC residue contains 20% quaternary carbon content, indicating a high concentration of cross-linked molecules. We predict that the most probable structure in the cross-linked centers of the PVC residue is cyclohexadiene, which is supported by DFT calculations, FTIR, and NMR.</description><subject>benzene</subject><subject>carbon</subject><subject>chlorides</subject><subject>crosslinking</subject><subject>density functional theory</subject><subject>DFT calculations</subject><subject>Fourier transform infrared spectroscopy</subject><subject>green chemistry</subject><subject>homolytic cleavage</subject><subject>hydrochloric acid</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>kinetic model</subject><subject>kinetics</subject><subject>nuclear magnetic resonance spectroscopy</subject><subject>plastic pyrolysis</subject><subject>poly(vinyl chloride)</subject><subject>PVC dehydrochlorination</subject><subject>pyrolysis</subject><subject>thermogravimetry</subject><issn>2168-0485</issn><issn>2168-0485</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNqFkMtOwzAQRSMEElXhE5AiVmxa7NhJ7CUqT1GJSjx2yHKdCXGV2sV2QOHrcUkXsGI2M5q550pzk-QEoylGGT6XyvvOqwbWYN6mVCGUF3QvGWW4YBNEWb7_az5Mjr1foVick4zhUfJ6rw0ErdLH0FV9aut0Ydv-Q5u-TWdNa52uIF30Li699umnDk3cSydVAKe_ZNDWbKlLaPrKWfWDGBmgShcvs6PkoJath-NdHyfP11dPs9vJ_OHmbnYxn0iCSJhUGCOq6BJyjFnB2LLgAFWpABDjmOOSVETygtGSF0ALmnOEliwrsZJVrJqMk9PB1_qghVc6gGqUNQZUEBnJM5rhKDobRBtn3zvwQay1V9C20oDtvCA4JznPonmU5oNUOeu9g1psnF5L1wuMxDZ28Sd2sYs9cnjg4lmsbOdM_Pof5huD54th</recordid><startdate>20240513</startdate><enddate>20240513</enddate><creator>Wu, Jiayang</creator><creator>Papanikolaou, Konstantinos G.</creator><creator>Cheng, Feng</creator><creator>Addison, Bennett</creator><creator>Cuthbertson, Amy A.</creator><creator>Mavrikakis, Manos</creator><creator>Huber, George W.</creator><general>American Chemical Society</general><general>American Chemical Society (ACS)</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7S9</scope><scope>L.6</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0002-5293-5356</orcidid><orcidid>https://orcid.org/0000-0002-5948-7955</orcidid><orcidid>https://orcid.org/0000-0002-7838-6893</orcidid><orcidid>https://orcid.org/0000000252935356</orcidid><orcidid>https://orcid.org/0000000259487955</orcidid><orcidid>https://orcid.org/0000000278386893</orcidid></search><sort><creationdate>20240513</creationdate><title>Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC</title><author>Wu, Jiayang ; Papanikolaou, Konstantinos G. ; Cheng, Feng ; Addison, Bennett ; Cuthbertson, Amy A. ; Mavrikakis, Manos ; Huber, George W.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a303t-d1104c4be5118688b69eed7cee08919173d3a9684796e4645900b8271caddddf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>benzene</topic><topic>carbon</topic><topic>chlorides</topic><topic>crosslinking</topic><topic>density functional theory</topic><topic>DFT calculations</topic><topic>Fourier transform infrared spectroscopy</topic><topic>green chemistry</topic><topic>homolytic cleavage</topic><topic>hydrochloric acid</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>kinetic model</topic><topic>kinetics</topic><topic>nuclear magnetic resonance spectroscopy</topic><topic>plastic pyrolysis</topic><topic>poly(vinyl chloride)</topic><topic>PVC dehydrochlorination</topic><topic>pyrolysis</topic><topic>thermogravimetry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wu, Jiayang</creatorcontrib><creatorcontrib>Papanikolaou, Konstantinos G.</creatorcontrib><creatorcontrib>Cheng, Feng</creatorcontrib><creatorcontrib>Addison, Bennett</creatorcontrib><creatorcontrib>Cuthbertson, Amy A.</creatorcontrib><creatorcontrib>Mavrikakis, Manos</creatorcontrib><creatorcontrib>Huber, George W.</creatorcontrib><creatorcontrib>National Renewable Energy Laboratory (NREL), Golden, CO (United States)</creatorcontrib><creatorcontrib>Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)</creatorcontrib><collection>CrossRef</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>OSTI.GOV</collection><jtitle>ACS sustainable chemistry & engineering</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wu, Jiayang</au><au>Papanikolaou, Konstantinos G.</au><au>Cheng, Feng</au><au>Addison, Bennett</au><au>Cuthbertson, Amy A.</au><au>Mavrikakis, Manos</au><au>Huber, George W.</au><aucorp>National Renewable Energy Laboratory (NREL), Golden, CO (United States)</aucorp><aucorp>Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC</atitle><jtitle>ACS sustainable chemistry & engineering</jtitle><addtitle>ACS Sustainable Chem. Eng</addtitle><date>2024-05-13</date><risdate>2024</risdate><volume>12</volume><issue>19</issue><spage>7402</spage><epage>7413</epage><pages>7402-7413</pages><issn>2168-0485</issn><eissn>2168-0485</eissn><abstract>In this paper, we study the kinetics of polyvinyl chloride (PVC) decomposition using a combination of experimental and computational approaches. We develop a simplified kinetic model that contains only two steps: dehydrochlorination of PVC and further decomposition of the PVC residue. The model is consistent with density functional theory (DFT) calculations and experimental data. Dehydrochlorination is an autocatalytic reaction that starts with a tertiary chloride (Cl) and generates hydrogen chloride (HCl) and benzene as the main products. Benzene and HCl formation rates showed similar trends, indicating that HCl likely catalyzes a homolytic carbon–carbon (C–C) bond cleavage, which gives rise to benzene and an aliphatic fragment. We characterized the structure of dehydrochlorinated PVC (PVC residue) by using thermal gravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). FTIR and NMR results indicate that the PVC residue contains 20% quaternary carbon content, indicating a high concentration of cross-linked molecules. We predict that the most probable structure in the cross-linked centers of the PVC residue is cyclohexadiene, which is supported by DFT calculations, FTIR, and NMR.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/acssuschemeng.4c00564</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0002-5293-5356</orcidid><orcidid>https://orcid.org/0000-0002-5948-7955</orcidid><orcidid>https://orcid.org/0000-0002-7838-6893</orcidid><orcidid>https://orcid.org/0000000252935356</orcidid><orcidid>https://orcid.org/0000000259487955</orcidid><orcidid>https://orcid.org/0000000278386893</orcidid></addata></record> |
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| subjects | benzene carbon chlorides crosslinking density functional theory DFT calculations Fourier transform infrared spectroscopy green chemistry homolytic cleavage hydrochloric acid INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY kinetic model kinetics nuclear magnetic resonance spectroscopy plastic pyrolysis poly(vinyl chloride) PVC dehydrochlorination pyrolysis thermogravimetry |
| title | Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC |
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