Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent

ABSTRACT: The kinetics of the catalytic synthesis of nopol from b-pinene and paraformaldehyde over Sn-MCM-41 catalyst and using ethyl acetate as solvent is presented and compared with previous studies in toluene. Reaction rate data were fitted to a kinetic expression based on the Langmuir–Hinshelwoo...

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Autores:
Alarcón Durango, Edwin Alexis
Villa Holguín, Aída Luz
Tipo de recurso:
Article of investigation
Fecha de publicación:
2015
Institución:
Universidad de Antioquia
Repositorio:
Repositorio UdeA
Idioma:
eng
OAI Identifier:
oai:bibliotecadigital.udea.edu.co:10495/13122
Acceso en línea:
http://hdl.handle.net/10495/13122
http://dx.doi.org/10.1016/j.fuel.2014.08.067
Palabra clave:
Estudio cinético
Síntesis de nopol
Acetato de etilo
Rights
openAccess
License
Atribución-NoComercial-SinDerivadas 2.5 Colombia
id UDEA2_5d7800424690d6b3868e0a9f2b006848
oai_identifier_str oai:bibliotecadigital.udea.edu.co:10495/13122
network_acronym_str UDEA2
network_name_str Repositorio UdeA
repository_id_str
dc.title.spa.fl_str_mv Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
title Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
spellingShingle Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
Estudio cinético
Síntesis de nopol
Acetato de etilo
title_short Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
title_full Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
title_fullStr Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
title_full_unstemmed Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
title_sort Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent
dc.creator.fl_str_mv Alarcón Durango, Edwin Alexis
Villa Holguín, Aída Luz
dc.contributor.author.none.fl_str_mv Alarcón Durango, Edwin Alexis
Villa Holguín, Aída Luz
dc.subject.none.fl_str_mv Estudio cinético
Síntesis de nopol
Acetato de etilo
topic Estudio cinético
Síntesis de nopol
Acetato de etilo
description ABSTRACT: The kinetics of the catalytic synthesis of nopol from b-pinene and paraformaldehyde over Sn-MCM-41 catalyst and using ethyl acetate as solvent is presented and compared with previous studies in toluene. Reaction rate data were fitted to a kinetic expression based on the Langmuir–Hinshelwood formalism, using the initial rates method. Reaction rate constant and adsorption constants were determined by regression of experimental data. The highest adsorption constant for nopol respect to reactants (KC = 14.948 M-1) allows to explain the strong inhibition effect of this compound that is experimentally observed. Solvent effects were discussed in terms of formaldehyde solubility, solvation of activated complex and reactants, and competitive adsorption on active sites. Higher solubility of formaldehyde in ethyl acetate respect to toluene, determined with Henry’s law, along with the competitive adsorption of solvent and a more probable solvation of b-pinene and nopol may explain the better selectivity in ethyl acetate. Dependency of reaction constant on temperature was evaluated between 75 °C and 90 °C, resulting in an apparent activation energy of 98 kJ mol-1, which is higher than in toluene, suggesting stabilization of carbocation intermediates by solvation in the polar ethyl acetate solvent.
publishDate 2015
dc.date.issued.none.fl_str_mv 2015
dc.date.accessioned.none.fl_str_mv 2020-01-14T03:18:43Z
dc.date.available.none.fl_str_mv 2020-01-14T03:18:43Z
dc.type.spa.fl_str_mv info:eu-repo/semantics/article
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dc.identifier.citation.spa.fl_str_mv Casas Orozco, D., Alarcón Durango, E. A., and Villa, A. L. (2015). Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent. Fuel. 149, 130-137. http://dx.doi.org/10.1016/j.fuel.2014.08.067
dc.identifier.issn.none.fl_str_mv 0016-2361
dc.identifier.uri.none.fl_str_mv http://hdl.handle.net/10495/13122
dc.identifier.doi.none.fl_str_mv http://dx.doi.org/10.1016/j.fuel.2014.08.067
identifier_str_mv Casas Orozco, D., Alarcón Durango, E. A., and Villa, A. L. (2015). Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent. Fuel. 149, 130-137. http://dx.doi.org/10.1016/j.fuel.2014.08.067
0016-2361
url http://hdl.handle.net/10495/13122
http://dx.doi.org/10.1016/j.fuel.2014.08.067
dc.language.iso.spa.fl_str_mv eng
language eng
dc.relation.ispartofjournalabbrev.spa.fl_str_mv Fuel
dc.rights.*.fl_str_mv Atribución-NoComercial-SinDerivadas 2.5 Colombia
dc.rights.spa.fl_str_mv info:eu-repo/semantics/openAccess
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rights_invalid_str_mv Atribución-NoComercial-SinDerivadas 2.5 Colombia
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dc.format.extent.spa.fl_str_mv 7
dc.format.mimetype.spa.fl_str_mv application/pdf
dc.publisher.spa.fl_str_mv Elsevier
dc.publisher.group.spa.fl_str_mv Catálisis Ambiental
dc.publisher.place.spa.fl_str_mv Holanda
institution Universidad de Antioquia
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spelling Alarcón Durango, Edwin AlexisVilla Holguín, Aída Luz2020-01-14T03:18:43Z2020-01-14T03:18:43Z2015Casas Orozco, D., Alarcón Durango, E. A., and Villa, A. L. (2015). Kinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solvent. Fuel. 149, 130-137. http://dx.doi.org/10.1016/j.fuel.2014.08.0670016-2361http://hdl.handle.net/10495/13122http://dx.doi.org/10.1016/j.fuel.2014.08.067ABSTRACT: The kinetics of the catalytic synthesis of nopol from b-pinene and paraformaldehyde over Sn-MCM-41 catalyst and using ethyl acetate as solvent is presented and compared with previous studies in toluene. Reaction rate data were fitted to a kinetic expression based on the Langmuir–Hinshelwood formalism, using the initial rates method. Reaction rate constant and adsorption constants were determined by regression of experimental data. The highest adsorption constant for nopol respect to reactants (KC = 14.948 M-1) allows to explain the strong inhibition effect of this compound that is experimentally observed. Solvent effects were discussed in terms of formaldehyde solubility, solvation of activated complex and reactants, and competitive adsorption on active sites. Higher solubility of formaldehyde in ethyl acetate respect to toluene, determined with Henry’s law, along with the competitive adsorption of solvent and a more probable solvation of b-pinene and nopol may explain the better selectivity in ethyl acetate. Dependency of reaction constant on temperature was evaluated between 75 °C and 90 °C, resulting in an apparent activation energy of 98 kJ mol-1, which is higher than in toluene, suggesting stabilization of carbocation intermediates by solvation in the polar ethyl acetate solvent.7application/pdfengElsevierCatálisis AmbientalHolandainfo:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_2df8fbb1https://purl.org/redcol/resource_type/ARTArtículo de investigaciónhttp://purl.org/coar/version/c_970fb48d4fbd8a86http://purl.org/coar/version/c_970fb48d4fbd8a85Atribución-NoComercial-SinDerivadas 2.5 Colombiainfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/2.5/co/http://purl.org/coar/access_right/c_abf2https://creativecommons.org/licenses/by-nc-nd/4.0/Estudio cinéticoSíntesis de nopolAcetato de etiloKinetic study of the nopol synthesis by the Prins reaction over tin impregnated MCM-41 catalyst with ethyl acetate as solventFuelFuel130137149ORIGINALAlarconEdwin_2015_KineticStudyNopol.pdfAlarconEdwin_2015_KineticStudyNopol.pdfArtículo de investigaciónapplication/pdf660299http://bibliotecadigital.udea.edu.co/bitstream/10495/13122/1/AlarconEdwin_2015_KineticStudyNopol.pdf95a299f94e3e15bd6b87a326e4a6cb10MD51CC-LICENSElicense_urllicense_urltext/plain; charset=utf-849http://bibliotecadigital.udea.edu.co/bitstream/10495/13122/2/license_url4afdbb8c545fd630ea7db775da747b2fMD52license_textlicense_texttext/html; charset=utf-80http://bibliotecadigital.udea.edu.co/bitstream/10495/13122/3/license_textd41d8cd98f00b204e9800998ecf8427eMD53license_rdflicense_rdfapplication/rdf+xml; charset=utf-80http://bibliotecadigital.udea.edu.co/bitstream/10495/13122/4/license_rdfd41d8cd98f00b204e9800998ecf8427eMD54LICENSElicense.txtlicense.txttext/plain; charset=utf-81748http://bibliotecadigital.udea.edu.co/bitstream/10495/13122/5/license.txt8a4605be74aa9ea9d79846c1fba20a33MD5510495/13122oai:bibliotecadigital.udea.edu.co:10495/131222021-06-17 13:33:26.624Repositorio Institucional Universidad de Antioquiaandres.perez@udea.edu.coTk9URTogUExBQ0UgWU9VUiBPV04gTElDRU5TRSBIRVJFClRoaXMgc2FtcGxlIGxpY2Vuc2UgaXMgcHJvdmlkZWQgZm9yIGluZm9ybWF0aW9uYWwgcHVycG9zZXMgb25seS4KCk5PTi1FWENMVVNJVkUgRElTVFJJQlVUSU9OIExJQ0VOU0UKCkJ5IHNpZ25pbmcgYW5kIHN1Ym1pdHRpbmcgdGhpcyBsaWNlbnNlLCB5b3UgKHRoZSBhdXRob3Iocykgb3IgY29weXJpZ2h0Cm93bmVyKSBncmFudHMgdG8gRFNwYWNlIFVuaXZlcnNpdHkgKERTVSkgdGhlIG5vbi1leGNsdXNpdmUgcmlnaHQgdG8gcmVwcm9kdWNlLAp0cmFuc2xhdGUgKGFzIGRlZmluZWQgYmVsb3cpLCBhbmQvb3IgZGlzdHJpYnV0ZSB5b3VyIHN1Ym1pc3Npb24gKGluY2x1ZGluZwp0aGUgYWJzdHJhY3QpIHdvcmxkd2lkZSBpbiBwcmludCBhbmQgZWxlY3Ryb25pYyBmb3JtYXQgYW5kIGluIGFueSBtZWRpdW0sCmluY2x1ZGluZyBidXQgbm90IGxpbWl0ZWQgdG8gYXVkaW8gb3IgdmlkZW8uCgpZb3UgYWdyZWUgdGhhdCBEU1UgbWF5LCB3aXRob3V0IGNoYW5naW5nIHRoZSBjb250ZW50LCB0cmFuc2xhdGUgdGhlCnN1Ym1pc3Npb24gdG8gYW55IG1lZGl1bSBvciBmb3JtYXQgZm9yIHRoZSBwdXJwb3NlIG9mIHByZXNlcnZhdGlvbi4KCllvdSBhbHNvIGFncmVlIHRoYXQgRFNVIG1heSBrZWVwIG1vcmUgdGhhbiBvbmUgY29weSBvZiB0aGlzIHN1Ym1pc3Npb24gZm9yCnB1cnBvc2VzIG9mIHNlY3VyaXR5LCBiYWNrLXVwIGFuZCBwcmVzZXJ2YXRpb24uCgpZb3UgcmVwcmVzZW50IHRoYXQgdGhlIHN1Ym1pc3Npb24gaXMgeW91ciBvcmlnaW5hbCB3b3JrLCBhbmQgdGhhdCB5b3UgaGF2ZQp0aGUgcmlnaHQgdG8gZ3JhbnQgdGhlIHJpZ2h0cyBjb250YWluZWQgaW4gdGhpcyBsaWNlbnNlLiBZb3UgYWxzbyByZXByZXNlbnQKdGhhdCB5b3VyIHN1Ym1pc3Npb24gZG9lcyBub3QsIHRvIHRoZSBiZXN0IG9mIHlvdXIga25vd2xlZGdlLCBpbmZyaW5nZSB1cG9uCmFueW9uZSdzIGNvcHlyaWdodC4KCklmIHRoZSBzdWJtaXNzaW9uIGNvbnRhaW5zIG1hdGVyaWFsIGZvciB3aGljaCB5b3UgZG8gbm90IGhvbGQgY29weXJpZ2h0LAp5b3UgcmVwcmVzZW50IHRoYXQgeW91IGhhdmUgb2J0YWluZWQgdGhlIHVucmVzdHJpY3RlZCBwZXJtaXNzaW9uIG9mIHRoZQpjb3B5cmlnaHQgb3duZXIgdG8gZ3JhbnQgRFNVIHRoZSByaWdodHMgcmVxdWlyZWQgYnkgdGhpcyBsaWNlbnNlLCBhbmQgdGhhdApzdWNoIHRoaXJkLXBhcnR5IG93bmVkIG1hdGVyaWFsIGlzIGNsZWFybHkgaWRlbnRpZmllZCBhbmQgYWNrbm93bGVkZ2VkCndpdGhpbiB0aGUgdGV4dCBvciBjb250ZW50IG9mIHRoZSBzdWJtaXNzaW9uLgoKSUYgVEhFIFNVQk1JU1NJT04gSVMgQkFTRUQgVVBPTiBXT1JLIFRIQVQgSEFTIEJFRU4gU1BPTlNPUkVEIE9SIFNVUFBPUlRFRApCWSBBTiBBR0VOQ1kgT1IgT1JHQU5JWkFUSU9OIE9USEVSIFRIQU4gRFNVLCBZT1UgUkVQUkVTRU5UIFRIQVQgWU9VIEhBVkUKRlVMRklMTEVEIEFOWSBSSUdIVCBPRiBSRVZJRVcgT1IgT1RIRVIgT0JMSUdBVElPTlMgUkVRVUlSRUQgQlkgU1VDSApDT05UUkFDVCBPUiBBR1JFRU1FTlQuCgpEU1Ugd2lsbCBjbGVhcmx5IGlkZW50aWZ5IHlvdXIgbmFtZShzKSBhcyB0aGUgYXV0aG9yKHMpIG9yIG93bmVyKHMpIG9mIHRoZQpzdWJtaXNzaW9uLCBhbmQgd2lsbCBub3QgbWFrZSBhbnkgYWx0ZXJhdGlvbiwgb3RoZXIgdGhhbiBhcyBhbGxvd2VkIGJ5IHRoaXMKbGljZW5zZSwgdG8geW91ciBzdWJtaXNzaW9uLgo=