Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications
Autor(a) principal: | |
---|---|
Data de Publicação: | 2022 |
Tipo de documento: | Tese |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/17020 |
Resumo: | Lubricants are among the many products whose manufacture is highly dependent on nonrenewable fossil resources, with high levels of production and a vast marketplace, so they are the focus of many environmental laws around the word. Currently, this market includes some biobased products, known as biolubricants, although they represent a very small fraction of this sector and have certain limitations. Studies concerning the development of new products, raw materials, and processes are essential for the expansion and commercial success of biolubricants. Therefore, the aim of this work was: evaluating the production of biolubricant base stocks such as fatty acid isoamyl esters (FAIEs) from soybean oil deodorizer distillate (SODD) as a fatty acids source, together with isoamyl alcohol (a byproduct from bioethanol fermentation and the main constituent of fusel oil), catalyzed by free Eversa Transform 2.0 lipase and Pseudomonas fluorescens lipase (PFL) immobilized by the hybrid nanoflower (hNF) method. Experimental design and response surface methodology were applied to define the parameters for PFL immobilization using hNFs (hNF-PFL), viz. protein concentration, metal concentration and immobilization pH, and for FAIEs production, viz. SODD/isoamyl alcohol molar ratio, reaction temperature, the enzyme mass and secant salt mass (for the reactions with hNF-PFL). Studies of the incubation step of the synthesis using hNF-PFL enabled the incubation time to be reduced from 72 h (static immobilization medium at 25 °C) to just 20 min using ultrasound, without losses of immobilization yield (IY) or immobilized activity (IA). The optimized IY and IA values for hNF-PFL were 54 and 64 TBU%, respectively. The hNF-PFL showed high operational stability, maintaining practically the same reaction yield (RY) values during 8 cycles, over a total of 192 h. At the 10th cycle (total of 240 h), the material presented relative RY of 80%, compared to the earlier cycles. In the production of FAIEs using ETL 2.0 with molecular sieve (for moisture control) at 39 and 9 wt.% (molecular sieve mass / SODD mass), RY values of 50 and 70 wt.% were achieved, respectively. When hNF-PFL was employed in the FAIEs synthesis, RY of 64 wt.% was obtained, without the use of a moisture control agent. Products of partial conversion of SODD into FAIEs, catalyzed by ETL 2.0, with RY of 44 and 55 wt.%, and catalyzed by hNF-PFL, with RY of 56 and 57 wt.%, presented physicochemical characteristics similar to those of commercial biolubricant base stocks. Therefore, this doctoral thesis has the potential to contribute economically to the lubricant market through an environmentally friendly enzymatic process for the synthesis of a base stock from by-products of the national industry. |
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Silva, Rafael de AraujoTardioli, Paulo Waldirhttp://lattes.cnpq.br/0808991927126468http://lattes.cnpq.br/36440409526952361f5693a8-2229-4cc3-8bfd-412aad4c8ed72022-11-11T11:40:26Z2022-11-11T11:40:26Z2022-07-26SILVA, Rafael de Araujo. Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications. 2022. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/17020.https://repositorio.ufscar.br/handle/ufscar/17020Lubricants are among the many products whose manufacture is highly dependent on nonrenewable fossil resources, with high levels of production and a vast marketplace, so they are the focus of many environmental laws around the word. Currently, this market includes some biobased products, known as biolubricants, although they represent a very small fraction of this sector and have certain limitations. Studies concerning the development of new products, raw materials, and processes are essential for the expansion and commercial success of biolubricants. Therefore, the aim of this work was: evaluating the production of biolubricant base stocks such as fatty acid isoamyl esters (FAIEs) from soybean oil deodorizer distillate (SODD) as a fatty acids source, together with isoamyl alcohol (a byproduct from bioethanol fermentation and the main constituent of fusel oil), catalyzed by free Eversa Transform 2.0 lipase and Pseudomonas fluorescens lipase (PFL) immobilized by the hybrid nanoflower (hNF) method. Experimental design and response surface methodology were applied to define the parameters for PFL immobilization using hNFs (hNF-PFL), viz. protein concentration, metal concentration and immobilization pH, and for FAIEs production, viz. SODD/isoamyl alcohol molar ratio, reaction temperature, the enzyme mass and secant salt mass (for the reactions with hNF-PFL). Studies of the incubation step of the synthesis using hNF-PFL enabled the incubation time to be reduced from 72 h (static immobilization medium at 25 °C) to just 20 min using ultrasound, without losses of immobilization yield (IY) or immobilized activity (IA). The optimized IY and IA values for hNF-PFL were 54 and 64 TBU%, respectively. The hNF-PFL showed high operational stability, maintaining practically the same reaction yield (RY) values during 8 cycles, over a total of 192 h. At the 10th cycle (total of 240 h), the material presented relative RY of 80%, compared to the earlier cycles. In the production of FAIEs using ETL 2.0 with molecular sieve (for moisture control) at 39 and 9 wt.% (molecular sieve mass / SODD mass), RY values of 50 and 70 wt.% were achieved, respectively. When hNF-PFL was employed in the FAIEs synthesis, RY of 64 wt.% was obtained, without the use of a moisture control agent. Products of partial conversion of SODD into FAIEs, catalyzed by ETL 2.0, with RY of 44 and 55 wt.%, and catalyzed by hNF-PFL, with RY of 56 and 57 wt.%, presented physicochemical characteristics similar to those of commercial biolubricant base stocks. Therefore, this doctoral thesis has the potential to contribute economically to the lubricant market through an environmentally friendly enzymatic process for the synthesis of a base stock from by-products of the national industry.Os lubrificantes são produtos cuja fabricação atualmente é muito dependente de recursos fósseis não renováveis, possuem mercado e produção expressivos e se encontram na mira de várias leis ambientais em todo o planeta. Atualmente já existem alguns produtos de base biológicas inseridos neste mercado, denominados de biolubrificantes, porém compõem uma fração muito pequena deste segmento e possuem limitações. Estudos que envolvam o desenvolvimento de novos produtos, insumos e processos são essenciais para o sucesso e a ampliação dos biolubrificantes neste mercado. Assim, esta tese de doutorado teve como objetivo: avaliar a produção de bases biolubrificantes na forma de ésteres isoamílicos de ácidos graxos (“fatty acid isoamyl ester” – FAIE), a partir do destilado da desodorização do óleo de soja (DDOS – como fonte de ácidos graxos) com álcool isoamílico (coproduto gerado na fermentação de bioetanol e o principal constituinte do óleo fúsel) catalisada por lipase comercial Eversa Transform 2.0 (ETL 2.0) na sua forma livre, e por lipase de Pseudomonas fluorescens (PFL) imobilizada pelo método “hybrid nanoflower” (hNF). Planejamento experimental e metodologia de superfície de resposta foram utilizadas para definir parâmetros tanto para a imobilização da PFL por hNF (hNF-PFL), sendo estes parâmetros: a concentração de proteína, a concentração de metal e o pH de imobilização; quanto para a produção dos FAIEs, sendo estes parâmetros: a relação molar DDOS/álcool isoamílico, a temperatura de reação, a quantidade de enzima (para as reações com ETL 2.0) e a massa de material secante (para as reações com hNF-PFL). Estudos voltados para a etapa de incubação na síntese da hNF-PFL permitiram reduzir o tempo de incubação de 72 horas (meio estático a 25 °C) para apenas 20 minutos usando ultrassom, sem perdas no rendimento de imobilização (RI) ou atividade imobilizada (AI). Os valores otimizados de RI e AI para a hNF-PFL foram de 54 e 64 TBU%, respectivamente. A hNF-PFL mostrou alta estabilidade operacional mantendo praticamente os mesmos valores de rendimento de reação (RR) por 8 ciclos, um total de 192 h, e no 10º ciclo, total de 240 h, apresentou RR de 80 % em relação aos primeiros ciclos. A produção de FAIE utilizando ETL 2.0 com controle de umidade por peneira molecular nas condições de 39 e 9 % (relação massa de peneira molecular / massa de DDOS) atingiu valores de RR de 50 e 70 %, respectivamente. Quando a hNF-PFL foi utilizada para a síntese de FAIE, chegou-se ao RR de 64 % sem o uso de agentes de controle de humidade. Produtos com conversões parciais de DDOS em FAIE catalisados por ETL 2.0, com RR de 44 e 55 %, e por hNF-PFL, com RR de 56 e 57 %, apresentaram características físico-químicas similares a bases biolubrificantes comerciais. Assim, esta tese de doutorado tem potencial para contribuir economicamente para o mercado de lubrificantes por meio de um processo enzimático ambientalmente amigável para a síntese de uma base estoque a partir de coprodutos da indústria nacional.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Processo n° 8887.335022/2019-00, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)engUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Engenharia Química - PPGEQUFSCarAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessMonoésteres isoamílicos de ácidos graxosLipase de Pseudomonas fluorescensDDOSEversaPseudomonas fluorescens lipaseSODDHybrid nanoflowerFatty acid isoamyl monoestersENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICASynthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applicationsSíntese de ésteres isoamílicos a partir do destilado da desodorização do óleo de soja por catálise enzimática para aplicações como biolubrificanteinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis60060057a91b28-06b2-4fc7-b127-2a5005569c49reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTese Texto Final - Rafael de A Silva.pdfTese Texto Final - Rafael de A Silva.pdfTexto da Tese - Rafael de Araujo Silvaapplication/pdf4716401https://repositorio.ufscar.br/bitstream/ufscar/17020/1/Tese%20Texto%20Final%20-%20Rafael%20de%20A%20Silva.pdfc35845778d08342694c24f3260aa9818MD51Carta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdfCarta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdfCarta Comprovanteapplication/pdf133682https://repositorio.ufscar.br/bitstream/ufscar/17020/3/Carta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdf5e85551d72c141308bcf3119b7178477MD53CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/17020/4/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD54TEXTTese Texto Final - Rafael de A Silva.pdf.txtTese Texto Final - Rafael de A Silva.pdf.txtExtracted texttext/plain268971https://repositorio.ufscar.br/bitstream/ufscar/17020/5/Tese%20Texto%20Final%20-%20Rafael%20de%20A%20Silva.pdf.txtae8bc557ed922f84803760de361206dcMD55Carta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdf.txtCarta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdf.txtExtracted texttext/plain1423https://repositorio.ufscar.br/bitstream/ufscar/17020/7/Carta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdf.txt8e7c88f2be71e734f4f7d98cc9aa80c3MD57THUMBNAILTese Texto Final - Rafael de A Silva.pdf.jpgTese Texto Final - Rafael de A Silva.pdf.jpgIM Thumbnailimage/jpeg5816https://repositorio.ufscar.br/bitstream/ufscar/17020/6/Tese%20Texto%20Final%20-%20Rafael%20de%20A%20Silva.pdf.jpg384db0416dfe519d12825ae893ddb4f4MD56Carta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdf.jpgCarta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdf.jpgIM Thumbnailimage/jpeg11402https://repositorio.ufscar.br/bitstream/ufscar/17020/8/Carta_Comprovante_Versao_Final_DR_Rafael_de_Araujo_Silva_assinado.pdf.jpg562715656829dc63d68451f2f2a06c91MD58ufscar/170202023-09-18 18:32:25.938oai:repositorio.ufscar.br:ufscar/17020Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32:25Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.eng.fl_str_mv |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications |
dc.title.alternative.por.fl_str_mv |
Síntese de ésteres isoamílicos a partir do destilado da desodorização do óleo de soja por catálise enzimática para aplicações como biolubrificante |
title |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications |
spellingShingle |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications Silva, Rafael de Araujo Monoésteres isoamílicos de ácidos graxos Lipase de Pseudomonas fluorescens DDOS Eversa Pseudomonas fluorescens lipase SODD Hybrid nanoflower Fatty acid isoamyl monoesters ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA |
title_short |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications |
title_full |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications |
title_fullStr |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications |
title_full_unstemmed |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications |
title_sort |
Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications |
author |
Silva, Rafael de Araujo |
author_facet |
Silva, Rafael de Araujo |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/3644040952695236 |
dc.contributor.author.fl_str_mv |
Silva, Rafael de Araujo |
dc.contributor.advisor1.fl_str_mv |
Tardioli, Paulo Waldir |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/0808991927126468 |
dc.contributor.authorID.fl_str_mv |
1f5693a8-2229-4cc3-8bfd-412aad4c8ed7 |
contributor_str_mv |
Tardioli, Paulo Waldir |
dc.subject.por.fl_str_mv |
Monoésteres isoamílicos de ácidos graxos Lipase de Pseudomonas fluorescens DDOS Eversa |
topic |
Monoésteres isoamílicos de ácidos graxos Lipase de Pseudomonas fluorescens DDOS Eversa Pseudomonas fluorescens lipase SODD Hybrid nanoflower Fatty acid isoamyl monoesters ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Pseudomonas fluorescens lipase SODD Hybrid nanoflower Fatty acid isoamyl monoesters |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA |
description |
Lubricants are among the many products whose manufacture is highly dependent on nonrenewable fossil resources, with high levels of production and a vast marketplace, so they are the focus of many environmental laws around the word. Currently, this market includes some biobased products, known as biolubricants, although they represent a very small fraction of this sector and have certain limitations. Studies concerning the development of new products, raw materials, and processes are essential for the expansion and commercial success of biolubricants. Therefore, the aim of this work was: evaluating the production of biolubricant base stocks such as fatty acid isoamyl esters (FAIEs) from soybean oil deodorizer distillate (SODD) as a fatty acids source, together with isoamyl alcohol (a byproduct from bioethanol fermentation and the main constituent of fusel oil), catalyzed by free Eversa Transform 2.0 lipase and Pseudomonas fluorescens lipase (PFL) immobilized by the hybrid nanoflower (hNF) method. Experimental design and response surface methodology were applied to define the parameters for PFL immobilization using hNFs (hNF-PFL), viz. protein concentration, metal concentration and immobilization pH, and for FAIEs production, viz. SODD/isoamyl alcohol molar ratio, reaction temperature, the enzyme mass and secant salt mass (for the reactions with hNF-PFL). Studies of the incubation step of the synthesis using hNF-PFL enabled the incubation time to be reduced from 72 h (static immobilization medium at 25 °C) to just 20 min using ultrasound, without losses of immobilization yield (IY) or immobilized activity (IA). The optimized IY and IA values for hNF-PFL were 54 and 64 TBU%, respectively. The hNF-PFL showed high operational stability, maintaining practically the same reaction yield (RY) values during 8 cycles, over a total of 192 h. At the 10th cycle (total of 240 h), the material presented relative RY of 80%, compared to the earlier cycles. In the production of FAIEs using ETL 2.0 with molecular sieve (for moisture control) at 39 and 9 wt.% (molecular sieve mass / SODD mass), RY values of 50 and 70 wt.% were achieved, respectively. When hNF-PFL was employed in the FAIEs synthesis, RY of 64 wt.% was obtained, without the use of a moisture control agent. Products of partial conversion of SODD into FAIEs, catalyzed by ETL 2.0, with RY of 44 and 55 wt.%, and catalyzed by hNF-PFL, with RY of 56 and 57 wt.%, presented physicochemical characteristics similar to those of commercial biolubricant base stocks. Therefore, this doctoral thesis has the potential to contribute economically to the lubricant market through an environmentally friendly enzymatic process for the synthesis of a base stock from by-products of the national industry. |
publishDate |
2022 |
dc.date.accessioned.fl_str_mv |
2022-11-11T11:40:26Z |
dc.date.available.fl_str_mv |
2022-11-11T11:40:26Z |
dc.date.issued.fl_str_mv |
2022-07-26 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
SILVA, Rafael de Araujo. Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications. 2022. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/17020. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/17020 |
identifier_str_mv |
SILVA, Rafael de Araujo. Synthesis of isoamyl esters from soybean oil deodorizer distillate by enzymatic catalysis for biolubricant applications. 2022. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/17020. |
url |
https://repositorio.ufscar.br/handle/ufscar/17020 |
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eng |
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eng |
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600 600 |
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57a91b28-06b2-4fc7-b127-2a5005569c49 |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ |
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openAccess |
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Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Engenharia Química - PPGEQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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