Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst

The almond industry leaves behind substantial amounts of by-products, with almond hulls being the primary residue generated. Given that one way to improve food security is by decreasing waste to reduce environmental impacts, developing sustainable processes to manage this by-product is necessary. He...

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Autores: Remón, Javier, Sevilla-Gasca, Raquel, Frecha, Esther, Pinilla, José Luis, Suelves, Isabel
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2022
País:España
Recursos:Universidad de Zaragoza
Repositório:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:129475
Acesso em linha:http://zaguan.unizar.es/record/129475
Access Level:Acceso aberto
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spelling Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalystRemón, JavierSevilla-Gasca, RaquelFrecha, EstherPinilla, José LuisSuelves, IsabelThe almond industry leaves behind substantial amounts of by-products, with almond hulls being the primary residue generated. Given that one way to improve food security is by decreasing waste to reduce environmental impacts, developing sustainable processes to manage this by-product is necessary. Herein, we report on the hydrothermal hydrogenation of almond hulls over a carbon-neutral Ru supported on carbon nanofibres (Ru/CNF) catalyst, addressing the temperature, H2 pressure, time and catalyst loading. These variables controlled the distribution of the reaction products: gas (0–5%), liquid (49–82%) and solid (13–51%), and ruled the composition of the liquid effluent. This aqueous fraction comprised oligomers (46–81 wt%), saccharides (2–7 wt%), sugar alcohols (2–15 wt%), polyhydric alcohols (1–8 wt%) and carboxylic acids (7–31 wt%). The temperature and reaction time influenced the extension of hydrolysis, depolymerisation, deamination, hydrolysis, hydrogenation and dehydration reactions. Additionally, the initial H2 pressure and catalyst loading kinetically promoted these transformations, whose extensions were ruled by the amount of H2 effectively dissolved in the reaction medium and the prevalence of hydrogenations over dehydration/decarboxylation reactions or vice versa depending on the catalyst loading. Process optimisation revealed that it is feasible to convert up to 67% of almond hulls into merchantable oligomers at 230 °C, 35 bar initial H2, using 1 g catalyst/g biomass (0.4 g Ru/g biomass) for 360 min. Additionally, decreasing the temperature to 187 °C without modifying the other parameters could convert this material into oligomers (31 wt%) and small oxygenates (17 wt% carboxylic acids, 11 wt% sugar alcohols and 6 wt% polyhydric alcohols) concurrently. The theoretical energy assessment revealed that the total and partial combustion of the spent solid material could provide the required energy for the process and allow catalyst recovery and reutilisation. This environmental friendliness and holistic features exemplify a landmark step-change to valorising unavoidable food waste.2022info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/129475reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/MICINN/IJC-2018-037110-Iinfo:eu-repo/grantAgreement/ES/MICINN/Juan de la Cierva Program-FJCI-2016-30847info:eu-repo/grantAgreement/ES/MINECO/ENE2017-83854-Rinfo:eu-repo/semantics/openAccessoai:zaguan.unizar.es:1294752026-05-29T13:59:51Z
dc.title.none.fl_str_mv Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
title Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
spellingShingle Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
Remón, Javier
title_short Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
title_full Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
title_fullStr Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
title_full_unstemmed Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
title_sort Direct conversion of almond waste into value-added liquids using carbon-neutral catalysts: Hydrothermal hydrogenation of almond hulls over a Ru/CNF catalyst
dc.creator.none.fl_str_mv Remón, Javier
Sevilla-Gasca, Raquel
Frecha, Esther
Pinilla, José Luis
Suelves, Isabel
author Remón, Javier
author_facet Remón, Javier
Sevilla-Gasca, Raquel
Frecha, Esther
Pinilla, José Luis
Suelves, Isabel
author_role author
author2 Sevilla-Gasca, Raquel
Frecha, Esther
Pinilla, José Luis
Suelves, Isabel
author2_role author
author
author
author
description The almond industry leaves behind substantial amounts of by-products, with almond hulls being the primary residue generated. Given that one way to improve food security is by decreasing waste to reduce environmental impacts, developing sustainable processes to manage this by-product is necessary. Herein, we report on the hydrothermal hydrogenation of almond hulls over a carbon-neutral Ru supported on carbon nanofibres (Ru/CNF) catalyst, addressing the temperature, H2 pressure, time and catalyst loading. These variables controlled the distribution of the reaction products: gas (0–5%), liquid (49–82%) and solid (13–51%), and ruled the composition of the liquid effluent. This aqueous fraction comprised oligomers (46–81 wt%), saccharides (2–7 wt%), sugar alcohols (2–15 wt%), polyhydric alcohols (1–8 wt%) and carboxylic acids (7–31 wt%). The temperature and reaction time influenced the extension of hydrolysis, depolymerisation, deamination, hydrolysis, hydrogenation and dehydration reactions. Additionally, the initial H2 pressure and catalyst loading kinetically promoted these transformations, whose extensions were ruled by the amount of H2 effectively dissolved in the reaction medium and the prevalence of hydrogenations over dehydration/decarboxylation reactions or vice versa depending on the catalyst loading. Process optimisation revealed that it is feasible to convert up to 67% of almond hulls into merchantable oligomers at 230 °C, 35 bar initial H2, using 1 g catalyst/g biomass (0.4 g Ru/g biomass) for 360 min. Additionally, decreasing the temperature to 187 °C without modifying the other parameters could convert this material into oligomers (31 wt%) and small oxygenates (17 wt% carboxylic acids, 11 wt% sugar alcohols and 6 wt% polyhydric alcohols) concurrently. The theoretical energy assessment revealed that the total and partial combustion of the spent solid material could provide the required energy for the process and allow catalyst recovery and reutilisation. This environmental friendliness and holistic features exemplify a landmark step-change to valorising unavoidable food waste.
publishDate 2022
dc.date.none.fl_str_mv 2022
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url http://zaguan.unizar.es/record/129475
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/MICINN/IJC-2018-037110-I
info:eu-repo/grantAgreement/ES/MICINN/Juan de la Cierva Program-FJCI-2016-30847
info:eu-repo/grantAgreement/ES/MINECO/ENE2017-83854-R
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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