Dalma S. Argüello, Isabel Barroso-Martín, Nancy F. Bálsamo, Griselda A. Eimer, Mónica E. Crivello, Enrique Rodríguez-Castellón
{"title":"优化双功能CuNiMgAl催化剂,高效合成可再生生物产品碳酸甘油","authors":"Dalma S. Argüello, Isabel Barroso-Martín, Nancy F. Bálsamo, Griselda A. Eimer, Mónica E. Crivello, Enrique Rodríguez-Castellón","doi":"10.1002/bbb.70008","DOIUrl":null,"url":null,"abstract":"<p>This paper presents a novel technology for converting glycerol, a byproduct of the biodiesel industry, into glycerol carbonate, a high-value bioproduct. The effect of calcination temperature on the synthesis of quaternary Cu-Ni-Mg-Al catalysts (MMO-Cu<sub>15</sub>Ni<sub>15</sub>-T<sub><i>z</i></sub>) and their application in the transesterification reaction was investigated. Glycerol conversion remained largely unaffected by calcination temperature; however, selectivity toward glycerol carbonate was influenced. Physicochemical analyses showed increased crystallinity and spinel phase formation with higher calcination temperatures, resulting in lower oxide dispersion and decreased specific surface area. Nonetheless, the preservation of nanolayer morphology and increased pore diameter maintained high conversion rates at elevated temperatures. X-ray photoelectron spectroscopy (XPS) confirmed Cu<sup>2+</sup> interactions with the MgAl matrix and the formation of a solid solution. Ultraviolet-visible diffuse reflectance (UV-visible DR) spectroscopy indicated the dominance of octahedrally coordinated Cu<sup>2+</sup> and spinel phases at the highest temperature. The MMO-Cu<sub>15</sub>Ni<sub>15</sub>-T<sub>450</sub> catalyst exhibited the highest concentration of strong basic sites and the lowest concentration of very strong basic sites. Acid–base characterization suggested that very strong basic sites and abundant acid sites promote glycidol formation by glycerol carbonate decarboxylation. Calcination at 450 °C was identified as optimal, maximizing glycerol carbonate yield while minimizing byproduct formation. This work supports a biorefinery approach aligned with circular economy principles to reduce the environmental impact of biodiesel production through the use of cost-effective catalysts and efficient processes.</p>","PeriodicalId":55380,"journal":{"name":"Biofuels Bioproducts & Biorefining-Biofpr","volume":"19 5","pages":"1271-1288"},"PeriodicalIF":2.9000,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://scijournals.onlinelibrary.wiley.com/doi/epdf/10.1002/bbb.70008","citationCount":"0","resultStr":"{\"title\":\"Optimized bifunctional CuNiMgAl catalysts for efficient synthesis of the renewable bioproduct glycerol carbonate\",\"authors\":\"Dalma S. Argüello, Isabel Barroso-Martín, Nancy F. Bálsamo, Griselda A. Eimer, Mónica E. Crivello, Enrique Rodríguez-Castellón\",\"doi\":\"10.1002/bbb.70008\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>This paper presents a novel technology for converting glycerol, a byproduct of the biodiesel industry, into glycerol carbonate, a high-value bioproduct. The effect of calcination temperature on the synthesis of quaternary Cu-Ni-Mg-Al catalysts (MMO-Cu<sub>15</sub>Ni<sub>15</sub>-T<sub><i>z</i></sub>) and their application in the transesterification reaction was investigated. Glycerol conversion remained largely unaffected by calcination temperature; however, selectivity toward glycerol carbonate was influenced. Physicochemical analyses showed increased crystallinity and spinel phase formation with higher calcination temperatures, resulting in lower oxide dispersion and decreased specific surface area. Nonetheless, the preservation of nanolayer morphology and increased pore diameter maintained high conversion rates at elevated temperatures. X-ray photoelectron spectroscopy (XPS) confirmed Cu<sup>2+</sup> interactions with the MgAl matrix and the formation of a solid solution. Ultraviolet-visible diffuse reflectance (UV-visible DR) spectroscopy indicated the dominance of octahedrally coordinated Cu<sup>2+</sup> and spinel phases at the highest temperature. The MMO-Cu<sub>15</sub>Ni<sub>15</sub>-T<sub>450</sub> catalyst exhibited the highest concentration of strong basic sites and the lowest concentration of very strong basic sites. Acid–base characterization suggested that very strong basic sites and abundant acid sites promote glycidol formation by glycerol carbonate decarboxylation. Calcination at 450 °C was identified as optimal, maximizing glycerol carbonate yield while minimizing byproduct formation. This work supports a biorefinery approach aligned with circular economy principles to reduce the environmental impact of biodiesel production through the use of cost-effective catalysts and efficient processes.</p>\",\"PeriodicalId\":55380,\"journal\":{\"name\":\"Biofuels Bioproducts & Biorefining-Biofpr\",\"volume\":\"19 5\",\"pages\":\"1271-1288\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-07-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://scijournals.onlinelibrary.wiley.com/doi/epdf/10.1002/bbb.70008\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Biofuels Bioproducts & Biorefining-Biofpr\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://scijournals.onlinelibrary.wiley.com/doi/10.1002/bbb.70008\",\"RegionNum\":4,\"RegionCategory\":\"生物学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"BIOTECHNOLOGY & APPLIED MICROBIOLOGY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Biofuels Bioproducts & Biorefining-Biofpr","FirstCategoryId":"5","ListUrlMain":"https://scijournals.onlinelibrary.wiley.com/doi/10.1002/bbb.70008","RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"BIOTECHNOLOGY & APPLIED MICROBIOLOGY","Score":null,"Total":0}
Optimized bifunctional CuNiMgAl catalysts for efficient synthesis of the renewable bioproduct glycerol carbonate
This paper presents a novel technology for converting glycerol, a byproduct of the biodiesel industry, into glycerol carbonate, a high-value bioproduct. The effect of calcination temperature on the synthesis of quaternary Cu-Ni-Mg-Al catalysts (MMO-Cu15Ni15-Tz) and their application in the transesterification reaction was investigated. Glycerol conversion remained largely unaffected by calcination temperature; however, selectivity toward glycerol carbonate was influenced. Physicochemical analyses showed increased crystallinity and spinel phase formation with higher calcination temperatures, resulting in lower oxide dispersion and decreased specific surface area. Nonetheless, the preservation of nanolayer morphology and increased pore diameter maintained high conversion rates at elevated temperatures. X-ray photoelectron spectroscopy (XPS) confirmed Cu2+ interactions with the MgAl matrix and the formation of a solid solution. Ultraviolet-visible diffuse reflectance (UV-visible DR) spectroscopy indicated the dominance of octahedrally coordinated Cu2+ and spinel phases at the highest temperature. The MMO-Cu15Ni15-T450 catalyst exhibited the highest concentration of strong basic sites and the lowest concentration of very strong basic sites. Acid–base characterization suggested that very strong basic sites and abundant acid sites promote glycidol formation by glycerol carbonate decarboxylation. Calcination at 450 °C was identified as optimal, maximizing glycerol carbonate yield while minimizing byproduct formation. This work supports a biorefinery approach aligned with circular economy principles to reduce the environmental impact of biodiesel production through the use of cost-effective catalysts and efficient processes.
期刊介绍:
Biofuels, Bioproducts and Biorefining is a vital source of information on sustainable products, fuels and energy. Examining the spectrum of international scientific research and industrial development along the entire supply chain, The journal publishes a balanced mixture of peer-reviewed critical reviews, commentary, business news highlights, policy updates and patent intelligence. Biofuels, Bioproducts and Biorefining is dedicated to fostering growth in the biorenewables sector and serving its growing interdisciplinary community by providing a unique, systems-based insight into technologies in these fields as well as their industrial development.