Person: Rodríguez Llorente, Diego
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First Name
Diego
Last Name
Rodríguez Llorente
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Ingeniería Química y de Materiales
Area
Identifiers
3 results
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Item Novel approach for azole fungicides extraction from aqueous environments using terpenes and eutectic solvents(Journal of Environmental Chemical Engineering, 2023) Rodríguez Llorente, Diego; García Fernández de la Puente, Enrique; García Rodríguez, Juan; Larriba Martínez, MarcosThe presence of azole fungicides in aquatic environments is a significant issue due to their toxicity and persistence related to a low removal of these compounds by conventional processes in wastewater treatment plants. A growing environmental public concern is reflected in the inclusion of these compounds in the 2020 and 2022 European Surface Water Watch Lists. Therefore, it is necessary to develop efficient processes that allow their removal sustainably. This work applies liquid-liquid extraction using terpenes as green solvents and terpene-based eutectic solvents to remove azole fungicides from aqueous streams imazalil, metconozale, penconazole, prochloraz, and tebuconazole. First, an initial screening was performed by molecular simulation using the COSMO-RS method. The selected solvents were applied in the individual extraction of azole fungicides, and selecting the solvents thymol+octanoic acid and carvacrol. These solvents have been tested in studies with surface water matrix on the effect of temperature, initial concentration, and pH on extraction performance. From these results, it has been shown that carvacrol is the solvent that is least affected by these variables and obtains extraction yields higher than 97.88%, with a Solvent/Feed ratio up to 0.050, outperforming the conventional solvent methyl isobutyl ketone. This solvent has been used in solvent reuse cycles obtaining a reduction of less than 1% in three extraction cycles. Therefore, carvacrol is presented as a sustainable solvent for the extraction of azole fungicides from aqueous environments.Item Sustainable recovery of phenolic antioxidants from real olive vegetation water with natural hydrophobic eutectic solvents and terpenoids(Environmental Research, 2023) Rodríguez Llorente, Diego; Martín Gutiérrez, Diego; Suárez Rodríguez, Pablo; Navarro Tejedor, Pablo; Álvarez Torrellas, Silvia; García Rodríguez, Juan; Larriba Martínez, MarcosOlive oil production leads to the generation of olive mill wastewater (OMWW). Due to the presence of phenolic compounds, they are difficult to process, but they represent a source of high-added value chemicals since they have antioxidant and therapeutic properties. This work has studied the extraction of phenolic compounds from a type of OMWW, olive vegetation water, which presents these compounds in a more diluted dosage than in other studied to date, to revalue this waste stream. A real olive vegetation water from a Spanish olive oil producer was used, and liquid-liquid extraction was applied. Terpenoids and terpene-based hydrophobic eutectic solvents were systematically used to extract phenolic compounds following the concentrations of tyrosol, catechol, caffeic acid, and total phenolic content. By molecular simulation with the COSMO-RS method, 4 terpenoids, and 2 eutectic solvents were selected and compared with 2 conventional solvents. The Solvent/Feed ratio in the extraction of phenolic compounds was studied, showing that the solvents with the highest extraction results were geraniol, eucalyptol, and eutectic solvent menthol + camphor, which outperformed conventional solvents methyl isobutyl ketone and diisopropyl ether. Menthol + camphor gave total phenol extraction yields of 88.73% at a Solvent/Feed ratio in volume of 0.50, surpassing all solvents tested. A solvent reuse and regeneration process was applied by back-extraction of the 4 solvents: FTIR results showed the stability of the solvents while maintaining yields in the solvent reuse process. The phenolic compounds could be concentrated in the alkaline phase to factors up to 49.3 to the initial concentration in olive vegetation water. The alkaline phases were neutralized to obtain a precipitate with a caffeic acid content of up to 26 % wt%, and a tyrosol-rich supernatant with a concentration of up to 6.54 g/L. This work proposes a process using natural solvents to extract phenolic compounds from olive vegetation water.Item Flow-based recovery of acetic acid from aqueous solutions using bio-derived terpenes as extracting solvents(Separation and Purification Technology, 2023) Rodríguez Llorente, Diego; Liu, Yu; de Mello, John C.; García Rodríguez, Juan; Larriba Martínez, MarcosThe ability to recover acetic acid and related byproducts from wastewater treatment plants would unlock a sustainable source of important building block-chemicals that are currently derived from fossil fuels. We report here a two-stage flow-based procedure for the extraction and alkaline back-extraction of acetic acid from an aqueous feed solution, using geraniol or eucalyptol as bio-derived organic solvents. In the first stage, acetic acid is extracted from the feed solution into the organic solvent; and, in the second stage, acetic acid is back-extracted into a 2-M NaOHaq solution, leaving a regenerated solvent that may be used for further extractions. Recovery efficiencies of up to 51 % and 37 % were obtained using geraniol and eucalyptol, respectively. By back-extracting acetic acid into a smaller volume of NaOH than the feed solution from which it was extracted, more than threefold enhancements in acetic acid concentration were achieved with respect to the feed solution. Overall acetic acid recovery efficiencies of 57 ±1% and 46 ±2% were obtained for geraniol and eucalyptol, respectively. Both solvents were successfully used for multiple extraction/back-extraction cycles, with geraniol giving a stable concentration of back-extracted acetic acid over the course of ten cycles.