Person: Gutiérrez Sánchez, Pablo
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First Name
Pablo
Last Name
Gutiérrez Sánchez
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Ingeniería Química y de Materiales
Area
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9 results
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Item Extraction of neonicotinoid pesticides from aquatic environmental matrices with sustainable terpenoids and eutectic solvents(Separation and Purification Technology, 2022) Gutiérrez Sánchez, Pablo; Navarro, Pablo; Álvarez Torrellas, Silvia; García, Juan; Larriba Martínez, MarcosThe potential environmental impact and adverse effects of the occurrence of pesticides in the aquatic environment have raised great social and political concern, leading to their control by means of several regulations, such as the European Directive 98/83/EC. In this regard, the three neonicotinoid pesticides analyzed in this work (acetamiprid, imidacloprid, and thiamethoxam) have been included in the surface water European Watch Lists under the Water Framework Directive. This research proposes the use of terpenoid-based solvents for the extraction of the three emerging contaminants previously mentioned. An initial screening of the extraction solvents was carried out through the COSMO-RS methodology, selecting the most favourable pure terpenes, eutectic terpenoid-based and conventional solvents. Furthermore, relevant issues were experimentally analyzed, such as extraction in more realistic multicomponent mixtures together with key parametric studies covering operating temperature and matrix influence. Carvacrol, a pure terpenoid not applied before as an extraction solvent of pesticides, has been revealed as an effective and sustainable substitute for conventional solvents for the first time to the best of our knowledge. Specifically, carvacrol exhibited overall extraction yields of around 97.5 % from a river water matrix at a volumetric S/F ratio of 0.1 and 303.2 K. High extraction yields from river water matrices regardless of temperature pointed to the potential of this solvent for a wide range of industrial application.Item Efficient removal of antibiotic ciprofloxacin by catalytic wet air oxidation using sewage sludge-based catalysts: degradation mechanism by DFT studies(Journal of Environmental Chemical Engineering, 2023) Gutiérrez Sánchez, Pablo; Álvarez Torrellas, Silvia; Larriba Martínez, Marcos; Gil, María Victoria; Garrido Zoido, Juan Manuel; García Rodríguez, JuanIn this work, the sewage sludge-derived activated carbon (SAC) loaded with iron nanoparticles (FeSAC) showed a highly effective catalytic activity in the degradation of the antibiotic ciprofloxacin by the CWAO reaction. The properties of FeSAC catalyst were studied by using N2 adsorption-desorption measurements at 77 K, scanning electron microscopy, X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis. The CWAO reaction was evaluated at different temperatures (120–140 ºC), total pressure (10–30 bar) and catalyst doses (0.1–0.7 g/L) in a batch reactor. In this regard, temperature and catalyst dosage showed a significant impact on the removal of the tested antibiotic. By using a catalyst dose of 0.7 g/L, ciprofloxacin degradation and CO2 selectivity were higher than 99 % and 60 %, respectively, and were achieved within two hours at 140 °C and 20 bar. The loss of the active phase (Fe) of the catalyst in the reaction medium was measured, obtaining negligible values (less than 24 ppb). This catalyst showed high stability under the tested reaction conditions. In addition, a potential equation was proposed to correctly describe the evolution of ciprofloxacin degradation. The calculated activation energy of the CWAO process was 53.8 kJ/mol. Additionally, Density Functional Theory (DFT) calculations were performed to illustrate the degradation mechanism of ciprofloxacin, where the electronic energies indicated the compounds that are most difficult to degrade by CWAO. Finally, a proof of concept using an environmentally-relevant matrix was carried out, verifying the technical feasibility of the synthesized catalyst for its application with more complex matrices, consecutive reaction cycles and at a low treatment costItem Influence of transition metal-based activating agent on the properties and catalytic activity of sewage sludge-derived catalysts. Insights on mechanism, DFT calculation and degradation pathways(Journal of Molecular Liquids, 2023) Gutiérrez Sánchez, Pablo; Álvarez Torrellas, Silvia; Larriba Martínez, Marcos; Gil, María Victoria; Garrido Zoido, Juan Manuel; García Rodríguez, JuanResearch studies combining the detailed physicochemical properties' analysis, the catalytic activity in different real aqueous matrices, the proposal of degradation mechanisms and the stability of the intermediates/by-products by means of the Density-functional theory (DFT) are scarce. Therefore, this work gives a step forward in the field of circular economy and the removal of emerging pollutants such as the antibiotic ciprofloxacin, covering all the previously aspects mentioned, using four iron and nickel-based catalysts from two different sewage sludge. Experimental results revealed a significant influence of both the source of the sewage sludge and the activating agent used (iron chloride, nickel chloride and a mixture of both) on the physicochemical properties of the materials and, hence, on their catalytic activity. FTIR studies and chemical composition evidenced that the use of this biomass precursor leads to the generation of a wide variety of functional groups and heteroatoms in the synthesized catalyst structure. Moreover, they showed a combination of Type I-IV isotherms with H3-H4 type hysteresis loops, being mainly mesoporous materials and exhibiting a moderate microporosity except when nickel chloride was used solely as activating agent. The carbonaceous materials reached ciprofloxacin adsorption capacities in the range of 40.4–73.9 mg/g. The use of nickel chloride showed the lowest adsorption contribution and catalytic activity. The bimetallic catalyst (synthesized from a mixture of iron and nickel chloride) showed slightly higher catalytic activity than that found for the iron catalyst, but the metal leaching was also considerably higher. Consequently, the use of iron chloride solely as activating agent seems to be the better alternative, achieving a maximum ciprofloxacin removal around 99.7 % and an iron leaching concentration into the reaction medium of 0.48–0.61 mg/L. The main degradation pathways of ciprofloxacin were proposed according to the detection of LC-MS intermediates and DFT calculation, indicating the most likely areas of attack of reactive species on atoms with a high Fukui index (f0)- Project number: 208
Item Practicando Ingeniería Química: Prácticas colaborativas de bajo coste para grupos numerosos() Larriba Martínez, Marcos; Ovejero Escudero, Gabriel; García Rodríguez, Juan; Delgado Dobladez, José Antonio; Águeda Maté, Vicente Ismael; Álvarez Torrellas, Silvia; Martín Martínez, María; Carbajo Olleros, Jaime; García Sánchez, Laura; Guerrero Moreno, Elisa; Aranda López, Daniel; Serra Pérez, Estrella; Pascual Muñoz, Gonzalo; Rodríguez Llorente, Diego; Cañada Barcala, Andrés; Sanz Santos, Eva; Gutiérrez Sánchez, Pablo; Calero Berrocal, Rubén; Sánchez Quiñones, Carlos Alberto Augusto; Cañas Jiménez, Javier; Huber Benito, Diego; Portillo Sánchez, Eva; Martín Gutiérrez, Diego; Suárez Rodríguez, Pablo; Sánchez Fernández, IgnacioElaboración de un catálogo de prácticas de laboratorio de bajo coste para trabajar los fundamentos de ingeniería química con grupos numerosos, usando metodologías activas de aprendizaje para incrementar la motivación de los estudiantes. Item Extraction of pharmaceuticals from hospital wastewater with eutectic solvents and terpenoids: computational, experimental, and simulation studies(Chemical Engineering Journal, 2022) Rodríguez Llorente, Diego; Hernández, Elisa; Gutiérrez Sánchez, Pablo; Navarro, Pablo; Águeda Maté, V. Ismael; Álvarez Torrellas, Silvia; García Rodríguez, Juan; Larriba Martínez, MarcosThe presence of pharmaceuticals in wastewater, mainly in hospital wastewater, is a serious environmental concern, as they are not removed by conventional processes in wastewater treatment plants and are discharged into the natural environment. This work proposes extracting drugs from hospital wastewater using natural, renewable, and non-toxic solvents such as terpenes and eutectic solvents. First, molecular simulation has been used with the COSMO-RS method performing a massive screening of 43 terpenes, 11 eutectic solvents, and 5 conventional solvents with 31 common pharmaceuticals. The most promising solvents in the screening have been chosen to extract 11 pharmaceuticals simultaneously. Experimental tests with ultrapure water and real hospital wastewater matrices showed a strong influence of pH and matrix on extraction. Under the optimal conditions, global pharmaceutical extraction yields with carvacrol of 94.16 % and the eutectic solvent thymol+dodecanoic acid of 96.86 % were obtained. The regeneration and reuse of both solvents were studied in 5 consecutive stages, showing the carvacrol's high stability and regenerability. Using carvacrol, countercurrent extraction tests showed a fast mass transfer of pharmaceuticals and high extraction yields using low solvent-to-feed (S/F) ratios. The predictions obtained with COSMO-RS were similar to the experimental results, confirming the reliability of this method for selecting alternative solvents for the extraction of pharmaceuticals. Finally, the drug removal process was simulated in a countercurrent extraction. The complete removal of pharmaceuticals from hospital wastewater could be achieved using carvacrol with an S/F of 2.00 at pH 4.00 in an extractor with six equilibrium stages.Item Si l@s estudiantes universitari@s no eligen ingenierías que las ingenierías vayan al colegio.(2022) Águeda Maté, Vicente Ismael; Ovejero Escudero, Gabriel; Delgado Dobladez, José Antonio; García Rodríguez, Juan; Álvarez Torrellas, Silvia; Larriba Martínez, Marcos; Serra Pérez, Estrella; Uguina Zamorano, María de los Ángeles; Curto Maldonado, Andrés; Pascual Muñoz, Gonzalo; García Dávila, Oscar; Rodríguez Llorente, Diego; Corral Pumarega, Jose Luis; Hernández Abreu, Ana Belén; García López, Inmaculada; Sánchez Quiñones, Carlos Alberto Augusto; Cañas Jiménez, Javier; Cañada Barcala, Andrés; Sanz Santos, Eva; Gutiérrez Sánchez, Pablo; Sanz Santos, Alberto; Sánchez Morales, Laura LailaLa pandemia provocada por el virus SARS-CoV-2 ha puesto de manifiesto la imperiosa necesidad de construir una sociedad basada en el conocimiento. Otros grandes retos sociales como son revertir el cambio climático y la conservación y/o recuperación del entorno natural hacen énfasis en la necesidad de un desarrollo sostenible e igualitario. En este sentido es necesario concienciar a las nuevas generaciones del papel primordial que deben jugar las ingenieras e ingenieros en el desarrollo futuro como motores de ese cambio necesario. Sin embargo, el número de estudiantes de ingenierías disminuye paulatinamente, siendo además profesiones copadas mayoritariamente por hombres. En el presente proyecto se plantea ir a colegios e institutos de la Comunidad de Madrid a realizar actividades que pongan de manifiesto lo que la ingeniería puede hacer por la sociedad, presentado por los y las estudiantes de ingeniería química de la UCM que servirán de referentes tanto femeninos como masculinos para las generaciones venideras.Item Extraction of antibiotics identified in the EU Watch List 2020 from hospital wastewater using hydrophobic eutectic solvents and terpenoids(Separation and Purification Technology, 2022) Gutiérrez Sánchez, Pablo; Rodríguez Llorente, Diego; Navarro, Pablo; Águeda Maté, Vicente Ismael; Álvarez Torrellas, Silvia; García, Juan; Larriba Martínez, MarcosThe increasing consumption of pharmaceuticals, along with the ineffectiveness of conventional wastewater treatment, has resulted in an increased presence of these pollutants in both drinking water supplies and aquatic environments. The potential adverse health effects and environmental impact of these chemicals are drawing the attention of several bodies around the world. For instance, some antibiotics such as ciprofloxacin, trimethoprim, and sulfamethoxazole have been included in the most recent European Surface Water Watch List under the EU Water Framework Directive (Decision 2020/1161). The present work proposes the use of terpenoids and eutectic solvents, as effective and green solvents with low toxicity, for multicomponent liquid-liquid extraction of ciprofloxacin, trimethoprim, and sulfamethoxazole from ultrapure water and hospital wastewater. The COSMO-RS method was used for a predictive initial solvent screening. Thymol, carvacrol, eutectic solvents (thymol + fatty acids), and conventional solvents (methyl isobutyl ketone and ethyl acetate) were selected to be used in the experiments. The influence of the volume S/F ratio, aqueous matrix, and pH was analysed. Conventional solvents show significantly lower overall extraction yields than those observed for eutectic solvents and terpenoids at any pH and matrix. Carvacrol presented the most favourable conditions, reaching overall extraction yields above 98.0% (98.9% for trimethoprim, 99.5% for ciprofloxacin, and 97.0% for sulfamethoxazole) with hospital wastewater at pH 5.0 and S/F ratio of 1.00. Carvacrol showed a feasible operating in a continuous extraction column at room temperature, providing effective reuse and regeneration processes in this study.The increasing consumption of pharmaceuticals, along with the ineffectiveness of conventional wastewater treatment, has resulted in an increased presence of these pollutants in both drinking water supplies and aquatic environments. The potential adverse health effects and environmental impact of these chemicals are drawing the attention of several bodies around the world. For instance, some antibiotics such as ciprofloxacin, trimethoprim, and sulfamethoxazole have been included in the most recent European Surface Water Watch List under the EU Water Framework Directive (Decision 2020/1161). The present work proposes the use of terpenoids and eutectic solvents, as effective and green solvents with low toxicity, for multicomponent liquid-liquid extraction of ciprofloxacin, trimethoprim, and sulfamethoxazole from ultrapure water and hospital wastewater. The COSMO-RS method was used for a predictive initial solvent screening. Thymol, carvacrol, eutectic solvents (thymol + fatty acids), and conventional solvents (methyl isobutyl ketone and ethyl acetate) were selected to be used in the experiments. The influence of the volume S/F ratio, aqueous matrix, and pH was analysed. Conventional solvents show significantly lower overall extraction yields than those observed for eutectic solvents and terpenoids at any pH and matrix. Carvacrol presented the most favourable conditions, reaching overall extraction yields above 98.0% (98.9% for trimethoprim, 99.5% for ciprofloxacin, and 97.0% for sulfamethoxazole) with hospital wastewater at pH 5.0 and S/F ratio of 1.00. Carvacrol showed a feasible operating in a continuous extraction column at room temperature, providing effective reuse and regeneration processes in this study.Item Evaluation of the adsorptive and catalytic properties of sludge-based carbon materials for the efficient removal of antibiotics listed in the European Decision 2020/1161/EU(Journal of Environmental Chemical Engineering, 2023) Álvarez Torrellas, Silvia; Segura, Yolanda; de Mora, A.; Gutiérrez Sánchez, Pablo; Sanz Santos, Eva; Corrochano, Noelia; Larriba Martínez, Marcos; Pariente, M. I.; Martínez, Fernando; García, Juan JoséIn this work, sludge from an oily refinery and urban wastewater treatment plant have been used for the synthesis of activated carbons using ZnCl2 and KOH as activating agents. The materials were used as adsorbents and catalysts for the removal of three antibiotics, e.g., sulfamethoxazole (SMX), trimethoprim (TMP) and ciprofloxacin (CPX). The activated carbons have been fully characterized. Thus, the BET surface area of the materials ranged from 183 to 784 m2/g. Qe values of 127.3 mg/g for SMX onto U-ZnCl2; 168.5, and 179.6 mg/g for TMP and CPX, respectively, onto R-KOH were obtained. The best fitting of kinetic data was found by using pseudo-second order (PSO) model, while Freundlich and Liu models successfully fitted the equilibrium adsorption isotherms. SMX, TMP and CPX adsorption mechanisms were governed by pore filling, π-π interactions and H-bonds. R-KOH material was used for wastewater treatment, finding that the adsorption capacity decreased due to a competitive effect. Regarding the Fenton process, the U-ZnCl2 carbon achieved the total SMX degradation after 60 min. In contrast, TMP and CPX showed the highest depletion in only 20 min. The higher performances of the U-ZnCl2 material may be due to a higher C/O ratio and high N and Zn contents. In the experiments with a real aqueous matrix, similar conversions were achieved, although the kinetic constants resulted in slightly lower values. So, it could be stated that adsorption and Fenton oxidation performance were influenced by the different properties of the carbon materials.- Project number: 142
Item Lab at home: prácticas experimentales de Ingeniería Química en tiempos de pandemia(2022) Larriba Martínez, Marcos; Ovejero Escudero, Gabriel; García Rodríguez, Juan; Delgado Dobladez, José Antonio; Águeda Maté, Vicente Ismael; Álvarez Torrellas, Silvia; Martín Martínez, María; García Sánchez, Laura; Peinado Serrano, María Cristina; Serra Pérez, Estrella; Pascual Muñoz, Gonzalo; Rodríguez Llorente, Diego; Cañada Barcala, Andrés; Sanz Santos, Eva; Gutiérrez Sánchez, Pablo; Calero Berrocal, Rubén; Sánchez Quiñones, Carlos Alberto Augusto; Cañas Jiménez, Javier; Santos Sanz, Alberto; Carreras Navarro, Francisco Javier; Sánchez Morales, Laura Laila; Nájera García, Roberto