Examinando por Autor "Martínez, F."

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Activity and resistance of iron-containing amorphous, zeolitic and mesoestructured materials for wet peroxide oxidation of phenol
(ELSEVIER, 2005) Calleja, G.; Melero, J.A.; Martínez, F.; Molina, R.
Iron containing materials have been prepared following several strategies of synthesis and using different silica supports (amorphous, zeolitic and mesostructured materials). Activity and stability of these materials was evaluated on heterogeneous Fenton-type processes for the removal of phenol under mild reaction conditions (T=100º, P=0.1 MPa). Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversions, by-products distribution (aromatics compounds and carboxylic acids) and degree of metal leached into the aqueous solution. The nature and local environment of iron species is strongly dependent on the synthetic route, which dramatically influences on their catalytic performance. Crystalline iron oxide species supported over mesostructured SBA-15 materials have demonstrated to be the most interesting catalysts for phenol degradation according to its high organic mineralization, low sensitive to be leached out and better oxidant efficiency for Fenton like reactions.
Activity and stability of bifunctional perovskite/carbon-based electrodes for the removal of antipyrine by electro-Fenton process
(Elsevier, 2023) Cruz del Álamo, Ana; Puga, Alicia; Pari, Miguel Ángel; Rosales, E.; Molina, Raúl; Pazos, M.; Martínez, F.; Sanromán, M.A.
Bifunctional perovskite/carbon-black(CB)/polytetrafluoroethylene(PTFE) electrodes for electro-generation and catalytic decomposition of hydrogen peroxide to oxidizing hydroxyl radicals have been fabricated. These electrodes were tested for electroFenton (EF) removal of antipyrine (ANT) as a model antipyretic and analgesic drug. The influence of the binder loading (20 and 40 wt % PTFE) and type of solvent (1,3-dipropanediol and water) was studied for the preparation of CB/PTFE electrodes. The electrode prepared with 20 wt % PTFE and water exhibited a low impedance and remarkable H2O2 electro-generation (about 1 g/L after 240 min, a production rate of ca. 6.5 mg/h⋅cm2 ). The incorporation of perovskite on CB/PTFE electrodes was also studied following two different methods: i) direct deposition on the CB/PTFE electrode surface and ii) addition in the own CB/PTFE/ water paste used for the fabrication. Physicochemical and electrochemical characterization techniques were used for the electrode’s characterization. The dispersion of perovskite particles in the own electrode matrix (method ii) exhibited a higher EF performance than the immobilisation onto the electrode surface (method i). EF experiments at 40 mA/cm2 and pH 7 (non-acidified conditions) showed ANT and TOC removals of 30% and 17%, respectively. The increase of current intensity up to 120 mA/cm2 achieved the complete removal of ANT and 92% of TOC mineralisation in 240 min. The bifunctional electrode also proved high stability and durability after 15 h of operation.
Advanced bio-oxidation of fungal mixed cultures immobilized on rotating biological contactors for the removal of pharmaceutical micropollutants in a real hospital wastewater
(Elsevier, 2021) Cruz del Álamo, A.; Pariente, M.I.; Molina, R.; Martínez, F.
Hospital wastewater represents an important source of pharmaceutical active compounds (PhACs) as contaminants of emerging concern for urban wastewater treatment plants. This work evaluates a fungal biological treatment of a hospital effluent before discharging in the municipal sewer system. This treatment was performed in rotating biological contactors (RBCs) covered with wooden planks in order to promote the attachment of the fungal biomass. These bioreactors, initially inoculated with Trametes versicolor as white rot fungi, have created biofilms of a diversified population of fungal (wood-decaying fungi belonging to Basidiomycota and Ascomycetes) and bacterial (Beta-proteobacteria, Firmicutes, and Acidobacteria) microorganisms. The mixed fungal/bacterial community achieved a stable performance in terms of carbon, nitrogen, and phosphorous reductions for 75 days of continuous operation. Moreover, a remarkable removal of pharmaceutical micropollutants was accomplished especially for antibiotics (98.4 ± 0.7, 83 ± 8% and 76 ± 10 for azithromycin, metronidazole and sulfamethoxazole, respectively). Previous studies have proven a high efficiency of fungi for the removal of microcontaminants as a result of advanced bio-oxidation processes mediated by oxidizing hydroxyl radicals. This study evidences the development of a stable fungal-bacterial mixed culture over wooden-modified RBCs for in-situ removal of pharmaceutical compounds of hospital wastewater under non-sterile conditions and non-strict temperature control, avoiding periodical fungal inoculation due to destabilization and displacement of fungal cultures by indigenous wastewater bacteria.
Assessment of Fe2O3/SiO2 catalyst for the continuous treatment of phenol aqueous solutions in a fixed bed reactor
(ELSEVIER, 2010) Botas, Juan Ángel; Melero, J.A.; Martínez, F.; Pariente, M.I.
Different iron-containing catalysts have been tested for the oxidation of phenol aqueous solutions in a catalytic fixed bed reactor in presence of hydrogen peroxide. All the catalysts consist of iron oxide, mainly crystalline hematite particles, over different silica supports(mesostructured SBA-15 silica and non-ordered mesoporous silica). The immobilization of iron species over different silica supports was addressed by direct incorporation of metal during the synthesis or post-synthesis impregnation. The synthesis conditions were tuned up to yield agglomerated catalysts with iron loadings between 10 and 15 wt. %. The influence of the preparation method and the type of silica support was evaluated in a catalytic fixed bed reactor for the continuous oxidation of phenol in terms of its activity (phenol and total organic carbon degradation) as well as its stability (catalyst deactivation by iron leaching). Those catalyst prepared by direct synthesis either in presence (Fe2O3/SBA-15(DS)) or absence(Fe2O3/SiO2(DS)) of template molecules achieved high catalytic performances (TOC reduction of 65 and 52 %, respectively) with remarkable low iron leaching in comparison with the impregnated iron catalysts. Catalytic results demonstrated that the synthesis method plays a crucial role in the dispersion and stability of active species and hence resulting in superior catalytic performances.
Chemically activated hydrochars as catalysts for the treatment of HTC liquor by catalytic wet air oxidation
(Elsevier, 2023) Mora, A. de; Diaz de Tuesta, J.L.; Pariente, M.I.; Segura, Y.; Puyol, D.; Castillo, E.; Lissitsyna, K.; Melero, J.A.; Martínez, F.
Hydrothermal carbonization (HTC) is a highly efficient and valuable technology for treating wet solid wastes and producing solid carbon-based materials named hydrochar. In this work, a hydrochar coming from the HTC of an anaerobic digestion sludge of wastewater treatment plant was used to assess the influence of several activation agents, a base (KOH) and different chloride salts (FeCl3, ZnCl2, and CuCl2) with the exact molar quantities, to develop materials with enhanced surface area and potential inclusion of metal active species for application in wet air oxidation processes. The KOH as an activating agent increased the surface area of hydrochar up to ca. 1000 m2/g of BET surface area. The employment of CuCl2 and FeCl3 as activating agents allows Cu- and Fe-rich doped materials of remarkable surface areas with 49.1 and 42.5 wt% of each metal, respectively. Likewise, the catalytic behavior of the different synthesized carbon-based materials as metal-free and metal-doped catalysts was evaluated for the Catalytic Wet Air Oxidation (CWAO) of a HTC aqueous liquor from a HTC process of animal manure to produce a valuable stream of higher biochemical methane potential in anaerobic digestion. CWAO effluents increased the proportion of carboxylic acids as final by-products due to the oxidation of more complex organic compounds of the initial effluent (ketones, phenols, aromatics and olefins). The CWAO treatments improve the anaerobic digestion rate in biochemical methane potential tests, although the methane production was limited by the lower TOC concentration of the treated streams after CWAO. This research contributes to developing sustainable and efficient strategies for the HTC-liquor treatment, using its solid hydrochar as catalysts, closing the loop of a Circular Economy.
Comprehensive characterization of an oily sludge from a petrol refinery: A step forward for its valorization within the circular economy strategy
(Elsevier, 2021) Jerez, S.; Ventura, M.; Molina, R.; Pariente, M.I.; Martínez, F.; Melero, J.A.
Refinery treatment plants produce large quantities of oily sludge during the petroleum refining processes. The hazardousness associated with the disposal of these wastes, make necessary the development of innovative technologies to handle it adequately, linked to the concepts of circular economy and environmental sustainability. This work provides for the first time a methodology for the deep characterization of this kind of wastes and consequently new insights regarding its valorization. A review of works dealing with the characterization of this type of wastes has been addressed evidencing the complexity and variability of these effluents. The oily sludge under study contains a high concentration of Chemical Oxygen Demand of 196 g COD/L, a Total Kjeldahl Nitrogen of 2.8 g TKN/kg, a phosphorous content as PO43− of 7 g/kg, as well as a great presence of heavy metals in a different range of concentrations. This sludge is composed of three different phases: oily, aqueous and solid. The oily and the solid phases present high percentages of carbon content (84 and 26%, respectively), related to the presence of alkanes ranged from n-C9 to n-C44. Therefore, it could be possible their valorization by the synthesis of catalyst and/or adsorbents. A dark fermentation process could be also proposed for the oily phase to obtain H2 as an alternative energy source. Finally, the aqueous phase contains low carbon and nutrients concentration. A previous thermal pre-treatment applied to the oily sludge might increase nutrient and organic loading in the aqueous phase due to solid destruction, making this aqueous effluent suitable for a further conventional biological treatment.
Coupling membrane separation and photocatalytic oxidation processes for the degradation of pharmaceutical pollutants
(Elsevier, 2013) Martínez, F.; López-Muñoz, M.J.; Aguado, J.; Melero, J.A.; Arsuaga, J.; Sotto, A.; Molina, R.; Segura, Y.; Pariente, M.I.; Revilla, A.; Cerro, L.; Carenas, G.
The coupling of membrane separation and photocatalytic oxidation has been studied for the removal of pharmaceutical pollutants. The retention properties of two different membranes (nanofiltration and reverse osmosis) were assessed. Comparable selectivity on the separation of pharmaceuticals were observed for both membranes, obtaining a permeate stream with concentrations of each pharmaceutical below 0.5 mg/L and a rejected flux highly concentrated (in the range of 16-25 mg/L and 18-32 mg/L of each pharmaceutical for NF-90 and BW-30 membranes, respectively), when an initial stream of six pharmaceuticals was feeding to the membrane system (10 mg/L of each pharmaceutical). The abatement of concentrated pharmaceuticals of the rejected stream was evaluated by means of heterogeneous photocatalytic oxidation using TiO2 and Fe2O3/SBA-15 in presence of hydrogen peroxide as photo-Fenton system. Both photocatalytic treatments showed remarkable removals of pharmaceutical compounds, achieving values between 80 and 100 %. The nicotine was the most refractory pollutant of all the studied pharmaceuticals. Photo-Fenton treatment seems to be more effective than TiO2 photocatalysis, as high mineralization degree and increased nicotine removal were attested. This work can be considered an interesting approach of coupling membrane separation and heterogeneous photocatalytic technologies for the successful abatement of pharmaceutical compounds in effluents of wastewater treatment plants.
Critical review of technologies for the on-site treatment of hospital wastewater: From conventional to combined advanced processes
(Elsevier, 2022) Pariente, María Isabel; Segura, Yolanda; Alvarez, Silvia; Casas, J.A.; Pedro, Z.M. de; Diaz, E.; García, J.; López-Muñoz, M.J.; Marugán, Javier; Mohedano, Ángel Fernandez; Molina, Raúl; Muñoz, M.; Pablos, Cristina; Perdigón-Melón, J.A.; Petre, A.L.; Rodríguez, J.J.; Tobajas, M.; Martínez, F.
This review aims to assess different technologies for the on-site treatment of hospital wastewater (HWW) to remove pharmaceutical compounds (PhCs) as sustances of emerging concern at a bench, pilot, and full scales from 2014 to 2020. Moreover, a rough characterisation of hospital effluents is presented. The main detected PhCs are antibiotics and psychiatric drugs, with concentrations up to 1.1 mg/L. On the one hand, regarding the presented technologies, membrane bioreactors (MBRs) are a good alternative for treating HWW with PhCs removal values higher than 80% in removing analgesics, anti-inflammatories, cardiovascular drugs, and some antibiotics. Moreover, this system has been scaled up to the pilot plant scale. However, some target compounds are still present in the treated effluent, such as psychiatric and contrast media drugs and recalcitrant antibiotics (erythromycin and sulfamethoxazole). On the other hand, ozonation effectively removes antibiotics found in the HWW (>93%), and some studies are carried out at the pilot plant scale. Even though, some families, such as the X-ray contrast media, are recalcitrant to ozone. Other advanced oxidation processes (AOPs), such as Fenton-like or UV treatments, seem very effective for removing pharmaceuticals, Antibiotic Resistance Bacteria (ARBs) and Antibiotic Resistance Genes (ARGs). However, they are not implanted at pilot plant or full scale as they usually consider extra reactants such as ozone, iron, or UV-light, making the scale-up of the processes a challenging task to treat high-loading wastewater. Thus, several examples of biological wastewater treatment methods combined with AOPs have been proposed as the better strategy to treat HWW with high removal of PhCs (generally over 98%) and ARGs/ARBs (below the detection limit) and lower spending on reactants. However, it still requires further development and optimisation of the integrated processes.
Crystallization mechanism of Fe-MFI from wetness impregnated Fe2O3-SiO2
(ELSEVIER, 2004) Melero, J. A.; Calleja, G.; Martínez, F.; Molina, R.; Lázár, K.
The crystallization mechanism of Fe-MFI zeolite synthesized from amorphous Fe2O3- SiO2 xerogels wetness impregnated with aqueous TPAOH solutions has been studied. Samples with different degrees of crystallinity were prepared and characterized by means of conventional techniques. Activity and stability of these iron-containing samples has been tested in the catalytic wet peroxide oxidation (CWPO) of phenolic aqueous solutions. The crystallization mechanism involves a partial dissolution of the initial xerogel to yield an amorphous material. Nucleation and growth of the MFI phase is effected by reorganisation of the amorphous phase, although crystal growth also involves the incorporation of iron and silicon species during the last stage of the crystallization. A highly crystalline Fe-silicalite material is obtained after 3 hours of synthesis at 170 ºC. Spectroscopic studies reveal that iron species are in framework positions (isomorphously substituted) in this highly crystalline material. In addition, the environment of Fe atoms as well as textural properties of the samples is dramatically modified along the crystallization affecting significantly to their catalytic activity and stability in CWPO processes.
Enhancement of the Advanced Fenton process (Fe0/H2O2) by ultrasound for the mineralization of Phenol
(ELSEVIER, 2012-02) Segura, Y.; Martínez, F.; Melero, J.M.; Molina, R.; Chand, R; Bremner, D.H.
In this study, a successful mineralization of phenol was achieved by means of coupling zero-valent iron (ZVI) particles, hydrogen peroxide and a short input of ultrasonic irradiation. This short Sono-Advanced Fenton process (AFP) provided a better performance of ZVI in a subsequent silent degradation stage, which involves neither extra cost of energy nor additional oxidant. The short input of ultrasound irradiation enhanced the activity of the Fe0/H2O2 system in terms of the TOC removal. Then, the TOC mineralization continued during the silent stage, even after the total consumption of hydrogen peroxide, reaching values of ca. 90% TOC conversions over 24 hours. This remarkable activity was attributed to the capacity of the ZVI/iron oxide composite formed during the degradation for the generation of oxidizing radical species and to the formation of another reactive oxidant species, such as the ferryl ion. The modification of the initial conditions of the sono-AFP system such as the ultrasonic irradiation time and the hydrogen peroxide dosage, showed significant variations in terms of TOC mineralization for the ongoing silent degradation stage. An appropriate selection of operation conditions will lead to an economical and highly efficient technology with eventual large-scale commercial applications for the degradation organic pollutants in aqueous effluents.
Heterogeneous catalytic Wet Peroxide Oxidation Systems for the Treatment of an Industrial Pharmaceutical Wastewater
(ELSEVIER, 2009) Melero, J.A.; Martínez, F.; Botas, Juan Ángel; Molina, R.; Pariente, M.I.
The aim of this work was to assess the treatment of a wastewater coming from a pharmaceutical plant through a continuous heterogeneous catalytic wet peroxide oxidation (CWPO) process using a Fe2O3/SBA-15 nanocomposite catalyst. This catalyst was preliminary tested in a batch stirred tank reactor (STR), to elucidate the influence of significant parameters on the oxidation system, such as temperature, initial oxidant concentration and initial pH of the reaction medium. In that case, a temperature of 80ºC using an initial oxidant concentration corresponding to twice the theoretical stoichiometric amount for a complete carbon depletion and initial pH of ca. 3 allow obtaining TOC degradation around 50% after 200 minutes of contact time. Thereafter, the powder catalyst was extruded with bentonite to prepare pellets that could be used in a fixed bed reactor (FBR). Results in the up-flow FBR indicate that the catalyst shows high activity in terms of TOC mineralization (ca. 60% under steady-state conditions), with an excellent use of the oxidant and high stability of the supported iron species. The activity of the catalyst is kept constant, at least, for 55 hours of reaction. Furthermore, BOD5/COD ratio is increased from 0.20 up to 0.30, whereas the Average Oxidation Stage (AOS) changed from 0.70 to 2.35. These two parameters show a high oxidation degree of organic compounds in the outlet effluent, which enhances its biodegradability, and favours the possibility of a subsequent coupling with a conventional biological treatment.
Heterogeneous photo-Fenton degradation of phenolic aqueous solutions
(ELSEVIER, 2005) Martínez, F.; Calleja, G.; Melero, J.A.; Molina, R.
A novel iron-containing mesostructured material has been successfully tested for the heterogeneous photo-Fenton degradation of phenolic aqueous solutions using near UV-visible irradiation (higher than 313 nm) at room temperature and close to neutral pH. This catalyst is a composite material that contains crystalline hematite particles embedded into the mesostructured SBA-15 matrix in a wide distribution of size (30 ¿ 300 nm) and well dispersed ionic iron species within the siliceous framework. The outstanding physicochemical properties make this material a promising photocatalyst leading to better activity than other unsupported iron oxides. An experimental design model has been applied to assign the weight of catalyst and hydrogen peroxide concentrations in the photo-Fenton processes over this particular material. The catalytic performance has been monitored in terms of aromatics and total organic carbon (TOC) conversions, whereas the catalyst stability was evaluated according to the metal leached into the aqueous solution. Hydrogen peroxide concentration plays an important role in the stability of the iron species, preventing their leaching out into the solution, in contrast to the effect shown in typical dark Fenton reaction. The homogeneous leached iron species result in very little contribution to the overall photocatalysis process. Catalyst loadings of 0.5 g/L and concentration of hydrogen peroxide close to the stoichiometric amount have yielded a total abatement of phenol and a remarkable organic mineralization.
Improvement of biogas production and nitrogen recovery in anaerobic digestion of purple phototrophic bacteria by thermal hydrolysis
(Elsevier, 2022) Segura, Yolanda; Molina, Raúl; Rodríguez, I.; Hülsen, T.; Batstone, D.; Monsalvo, V.; Martínez, F.; Melero, José Antonio; Puyol, D.
Purple phototrophic bacteria (PPB) are a novel driver to recover organics and nutrients from wastewater by assimilative growth. Depending on the source, assimilated resources from the PPB biomass can still be recovered after a releasing step. Anaerobic digestion (AD) releases carbon and nutrients, but the release is incomplete. Thermal hydrolysis (TH) as a pretreatment before AD improves the digestibility, release, and subsequent recovery potentials. This work determines the effects of TH in batch and continuous modes regarding methane potential, nutrients’ release efficiencies, volatile solids destruction, degradability, and hydrolysis rates. Continuous runs over 165 days (d) confirmed enhanced recovery potentials, achieving up to 380 LCH4/kgVS (83 % solids destruction) and 73 % N release, respectively. The TH pretreatment is energy-intensive, but with appropriate heat recovery and increased methane production in the AD of the pretreated biomass, a combined configuration is energy positive.
Iron species incorporated over different silica supports for the Phenol
(ELSEVIER, 2007) Martínez, F.; Calleja, G.; Melero, J. A.; Molina, R.
Iron-containing catalysts have been prepared following different synthesis routes and silica supports (amorphous, zeolitic and mesostructured materials). Activity and stability of these materials were assessed on the photo-Fenton degradation of phenolic aqueous solutions using near UV irradiation (higher than 313 nm) at room temperature and initial neutral pH. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversions. Aromatic compounds and carboxylic acids as by-products coming from incomplete mineralization of phenol as well as the efficiency of each catalytic system in the use of the oxidant were also studied. Stability of the materials throughout the photo-Fenton reaction was evaluated in terms of metal leachibility. Activity and stability depend on the environment of iron species and features of silica support. The evolution of pH with the reaction time and their relationship with TOC degradation and leaching degree has been discussed. A nanocomposite material of crystalline iron oxides supported over mesostructured SBA- 15 material is shown the most successful catalyst for degradation of phenolic aqueous solutions by photo-Fenton processes, achieving an outstanding overall catalytic performance accompanied with a noteworthy stability.
Nanocomposite Fe203/SBA-15: An efficient and stable catalyst for the catalytic wet peroxidation of phenolic aqueous solutions
(ELSEVIER, 2007) Melero, J. A.; Calleja, G.; Martínez, F.; Molina, R.; Pariente, M. I.
In this work, the catalytic wet peroxide oxidation of phenolic aqueous solutions over a novel Fe2O3/SBA-15 nanocomposite material was deeply studied. The catalytic performance was monitored in terms of aromatics and total organic carbon (TOC) removals. In order to reduce the major operation cost, significant operating reactions parameters that affect remarkably the overall catalytic performance of these processes, such as temperature and hydrogen peroxide concentration, were studied by means of a design of experiments. High temperature is necessary to obtain a fast and complete degradation of aromatic compounds. At 100ºC, moderate catalyst loading and hydrogen peroxide concentration (0.6 g/L and 75 % of stoichiometric amount for phenol mineralization, respectively) were enough to achieve a total removal of aromatic compounds and remarkable TOC mineralization under non-controlled pH conditions. Resistance of iron species to be leached out into the aqueous solution has been also carefully examined with the purpose of elucidating the influence of different reaction parameters (temperature, oxidant concentration and pH). A schematic view of the heterogeneous catalytic peroxidation of phenol over this novel catalyst has been proposed. Finally, the stability of the catalyst has been established by recycling studies.
New strategies for the management of a primary refinery oily sludge: A techno-economical assessment of thermal hydrolysis, Fenton, and wet air oxidation treatments
(Elsevier, 2023) Jerez, S.; Ventura, M.; Martínez, F.; Melero, J.A.; Pariente, M.I.
Petroleum refinery wastewater treatment plants produce a significant amount of oily sludge, a hazardous waste that requires proper disposal. It is necessary to develop technologies to treat and valorise it, avoiding the current environmental problems associated with its landfill disposal. This work explores the application of different advanced technologies for the pre-treatment and further valorisation of this oily sludge, which includes thermal hydrolysis, Fenton oxidation, and wet air oxidation. These treatments reduce the solid content by 51–78%. Moreover, the increasing dewaterability and settleability facilitate phase separation, thus enabling further valorisation, obtaining an aqueous effluent more biodegradable (ca. 63%). A conceptual design based on experimental data obtained at bench scale has been developed for the three pre-treatment systems under study. Techno-economic analysis of the three advanced treatments gave unitary costs ranging from 78 €/m3 for thermal hydrolysis to 192 €/m3 for the Fenton treatment, which are all in the low range of the current management cost (70–350 €/m3 ). Thus, the techno-economic analysis developed in this study demonstrates its feasibility compared to the current management of oily sludge from API separators. Thermal hydrolysis can be a low-cost and suitable strategy for producing biodegradable effluent that can be directly treated in the conventional biological treatment plant of the refinery. However, WAO might be a more appropriate option to recover carbon and nutrients for further valorisation in advanced biological processes.
Novel 3D electro-Fenton reactor based on a catalytic packed bed reactor of perovskite/carbon microelectrodes for the removal of carbamazepine in wastewater
(Elsevier, 2024-08) Cruz del Álamo, A.; Puga, A.; Dias Soares, C.M.; Pariente, M.I.; Pazos, M.; Molina, R.; Sanromán, M.A.; Martínez, F.; Delerue-Matos, C.
This presents the efficacy of a 3D-ElectroFenton (3D-EF) reactor with active perovskite/carbon black/PTFE microelectrodes for the removal of carbamazepine (CZP) present in wastewater. Incorporating particle microelectrodes in the reactor enhanced the electron transfer and improved the electrocatalytic efficiency, leading to a more effective CZP removal. The optimal operational conditions were meticulously determined, including current intensity (0.05 – 0.3 A) and particle loading (0 – 1.5 g), to optimize the process and minimize energy consumption. The findings reveal that a current intensity of 0.2 A was the most effective, achieving 90% of CZP removal in 60 min and 3.86 kWh/mg of CZP. A higher current intensity of 0.3 A significantly increased the energy consumption (6.02 kWh/mg of CZP) for a total and faster CZP removal. The 3D-EF reactor was also operated continuously with ultrapure water and real urban wastewater fortified with CZP. A remarkable 62% CZP removal after 96 h on continuous operation was achieved with urban wastewater. Physicochemical and electrochemical characterization of microelectrodes demonstrated their high mechanical integrity and chemical stability. Our study underscores the potential of a 3D-EF system as a promising advanced oxidation process to address the continuous removal of antidepressant carbamazepine as one of the more resistant micropollutants of emerging concern in wastewater treatment, offering hope for a more efficient and sustainable future
Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
(ELSEVIER, 2008) Martínez, F.; Morales, G.; Martín, A.; van Grieken, R.
Mesoporous SBA-15 silica materials have been functionalized with perfluorosulfonic acidic Nafion resin using a post-synthetic impregnation method. The remarkable physicochemical properties of hexagonally ordered SBA-15 silicas (high surface area, large and narrow pore size distribution and thermal stability) make them particularly attractive for the immobilization of strongly acidic perfluorosulfonic sites. The loading of Nafion resin was varied between 10 and 20 wt%. The synthesized Nafion/SBA-15 hybrid materials were evaluated in the Friedel Crafts acylation of anisole. The optimum catalytic performance of Nafion/SBA-15 hybrid material with a resin loading around 13 wt% was compared with other perfluorosulfonic acid-based catalysts either commercially available or prepared following recipes reported in the literature. The influence of several variables on the acylation of anisole, such as the reaction temperature and the anisole/acylating agent ratio, has also been assessed by means of a factorial design of experiments. The catalytic activity of Nafion-modified SBA-15 materials is strongly affected by the reaction temperature, whereas a lesser effect was evidenced for the reaction mixture composition in the range under study. The optimal operation conditions in terms of anisole conversion were achieved at 150ºC and equimolar anisole/acetic anhydride mixture. The deposition of poly-acetylated by-products on the catalytic acid sites is mainly responsible for the catalyst deactivation, whereas the leaching of sulfonic groups and their contribution in the anisole acylation via homogeneous catalysis has been ruled out. Finally, the recovery of the catalytic activity by regeneration of the spent catalyst by refluxing in nitric acid solution was demonstrated. The characterization of the regenerated catalyst indicates that the regained activity is likely related to the displacement of the deactivating by-products out of the perflurorosulfonic acid sites during the nitric acid regeneration.
Selective extraction of high-added value carboxylic acids from aqueous fermentative effluents with new hydrophobic eutectic solvents (HES)
(Elsevier, 2024-10-30) Vidal, N.; Ventura, M.; Martínez, F.; Melero, J.A.
Recovering these carboxylic acids from the fermentative streams in a sustainable, green, and economical way is a significant challenge. This work assessed hydrophobic eutectic solvents (HES) – water-immiscible – for the selective recovery of carboxylic acids via liquid–liquid extraction. Different trioctylphosphine oxide (TOPO) mixtures with menthol and thymol were studied and deeply characterized by 1H and 31P NMR to yield stable eutectic solvents, including a novel experiment of 31P NMR at variable temperatures for the first time. Those stable eutectic solvents were tested in the liquid extraction of complex aqueous mixtures containing C2–C6 carboxylic acids and simple sugars (glucose and xylose). The back-extraction of the carboxylic acids for the recovery of the HES was optimized, being necessary in three stages for the complete cleaning of the eutectic solvent using NaOH 0.1 M. The eutectic mixture of TOPO and thymol in a molar ratio of 1:2 exhibited an overall recovery of C5 and C6 carboxylic acids over 70 %, allowing its selective extraction from the rest of the compounds in the complex mixture. Likewise, this HES (after back extraction) was successfully reused in a second extraction cycle, keeping the performance of the fresh one. Therefore, this study demonstrated that HES can have a high extraction selectivity for carboxylic acids of ≥C5. Moreover, these solvents were stable and allowed reusability, reducing the environmental impact and process costs