Open Access
Microwave-assisted pillaring of a montmorillonite with al-polycations in concentrated media
(MDPI, 2017) González, Beatriz; Pérez, Alba Helena; Trujillano, Raquel; Gil Bravo, Antonio; Vicente, Miguel Ángel; Química Aplicada; Kimika Aplikatua
A montmorillonite has been intercalated with Al3+ polycations, using concentrated solutions and clay mineral dispersions. The reaction has been assisted by microwave radiation, yielding new intercalated solids and leading to Al-pillared solids after their calcination at 500 °C. The solids were characterized by elemental chemical analysis, X-ray diffraction, FTIR spectroscopy, thermal analyses, and nitrogen adsorption. The evolution of the properties of the materials was discussed as a function of the preparation conditions. Microwave treatment for 2.5 min provided correctly pillared solids.
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A layered titanosilicate AM-4 as a novel catalyst for the synthesis of 1-methoxy-2-propanole from propylene oxide and methanol
(Elsevier, 2019) Timofeeva, Maria N.; Kurchenko, Julia V.; Kalashnikova, Galina O.; Panchenko, Valentina N.; Nikolaev, Anatoliy I.; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
In this paper we report for the first time the catalytic properties of the titanosilicate AM-4 in the synthesis of 1-methoxy-2-propanol (PGME) from methanol and propylene oxide (PO). PGME is widely used as a pollution-free solvent and intermediate in the synthesis of propylene glycol methyl ether acetate, the herbicide metolachlor and in other industrial applications. We found that the catalytic properties of AM-4 could be adjusted by treatment with 0.0625–0.25 M HNO3. Increasing the concentration of HNO3 led to a decrease in basicity, which played a critical role in the reaction rate and the selectivity towards PGME. The yield of PGME decreased with increased acid concentration. The maximum conversion of PO (88.4%) and the selectivity towards PGME (92.3%) were found to be in the presence of AM-4 at 110 °C and 8 mol/mol MeOH/PO. Our results suggest that titanosilicate AM-4 has great potential for application in basic catalysis.
Open Access
Adsorption of rhodamine 6G and humic acids on composite bentonite-alginate in single and binary systems
(Springer, 2018) Gomri, Fatima; Finqueneisel, Gisele; Zimny, Thierry; Korili, Sophia A.; Gil Bravo, Antonio; Boutahala, Mokhtar; Institute for Advanced Materials and Mathematics - INAMAT2
In this work, the preparation, characterization, and sorption of rhodamine 6G and humic acids on a composite sodium alginate-bentonite were investigated. Their structure and morphology were analyzed by several techniques, including Fourier transform infrared spectroscopy, X-ray diffraction, and N-2 adsorption at - 196 degrees C. A synergetic sorption mechanism was observed in binary systems; humic acids adsorption was enhanced by the presence of Rh6G in the mixture. The kinetic studies revealed that the sorption follows a pseudo-first-order kinetic model and the sorption capacities of Rh6G increased with the pH value. The Langmuir isothermal model well described the adsorption isotherm data, showing a maximum adsorption capacity for Rh6G up to 429.5 mg/g at 20 degrees C. On the basis of the data of the present investigation, it is possible to conclude that the composite exhibited excellent affinity for the dye and humic acids, and it can be applied to treat wastewater containing dye and natural organic matter.
Open Access
Application of industrial wastes from chemically treated aluminum saline slags as adsorbents
(American Chemical Society, 2018) Gil Bravo, Antonio; Arrieta Chango, Ekhine; Vicente, Miguel Ángel; Korili, Sophia A.; Institute for Advanced Materials and Mathematics - INAMAT2
In this study, industrial wastes, which remain after aluminum extraction from saline slags, were used as adsorbents. The aluminum saline slags were treated under reflux with 2 mol/dm3 aqueous solutions of NaOH, H2SO4, and HCl for 2 h. After separation by filtration, aqueous solutions containing the extracted aluminum and residual wastes were obtained. The wastes were characterized by nitrogen adsorption at -196 °C, X-ray diffraction, scanning electron microscopy, and ammonia pulse chemisorption. The chemical treatment reduced the specific surface area, from 84 to 23 m2/g, and the pore volume, from 0.136 to 0.052 cm3/g, of the saline slag and increased the ammonia-adsorption capacity from 2.84 to 5.22 cm3/g, in the case of acid-treated solids. The materials were applied for the removal of Acid Orange 7 and Acid Blue 80 from aqueous solutions, considering both single and binary systems. The results showed interesting differences in the adsorption capacity between the samples. The saline slag treated with HCl rapidly adsorbed all of the dyes present in solution, whereas the other materials retained between 50 and 70% of the molecules present in solution. The amount of Acid Orange 7 removed by the nontreated material and by the material treated with NaOH increased in the presence of Acid Blue 80, which can be considered as a synergistic behavior. The CO2 adsorption of the solids at several temperatures up to 200 °C was also evaluated under dry conditions. The aluminum saline slag presented an adsorption capacity higher than the rest of treated samples, a behavior that can be explained by the specific sites of adsorption and the textural properties of the solids. The isosteric heats of CO2 adsorption, determined from the Clausius-Clapeyron equation, varied between 1.7 and 26.8 kJ/mol. The wastes should be used as adsorbents for the selective removal of organic contaminants in wastewater treatment.
Open Access
White and red Brazilian Sao Simao's kaolinite-TiO2 nanocomposites as catalysts for toluene photodegradation from aqueous solutions
(MDPI, 2019) Mora, Lucas D.; Trujillano, Raquel; Rives, Vicente; Pérez Bernal, María Elena; Korili, Sophia A.; Gil Bravo, Antonio; Faria, Emerson H. de; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
The presence of volatile organic compounds in groundwater is a major concern when it is used as a drinking water source because many of these compounds can adversely affect human health. This work reports on the preparation and characterization of white and red Brazilian Sao Simao's kaolinite-TiO2 nanocomposites and their use as catalysts in the photochemical degradation of toluene, a significant volatile organic compound. The nanocomposites were prepared by a sol-gel procedure, using titanium bis(triethanolaminate)diisopropoxide as a precursor. Thermal treatments of the nanocomposites led to different polymorphic titania phases, while the clay changed from kaolinite to metakaolinite. This structural evolution strongly affected the photocatalytic degradation behavior-all the solids efficiently degraded toluene and the solid calcined at 400 degrees C, formed by kaolinite and anatase, showed the best behavior (90% degradation). On extending the photochemical treatment up to 48 h, high mineralization levels were reached. The advantage of photodegradation using the nanocomposites was confirmed by comparing the results from isolated components (titanium dioxide and kaolinite) to observe that the nanocomposites displayed fundamental importance to the photodegradation pathways of toluene.
Open Access
A response surface methodology for optimization of 2,4-dichlorophenoxyacetic acid removal from synthetic and drainage water: a comparative study
(Springer, 2018) Amiri, Mohammad Javad; Bahrami, Mehdi; Beigzadeh, Bahare; Gil Bravo, Antonio; Institute for Advanced Materials and Mathematics - INAMAT2
The potential of a granular activated carbon (GAC), a rice husk biochar (BRH), and multi-walled carbon nanotubes (MWCNTs) for removing 2,4-dichlorophenoxyacetic acid (2,4-D) from simulated wastewater and drainage water has been evaluated. In this regard, a response surface methodology (RSM) with a central composite design (CCD) (CCD-RSM design) was used to optimize the removal of 2,4-D from simulated wastewater under different operational parameters. The maximum adsorption capacities followed the order GAC > BRH > MWCNTs, whereas the equilibrium time increased in the order MWCNTs < GAC < BRH. In the case of GAC and BRH, the 2,4-D removal percentage increased significantly upon increasing the adsorbent dosage and temperature and decreased upon increasing the initial 2,4-D concentration and pH. The results showed that the contact time and temperature were not important as regards the adsorption efficiency of 2,4-D by MWCNTs, whereas rapid removal of 2,4-D from simulated wastewater was achieved within the first 5 min of contact with the MWCNTs. The results confirmed that the Freundlich isotherm model with the highest coefficient of determination (R2) and the lowest standard error of the estimate (SEE) satisfactorily fitted the 2,4-D experimental data. In addition, successful usage of the three adsorbents investigated was observed for removal of 2,4-D from drainage water from an agricultural drainage system. An economic analysis with a rate of return (ROR) method indicated that BRH could be used as an eco-friendly, low-cost, versatile, and high adsorption capacity alternative to GAC and MWCNTs for the removal of 2,4-D. © 2018, Springer-Verlag GmbH Germany, part of Springer Nature.
Open Access
Efficient recovery of aluminum from saline slag wastes
(Elsevier, 2019) Yoldi Sangüesa, María; Fuentes Ordóñez, Edwin Gustavo; Korili, Sophia A.; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua, PI017 CORRAL
This work presents the procedure to improve the aluminum extracted from a hazardous waste from the recycling of aluminum, aluminum that could be used in the production of value-added materials, as well as with the generation of non-hazardous waste. The aluminum waste was treated under reflux and stirring with NaOH aqueous solutions taking into account two concentrations (1 and 2 mol/dm3), various times of extraction (1, 2 and 4 h) and 4th consecutive steps of extraction in order to obtain solutions with Al3+. The activation of the waste by milling is also analyzed. After extraction, the solution is filtered to separate an aqueous solution that contain the extracted Al3+ and a residual waste. A maximum of 7.54 g/dm3 of aluminum was extracted in the first step, for a total accumulated of 9.59 g/dm3 of aluminum. The extracted aluminum can be used to synthesize added-value products applied as adsorbents and catalysts. Finally, the residual waste generated was characterized by N2 adsorption at −196 °C, X-ray diffraction, X-ray fluorescence, energy-dispersive X-ray and scanning electron microscopy in order to apply it as in future works adsorbent or catalyst.
Open Access
Synthesis of zeolite a from metakaolin and its application in the adsorption of cationic dyes
(MDPI, 2018) Pereira, Priscila Martins; Ferreira, Breno Freitas; Oliveira, Nathalia Paula; Gil Bravo, Antonio; Korili, Sophia A.; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2; Química Aplicada
The present work reports the synthesis of zeolites from two metakaolins, one derived from the white kaolin and the other derived from the red kaolin, found in a deposit in the city of São Simão (Brazil). The metakaolins were prepared by calcination of the kaolins at 600 ◦C; zeolite A was obtained after alkali treatment of the metakaolins with NaOH. The resulting solids were characterized by powder X-ray diffraction, thermal analysis, scanning electron microscopy, and nitrogen adsorption/desorption at −196 ◦C, which confirmed formation of zeolite A. The zeolites were applied as adsorbents to remove methylene blue, safranine, and malachite green from aqueous solutions. The zeolites displayed high adsorption capacity within short times (between one and five minutes); qt was 0.96 mg/g. The equilibrium study showed that the zeolites had higher adsorption capacity for malachite green (qe = 55.00 mg/g) than for the other two cationic dyes, and that the Langmuir isotherm was the model that best explained the adsorption mechanism.
Open Access
Effect of high pressure on the reducibility and dispersion of the active phase of Fischer-Tropsch catalysts
(MDPI, 2019) Yunes, Simón; Vicente, Miguel Ángel; Korili, Sophia A.; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
The effect of high pressure on the reducibility and dispersion of oxides of Co and Fe supported on -Al2O3, SiO2, and TiO2 has been studied. The catalysts, having a nominal metal content of 10 wt.%, were prepared by incipient wetness impregnation of previously calcined supports. After drying at 60 °C for 6 h and calcination at 500 °C for 4 h, the catalysts were reduced by hydrogen at two pressures, 1 and 25 bar. The metal reduction was studied by temperature-programmed reduction up to 750 °C at the two pressures, and the metal dispersion was measured by CO chemisorption at 25 °C, obtaining values between 1% and 8%. The physicochemical characterization of these materials was completed by means of chemical analysis, X-ray diffraction, N2 adsorption-desorption at -196 °C and scanning electron microscopy. The high pressure lowered the reduction temperature of the metal oxides, improving their reducibility and dispersion. The metal reducibility increased from 42%, in the case of Fe/Al2O3 (1 bar), to 100%, in the case of Fe/TiO2 (25 bar).
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Zeolite synthesis from industrial wastes
(Elsevier, 2019) Yoldi Sangüesa, María; Fuentes Ordóñez, Edwin Gustavo; Korili, Sophia A.; Gil Bravo, Antonio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua, PI017 CORRAL
Conventional synthesis conditions for each type of zeolite are tabulated and reported by the International Zeolite Association Structure Commission (IZA) and most of them are synthesized from commercial reagents, but they can also be synthesized from industrial by-products rich in Si and/or Al. In zeolite synthesis from wastes, concentration of alkali source, temperature, reaction time, liquid/solid ratio and type of waste determine the textural properties, crystal structure, Si/Al ratio and ion exchange characteristics of the fabricated zeolite and its applications. This work summarizes the main methods that have been developed to synthesize zeolites using industrial wastes as Al and/or Si sources, the parameters of synthesis and the advantages and limitations of each synthesis process. The main characteristics and the applications of these synthetic waste zeolites are also reported.