RESUMO: Este trabalho teve como objetivo a valorização das cascas dos frutos da Pachira aquatica Aubl. (PAC) através da sua caracterização energética e pirólise flash para produção de biocombustíveis ou produtos químicos. A caracterização foi realizada através de análises imediata e final, densidade aparente, poder calorífico superior (PCS), conteúdos de hemicelulose, celulose e lignina, análise termogravimétrica e espectros de absorção na região do infravermelho obtidos pela técnica de espectroscopia no infravermelho com transformada de Fourier (FTIR). A pirólise flash analítica foi realizada a 500 °C em equipamento Py-5200 HP-R acoplado a um cromatógrafo à gás (Py-GC/MS). A biomassa das PAC apresenta potencial para processos de conversão termoquímica de energia devido ao seu baixo teor de umidade e cinzas, além de 76,90% de materiais voláteis, densidade aparente de 252,6 kg/m3 e PCS igual a 16,24 MJ / kg. Os produtos da pirólise rápida são principalmente fenóis ou ácidos orgânicos leves derivados da decomposição de polissacarídeos. Os resultados confirmam o potencial das PAC para produzir bio-fenólicos, como o 4-metoxifenol que é um importante ingrediente ativo para despigmentação da pele usado em medicamentos e cosméticos, e como extrato fenólico que pode ser usado como precursor de resinas. Estas aplicações convertem esses resíduos florestais em produtos biológicos para a indústria em uma economia circular verde.

ABSTRACT: This research valorized Pachira aquatica Aubl.’s fruit shells (PAS) through its energetic characterization and flash pyrolysis for biofuels or chemicals production. The characterization was performed through proximate and ultimate analysis, bulk density, higher heating value (HHV), hemicellulose, cellulose and lignin content, thermogravimetric analysis and absorption spectra in the infrared region obtained by Fourier-transform infrared spectroscopy technique (FTIR). The analytical flash pyrolysis was performed at 500°C in a Py-5200 HP-R coupled to a gas chromatograph (Py-GC/MS). The PAS biomass presents potential for thermochemical energy conversion processes due to its low moisture and ash content, 76.90% of volatile matter, bulk density of 252.6 kg/m3 and HHV of 16.24 MJ/kg. Flash pyrolysis products are mostly phenols or light organic acids derived from the decomposition of polysaccharides. Results confirmed the potential of PAS to produce bio-phenolics, such as 4-methoxyphenol which is an important active ingredient for skin depigmentation used in drugs and cosmetics, and as phenolic extract that can be used as a precursor to resins, applications that convert this forest waste into bio products for industry into a green circular economy.

RESUMO Dentre os parâmetros do processo de carbonização, a taxa de aquecimento é um dos mais importantes. O objetivo do presente trabalho foi avaliar a influência de diferentes taxas de aquecimento na composição química do extrato pirolenhoso (EP) de duas espécies de madeira. Discos secos de madeira de Eucalyptus grandis e Mimosa tenuiflora foram utilizados como matéria prima. As carbonizações foram conduzidas em mufla de laboratório em três taxas de aquecimento (0,7, 1,0 e 1,4 °C min-1), com 10 repetições para cada taxa de aquecimento, atingindo temperatura final de 450 °C. Rendimentos gravimétricos em carvão, líquidos e gases de foram obtidas para todas as carbonizações. Os respectivos líquidos brutos da pirólise para cada espécie e taxa de aquecimento foram bidestilados, obtendo-se as amostras de EP purificado. As amostras foram extraídas com acetato de etila e a fração orgânica foi analisada por cromatografia gasosa/espectrometria de massas obtendo-se dados qualitativos e semi-quantitativos. Um total de 57 e 42 compostos químicos foram identificados nos EP’s de Eucalyptus e Mimosa, respectivamente, divididos nos principais grupos: álcoois, cetonas, furanos, piranos e compostos fenólicos. Para as duas espécies, altas taxas de aquecimento favorecem a formação de furanos e piranos e acarretam baixas concentrações de compostos fenólicos.

ABSTRACT Among the parameters used in the biomass carbonization process, the heating rate is one of the most important. The objective of the present work was to assess the influence of different heating rates on the chemical composition of wood vinegar (WV) from two wood species. Dried disks of Eucalyptus grandis and Mimosa tenuiflora wood were used as raw material. Carbonization runs were carried out in a laboratory muffle furnace at three heating rates (0.7, 1.0 and 1.4 °C/min), with 10 runs at each heating rate, reaching 450 °C. Yields of charcoal, pyrolysis liquids and gases were determined for all carbonization conditions. Crude pyrolysis liquid from each wood species and each heating rate was bi-distilled, yielding purified WV samples. These samples were extracted with ethyl acetate and the organic fraction was analyzed by gas chromatography-mass spectrometry to obtain qualitative and semi-quantitative data. Results showed that lower heating rates produce higher yields of charcoal, while higher heating rates lead to higher yields of pyrolysis liquids and gases. Totals of 57 and 42 chemical compounds were identified in the WV of Eucalyptus and Mimosa, respectively, divided into the following groups: alcohols, ketones, furans and pyrans, and phenolic compounds. In general, higher heating rates led to greater contents of furans and pyrans and lower concentrations of phenolic compounds.

ABSTRACT The NiCo2O4 catalyst with spinel structure was prepared by a modified polymeric-precursor method using gelatin as an organic-directing agent. The obtained powder was characterized by XRD, TPR and tested on the partial oxidation of methane. The Rietveld analysis performed on the XRD pattern confirmed the crystallization of two phases, the spinel NiCo2O4, and a solid solution NixCo1-xO. TPR profile revealed that both phases are entirely reduced up to 610 °C. The catalyst showed CH4 conversion of 75 % with H2/CO ratio around 2 and no signal of deactivation by coke formation, such as confirmed by XRD and TG analysis carried out after the catalytic test.

In this paper, magnesium aluminate spinels were prepared by microwave-assisted combustion, using urea as fuel. In order to evaluate the effect of the urea excess used in the synthesis, its mass was added in a range of 1.0 to 2.5 times the stoichiometric amount required. The materials produced were characterized by TGA, FTIR, XRF, XRD, BET, SEM and TEM. The results demonstrated that magnesium aluminate spinel was formed in all solids, but the crystallinity degree and the specific surface area increased according to the amount of urea that was used in the synthesis. The use of excess fuel in the preparation was therefore advantageous, since it eliminated the need of the calcination step, at high temperatures, in order to stabilize the spinel phase and improve the crystallinity of the solid. The heat generated in the combustion process was sufficient to develop the formation of a nanocrystalline structure and produce high purity materials, with a save of 99.4% in energy.

The control of the size and morphology of Metal-Organic Frameworks is a challenge that must be overcome to ensure the use of these materials in advanced applications. Mixed Lanthanide-Organic Frameworks (MLOFs) were synthesized via solvo(hydro)thermal method and then characterized by PXRD, IR, TG/DTA, SEM and PL spectroscopy. The effect of the modulator (acetic acid) on the morphological characteristics of the obtained powders was investigated. Trivalent terbium ions were successfully incorporated into La-framework conferring green luminescence to the prepared samples. It was observed that a gradual increase in acetic acid concentration led to the morphology change from micro-rods to flower-like small particle agglomerates. Moreover, a higher concentration of the acetic acid prevented the crystallization of secondary phases.

Magnesium aluminate can be obtained by the methods: ceramic method, sol-gel, co-precipitation, hydrothermal and combustion. However, this work presents a simple and low cost route to obtain MgAl2O4 through the gelatin method. The main objective was to use gelatin as an organic precursor and to verify the influence of temperature and time of calcination on the structural and morphological properties of obtained materials. Al and Mg nitrates were used as metal precursors with Al/Mg = 2 ratio. Samples were calcined as follows: 700 ºC, 900 ºC and 1100 ºC during 2 and 4 h. The powders were characterized by TGA, XRD and SEM. A single phase material with a crystallinity of 39.18 - 90.40% and crystallite size in the range of 12.4 to 55.5 nm was obtained. The materials exhibited morphology in the form of plates and small agglomerates. It was found that increasing temperature and time of calcination favored the growth of crystallites and increased crystallinity.

In this work, zinc aluminate spinel was prepared by two methods of directly synthesis (without calcination): microwave assisted combustion and hydrothermal method. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and N2-adsorption/desorption isotherms. The XRD patterns confirmed the formation of cubic ZnAl2O4 spinel structure with no secondary phases for both synthesis routes, whereas the hydrothermal method yielded powders with crystallite size 3 times smaller (6.9 nm), as compared to the powders produced by microwave assisted combustion method (25.6 nm). The micrographs revealed agglomerated powders with plate-like morphologies for both routes. Nitrogen adsorption/desorption isotherms (BET) revealed higher surface area (183 m2.g-1) and greater pore volume (0.173 cm3.g-1) for ZnAl2O4 powders prepared by the hydrothermal method.

Inorganic compounds doped with rare earths (Ce3+, Pr3+, Nd3+, Sm3+, Eu 3+, Gd 3+, Tb 3+, Tm3+) have been used in various applications including light-emitting devices such as fluorescent lamps, cathode ray tubes, lasers and inorganic pigments. In this study, Pr3+ is doped in spinel Li2ZnTi3O8 system and synthesized by the polymeric precursor method, which is based on the process developed by the Pechini, and characterized by X-ray diffraction, UV-visible and CIE-L colorimetric measures * a * b *., in order to study the effect of doping and thermal treatment on its colorimetric properties. With three different samples of Pr3+ doping (0.01; 0.05 and 0.1 mol%) were prepared and calcined at 500°C, 600°C, 700°C, 800°C and 900°C for 4 h. The analysis of X-ray diffraction confirmed the formation of pure phases with spinel structure and average crystallite size of less than 46 nm. It was found that the colorimetric properties ranging from green to red, in accordance with the increase in the concentration of Pr3+ and thermal processing temperature.

Nickel-based catalyst precursor for dry reforming of methane was successfully prepared by a self-combustion method. Three different amino acids: urea, glycine and citric acid were tested as fuels in the redox reaction with metal nitrates. For each fuel, a thermodynamic modeling of the combustion reaction was performed. The samples were characterized by X-ray diffraction (XRD), Thermogravimetric analysis (TG), Scanning electron microscopy (SEM), Attenuated total reflectance – Fourier transform infrared (ATR-FTIR) spectroscopy and Temperature-programmed reduction (TPR). XRD data confirmed the presence of several crystalline phases in the as-prepared powders. The sample prepared with citric acid showed very low crystallinity when compared to the other samples. It was found that the heat release rate of the self-combustion is the determinant factor of the crystallization, and it is fuel dependent. SEM results suggest that the distribution and average particle size of as-prepared powders can be controlled by the appropriate selection of the fuel. Further calcination of these samples at 800 °C/4h led to the crystallization of perovskite-type structure LaNiO3. Nanostructured Ni0/La2O3 obtained after reduction of LaNiO3 precursor showed high catalytic activity in dry reforming of methane.

There is a growing concern on the relationship between anthropogenic carbon dioxide and climate changes. A promising approach is the adsorption technology using mesoporous MCM-41 materials that can be easily synthesized to depict structures adequate to the flow of gas. The aim of this study was to improve the synthesis of MCM-41 using cationic surfactant mixtures and apply the resulting materials to CO2 adsorption. To that end, the simplex-centroid design was applied to optimize CO2 adsorption from seven mesoporous MCM-41 materials synthesized by the hydrothermal method using surfactants from hydrophobic chains of different sizes. The cationic surfactants used were tetradecyltrimetylammonium bromide, cetyltrimethylammonium bromide, trimethyloctadecylammonium bromide and their mixture at ratios of 1:1 and 1:1:1. The CO2 adsorption was investigated using thegravimetric method at 298 K and pressures up to 40 bar. The resulting materials, labelled C17, C19, C21, C17C19, C19C21, C17C21 and C17C19C21, were characterized by XRD, FTIR, TG and SEM and showed significant differences in structure as well as in the mass of CO2 adsorption. The response models showed that the best combination of the surfactants resulted from C17C19 sample, which presented synergistic interactions reaching the highest value of CO2 adsorption (0.62 g CO2/g adsorbent), compared to other samples.

This work aimed to determine and compare the apparent activation energy, involved in thermal decomposition of CTMA+ from the pores of Ti-MCM-41 synthesized by two different source of silica in order to evaluate their influence in the template removal. The molecular sieves Ti-MCM-41 were synthesized using rice husk ash (RHA), as alternative low cost source of silica, and commercial silica gel, obtaining two mesoporous material by hydrothermal synthesis of gel molar composition of: 1.0 CTMABr: 4.0 SiO2: X TiO2: 1.0 Na2O: 200.0 H2O. The samples were characterized to compare its properties by X-ray diffraction, IR spectroscopy, BET method and thermogravimetric analysis (TGA). The kinetic study using the model proposed by Flynn and Wall to determine the apparent activation energy for CTMA+ removal was performed using TGA data. The thermogravimetric analysis results of the material obtained from RHA confirmed intrinsic properties of mesoporous MCM-41 as the synthesized with commercial silica gel, such as high specific area, mesoporous range of pore diameter and hexagonal structure. According to the kinetics results the RHA showed similar chemical interaction to commercial silica gel, which makes it an interesting material, since it is a low cost source of natural silica from agricultural waste.

Biodiesel is a fuel renewable, biodegradable and environmentally correct fuel, which can be obtained from the esterification reactions, transesterification and pyrolisis. Montmorillonite is a clay mineral of the smectite group and are of great interest for industrial processes such as catalysis and adsorption. Acid activation of clay minerals is one of the most effective methods proposed to produce active materials. In this work, montmorillonite clay was treated with H2SO4 in different concentrations (0.2 – 0.8 mol L–1), characterized by X-ray diffraction (XRD), infrared spectroscopy (FT-IR) and applied in the catalytic esterification of oleic acid. The results reveal that the clay treated with aqueous solutions 0.8 mol L–1 H2SO4 shows promising catalytic activity toward the studied reaction, with maximum conversion of oleic acid of 65% at 30 °C.

This work aimed to study the kinetics of thermal and catalytic pyrolysis using Ti-MCM-41 as catalyst in order to assess the catalytic pyrolysis efficiency compared to thermal pyrolysis of elephant grass. Ti-MCM-41 molecular sieve was synthesized by hydrothermal method from hydrogel with the following molar composition:1.00 CTMABr: 4.00 SiO2:X TiO2: 1 + X Na2O: 200.00 H2O, whichstructure template used was cetyltrimethylammonium bromide (CTMABr). The materials synthesized were characterized by X-ray diffraction, IR spectroscopy, thermogravimetric analysis and specific area by the BET method, for subsequent application in the biomass pyrolysis process. The kinetic models proposed by Vyazovkin and Flynn-Wall were used to determine the apparent activation energy involved in the thermal and catalytic pyrolysis of elephant grass and the results showed that the catalyst used was effective in reducing the apparent activation energy involved in the thermal decomposition of elephant grass.

Polycrystalline strontium-doped lanthanum manganite (LSM) powders with 0.15, 0.22, and 0.30 mol % Sr were synthesized by the polymeric precursor route using a molar ratio of 3:1 citric acid and metal cations. The powders were characterized by Fourier transform infrared spectroscopy, thermal analysis, high-temperature X-ray diffraction to determine the crystalline perovskite phase and crystallite sizes, scanning electron microscopy for the morphological analysis, nitrogen adsorption to determine the specific surface area, and laser scattering to evaluate the particle size distribution. The LSM perovskite-type oxides containing intermediate 0.22 mol % Sr were found to exhibit a tendency to decrease in crystallite size and increase in specific surface area and, when calcined at 700-900 ºC exhibited a pure phase of perovskite, had a crystallite size of about 17-20 nm and a specific surface area for 900 ºC of 34.3 m².g-1.

The major applications of organoclays are in adsorption of organic polluents. The objective of this work was the synthesis and characterization of organoclays using differents amounts of cationic surfactant hexadecyltrimethylammonium bromide. The clays were characterized by low angle x-ray diffraction (XRD), scanning electron microscope (SEM), infrared with Fourier tranformation (FTIR), BET surface area, elemental analysis (CHN), Foster swell and adsorption of methylene blue. The surfactant can adsorb in differents forms in the interlamelar region changed the basal spacing. The presence of the surfactant adsorbed can be favorable or not in adsorption of the methylene blue due the different interactions dye-organoclays.