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 A preocupação com a exploração desenfreada dos recursos naturais tem aumentado nas últimas décadas, principalmente envolvendo a água e seu tratamento. Paradoxalmente, uma das fontes de poluição da água é justamente o seu tratamento, devido ao uso de floculantes químicos, que acabam gerando lodos que podem ser altamente agressivos ao meio ambiente. Uma das formas de resolver este problema é utilizar floculantes naturais para esta finalidade, uma vez que são biodegradáveis e não agridem a natureza. O objetivo deste trabalho foi avaliar a eficiência de um floculante natural produzido com taninos extraídos da casca do cajueiro (Anacardium occidentale) e compará-lo com dois coagulantes comerciais, Tanfloc® e cloreto de ferro. A água para tratamento foi coletada de um açude. A casca do cajueiro foi coletada, moída e submetida à extração em água quente para obtenção dos taninos, e o produto da extração foi cationizado. Os testes de floculação foram realizados utilizando-se o jar test com soluções nas concentrações de 33,3, 66,7 e 100 mg L-1. A turbidez e o pH foram analisados antes e após a floculação. Dentre os floculantes avaliados, os taninos cationizados produziram as melhores respostas tanto para remoção de turbidez quanto para pH final da água tratada. O Tanfloc® também apresentou resultados satisfatórios quanto à remoção de turbidez. O cloreto de ferro, além de não clarificar adequadamente a água, a deixou muito ácida. Como os taninos cationizados praticamente não alteraram o pH e foram eficazes na remoção da turbidez, consistem em um produto interessante para o tratamento da água.

Abstract Concern about the overexploitation of natural resources has increased in recent decades, especially involving water and its treatment. Paradoxically, one of the sources of water pollution is the treatment itself, due to the use of chemical flocculants, which end up generating sludge that may be highly aggressive to the environment. One of the ways to solve this problem is to use natural flocculants for this purpose, since they are biodegradable and do not harm nature. This study evaluated the efficiency of a natural flocculant produced from tannins extracted from the bark of the cashew tree (Anacardium occidentale) and compared it with two commercial coagulants, Tanfloc® and iron chloride. The water for treatment was collected from a weir. The cashew trees’ bark was collected, ground, and submitted to hot-water extraction to yield the tannins, and the extraction product was cationized. The flocculation tests were carried out using the jar test with solutions having concentrations of 33.3, 66.7, and 100 mg L-1. Turbidity and pH were analyzed before and after flocculation. Among the assessed flocculants, the cationized tannins produced the best responses both for removal of turbidity and final pH of the treated water. Tanfloc® also produced satisfactory results regarding turbidity removal. The iron chloride, besides not properly clarifying the water, left it very acidic. Since the cationized tannins practically did not change the pH and were effective in the removal of turbidity, they represent an interesting, sustainable alternative product to treat the water.

RESUMO Taninos condensados são compostos oriundos do metabolismo secundário das plantas. Eles são de especial interesse devido à sua ampla gama de aplicações e usos tecnológicos. O objetivo do presente trabalho foi extrair, quantificar e caracterizar por espectroscopia de infravermelho com transformada de Fourier (FTIR) os taninos da casca de quatro espécies cultivadas na região Nordeste do Brazil: Acacia mangium, Azadirachta indica, Mimosa tenuiflora (‘jurema preta’) e Mimosa caesalpiniifolia (‘sabiá’ ou ‘sansão-do-campo). Amostras de 5 árvores de cada espécie foram coletadas, moídas e extraídas com água quente, determinandose os rendimentos de extração. A partir dos extratos foram determinados o teor de sólidos totais (TST), o índice de Stiasny (IS) e o teor de taninos condensados (TTC). Os espectros de FTIR foram adquiridos a partir de amostras de taninos imobilizados em pastilhas de brometo de potássio. Dentre as quatro espécies, M. tenuiflora teve o mais alto TTC igual a 23,4% e o extrato bruto mais puro com IS de 91,27%. Com base na caracterização por FTIR, os taninos das cascas de M. caesalpiniifolia, A. indica e A. mangium foram classificados como proantocianidinas e os da casca de M. tenuiflora como prodelfinidinas.

ABSTRACT Condensed tannins are chemical compounds derived from the secondary metabolism of plants. They are of particular interest due to their broad range of technological uses and applications. The objective of this study was to extract, quantify, and characterize by Fourier-transform infrared spectroscopy (FTIR) the bark tannins of four forest species grown in Northeast Brazil: Acacia mangium, Azadirachta indica, Mimosa tenuiflora, and Mimosa caesalpiniifolia. Bark samples were collected from 5 trees of each species grown in a five-year-old forest stand. Samples were collected, grounded, and submitted to extraction with hot water, then measured to determine total solids content (TSC), Stiasny number (SN), and condensed tannins content (CTC). FTIR spectra were acquired from tannin samples fixed in potassium bromide pellets. Among the four species, M. tenuiflora presented the highest CTC, equal to 23.4%, and the purest crude hot-water extract with SN of 91.27%. Based on FTIR characterization, tannins from M. caesalpiniifolia, A. indica, and A. mangium barks were classified as proanthocyanidins and those from M. tenuiflora bark as prodelphinidins.

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.

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.

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.

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.