Valorization of Wastes for Biodiesel Production: The Brazilian Case

This chapter intends to bring an overview about the Brazilian researches and their contributions to the production of biodiesel from wastes. Currently, the main obstacles to spread the use of biodiesel are its high cost of production and the competition between biodiesel and food industries. So, the use of wastes plays an important role in reducing the biodiesel costs and reusing the materials that have no other applications, as deodorization residues, neutralization soap sticks, and animal fats, among others. Then, we present a review about Brazilian studies involving waste oils and fatty–acid-rich raw materials that helped the advancement in this field of knowledge during the last few years

Acetylation of Eugenol on Functionalized Mesoporous Aluminosilicates Synthesized from Amazonian Flint Kaolin

The present work was aimed to investigate the catalytic activity of a mesoporous catalyst synthesized from 3-mercaptopropyltrimethoxysilane (MPTS) functionalized Amazonian flint kaolin in the acetylation of eugenol with acetic anhydride. Materials were characterized by thermogravimetry (TGA), N2 adsorption (BET), X-ray dispersive energy spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and acid-base titration. The results presented proved the efficiency of flint kaolin as an alternative source in the preparation of mesoporous materials, since the material exhibited textural properties (specific surface area of 1071 m2 g−1, pore volume of 1.05 cm3 g−1 and pore diameter of 3.85 nm) and structural properties (d100 = 4.35 nm, a0 = 5.06 nm and Wt = 1.21 nm) within the required and characteristic material standards. The catalyst with the total amount of acidic sites of 4.89 mmol H+ g−1 was efficient in converting 99.9% of eugenol (eugenol to acetic anhydride molar ratio of 1:5, 2% catalyst, temperature and reaction time 80 °C and 40 min reaction). In addition, the reused catalyst could be successfully recycled with 92% conversion activity under identical reaction conditions

Acetylation of Eugenol over 12-Molybdophosphoric Acid Anchored in Mesoporous Silicate Support Synthesized from Flint Kaolin

A new prepared catalyst, 12-molybdophosphoric acid (HPMo) anchored to the mesoporous aluminosilicate AlSiM, synthesized from Amazon kaolin, was characterized and used as a heterogeneous acid catalyst for the production of eugenyl acetate by acetylation of eugenol with acetic anhydride. The effect of various reaction parameters, such as catalyst concentration, eugenol/acetic anhydride molar ratio, temperature and reaction time, was studied to optimize the conditions of maximum conversion of eugenol. The kinetics studies showed that in eugenol acetylation, the substrate concentration follows a first order kinetics. The results of activation energy was 19.96 kJ mol−1 for HPMo anchored to AlSiM. The reuse of the catalyst was also studied and there was no loss of catalytic activity after four cycles of use (from 99.9% in the first cycle to 90% in the fifth cycle was confirmed), and an excellent stability of the material was observed. Based on catalytic and kinetic studies, HPMo anchored to AlSiM is considered an excellent catalyst

Glycerol and Catalysis by Waste/Low-Cost Materials—A Review

The growing global demand for renewable energy sources can be reached using biofuels such as biodiesel, for example. The most used route to produce biodiesel is the transesterification reaction of oils or fats with short-chain alcohols, generating fatty acid esters (biodiesel) and a very important by-product, glycerol (Gly). Gly is widely used in different sectors of the industry, and in order to add value to this by-product, heterogeneous catalysis becomes a relevant tool, whether to transform glycerol into other chemical products of interest or even use it in the production of catalysts. Among the several studies found in the literature, the use of low-cost materials and/or wastes from the most diverse activities to prepare active catalytic materials for the transformation of Gly has been increasingly reported due to its valuable advantages, especially related to the cost of raw materials and environmental aspects. Thus, this brief review article presents the relationship between catalysis, low-cost materials, waste, and glycerol, through different studies that show glycerol being transformed through reactions catalyzed by materials produced from low-cost sources/waste or with the glycerol itself used as a catalyst

Bentonites Modified with Phosphomolybdic Heteropolyacid (HPMo) for Biowaste to Biofuel Production

Two bentonites from Paraíba (Northeastern Brazil) were impregnated with heteropoly phosphomolybdic H3PMo12O40 (HPMo). The materials produced were characterized by various techniques such as N2 adsorption-desorption (specific surface area, SSA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermogravimetric analysis (TGA/DTG), Scanning Electron Microscopy (SEM) equipped with Dispersive Energy X-ray spectroscopy (EDS), ultraviolet-visible spectroscopy (UV-vis), acid-base titration analysis. The catalytic activity of these materials was tested in the esterification of a waste from palm oil deodorization and the main results obtained (about 93.3% of conversion) indicated that these materials have potential to act as heterogeneous solid acid catalysts. The prepared materials exhibited satisfactory catalytic performance even after a very simple recycling process in three reuse cycles, without significant loss of their activities

Zeolites: A Theoretical and Practical Approach with Uses in (Bio)Chemical Processes

This review provides a state-of-the-art summary of distributed zeolite technology, as well as identifying strategies to further promote the absorption of these materials in various areas of study. Zeolites are materials that can be synthesized or found in natural rock deposits a with a basic composition consisting in Al, Si, and O. Zeolite’s consideration as a future material is due to many facile synthesis methods to obtain different structures with variations in pore size, surface area, pore volume and physical properties. These methods are developed using the control of relevant synthesis parameters that influences structure formation, such as crystallization temperature, time of aging and/or crystallization, stoichiometric relationships between components of synthesis gel, pH of the medium, and in some cases the type of structure-directing agent. Each method will lead to geometric changes in the framework formation, making possible the formation of typical chemical bonds that are the fingerprint of any zeolitic structure (O-Si-O and Al-O-Si), forming typical acid sites that give specificity in zeolite and allows it to act as a nanoreactor. The specificity is a characteristic that in some cases depends on selectivity, a fundamental property derived of the porosity, mostly in processes that occur inside the zeolite. In processes outside the structure, the surface area is the main factor influencing this property. Moreover, there are many natural sources with adequate chemical composition to be used as precursors. Some of these sources are waste, minimizing the deposition of potential hazardous materials that can be recalcitrant pollutants depending on the environment. Besides its uses as a catalyst, zeolite serves as a support for many bioprocesses; therefore, this review aims to explain relevant aspects in chemical nature, physical properties, main methods of synthesis, main precursors used for synthesis, and relevant applications of zeolites in chemical catalysis and biological processes

Bentonites Modified with Phosphomolybdic Heteropolyacid (HPMo) for Biowaste to Biofuel Production

Two bentonites from Paraíba (Northeastern Brazil) were impregnated with heteropoly phosphomolybdic H3PMo12O40 (HPMo). The materials produced were characterized by various techniques such as N2 adsorption-desorption (specific surface area, SSA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermogravimetric analysis (TGA/DTG), Scanning Electron Microscopy (SEM) equipped with Dispersive Energy X-ray spectroscopy (EDS), ultraviolet-visible spectroscopy (UV-vis), acid-base titration analysis. The catalytic activity of these materials was tested in the esterification of a waste from palm oil deodorization and the main results obtained (about 93.3% of conversion) indicated that these materials have potential to act as heterogeneous solid acid catalysts. The prepared materials exhibited satisfactory catalytic performance even after a very simple recycling process in three reuse cycles, without significant loss of their activities

Ene-reductases: Contribution from Brazilian fungi in organic synthesis

Brazil’s territory encloses six terrestrial biomes (Amazon, Pantanal, Savannah, Atlantic Rainforest, and Caatinga-Savannah cactus) and a marine biome following the long coastline, yielding a wealth of native microbial species. Fungi found in different parts of Brazil are being studied for their enzymatic potential in biotransformation in organic synthesis processes. This review summarizes various studies on the bioreduction of activated C = C double bonds catalyzed by ene-reductases using fungi (filamentous and yeast) from the Brazilian environmental

Microwave-assisted preparation of a new esterification catalyst from wasted flint kaolin

AbstractAmazon flint kaolin, considered useless from an economic and industrial point of view, was calcined at 850 and 950°C to obtain metakaolin samples. These samples were subsequently treated with sulfuric acid (4M) by assisted heating with microwave radiation. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy and N2 physisorption; the surface acidity was determined by titration with 0.2M KOH. The materials obtained were used as catalysts in the esterification of oleic acid with methanol. Metakaolin that was calcined at 850°C and activated at 400W for 15min presented a surface area of 187m2g−1, yielding acidic sites with a concentration of 4.32mmolg−1 and a conversion of 96.5% (115°C, 40min, molar ratio of oleic acid: methanol 1:60). In addition to a lower preparation time, the flint metakaolin activated by microwave radiation gave a catalytic performance equivalent or superior to the one prepared by reflux, as well as it showed considerably reduced reaction time and temperature