Síntese, caracterização e aplicação de LaSBA-15 e como catalisador para obtenção de biodiesel de soja via rota etílica

Biodiesel is an alternative fuel, renewable, biodegradable and nontoxic. The transesterification of vegetable oils or animal fat with alcohol is most common form of production of this fuel. The procedure for production of biodiesel occurs most commonly through the transesterification reaction in which catalysts are used to accelerate and increase their income and may be basic, acid or enzyme. The use of homogeneous catalysis requires specific conditions and purification steps of the reaction products (alkyl ester and glycerol) and removal of the catalyst at the end of the reaction. As an alternative to improve the yield of the transesterification reaction, minimize the cost of production is that many studies are being conducted with the application of heterogeneous catalysis. The use of nano-structured materials as catalysts in the production of biodiesel is a biofuel alternative for a similar to mineral diesel. Although slower, can esterify transesterified triglycerides and free fatty acids and suffer little influence of water, which may be present in the raw material. This study aimed at the synthesis, characterization and application of nano-structured materials as catalysts in the transesterification reaction of soybean oil to produce biodiesel by ethylic route. The type material containing SBA-15 mesoporous lanthanum embedded within rightly Si / La = 50 was used catalyst. Solid samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, nitrogen adsorption and desorption. For the transesterification process, we used a molar ratio of 20:1 alcohol and oil with 0.250 g of catalyst at 60°C and times of 6 hours of reaction. It was determined the content of ethyl esters by H-NMR analysis and gas chromatography. It was found that the variable of conversion obtained was 80%, showing a good catalytic activity LaSBA-15 in the transesterification of vegetable oils via ethylic route

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline

Obtenção de diesel verde por craqueamento termocatalítico de óleo de buriti (Mauritia flexuosa L.) sobre materiais nanoestruturados do tipo LaSBA-15

In order to obtain a biofuel similar to mineral diesel, lanthanum-incorporated SBA- 15 nanostructured materials, LaSBA-15(pH), with different Si/La molar ratios (75, 50, 25), were synthesized in a two-steps hydrothermal procedure, with pH-adjusting of the synthesis gel at 6, and were used like catalytic solids in the buriti oil thermal catalytic cracking. These solids were characterized by X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), infrared spectroscopy (FTIR), nitrogen porosimetry and ethanol dehydration, aiming to active sites identify. Taken together, the analyses indicated that the synthesis method has employed to obtain materials highly ordered mesostructures with large average pore sizes and high surface area, besides suggested that the lanthanum was incorporated in the SBA-15 both into the framework as well as within the mesopores. Catalytic dehydration of ethanol over the LaSBA-15(pH) products has shown that they have weak Lewis acid and basic functionalities, indicative of the presence of lanthanum oxide in these samples, especially on the La75SBA-15(pH) sample, which has presented the highest selectivity to ethylene. The buriti oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ºC in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. One the other hand, OL coming from second ones, called green diesel (GD), have presented low acid index, particularly that one obtained from the thermal catalytic process realized over LaSBA-15(pH) samples. The acid sites presence in these samples, associated to their large average pore sizes and high surface areas, have allowed them, especially the La75SBA-15(pH), to present deoxygenating activity in the buriti oil thermal catalytic cracking, providing an oxygenates content reduction, particularly carboxylic acids, in the GD. Furthermore, the GD comes from the second liquid fraction obtained in the buriti oil thermal catalytic cracking over this latest solid sample has shown hydrocarbons composition and physic-chemical properties similar to that mineral diesel, beyond sulfur content low

Estudo comparativo entre a pirólise do polietileno de baixa densidade, utilizando vermiculita modificada e SBA-15

Catalytic processes are widely present in everyday life. This results in large number of studies seeking materials that may combine the low cost catalytic efficiency. Based on this assumption, the clays have long been used as catalysts, with its huge availability, diversity and possibility of improving their properties from structural changes, primarily responsible for this great use. Among the natural clays, vermiculite due to their characteristic properties (high cation exchange capacity and expansion), is suitable for various applications including as catalysts and catalyst supports. In this work, the acid leaching of clay vermiculite was performed, coming from Santa Luzia-PB, with nitric acid (2, 3 and 4 mol / L) and subsequent calcination of the materials obtained. The materials were named as Vx/400, where x is the acid concentration employed and 400 used in calcination temperature. The effectiveness of changes made was determined by XRD techniques, FT-IR, EDS, TG/DTG, nitrogen physisorption and DTP of n-butylamine. Acid leaching has improved some properties of the clay - specific area and acidity - but the control of the acid concentration used is of vital importance, since the highest concentration caused the partial destruction of vermiculite entailing a decline in their properties. For analysis of the catalytic activity of the modified clay was made a comparative study with the SBA -15 mesoporous materials, synthesized via hydrothermal method, using the pyrolysis of low density polyethylene (LDPE). The results showed that the acid plays a fundamental role in the conversion of the polymer into smaller molecules, the material V3/400 was more selective for the source monomer (ethylene) due to their increased acidity, which promotes more breaks bonds in the polymeric chain, while materials and V0/400 V2/400, lower acidity, showed higher selectivity to light hydrocarbons, the range of fuel (41.96 and 41.23%, respectively), due to less breakage and secondary condensation reactions chains; already V4/400 SBA-15/550 and resulted in lower percentages of light hydrocarbons and the partial destruction of the structure and low acidity, respectively, responsible for the inefficiency of materials

Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR

Reciclagem química de Polietileno utilizando Sílica Mesoporosa tipo SBA-15 avalizada por Termogravimetriae Espectrometria de Massas

The chemical recycling of polyolefins has been the focus of increasing attention owing potential application as a fuel and as source chemicals. The use of plastic waste contributes to the solution of pollution problems.The use of catalysts can enhance the thermal degradation of synthetic polymers, which may be avaliated by Themogravimetry (TG) and mass spectrometry (MS) combined techniques. This work aims to propose alternatives to the chemistry recycling of low-density polyethylene (LDPE) on mesoporous silica type SBA-15 and AlSBA-15.The mesoporous materials type SBA-15 and AlSBA-15 were synthesized through the hydrothermal method starting from TEOS, pseudobohemite, cloridric acid HCl and water. As structure template was used Pluronic P123. The syntheses were accomplished during the period of three days. The best calcination conditions for removal of the organic template (P123) were optimized by thermal analysis (TG/DTG) and through analyses of Xray diffraction (XRD), infrared spectroscopy (FT-IR), nitrogen adsorption and scanning electron microscopy (SEM) was verified that as much the hydrothermal synthesis method as the calcination by TG were promising for the production of mesoporous materials with high degree of hexagonal ordination. The general analysis of the method of Analog Scan was performed at 10oC/min to 500 oC to avoid deterioration of capillary with very high temperatures. Thus, with the results, we observed signs mass/charge more evident and, using the MID method, was obtained curve of evolution of these signals. The addition of catalysis produced a decrease in temperature of polymer degradation proportional to the acidity of the catalyst. The results showed that the mesoporous materials contributed to the formation of compounds of lower molecular weight and higher value in the process of catalytic degradation of LDPE, representing an alternative to chemical recycling of solid waste

Alquilação de tolueno com propeno, através de complexo ferro (II) ᵦ- diimina homogêneo e heterogeneizado em MCM-41, Al-MCM-41 e SBA-15

This work describes the synthesis and aplication of homogeneous and heterogenized iron catalysts in the alkylation reaction of toluene with propene, empolying experimental design. The homogenous complex was obtained trough the synthesis of the organic ligand folowed by the complexation of the iron(II) chloride. As to the heterogenized complexes, first were synthetized the inorganic supports (SBA-15, MCM-41 and Al-MCM-41). Then, it was synthetized the ligand again, that through funcionalization with chloropropyltrimethoxysilane (CPTMS), was anchored on the support previously calcinated. To these anchored ligands, was complexed the iron(II) chloride, previously solubilizated in tetrahydrofuran (THF). The organic ligand characterization was accomplished trough nuclear magnetic resonance (NMR) and Infrared spectroscopy (IV). The supports were characterized with x-ray diffraction (DRX), texture analysis with nitrogen adsorption/desorption (before and after the anchoring), termogravimetric analysis (TG) and infrared (IV). The metalic content was quantified trough the atomic absorption spectrophotometry (AAS). The complexes were tested in catalytic reactions emolying ethylaluminium sesquichloride (EASC) as co-catalyst in steel reactor, under mecanic stirring. The reaction conditions ranged from 4 to 36 ◦C, with many aluminum/iron ratios. The catalysts were actives in homogeneous and heterogenized ways. The homogenous catalytic complex showed a maximum turnover frequency (TOF) of 8.63 ×103 · h −1 , while, in some conditions, the anchored complexes showed better results, with TOF of until 8.08 ×103 · h −1 . Aditionally, it was possible to determine an equation, to the homogenous catalyst, that describes the product quantity in function of reacional temperature and aluminum/iron ratio.

Síntese, caracterização e aplicação de LaSBA-15 e como catalisador para obtenção de biodiesel de soja via rota etílica

Biodiesel is an alternative fuel, renewable, biodegradable and nontoxic. The transesterification of vegetable oils or animal fat with alcohol is most common form of production of this fuel. The procedure for production of biodiesel occurs most commonly through the transesterification reaction in which catalysts are used to accelerate and increase their income and may be basic, acid or enzyme. The use of homogeneous catalysis requires specific conditions and purification steps of the reaction products (alkyl ester and glycerol) and removal of the catalyst at the end of the reaction. As an alternative to improve the yield of the transesterification reaction, minimize the cost of production is that many studies are being conducted with the application of heterogeneous catalysis. The use of nano-structured materials as catalysts in the production of biodiesel is a biofuel alternative for a similar to mineral diesel. Although slower, can esterify transesterified triglycerides and free fatty acids and suffer little influence of water, which may be present in the raw material. This study aimed at the synthesis, characterization and application of nano-structured materials as catalysts in the transesterification reaction of soybean oil to produce biodiesel by ethylic route. The type material containing SBA-15 mesoporous lanthanum embedded within rightly Si / La = 50 was used catalyst. Solid samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, nitrogen adsorption and desorption. For the transesterification process, we used a molar ratio of 20:1 alcohol and oil with 0.250 g of catalyst at 60°C and times of 6 hours of reaction. It was determined the content of ethyl esters by H-NMR analysis and gas chromatography. It was found that the variable of conversion obtained was 80%, showing a good catalytic activity LaSBA-15 in the transesterification of vegetable oils via ethylic route

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline