Preparação, caracterização e aplicação de derivados do ácido 12- tungstofosfórico suportado em SBA-15

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2016.

Development of advanced catalytic systems for the selective hydrogenolysis of biomass-derived polyols

195 p.

UHMWPE/SBA-15 nanocomposites synthesized by in situ polymerization

Different nanocomposites have been attained by in situ polymerization based on ultra-high molecular weight polyethylene (UHMWPE) and mesoporous SBA-15, this silica being used for immobilization of the FI catalyst bis [N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato] titanium (IV) dichloride and as filler as well. Two distinct approaches have been selected for supporting the FI catalyst on the SBA-15 prior polymerization. A study on polymerization activity of this catalyst has been performed under homogenous conditions and upon heterogenization. A study of the effect of presence of mesoporous particles and of the immobilization method is also carried out. Moreover, the thermal characterization, phase transitions and mechanical response of some pristine UHMWPEs and UHMWPE/SBA-15 materials have been carried out. Relationships with variations on molar mass, impregnation method of catalyst and final SBA-15 content have been established.

Impregnação de metais em xisto retortado para uso como adsorventes

Concern with the environment has lead to an increase in the research for new adsorption techniques, low cost adsorvent materials and with high availability. Many works search the development of higher selectivity modified adsorvents. The Brazil has the second world reserve of oiled shale, because of it, the use of that reject is of great interest. This study has the goal of characterize and analyze the retorted shale, reject of the pirobetuminous shale pyrolysis, and the retorted shale modified through the humid impregnation method, wich the precursors were the metals nitrates ( Cobalt, Nickel and Copper), to the usage has adsorvent materials. The samples were characterized chemically, textually and structurally by the X ray fluorescence (XRF), BET, X ray diffraction (XRD) and scanning electronic microscopy (SEM) techniques. The impregnated samples showed a reduction in the superficial area and in the pore volume when compared with the retorted shale. Besides that, diffractions referred to the impregnated metals where observed in the XRD analysis, wich were the same metals detected in the XRF and SEM analysis. The materials showed homogeneity in it s composition. The results shows that the materials presents adequate adsorption characteristics

Effect of pre-treatments and post-treatments on drying products

Freeze drying technology can give good quality attributes of vegetables and fruits in terms of color, nutrition, volume, rehydration kinetics, stability during storage, among others, when compared with solely air dried ones. However, published scientific works showed that treatments applied before and after air dehydration are effective in food attributes, improving its quality. Therefore, the hypothesis of the present thesis was focus in a vast research of scientific work that showed the possibility to apply a pre-treatment and a post-treatment to food products combined with conventional air drying aiming being close, or even better, to the quality that a freeze dried product can give. Such attributes are the enzymatic inactivation, stability during storage, drying and rehydration kinetics, color, nutrition, volume and texture/structure. With regard to pre-treatments, the ones studied along the present work were: water blanching, steam blanching, ultrasound, freezing, high pressure and osmotic dehydration. High electric pulsed field was also studied but the food attributes were not explained on detailed. Basically, water and steam blanching showed to be adequate to inactivate enzymes in order to prevent enzymatic browning and preserve the product quality during long storage periods. With regard to ultrasound pre-treatment the published results pointed that ultrasound is an effective pre-treatment to reduce further drying times, improve rehydration kinetics and color retention. On the other hand, studies showed that ultrasound allow sugars losses and, in some cases, can lead to cell disruption. For freezing pre-treatment an overall conclusion was difficult to draw for some food attributes, since, each fruit or vegetable is unique and freezing comprises a lot of variables. However, for the studied cases, freezing showed to be a pre-treatment able to enhance rehydration kinetics and color attributes. High pressure pre-treatment showed to inactivate enzymes improving storage stability of food and showed to have a positive performance in terms of rehydration. For other attributes, when high pressure technology was applied, the literature showed divergent results according with the crops used. Finally, osmotic dehydration has been widely used in food processing to incorporate a desired salt or sugar present in aqueous solution into the cellular structure of food matrix (improvement of nutrition attribute). Moreover, osmotic dehydration lead to shorter drying times and the impregnation of solutes during osmose allow cellular strengthens of food. In case of post-treatments, puffing and a new technology denominated as instant controlled pressure drop (DIC) were reported in the literature as treatments able to improve diverse Abstract Effect of Pre-treatments and Post-treatments on Drying Products x food attributes. Basically, both technologies are similar where the product is submitted to a high pressure step and the process can make use of different heating mediums such as CO2, steam, air and N2. However, there exist a significant difference related with the final stage of both which can comprise the quality of the final product. On the other hand, puffing and DIC are used to expand cellular tissues improving the volume of food samples, helping in rehydration kinetics as posterior procedure, among others. The effectiveness of such pre and/or post-treatments is dependent on the state of the vegetables and fruits used which are also dependent of its cellular structure, variety, origin, state (fresh, ripe, raw), harvesting conditions, etc. In conclusion, as it was seen in the open literature, the application of pre-treatments and post-treatments coupled with a conventional air dehydration aim to give dehydrated food products with similar quality of freeze dried ones. Along the present Master thesis the experimental data was removed due to confidential reasons of the company Unilever R&D Vlaardingen

Platinum supported on highly-dispersed ceria on activated carbon for the total oxidation of VOCs

Catalysts consisting in platinum supported on cerium oxide highly dispersed on activated carbon, with a Pt loading of 1 wt.% and ceria loadings of 5, 10 and 20 wt.% have been prepared by impregnation method and characterized by several techniques (N2 adsorption at 77 K, ICP, XRD, H2-TPR and XPS). Their catalytic behavior has been evaluated in the total oxidation of ethanol and toluene after reduction at 473 K. The obtained results show that the prepared catalysts have better performances than platinum supported on bulk CeO2. The best catalytic performance was obtained for 10 wt.% ceria loading, likely due to an optimum synergistic interaction between highly dispersed cerium oxide and platinum particles. Pt-10Ce/C achieves total conversion of ethanol and toluene to CO2 at 433 K and 453 K, respectively, and shows no deactivation during a test for 100 h. Under humid conditions (relative humidity, RH, of 40 and 80%), the activity was only slightly influenced due to the hydrophobic character of the activated carbon support, which prevents the adsorption of water.

Highly dispersed Ptδ+ on TixCe(1−x)O2 as an active phase in preferential oxidation of CO

Structure–activity relationships for 1 wt.% Pt catalysts were investigated for a series of TixCe(1−x)O2 (x = 1, 0.98, 0.9, 0.5, 0.2 and 0) supports prepared by the sol–gel method. The catalysts prepared by impregnation were characterized in detail by applying a wide range of techniques as N2-isotherms, XRF, XRD, Raman, XPS, H2-TPR, Drifts, UV–vis, etc. and tested in the preferential oxidation of CO in the presence of H2. Also several reaction conditions were deeply analyzed. A strong correlation between catalyst performance and the electronic properties let us to propose, based in all the experimental results, a plausible reaction mechanism where several redox cycles are involved.

Carbon-supported ionic liquids as innovative adsorbents for CO2 separation from synthetic flue-gas

Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization.

Avaliação da abertura de filtração de geotêxteis sob confinamento e parcialmente colmatados

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Civil e Ambiental, 2016.

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials

Projeto, construção e análise de um prototipo vibracional em escala de bancada aplicável ao tratamento de água de produção de petróleo bruto, mediante inovadora operação híbrida de adsorção e auto-flotação

A self-flotator vibrational prototype electromechanical drive for treatment of oil and water emulsion or like emulsion is presented and evaluated. Oil production and refining to obtain derivatives is carried out under arrangements technically referred to as on-shore and off-shore, ie, on the continent and in the sea. In Brazil 80 % of the petroleum production is taken at sea and area of deployment and it cost scale are worrisome. It is associated, oily water production on a large scale, carrier 95% of the potential pollutant of activity whose final destination is the environment medium, terrestrial or maritime. Although diversified set of techniques and water treatment systems are in use or research, we propose an innovative system that operates in a sustainable way without chemical additives, for the good of the ecosystem. Labyrinth adsor-bent is used in metal spirals, and laboratory scale flow. Equipment and process patents are claimed. Treatments were performed at different flow rates and bands often monitored with control systems, some built, other bought for this purpose. Measurements of the levels of oil and grease (OGC) of efluents treaty remained within the range of legal framework under test conditions. Adsorbents were weighed before and after treatment for obtaining oil impregna-tion, the performance goal of vibratory action and treatment as a whole. Treatment technolo-gies in course are referenced, to compare performance, qualitatively and quantitatively. The vibration energy consumption is faced with and without conventional flotation and self-flotation. There are good prospects for the proposed, especially in reducing the residence time, by capillary action system. The impregnation dimensionless parameter was created and confronted with consecrated dimensionless parameters, on the vibrational version, such as Weber number and Froude number in quadratic form, referred to as vibrational criticality. Re-sults suggest limits to the vibration intensity

The role of nano colloid of TiO2 and butane tetra carboxylic acid on the alkali solubility and hydrophilicity of proteinous fibers

One of the main problems of wool as an important proteinous fiber is low resistance against alkali media. Finding a way to solve this problem without any influences on other fiber characteristics is still a matter of research. Using nano particles on textile materials is a new approach to produce novel properties. Here, nano titanium dioxide (NTO) particles along with butane tetra carboxylic acid (BTCA) were sonicated in the ultra sound bath and applied as a nano colloid on the wool fabric. BTCA played different roles as wool cross-linker, a polyanionic agent, and stabilizer for nano TiO2. Various concentrations of NTO and BTCA were applied through impregnation of the fabric in ultrasonic bath followed by curing. The resistance of fabrics against alkali was assessed by solubility in sodium hydroxide and the hydrophilicity monitored by the water drop absorption time and the contact angle before and after UV irradiation. Interestingly, the alkali solubility of the nano TiO2 treated wool fabrics reduced while the fabric became more hydrophilic. This fact was shown by the testing results and is thoroughly discussed in the article. The response surface methodology (RSM) was also applied to find the optimum conditions for the wool fabric treatment.

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.

State of the art of industrial wood protection in Portugal

This work intended to give a perspective of industrial wood protection in Portugal. A survey was made of the companies treating wood mainly for use classes 3 and 4 such as autoclave treatments with biocides and wood modification procedures. Currently there are 23 companies with 33 production plants with an autoclave installed for wood preservation by impregnation. There are also two companies producing modified wood by thermal treatment. Most of the plants are located in the central and northern regions of Portugal. The leading preservation chemicals used in Portugal are Tanalith E and Celcure brands. The main wood species used in all companies is Pinus pinaster from local producers. The products commercialized by the treating companies are diverse: pre-fabricated houses, garden furniture and playgrounds, decks, poles, stakes, and sawn wood. Modified wood producers sell mostly decks and cladding. Considerable changes are expected in the next few years due to the requirements of European Directives and the typical constraints of the Portuguese market.

A new post-metallocene-ti catalyst with maltolate bidentade ligand: an investigation in heterogeneous polymerization reactions in different mesoporous supports

A new titanium catalyst easily synthesized from ethylmaltol bidentate chelator ligand was studied in homogeneous and heterogeneous ethylene polymerization. The dichlorobis(3-hydroxy-2-ethyl-4-pyrone)titanium(IV) complex was characterized by 1H and 13C NMR (nuclear magnetic resonance), UV-Vis and elemental analysis. Theoretical study by density functional theory (DFT) showed that the complex chlorines exhibit cis configuration, which is important for the activity in olefin polymerization. The complex was supported by two methods, direct impregnation or methylaluminoxane (MAO) pre-treatment, in five mesoporous supports: MCM-41 (micro and nano), SBA-15 and also the corresponding modified Al species. All the catalytic systems were active in ethylene polymerization and the catalytic activity was strongly influenced by the method of immobilization of the catalyst and the type of support.