Obtenção de emulsões asfálticas modificadas utilizando resíduos industriais

The main objective of this research was the development and characterization of conventional and modified cationic asphalt emulsions. The asphalt emulsions were developed by using the Petroleum Asphalt Cement (CAP 50-70) from Fazenda Belém (Petrobras -Aracati-Ce). The first step in this research was the development of the oil phase (asphalt + solvent) and the aqueous phase (water + emulsifying agent + acid + additives), separately. During the experiments for the obtaining of the conventional asphalt emulsion, the concentration of each constituent was evaluated. For the obtaining of the oil phase, kerosene was used as solvent at 15 and 20 wt.%. For the development of the aqueous phase, the emulsifying agent was used at 0.3 and 3.0 wt.%, whereas the acid and the additive were set at 0.3 wt.%. The percentage of asphalt in the asphalt emulsion was varied in 50, 55, and 60 wt.% and the heating temperature was set at 120 °C. The aqueous phase in the asphalt emulsion was varied from 16.4 to 34.1 wt.% and the heating temperature was set at 60 °C. After the obtaining of the oil and the aqueous phases, they were added at a colloidal mill, remaining under constant stirring and heating during 15 minutes. Each asphalt emulsion was evaluated considering: sieve analysis, Saybolt Furol viscosity, pH determination, settlement and storage stability, residue by evaporation, and penetration of residue. After the characterization of conventional emulsions, it was chosen the one that presented all properties in accordance with Brazilian specifications (DNER-EM 369/97). This emulsion was used for the development of all modified asphalt emulsions. Three polymeric industrial residues were used as modifier agents: one from a clothing button industry (cutouts of clothing buttons) and two from a footwear industry (cutouts of sandals and tennis shoes soles), all industries located at Rio Grande do Norte State (Brazil).The polymeric residues were added into the asphalt emulsion (1 to 6 wt.%) and the same characterization rehearsals were accomplished. After characterization, it were developed the cold-mix asphalts. It was used the Marshall mix design. For cold-mix asphalt using the conventional emulsion, it was used 5, 6 and 7 wt.% asphalt emulsion. The conventional mixtures presented stability values according Brazilian specification (DNER-369/97). For mixtures containing asphalt modified emulsions, it was observed that the best results were obtained with emulsions modified by button residue

Estudo da incorporação de resíduo industrial polimérico ao CAP

This work presents the incorporation of an industrial polymeric waste into a petroleum asphalt cement with penetration grade 50-60 (CAP 50-60). The main goal of this research is the development of a polymer-modified asphalt, with improvements in its physical properties, in order to obtain a more resistant material to the traffic loads. Furthermore, the use of this polymeric waste will result in economic and environmental benefits. The CAP 50-60 used in this research was kindly supplied by LUBNOR Lubrificantes e Derivados de Petróleo do Nordeste (produced in Fazenda Belém Aracati - Ceará) and the industrial polymeric waste was provided by a button manufacturer industry, located in Rio Grande do Norte state. This polymeric waste represents an environmental problem due to its difficulty in recycling and disposal, being necessary the payment by the industry to a landfill. The difficulty in its reuse is for being this material a termofixed polymer, as a result, the button chips resulting from the molding process cannot be employed for the same purpose. The first step in this research was the characterization of the polymeric waste, using Differential Scanning Calorimetry (DSC) Infrared spectroscopy (IR spectroscopy), and Thermogravimetric analysis (TGA). Based on the results, the material was classified as unsaturated polyester. After, laboratory experiments were accomplished seeking to incorporate the polymeric waste into the asphalt binder according to a 23 experimental factorial design, using as main factors: the polymer content (2%, 7% and 14%), the temperature of the mixture (140 and 180 oC) and the reaction time (20 and 60 minutes). The characterization of the polymer-modified asphalt was accomplished by traditional tests, such as: penetration, ring and ball softening point, viscosity, ductility and flash point temperature. The obtained results demonstrated that the addition of the polymeric waste into the asphalt binder modified some of its physical properties. However, this addition can be considered as a feasible alternative for the use of the polymeric waste, which is a serious environmental and technological problem.

Kierrätyspolttoaineen käyttö leijupetikattilan konseptiin

Diplomityö tehtiin Rautjärven kunnassa sijaitsevalle M-real Simpeleen tehtaan voimalaitokselle. Voimalaitoksella on leijupetikattila ja se tuottaa prosessilämmön ja höyryn kartonki- ja paperikoneelle. Vuotuinen energiantuotanto on noin 115 GWh. Diplomityön tavoitteena oli tutkia kierrätyspolttoaineen käyttöä osana voimalaitoksen polttoainekonseptista. Voimalaitoksen biokattila on leijupetikattila, jossa poltetaan tehtaalta tulevaa kuorta ja lietettä sekä tehtaan ulkopuolisia puuperäisiä biopolttoaineita ja turvetta. Yksi työn päätavoitteista oli laatia voimassa olevan ympäristöluvan muutoshakemus, jotta kierrätyspolttoaineen käytölle saataisiin lupa. Suurten polttolaitosten päästöjen tarkkailu- ja raportointivaatimukset ovat uudistuneet viime vuosina paljon. Suurimpia muutosten aiheuttajia ovat Valtioneuvoston asetukset 1017/2002 ja 362/2003. Tässä työssä kuvataan uusien asetusten tuomia vaatimuksia itse kattilalle ja polttoaineen syötölle, jatkuvatoimisille mittalaitteille ja muille suoritettaville mittauksille. Uutena asiana on myös ilmapäästöjen seurantamittaukset ja -tapa, jolla tulokset ilmoitetaan. Mahdollisimman pieniin leijupetikattilamuutoksiin uskotaan pääsevän korvaamalla kierrätyspolttoaine REF1:llä 5 – 10 % turpeesta tai puupolttoaineista.

Environmental behavior of soils and mixtures of soil-whitewash mud

The present study sought to observe the behavior of soils in natural state and in mixtures, in different ratios, with the industrial solid residue called whitewash mud. The work was conducted with samples of typical soils from the region of Alagoinhas, Bahia-Brazil. Wet chemical analysis and atomic absorption spectrophotometry were used in order to obtain the classification of the industrial solid residue. Solubilization and leaching tests were performed and X-ray diffraction and electron microscopy techniques were carried out. The results showed that the whitewash mud was classified as non-inert, but with great capacity of heavy metal retention largely owed to the kaolinite and goethite presence in the clay fraction of the soils, making it difficult to have heavy metals readily available for exchange.

Efeito da introdução de resíduo de cinza de forno cerâmico em massa para cerâmica estrutural

The red ceramics and structural ceramics, as they are known, include ceramic materials made by blocks of seals and structures, bricks, tiles, smail flagstones manacles, rustic floors and ornamental materials. Their fabrication uses raw material such as clay and clay sites, with some content of impurity. It has good durability and mechanical strength to compression, low cost, making it one of the mainly used materials in civil engineering. The incorporation of many industrial activities residue to ceramic products is a technological alternative for reducing the environmental impact caused by its carefree disposal. This incorporation can promote chemical change and inertness of metals from residue, by fixation in the glassy phase of ceramic during the burning stage. The main aim of this project is to study the technical feasibility of the addition of ceramic oven ash into formulations of mass for structural ceramics. In this project two kinds of clay (plastic and non-plastic) were used, as well as the ash from firewood used in the process of burning of structural ceramics. A group of experiments was outlined, which permitted the evaluation of the influence of the burning cycle in different temperatures of the ash content in formulations for ceramic blocks through technological properties, mechanical behavior and microstructure. Five samples were processed of each one of the masses of plastic and non-plastic clay without addition of ash and with addition of ash on the percentages of 10 % and 20 %, for temperatures of 850 °C, 950 °C, 1050 °C and 1150 °C, obtained through sinterization process. Among the studied compositions, the one which presented best performance was the mass of clay with 10 % of ash, at temperature of 1150 °C, with the smallest absorption of water, the smallest apparent porosity, specific apparent mass a bit over the others and greatest mechanical resistance to flexion. The composition made confirmed the technical feasibility of the use of ash in the mass for structural ceramics with maintenance of its necessary characteristics for its purposes

In vitro and in vivo evaluation of the activity of pineapple (Ananas comosus) on Haemonchus contortus in Santa Inês sheep

The development of resistance to anthelmintics has prompted research into alternative methods of controlling intestinal nematodes in ruminants. This study aimed to assess the activity of Ananas comosus on Haemonchus contortus in Santa Inês sheep. The aqueous extract of pineapple skin (AEPS), bromelain from pineapple stems (B4882) and residue from pineapple processing was evaluated in in vitro and in vivo tests. The enzymatic activity of substances was analyzed by the azocasein method. The egg hatch test (EHT) and larval development test (LDT) were performed using the Embrapa2010 isolate of H. contortus. In the in vivo test, 36 sheep artificially infected with H. contortus were divided into six groups: G1: 2g/kg BW of the aqueous extract administered for three days; G2: 2g/kg BW of the industrial pineapple residue for 60 days; G3: 180mg/animal of bromelain in a single dose; G4: negative control I; G5: positive control (levamisole phosphate); and G6: negative control II. The eggs per gram (EPG) in the feces were counted till 28 days after treatment. LC50 and LC90 were obtained by the probit procedure, while the in vivo test results were analyzed by GLM. The aqueous extract in the in vitro and in vivo test, the bromelain and industrial residue presented 0.102, 0.157, 1.864 and 0.048 enzyme units/mL, respectively. In the egg hatch test, the LC50 and LC90 were respectively 31 and 81mg/mL for the aqueous extract and 0.50 and 2mg/mL for bromelain. In the larval development test, the LC50 and LC90 were respectively 1.7 and 7.3mg/mL for the aqueous extract and 0.019 and 0.086mg/mL for bromelain. In the in vivo test, the general efficacies of the treatments in relation to the negative control were 22.6%, 42.2%, 3.65% and 89% for the aqueous extract, industrial pineapple residue, bromelain and positive control respectively. The transformed EPG values were 3.19±0.59, 3.32±0.25, 2.85±0.66, 3.44±0.50, 2.28±0.93 and 2.75±0.94 for the aqueous extract, industrial residue, bromelain, negative control I, positive control and negative control II respectively. The results for all the treated groups differed significantly (p<0.05) from the positive control, and although the residue presented efficacy of 42.2%, there was no statistical difference (p>0.05) in relation to the negative control. Therefore, both the aqueous extract and bromelain were effective in vitro, but showed reduced anthelmintic efficacy in vivo. For the pineapple residue, the 42.2% in vivo efficacy in reducing the EPG and the possibility of reducing environmental contamination through reuse of industrial residue indicate it can also be useful for control of this parasite. © 2013 Elsevier B.V.

Avaliação da atividade carrapaticida e anti-helmíntica do abacaxi (Ananas comosus L.) em ruminantes

Pós-graduação em Medicina Veterinária - FCAV

An alternative application to the Portuguese agro-industrial residue: Wheat straw

The effects of alkaline treatments of the wheat straw with sodium hydroxide were investigated. The optimal condition for extraction of hemicelluloses was found to be with 0.50 mol/l sodium hydroxide at 55C for 2 h. This resulted in the release of 17.3% of hemicellulose (% dry starting material), corresponding to the dissolution of 49.3% of the original hemicellulose. The yields were determined by gravimetric analysis and expressed as a proportion of the starting material. Chemical composition and physico-chemical properties of the samples of hemicelluloses were elucidated by a combination of sugar analyses, Fourier transform infrared (FTIR), and thermal analysis. The results showed that the treatments were very effective on the extraction of hemicelluloses from wheat straw and that the extraction intensity (expressed in terms of alkali concentration) had a great influence on the yield and chemical features of the hemicelluloses. The FTIR analysis revealed typical signal pattern for the hemicellulosic fraction in the 1,200-1,000 cm(-1) region. Bands between 1,166 and 1,000 cm(-1) are typical of xylans.

Thermal Characteristics of Lignin Residue from Industrial Processes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electrospinning of polymeric composites with GRMs for different industrial applications

Electrospinning is the most common and industrially scalable technique for the production of polymeric nanofibers. Currently, nanocomposites are drawing much interest for their excellent properties in terms of flexibility, electrical conductivity and high surface area, which enhances the interaction with the surrounding environment. The objective of this thesis was the optimization of different electrospinning setups for the production of nanostructured polymeric composites using graphene-related materials as nanofillers. Such composites were obtained using different polymers as matrix (polyamide 6, polyinylidene fluoride and polylactic acid) that were selected and combined with the appropriate reinforcements based on their properties and their interest for specific applications. Moreover, this study highlighted the possibility to tune the morphology and size of the produced nanofibers by the addition of appropriate nanofillers even in low amounts. The addition of only 0.5% of GO allowed the production of smooth nanofibers with diameters up to 75% thinner (in the case of PLA) than the ones obtained from the pristine polymer. PVdF was charged with GO to produce triboelectric materials that can be exploited in a wearable nanogenerator for the conversion of human motion energy in electrical energy. The addition of GO improved the open-circuit voltage and power-output of a generator prototype by 3.5 times. Electrospun PA6 membranes were coated with rGO using a simple two-step technique to produce conductive textiles for wearable electronic applications. The sheet resistance of the produced materials was measured in approximately 500 Ω/sq and their resistance to washing and bending was successfully tested. These materials could be exploited as strain sensors or heating elements in smart textiles. PLA was co-electrospun with GO and cellulose nanofibers to produce high-surface area and porosity mats that could be exploited for the production of functionalized highly selective adsorption membranes with low pressure drops.

Greenhouse gases emission from soil contaminated with automobile industry residue in Brazil

Solid waste of the automobile industry containing large amounts of heavy metals might affect the emission of greenhouse gases (GHG) when applied to the soil. Accumulation of inorganic chemical elements in the environment generally occurs due to human activity (industry, agriculture, mining and waste landfills). Residues from human activities may release heavy metals to the soil solution, causing toxicity to plants and other soil organisms. Heavy metals may also be adsorbed to clay minerals and/or complexed by the soil organic matter, becoming a potential source of pollutants. Not much is known about the behavior of solid wastes in tropical soil as regarded as source of greenhouse gases (GHG). The emission of GHG (CO(2), CH(4) and N(2)O) was evaluated in incubated soil samples collected in an area contaminated with a solid residue from an automobile industry. Samples were randomly collected at 0 to 0.2 m (a mix of soil and residue), 0.2 to 0.4 m (only residue) and 0.4 to 0.6 m (only soil). A contiguous uncontaminated area, cultivated with sugarcane, was also sampled following the same protocol. Canonical Discriminant Analysis and Principal Component Analysis were applied to the data to evaluate the GHG emission rates. Emission rates of GHG were greater in the samples from the contaminated than the sugarcane area, particularly high during the first days of incubation. CO(2) emissions were greater in samples collected at the upper layer for both areas, while CH(4) and N(2)O emissions were similar in all samples. The emission rates of CH(4) were the most efficient variables to differentiate contaminated and uncontaminated areas.

Estudo comparativo da utilização do biodiesel produzido a partir de óleos alimentares usados e do gasóleo numa frota industrial

A definição de teores mínimos de incorporação de biocombustíveis, constitui objeto de discussão entre grupos pro-desenvolvimento e ambientalistas. Esses últimos argumentam que as consequências da utilização desta fonte energética ainda são desconhecidas. Além disso, alegam que a produção de biocombustíveis é, em parte, responsável pelo aumento no preço dos alimentos, encoraja a conversão de florestas em monoculturas e conduz à exploração de trabalhadores em países em desenvolvimento (PEDs). Para responder à dependência energética dos combustíveis de origem fóssil, e ajudar a reduzir as emissões de gases com efeito de estufa, sobretudo no sector dos transportes, o biodiesel produzido a partir de óleos alimentares usados têm sido apontado como uma “solução verde” capaz de minimizar o problema das alterações climáticas e valorizar um resíduo, e simultaneamente conferir ao setor energético um pouco mais de independência. De forma a desmistificar e clarificar um pouco estas premissas, a presente dissertação pretende fazer um estudo de avaliação do impacto da utilização do biodiesel, nomeadamente no que diz respeito às emissões gasosas. Posteriormente realizou-se, tomando como referência uma pequena frota industrial existente, uma análise comparativa dos consumos e emissões dos principais poluentes decorrentes da utilização do biodiesel em diferentes percentagens de incorporação no gasóleo, comparativamente ao gasóleo puro. O trabalho culmina com uma abordagem técnica sobre o comportamento de um veículo equipado com um motor de ignição por compressão, utilizando como biocombustível o biodiesel.

Preparation and characterization of microfiltration flat polymeric membranes for biomedical applications

Dissertation presented to Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa for obtaining the master degree in Membrane Engineering

Design and characterization of Chitin- Glucan polymeric structures for wound dressing materials

The main objective of this work was the development of polymeric structures, gel and films, generated from the dissolution of the Chitin-Glucan Complex (CGC) in biocompatible ionic liquids for biomedical applications. Similar as chitin, CGC is only soluble in some special solvents which are toxic and corrosive. Due to this fact and the urgent development of biomedical applications, the need to use biocompatible ionic liquids to dissolve the CGC is indispensable. For the dissolution of CGC, the biocompatible ionic liquid used was Choline acetate. Two different CGC’s, KiOnutrime from KitoZyme and biologically produced CGC from Faculdade de Ciencias e Tecnologia (FCT) - Universidade Nova de Lisboa, were characterized in order to develop biocompatible wound dressing materials. The similar result is shown in term of the ratio of chitin:glucan, which is 1:1.72 for CGC-FCT and 1:1.69 for CGC-Commercial. For the analysis of metal element content, water and inorganic salts content and protein content, both polymers showed some discrepancies, where the content in CGC-FCT is always higher compared to the commercial one. The different characterization results between CGC-FCT and CGC-Commercial could be addressed to differences in the purification method, and the difference of its original strain yeast, whereas CGC-FCT is derived from P.pastoris and the commercial CGC is from A.niger. This work also investigated the effect of biopolymers, temperature dissolution, non-solvent composition on the characteristics of generated polymeric structure with biocompatible ionic liquid. The films were prepared by casting a polymer mixture, immersion in a non-solvent, followed by drying at ambient temperature. Three different non-solvents were tested in phase inversion method, i.e. water, methanol, and glycerol. The results indicate that the composition of non-solvent in the coagulation bath has great influence in generated polymeric structure. Water was found to be the best coagulant for producing a CGC polymeric film structure. The characterizations that have been done include the analysis of viscosity and viscoelasticity measurement, as well as sugar composition in the membrane and total sugar that was released during the phase inversion method. The rheology test showed that both polymer mixtures exhibit a non- Newtonian shear thinning behaviour. Where the viscosity and viscoelasticity test reveal that CGCFCT mixture has a typical behaviour of a viscous solution with entangled polymer chains and CGCCommercial mixture has true gel behaviour. The experimental results show us that the generated CGC solution from choline acetate could be used to develop both polymeric film structure and gel. The generated structures are thermally stable at 100° C, and are hydrophilic. The produced films have dense structure and mechanical stabilities against puncture up to 60 kPa.

Chlorite Dismutase from perchlorate reducing bacteria. A potential biocatalyst to eliminate chlorinated species from polluted water resources and industrial wastes

Magnetospirillum (M.) sp. strain Lusitani, a perchlorate reducing bacteria (PRB), was previously isolated from a wastewater treatment plant and phylogenetic analysis was performed to classify the isolate. The DNA sequence of the genes responsible for perchlorate reduction and chlorite dismutation was determined and a model was designed based on the physiological roles of the proteins involved in the pcr-cld regulon. Chlorite dismutase (Cld) was purified from Magnetospirillum sp. strain Lusitani cells grown in anaerobiosis in the presence of perchlorate. The protein was purified up to electrophoretic grade using HPLC techniques as a 140 kDa homopentamer comprising five ~28 kDa monomers. Steady-state kinetic studies showed that the enzyme follows a Michaelis-Menten model with optimal pH and temperature of 6.0 and 5°C, respectively. The average values for the kinetic constants KM and Vmax were respectively 0.56 mM and 10.2 U, which correspond to a specific activity of 35470 U/mg and a turnover number of 16552 s-1. Cld from M. sp. strain Lusitani is inhibited by the product chloride, but not by dioxygen. Inhibition constants KiC= 460 mM and KiU= 480 mM indicated that sodium chloride is a weak mixed inhibitor of Cld, with a slightly stronger competitive character. The X-ray crystallography structure of M. sp. strain Lusitani Cld was solved at 3.0 Å resolution. In agreement with cofactor content biochemical analysis, the X-ray data showed that each Cld monomer harbors one heme b coordinated by a histidine residue (His188), hydrogen-bonded to a conserved glutamic acid residue (Glu238). The conserved neighboring arginine residue (Arg201) important for substrate positioning, was found in two different conformations in different monomers depending on the presence of the exogenous ligand thiocyanate. UV-Visible and CW-EPR spectroscopies were used to study the effect of redox agents, pH and exogenous ligands on the heme environment.