A preliminary physicochemical, exergetic and economic study of hydrogen production utilizing glycerol

This work has as objective to demonstrate technical and economic viability of hydrogen production utilizing glycerol. The volume of this substance, which was initially produced by synthetic ways (from oil-derived products), has increased dramatically due mainly to biodiesel production through transesterification process which has glycerol as main residue. The surplus amount of glycerol has been generally utilized to feed poultry or as fuel in boilers, beyond other applications such as production of soaps, chemical products for food industry, explosives, and others. The difficulty to allocate this additional amount of glycerol has become it in an enormous environment problem, in contrary to the objective of biodiesel chain, which is to diminish environmental impact substituting oil and its derivatives, which release more emissions than biofuels, do not contribute to CO2-cycle and are not renewable sources. Beyond to utilize glycerol in combustion processes, this material could be utilized for hydrogen production. However, a small quantity of works (theoretical and experimental) and reports concerning this theme could be encountered. Firstly, the produced glycerol must be purified since non-reacted amounts of materials, inclusively catalysts, contribute to deactivate catalysts utilized in hydrogen production processes. The volume of non-reacted reactants and non-utilized catalysts during transesterification process could be reutilized. Various technologies of thermochemical generation of hydrogen that utilizes glycerol (and other fuels) were evaluated and the greatest performances and their conditions are encountered as soon as the most efficient technology of hydrogen production. Firstly, a physicochemical analysis must be performed. This step has as objective to evaluate the necessary amount of reactants to produce a determined volume of hydrogen and determine thermodynamic conditions (such as temperature and pressure) where the major performances of hydrogen production could be encountered. The calculations are based on the process where advance degrees are found and hence, fractions of products (especially hydrogen, however, CO2, CO, CH4 and solid carbon could be also encountered) are calculated. To produce 1 Nm3/h of gaseous hydrogen (necessary for a PEMFC - Proton Exchange Membrane Fuel Cell - containing an electric efficiency of about 40%, to generate 1 kWh), 0,558 kg/h of glycerol is necessary in global steam reforming, 0,978 kg/h of glycerol in partial oxidation and cracking processes, and 0,782 kg/h of glycerol in autothermal reforming process. The dry reforming process could not be performed to produce hydrogen utilizing glycerol, in contrary to the utilization of methane, ethanol, and other hydrocarbons. In this study, steam reforming process was preferred due mainly to higher efficiencies of production and the need of minor amount of glycerol as cited above. In the global steam reforming of glycerine, for one mole of glycerol, three moles of water are necessary to produce three moles of CO2 and seven moles of H2. The response reactions process was utilized to predict steam reforming process more accurately. In this mean, the production of solid carbon, CO, and CH4, beyond CO2 and hydrogen was predicted. However, traces of acetaldehyde (C2H2), ethylene (C2H4), ethylene glycol, acetone, and others were encountered in some experimental studies. The rates of determined products obviously depend on the adopted catalysts (and its physical and chemical properties) and thermodynamic conditions of hydrogen production. Eight reactions of steam reforming and cracking were predicted considering only the determined products. In the case of steam reforming at 600°C, the advance degree of this reactor could attain its maximum value, i.e., overall volume of reactants could be obtained whether this reaction is maintained at 1 atm. As soon as temperature of this reaction increases the advance degree also increase, in contrary to the pressure, where advance degree decrease as soon as pressure increase. The fact of temperature of reforming is relatively small, lower costs of installation could be attained, especially cheaper thermocouples and smaller amount of thermo insulators and materials for its assembling. Utilizing the response reactions process in steam reforming, the predicted volumes of products, for the production of 1 Nm3/h of H2 and thermodynamic conditions as cited previously, were 0,264 kg/h of CO (13% of molar fraction of reaction products), 0,038 kg/h of CH4 (3% of molar fraction), 0,028 kg/h of C (3% of molar fraction), and 0,623 kg/h of CO2 (20% of molar fraction). Through process of water-gas shift reactions (WGSR) an additional amount of hydrogen could be produced utilizing mainly the volumes of produced CO and CH4. The overall results (steam reforming plus WGSR) could be similar to global steam reforming. An attention must to be taking into account due to the possibility to produce an additional amount of CH4 (through methanation process) and solid carbon (through Boudouard process). The production of solid carbon must to be avoided because this reactant diminishes (filling the pores) and even deactivate active area of catalysts. To avoid solid carbon production, an additional amount of water is suggested. This method could be also utilized to diminish the volume of CO (through WGSR process) since this product is prejudicial for the activity of low temperature fuel cells (such as PEMFC). In some works, more three or even six moles of water are suggested. A net energy balance of studied hydrogen production processes (at 1 atm only) was developed. In this balance, low heat value of reactant and products and utilized energy for the process (heat supply) were cited. In the case of steam reforming utilizing response reactions, global steam reforming, and cracking processes, the maximum net energy was detected at 700°C. Partial oxidation and autothermal reforming obtained negative net energy in all cited temperatures despite to be exothermic reactions. For global steam reforming, the major value was 114 kJ/h. In the case of steam reforming, the highest value of net energy was detected in this temperature (-170 kJ/h). The major values were detected in the cracking process (up to 2586 kJ/h). The exergetic analysis has as objective, associated with physicochemical analysis, to determine conditions where reactions could be performed at higher efficiencies with lower losses. This study was performed through calculations of exergetic and rational efficiencies, and irreversibilities. In this analysis, as in the previously performed physicochemical analysis, conditions such as temperature of 600°C and pressure of 1 atm for global steam reforming process were suggested due to lower irreversibility and higher efficiencies. Subsequently, higher irreversibilities and lower efficiencies were detected in autothermal reforming, partial oxidation and cracking process. Comparing global reaction of steam reforming with more-accurate steam reforming, it was verified that efficiencies were diminished and irreversibilities were increased. These results could be altered with introduction of WGSR process. An economic analysis could be performed to evaluate the cost of generated hydrogen and determine means to diminish the costs. This analysis suggests an annual period of operation between 5000-7000 hours, interest rates of up to 20% per annum (considering Brazilian conditions), and pay-back of up to 20 years. Another considerations must to be take into account such as tariffs of utilized glycerol and electricity (to be utilized as heat source and (or) for own process as pumps, lamps, valves, and other devices), installation (estimated as US$ 15.000 for a plant of 1 Nm3/h) and maintenance cost. The adoption of emission trading schemes such as carbon credits could be performed since this is a process with potential of mitigates environment impact. Not considering credit carbons, the minor cost of calculated H2 was 0,16288 US$/kWh if glycerol is also utilized as heat sources and 0,17677 US$/kWh if electricity is utilized as heat sources. The range of considered tariff of glycerol was 0-0,1 US$/kWh (taking as basis LHV of H2) and the tariff of electricity is US$ 0,0867 US$/kWh, with demand cost of 12,49 US$/kW. The costs of electricity were obtained by Companhia Bandeirante, localized in São Paulo State. The differences among costs of hydrogen production utilizing glycerol and electricity as heat source was in a range between 0,3-5,8%. This technology in this moment is not mature. However, it allows the employment generation with the additional utilization of glycerol, especially with plants associated with biodiesel plants. The produced hydrogen and electricity could be utilized in own process, increasing its final performance.

Propriedades químicas de um latossolo vermelho de cerrado cultivado com algodão sob diferentes preparos e adubações

The high rate of mineralization of organic matter on savannah soils, which is reached fi ve times faster than in temperate regions, leads us to the challenge of electing the best system of management that maintains and/or increase it in soil, guaranteeing its quality and sustainability. In this sense the present research aimed to study the effects of green, organic and mineral manure on the chemical properties on the chemical properties of an Oxisol, on Savannah area, cultivated with cotton (Gossypium hirsutum) under conventional tillage and no-tillage in the pasture fi eld (Brachiaria decumbens) for 20 years. The experimental design was a randomized block design with split plots. The main plots consisted of two treatments: conventional tillage and no-tillage, and the subplots of six treatments: control (no fertilizer), mineral fertilizer recommended for the crop, according to the soil chemical analysis, organic fertilizer (cattle manure - 20 t ha-1), organic fertilizer (cattle manure - 20 t ha-1) + 1/2mineral fertilization recommended according to the analysis of soil, green manure-1 (Crotalaria juncea) and green manure-2 (Pennisetum americanum). There were studied the following soil chemical properties: P, OM, pH, K, Ca, Mg, Al, Al + H, S, exchange capacity cations and base saturation. The soil samples for the analysis were performed on layers of 0,00-0,05 m, 0,05-0,10 and 0,10-0,20 m. Then it came the following conclusions: the fertilization interfere in soil chemical properties and the preparation did not interfere, the cattle manure and its association with the mineral fertilizer caused increasing level elements in the soil, Crotalaria juncea and Pennisetum americanum did not infl uence on soil chemical properties.

Evaluation of titanium implants with surface modification by laser beam. Biomechanical study in rabbit tibias

The purpose of the present study was to evaluate, using a biomechanical test, the force needed to remove implants with surface modification by laser (Nd:YAG) in comparison with implants with machined surfaces. Twenty-four rabbits received one implant with each surface treatment in the tibia, machined surface (MS) and laser-modified surface (LMS). After 4, 8 and 12 weeks of healing, the removal torque was measured by a torque gauge. The surfaces studied were analyzed according to their topography, chemical composition and roughness. The average removal torque in each period was 23.28, 24.0 and 33.85 Ncm for MS, and 33.0, 39.87 and 54.57 Ncm for LMS, respectively. The difference between the surfaces in all periods of evaluation was statistically significant (p < 0.05). Surface characterization showed that a deep and regular topography was provided by the laser conditioning, with a great quantity of oxygen ions when compared to the MS. The surface micro-topography analysis showed a statistical difference (p < 0.01) between the roughness of the LMS (R a = 1.38 ± 0.23 μm) when compared to that of the MS (R a = 0.33 ± 0.06 μm). Based on these results, it was possible to conclude that the LMS implants' physical-chemical properties increased bone-implant interaction when compared to the MS implants. © 2009 Sociedade Brasileira de Pesquisa Odontológica.

Influência do cancro basal em Eucalyptus grandis nas propriedades da madeira e polpação kraft

The objective of this research is to assess the influences of basal canker on wood properties for the kraft pulp production. The material consisted of seeded E. grandis trees classified into 4 levels of basal canker severity (0, 1, 2 and 3) and installed in three soil types classified by texture (AQ1 and AQ2 - 10 to 15% clay, and LEm2 - 26 to 35 clay). The sampling consisted of randomly selecting five trees for each for each canker severity level and soil type, totaling 60 trees (4 canker levels x 3 soil types x 5 trees). These trees were fallen and cut into sections at 0, 25, 50, 75 and 100% of the commercial height for the collection of disk and logs of wood. The results showed that the soil texture influences in the Eucalyptus canker severity and this fact should be considered when assessing the wood properties and their final destination. The texture of the soil and the severe levels of basal canker influence the wood properties, and therefore the kraft pulping.

Efeito do tratamento químico na sanidade de sementes de espécies florestais

This study evaluated the effect of different fungicide and sodium hypochlorite treatments in reducing the incidence of fungi on seeds of native species of the Atlantic rainforest. The experiment was done using the completely randomized design in a 5×5 factorial with five levels of factor A (forest species) and five levels of factor B (chemical treatment and surface disinfection with sodium hypochlorite) with four replications. The fungal genera Fusarium, Alternaria, Aspergillus and Penicillium were identified. The species 'Jacarandáda- Bahia' and 'Ipê-roxo' had lower fungal incidence, 1.0% and 1.3%, respectively. Except for 'Angico Vermelho', the fungicide pencycurom and sodium hypochlorite were not significantly different from the control in the species evaluated. Seed treatment with fungicides 'Captan' and 'Tiram' yielded satisfactory results in reducing the incidence of fungal contamination in forest species seeds.

Correlação linear e espacial entre a produtividade e o teor de proteína bruta do guandu anão e os atributos de um Latossolo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Tethered DNA scaffolds on optical sensor platforms for detection of hipO gene from Campylobacter jejuni

DNA biosensors have gained increased attention over traditional diagnostic methods due to their fast and responsive operation and cost-effective design. The specificity of DNA biosensors relies on single-stranded oligonucleotide probes immobilized to a transduction platform. Here, we report the development of biosensors to detect the hippuricase gene (hipO) from Campylobacter jejuni using direct covalent coupling of thiol- and biotin-labeled single-stranded DNA (ssDNA) on both surface plasmon resonance (SPR) and diffraction optics technology (DOT, dotLab) transduction platforms. This is the first known report of the dotLab to detect targeted DNA. Application of 6-mercapto-1-hexanol as a spacer thiol for SPR gold surface created a self-assembled monolayer that removed unbound ssDNA and minimized non-specific detection. The detection limit of SPR sensors was shown to be 2.5 nM DNA while dotLab sensors demonstrated a slightly decreased detection limit of 5.0 nM (0.005 μM). It was possible to reuse the SPR sensor due to the negligible changes in sensor sensitivity (∼9.7 × 10 -7 ΔRU) and minimal damage to immobilized probes following use, whereas dotLab sensors could not be reused. Results indicated feasibility of optical biosensors for rapid and sensitive detection of the hipO gene of Campylobacter jejuni using specific ssDNA as a probe. © 2011 Elsevier B.V.

Atributos químicos do solo sob plantio direto afetado por sistemas de culturas e fontes de adubação

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dinámica del suelo y estoque de carbono después de diez años de la restauración de tierras degradadas usando especies arbóreas del bosque atlántico

Brazil's Atlantic Forest ecosystem has been greatly affected by land use changes, with only 11.26% of its original vegetation cover remaining. Currently, Atlantic Forest restoration is receiving increasing attention because of its potential for carbon sequestration and the important role of soil carbon in the global carbon balance. Soil organic matter is also essential for physical, chemical and biological components of soil fertility and forest sustainability. This study evaluated the potential for soil recovery in contrasting restoration models using indigenous Atlantic Forest tree species ten years after their establishment. The study site is located in Botucatu municipality, São Paulo State-Brazil, in a loamy dystrophic Red-Yellow Argisol site (Typic Hapludult). Four treatments were compared: i) Control (Spontaneous Restoration); ii) Low Diversity (five fast-growing tree species established by direct seeding); iii) High Diversity (mixed plantings of 41 species established with seedlings) and; iv) Native Forest (well conserved neighboring forest fragment). The following soil properties were evaluated: (1) physical-texture, density and porosity; (2) chemical-C, N, P, S, K, Ca, Mg, Al and pH; (3) biological-microbial biomass. Litter nutrient concentrations (P, S, K, Ca and Mg) and C and N litter stocks were determined. Within ten years the litter C and N stocks of the Low Diversity treatment area were higher than Control and similar to those in both the High Diversity treatment and the Native Forest. Soil C stocks increased through time for both models and in the Control plots, but remained highest in the Native Forest. The methods of restoration were shown to have different effects on soil dynamics, mainly on chemical properties. These results show that, at least in the short-term, changes in soil properties are more rapid in a less complex system like the Low Diversity model than in the a High Species Diversity model. For both mixed plantation systems, carbon soil cycling can be reestablished, resulting in increases in carbon stocks in both soil and litter.

Avaliação das propriedades químicas em solo de cerrado SOB reflorestamento ciliar

The rapid growth of agriculture, promoted by public government initiatives, favored an out of control deforestation of our forests; today, reforestation of permanent preservation areas are necessary for the conservation of our natural resources, and recovery of such areas are required by public laws. In an area of 5.26 acres of riparian reforestation in the savanna soil chemical properties were evaluated after twenty years of planting. It was analyzed the following variables: (P, organic matter (MO), pH, K, Ca, Mg, H+Al, Al and S) in 13 modules, with three replicas in two depths (0 - 20 and 20 - 40 cm) in a randomized block design in hierarchical scheme. Reforestation with tree species on the edge of Parana river in Selvíria (MS) contributes to chemical soil attributes, under riparian reforestation, as similar as a soil without human disturbance in this region; it is also possible to verify that forestry plantation promotes deposition of organic material which is essential for nutrient cycling, which keep the chemical properties of such soil in good condition for the establishment of riparian vegetation.

Influence of organic and mineral soil fertilization on essential oil of Spilanthes oleracea cv. Jambuarana

In the present study, the composition of essential oil of leaves and inflorescences of jambu (Spilanthes oleracea. Jambuarana), under organic manuring and mineral fertilization, was stuhed. Jambu plants show important chemical properties and their production has been addressed for the extraction of the essential oils for cosmetics industries, due to their pharmacolopcal properties. The experimental area of treatments contained urea as mineral fertilizer (120 g m2), applied twice and organic fertilizer (8 kg m2), applied at the planting. Jambu leaves and flowers were harvested twice: the first at 90 days after seedling transplantation and at the opening of the flower buds. Branches were cut at 7 cm from the soil, thus new branches can bud for the accomplishment of the second crop which happened 40 days after the re-budhng. The essential oil was analyzed by gas chromatography coupled with mass-spectrometry. According to our results the most representative compounds were trans-caryophyllene, germacrene-D, 1-dodecene, spathulenol and spilanthol (a compound presenting anesthetic properties) occurring in inflorescences. Fertilization procedure does not affect the content and the quality of the essential oil in Jambu plants. © 2012 Academic Journals Inc.

Characterization and fatty acids profile of the oils from Amazon nuts and walnuts: Characterization and fatty acids profile of the oilseeds

Purpose: The purpose of this paper is to characterize oils extracted from Bertholletia excelsa, Lecythis pisonis, Dipteryx lacunifera, Carya illinoensis and Juglans regia, regarding their characterization and fatty acid profile. Design/methodology/approach: The oils were extracted from oilseeds by cold pressing and physico-chemical characterization was performed by using standard methods for oils and fats. The oxidative stability and fatty acid profile also were determined. Findings: According to the results, the physico-chemical properties of oils from nuts and walnuts were comparable to those of good quality conventional oils. The oil seeds are a good source of unsaturated fatty acids, especially oleic and linoleic acids. Research limitations/implications: Implies the identification of fatty acid profile and physico-chemical properties of oils extracted from nuts and walnuts, and to prevent certain types of diseases. Originality/value: The paper identifies a new source of essential fatty acids extracted from oilseeds. © Emerald Group Publishing Limited.

Influência de diferentes sistemas de cultivo nos atributos físicos e no carbono orgânico do solo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

New label free CA125 detection based on gold nanostructured screen-printed electrode

This paper describes the optimisation and the analytical performances of a label-free impedimetric immunosensor for the detection of tumour marker CA125 based on gold nanoparticles modified screen-printed graphite electrode. Experimental conditions of each step for the developed immunosensor were studied and optimised. The immunosensor response varied linearly (r2 = 0.996) with antigen concentration between 0 and 100 U/mL. The estimated detection limit was 6.7 U/mL. The electrochemical immunosensor allowed unambiguous identification of CA125, while no significant non-specific signal was detected in the case of all negative controls. The analytical usefulness of the impedimetric immunosensor was finally demonstrated analysing serum samples. © 2012 Elsevier B.V. All rights reserved.

Use of hemoglobin as alternative to peroxidases in cholesterol amperometric biosensors

Sophisticated molecular architectures can be produced with the layer-by-layer (LbL) method, which may combine distinct materials on the same film. In this study, we take advantage of this capability to produce cholesterol amperometric biosensors from LbL films containing hemoglobin (Hb) and cholesterol oxidase in addition to the polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(ethylene imine) (PEI). Following an optimization procedure, we found that an LbL film deposited onto ITO substrates, with the architecture ITO(PEI/Hb)5(PEI/COx)10, yielded a sensitivity of 93.4 μA μmol L-1 cm-2 for cholesterol incorporated into phospholipid liposomes, comparable to state-of-the-art biosensors. Hb acted as efficient electron mediator and did not suffer interference from phospholipids. Significantly, cholesterol could also be detected in real samples from chicken egg yolk, with no effects from potential interferents, including phospholipids. Taken together these results demonstrate the possible fabrication of low cost, easy-to-use cholesterol amperometric biosensors, whose sensitivity can be enhanced by further optimizing the molecular architectures of the LbL films. © 2012 Elsevier B.V.