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.

Performance of laying hens and economic viability of different climatization systems

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

A bi-objective genetic approach for the selection of sugarcane varieties to comply with environmental and economic requirements

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

Evaluation of a commercially available organic acid product on body weight loss, carcass yield, and meat quality during preslaughter feed withdrawal in broiler chickens: A poultry welfare and economic perspective

The effect of a commercial organic acid (OA) product on BW loss (BWL) during feed withdrawal and transportation, carcass yield, and meat quality was evaluated in broiler chickens. Two experiments were conducted in Brazil. Commercial houses were paired as control groups receiving regular water and treated groups receiving OA in the water. Treated birds had a reduction in BWL of 37 g in experiment 1 and 32.2 g in experiment 2. In experiment 2, no differences were observed in carcass yield between groups. Estimation of the cost benefit suggested a 1: 16 ratio by using the OA. In experiment 3, conducted in Mexico, significant differences on water consumption, BWL, and meat quality characteristics were observed in chickens that were treated with the OA (P < 0.05). These data suggest this OA product may improve animal welfare and economic concerns in the poultry industry by reducing BWL and improving meat quality attributes.

Stocking densities of juvenile Brycon orthotaenia: production parameters and economic benefits in net cages

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

Energetic and economic analysis of a Brazilian compact cogeneration system: Comparison between natural gas and biogas

Cogeneration may be defined as the simultaneous production of electric power and useful heat from the burning of a single fuel. This technique of combined heat and power production has been applied in both the industrial and tertiary sectors. It has been mainly used because of its overall efficiency, and the guarantee of electricity with a low level of environmental impact. The compact cogeneration systems using internal combustion engine as prime movers are thoroughly applied because of the good relationship among cost and benefit obtained in such devices. The cogeneration system of this study consists of an internal combustion engine using natural gas or biogas as fuel, combined with two heat exchangers and an absorption chiller utilising water-ammonia as working mixture. This work presents an energetic and economic comparison between natural gas and biogas as fuel used for the system proposed. The results are useful to identify the feasible applications for this system, such as residential sector in isolated areas, hotels, universities etc. (C) 2014 Elsevier Ltd. All rights reserved.

Correlation between structural and electronic order-disorder effects and optical properties in ZnO nanocrystals

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

Technical and economic evaluation of different types of control of Brevipalpus phoenicis (Acari: Tenuipalpidae) in citrus leprosies management

The objective of this work was to evaluate the effect of acaricide applications and pruning of symptomatic branches in citrus leprosis management in Brazil. It was conducted in an orange plantation of the 'Pera' variety, grafted onto the 'Cleopatra' tangerine, in two seasons (2006-2007 and 2007-2008). The experimental design was randomized blocks in a factorial scheme consisting of the following factors: (A) acaricide, in three levels: spirodiclofen and cyhexatin applied in rotation, lime sulphur; no acaricides; (B) pruning to remove branches that showed symptoms of leprosis, with two levels: with pruning, without pruning. We carried out periodic assessments of Brevipalpus phoenicis (Geijskes) populations (vector of the leprosis virus), leprosis incidence and severity, fruit yield, and the economic feasibility of the applied strategies. Based on the results, we concluded that spirodiclofen and cyhexatin were more effective than lime sulphur in B. phoenicis control. Control with lime sulphur required more applications than spirodiclofen and cyhexatin in rotation, making it more expensive. Pruning of symptomatic branches used in isolation was not sufficiently effective to control leprosis and significantly increased control costs. Profits were higher when the control involved sprayings of spirodiclofen and cyhexatin in alternation, with or without pruning.

MORPHO-PHYSIOLOGICAL INDICES AND ECONOMIC PRODUCTIVITY OF JAMBU CULTIVARS INFLUENCED BY THE ORGANIC AND MINERAL FERTILIZERS

The jambu belongs to the family Asteraceae, tropical crop, nowadays, this plant has been considered as a promising vegetable crop, because to its pharmacological properties. Despite this novelty, the vegetable remains invisible in the statistics of production and market in the state of Para, Brazil. This research was carried out with the aim of comparing the economic productivity and phenological development by the morpho-physiological growth indexes of two cultivars of jambu organic manure and mineral fertilizers. The experiment was carried out at the Sao Manuel Experimental Farm (Sao Manuel-SP), which belongs to the Faculdade de Ciencias Agronomicas - UNESP, campus Botucatu. The experimental design was a factorial randomized blocks (2 x 2) with two fertilization (organic and mineral) and two cultivars (Jambuarana and Nazareth), with six replications, two fertilization (organic and mineral) and two cultivars (Jambuarana and Nazareth). The following characteristics were evaluated: Plant height (cm), Leaf area (cm(2)), Fresh mass (g), Dry mass (g), Leaf area index (LAI), Leaf area ratio (LAR), Specific leaf Area (SLA), Leaf Weight Ratio (LWR), Amount of water in the plant (QAPA) (g per plant set), Leaf specific weight (LSW) (g cm(-2) per plant set) and Economic productivity. All data were statistically analyzed by analysis of variance and the Tukey test (1%) for mean comparison, with the software SISVAR. In the conditions of this experiment was carried out, it was possible to verify that the cultivar Jamburana had not only a good agronomic development and economic productivity under organic fertilization but also the best morpho-physiological indexes, showing that this kind of fertilization increases the agronomic effectiveness of this cultivar.

Saddle Point and Second Order Optimality in Nondifferentiable Nonlinear Abstract Multiobjective Optimization

This article deals with a vector optimization problem with cone constraints in a Banach space setting. By making use of a real-valued Lagrangian and the concept of generalized subconvex-like functions, weakly efficient solutions are characterized through saddle point type conditions. The results, jointly with the notion of generalized Hessian (introduced in [Cominetti, R., Correa, R.: A generalized second-order derivative in nonsmooth optimization. SIAM J. Control Optim. 28, 789–809 (1990)]), are applied to achieve second order necessary and sufficient optimality conditions (without requiring twice differentiability for the objective and constraining functions) for the particular case when the functionals involved are defined on a general Banach space into finite dimensional ones.

The current financial and economic crisis: empirical and methodological issues

In this paper we describe the main causes of the recent financial crisis as a result of many theoretical, methodological, and practical shortcomings mostly according to heterodox, but also including some important orthodox economists. At theoretical level, there are problems concerning teaching and using economic models with overly unrealistic assumptions. In the methodological front, we find the unsuspected shadow of Milton Friedman’s ‘unrealisticism of assumptions’ thesis lurking behind the construction of this kind of models and the widespread neglect of methodological issues. Of course, the most evident shortcomings are at the practical level: (i) huge interests of the participants in the financial markets (banks, central bankers, regulators, rating agencies mortgage brokers, politicians, governments, executives, economists, etc. mainly in the US, Canada and Europe, but also in Japan and the rest of the world), (ii) in an almost completely free financial and economic market, that is, one (almost) without any regulation or supervision, (iii) decision-taking upon some not well regarded qualities, like irresponsibility, ignorance, and inertia; and (iv) difficulties to understand the current crisis as well as some biases directing economic rescues by governments. Following many others, we propose that we take this episode as an opportunity to reflect on, and hopefully redirect, economic theory and practice.

Higher yield and economic benefits are achieved in the macadamia crop by irrigation and intercropping with coffee

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

Black liquor gasification combined cycle with CO2 capture-Technical and economic analysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A relationship between structural and electronic order-disorder effects and optical properties in crystalline TiO2 nanomaterials

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