Degradação do PMMA através da reação despolimerização uitlizando catalisadores de óxidos mistos

In this work, mixed oxides were synthesized by two methods: polymeric precursor and gel-combustion. The oxides, Niquelate of Lanthanum, Cobaltate of Lanthanum and Cuprate of Lanthanum were synthesized by the polymeric precursor method, and treated at 300 º C for 2 hours, calcined at 800 º C for 6h in air atmosphere. In gel-combustion method were produced and oxides using urea and citric acid as fuel, forming for each fuel the following oxides Ferrate of Lanthanum, Cobaltato of Lanthanum and Ferrato of Cobalt and Lanthanum, which were submitted to the combustion process assisted by microwave power maximum of 10min. The samples were characterized by: thermogravimetric analysis, X-ray diffraction; fisisorção of N2 (BET method) and scanning electron microscopy. The reactions catalytic of depolymerization of poly (methyl methacrylate), were performed in a reactor of silica, with catalytic and heating system equipped with a data acquisition system and the gas chromatograph. For the catalysts synthesized using the polymeric precursor method, the cuprate of lanthanum was best for the depolymerization of the recycled polymer, obtaining 100% conversion in less time 554 (min), and the pure polymer, was the Niquelate of Lanthanum, with 100% conversion in less time 314 (min). By gel-combustion method using urea as fuel which was the best result obtained Ferrate of Lanthanum for the pure polymer with 100% conversion in less time 657 (min), and the recycled polymer was Cobaltate of Lanthanum with 100 % conversion in less time 779 (min). And using citric acid to obtain the best result for the pure polymer, was Ferrate of Lanthanum with 100% conversion in less time 821 (min and) for the recycled polymer, was Ferrate of Lanthanum with 98.28% conversion in less time 635 (min)

Produção de bioetanol a partir de pedúnculo de caju (Anacardium occidentale L.) por fermentação submersa

Recently, global demand for ethanol fuel has expanded very rapidly, and this should further increase in the near future, almost all ethanol fuel is produced by fermentation of sucrose or glucose in Brazil and produced by corn in the USA, but these raw materials will not be enough to satisfy international demand. The aim of this work was studied the ethanol production from cashew apple juice. A commercial strain of Saccharomyces cerevisiae was used for the production of ethanol by fermentation of cashew apple juice. Growth kinetics and ethanol productivity were calculated for batch fermentation with different initial sugar (glucose + fructose) concentration (from 24.4 to 103.1 g.L-1). Maximal ethanol, cell and glycerol concentrations (44.4 g.L-1, 17.17 g.L-1, 6.4 g.L-1, respectively) were obtained when 103.1 g.L-1 of initial sugar concentration were used, respectively. Ethanol yield (YP/S) was calculated as 0.49 g (g glucose + fructose)-1. Pretreatment of cashew apple bagasse (CAB) with dilute sulfuric acid was investigated and evaluated some factors such as sulfuric acid concentration, solid concentration and time of pretreatment at 121°C. The maximum glucose yield (162.9 mg/gCAB) was obtained by the hydrolysis with H2SO4 0.6 mol.L-1 at 121°C for 15 min. Hydrolysate, containing 16 ± 2.0 g.L-1 of glucose, was used as fermentation medium for ethanol production by S. cerevisiae and obtained a ethanol concentration of 10.0 g.L-1 after 4 with a yield and productivity of 0.48 g (g glucose)-1 and 1.43 g.L-1.h-1, respectively. The enzymatic hydrolysis of cashew apple bagasse treated with diluted acid (CAB-H) and alkali (CAB-OH) was studied and to evaluate its fermentation to ethanol using S. cerevisiae. Glucose conversion of 82 ± 2 mg per g CAB-H and 730 ± 20 mg per g CAB-OH was obtained when was used 2% (w/v) of solid and loading enzymatic of 30 FPU/g bagasse at 45 °C. Ethanol concentration and productivity was achieved of 20.0 ± 0.2 g.L-1 and 3.33 g.L-1.h-1, respectively when using CAB-OH hydrolyzate (initial glucose concentration of 52.4 g.L-1). For CAB-H hydrolyzate (initial glucose concentration of 17.4 g.L-1), ethanol concentration and productivity was 8.2 ± 0.1 g.L-1 and 2.7 g.L-1.h-1, respectively. Hydrolyzates fermentation resulted in an ethanol yield of 0.38 g/g glucose and 0.47 g/g glucose, with pretreated CABOH and CAB-H, respectively. The potential of cashew apple bagasse as a source of sugars for ethanol production by Kluyveromyces marxianus CE025 was evaluated too in this work. First, the yeast CE025 was preliminary cultivated in a synthetic medium containing glucose and xylose. Results showed that it was able to produce ethanol and xylitol at pH 4.5. Next, cashew apple bagasse hydrolysate (CABH) was prepared by a diluted sulfuric acid pre-treatment. The fermentation of CABH was conducted at pH 4.5 in a batch-reactor, and only ethanol was produced by K. marxianus CE025. The influence of the temperature in the kinetic parameters was evaluated and best results of ethanol production (12.36 ± 0.06 g.L-1) was achieved at 30 ºC, which is also the optimum temperature for the formation of biomass and the ethanol with a volumetric production rate of 0.25 ± 0.01 g.L-1.h-1 and an ethanol yield of 0.42 ± 0.01 g/g glucose. The results of this study point out the potential of the cashew apple bagasse hydrolysate as a new source of sugars to produce ethanol by S. cerevisiae and K. marxianus CE025. With these results, conclude that the use of cashew apple juice and cashew apple bagasse as substrate for ethanol production will bring economic benefits to the process, because it is a low cost substrate and also solve a disposal problem, adding value to the chain and cashew nut production

Briquetting of charcoal from sugar-cane bagasse fly ash (scbfa) as an alternative fuel

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

Continuous ethanol production in a nonconventional five-stage system operating with yeast cell recycling at elevated temperatures

Three ranges of increasing temperatures (35-43, 37-45, 39-47degreesC) were sequentially applied to a five-stage system continuously operated with cell recycling so that differences of 2degreesC (between one reactor to the next) and 8degreesC (between the first reactor at the highest temperature and the fifth at the lowest temperature) were kept among the reactors for each temperature range. The entire system was fed through the first reactor. The lowest values of biomass and viability were obtained for reactor R-3 located in the middle of the system. The highest yield of biomass was obtained in the effluent when the system was operated at 35-43degreesC. This nonconventional system was set up to simulate the local fluctuations in temperature and nutrient concentrations that occur in different regions of the medium in an industrial bioreactor for fuel ethanol production mainly in tropical climates. Minimized cell death and continuous sugar utilization were observed at temperatures normally considered too high for Saccharomyces cerevisiae fermentations.

Analysis of a molten carbonate fuel cell: cogeneration to produce electricity and cold water

The fuel cell is an emerging cogeneration technology that has been applied successfully in Japan, the USA and some countries in the European Union. This system performs direct conversion of the chemical energy of the oxidation of hydrogen from fuel with atmospheric oxygen into direct current electricity and waste heat via an electrochemical process relying on the use of different electrolytes (phosphoric acid, molten carbonate and solid oxide, depending on operating temperature). This technology permits the recovery of waste heat, available from 200 degreesC up to 1000 degreesC depending on the electrolyte technology, which can be used in the production of steam, hot or cold water, or hot or cold air, depending on the associated recuperation equipment. In this paper, an energy, exergy and economic analysis of a fuel cell cogeneration system (FCCS) is presented. The FCCS is applied in a segment of the tertiary sector to show that it is a feasible alternative for rational decentralized energy production under Brazilian conditions. The technoeconomic analysis shows a global efficiency or fuel utilization efficiency of 86%. Analysis shows that the exergy losses in the fuel cell unit and the absorption refrigeration system are significant. Furthermore, the payback period estimated is about 3 and 5 years for investments in fuel cells of 1000 and 1500 US$/kW, respectively. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Fuel cell cogeneration system: a case of technoeconomic analysis

Fuel Cell is the emerging technology of cogeneration, and has been applied successfully in Japan, U.S.A. and some OECD countries. This system produces electric power by an electrolytic process, in which chemical substances (the most utilized substances are solid oxide, phosphoric acid and molten carbonate) absorb the components H-2 and O-2 of the combustion fuel. This technology allows the recovery of residual heat, available from 200 degrees C up to 1000 degrees C (depending on the electrochemical substance utilized), which can be used for the production of steam, hot or cold water, or hot or cold air, depending on the recuperation equipment used. This article presents some configurations of fuel cell cogeneration cycles and a study of the technical and economic feasibility for the installation of the cogeneration systems utilizing fuel cell, connected to an absorption refrigeration system for st building of the tertiary sector, subject to conditions in Brazil. (C) 1999 Elsevier B.V. Ltd. All rights reserved.

Thermodynamic analysis of direct steam reforming of ethanol in molten carbonate fuel cell

Fuel cell as molten carbonate fuel cell (MCFC) operates at high temperatures. Thus, cogeneration processes may be performed, generating heat for its own process or for other purposes of steam generation in the industry. The use of ethanol is one of the best options because this is a renewable and less environmentally offensive fuel, and is cheaper than oil-derived hydrocarbons, as in the case of Brazil. In that country, because of technical, environmental, and economic advantages, the use of ethanol by steam reforming process has been the most investigated process. The objective of this study is to show a thermodynamic analysis of steam reforming of ethanol, to determine the best thermodynamic conditions where the highest volumes of products are produced, making possible a higher production of energy, that is, a more efficient use of resources. To attain this objective, mass and energy balances were performed. Equilibrium constants and advance degrees were calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree (according to Castellan 1986, Fundamentos da Fisica/Quimica, Editora LTC, Rio de Janeiro, p. 529, in Portuguese) is a coefficient that indicates the evolution of a reaction, achieving a maximum value when all the reactants' content is used of reforming increases when the operation temperature also increases and when the operation pressure decreases. However, at atmospheric pressure (1 atm), the advance degree tends to stabilize in temperatures above 700 degrees C; that is, the volume of supplemental production of reforming products is very small with respect to high use of energy resources necessary. The use of unused ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at the same tension, is higher at 700 degrees C than other studied temperatures such as 600 and 650 degrees C. This fact occurs due to smaller use of hydrogen at lower temperatures that varies between 46.8% and 58.9% in temperatures between 600 and 700 degrees C. The higher calculated current density is 280 mA/cm(2). The power density increases when the volume of ethanol to be used also increases due to higher production of hydrogen. The highest produced powers at 190 mA/cm(2) are 99.8, 109.8, and 113.7 mW/cm(2) for 873, 923, and 973 K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describe a process of internal steam reforming of ethanol.

Hydrodynamic characterization and performance evaluation of an aerobic three phase airlift fluidized bed reactor in a recirculation aquaculture system for Nile Tilapia production

The hydrodynamic characterization and the performance evaluation of an aerobic three phase fluidized bed reactor in wastewater fish culture treatment are presented in this report. The objective of this study was to evaluate the organic matter, nitrogen and phosphorous removal efficiency in a physical and biological wastewater treatment system of an intensive Nile Tilapia laboratory production with recirculation. The treatment system comprised of a conventional sedimentation basin operated at a hydraulic detention time HDT of 2.94 h and an aerobic three phase airlift fluidized bed reactor AAFBR operated at an 11.9 min HDT. Granular activated carbon was used as support media with density of 1.64 g/cm(3) and effective size of 0.34 mm in an 80 g/L constant concentration. Mean removal efficiencies of BOD, COD, phosphorous, total ammonia nitrogen and total nitrogen were 47%, 77%, 38%, 27% and 24%, respectively. The evaluated system proved an effective alternative for water reuse in the recirculation system capable of maintaining water quality characteristics within the recommended values for fish farming and met the Brazilian standards for final effluent discharges with exception of phosphorous values. (C) 2011 Elsevier B.V. All rights reserved.

Preconcentration and determination of metal ions in commercial ethanol used as fuel for automotive engines

The present investigation reports the synthesis, characterization, and adsorption properties of a new nanomaterial based on organomodified silsesquioxane nanocages. The adsorption isotherms for CuCl,, CoCl2, ZnCl2, NiCl2, and FeCl3 from ethanol solutions were performed by using the batchwise method. The equilibrium condition is reached very quickly (3 min), indicating that the adsorption sites are well exposed. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of the nanomaterial, using 5 mL of 1.0 mol L-1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a method for preconcentration and determination of metal ions at trace level in commercial ethanol, used as fuel for car engines. The values determined by recommended method for plants 1, 2, and 3 indicated an amount of copper of 51, 60, and 78 mu g L-1, and of iron of 2, 15, and 13 mu g L-1, respectively. These values are very close to those determined by conventional analytical methods. Thus, these similar values demonstrated the accuracy of the determination by recommended method.

Voltammetric determination of total iron in fuel ethanol using a 1,10 fenantroline/nafion carbon paste-modified electrode

This work presents a methodology for iron determination in fuel ethanol using a modified carbon paste electrode with 1.10 fenantroline/nafion. The electrochemical parameters were optimized for the proposed system and the voltammetric technique of square wave was employed for iron determination. An accumulation time of 5 minutes, such as a 100 mV of pulse magnitude (E(sw)) and frequency (f) of 25 Hz were used as optimized experimental conditions. The modified carbon paste electrode presented linear dependence of amperometric signal with iron concentration in a work range from 6.0x10(-6) until 2.0x10(-5) mol L(-1) of iron, exhibiting a linear correlation coefficient of 0.9884, a detection limit of 2.4 x10(-6) mol L(-1) (n = 3) and amperometric sensibility of 4.5x10(5) mu A/mol L(-1). Analytical curve method was used for iron determination at a commercial fuel sample. Flame atomic absorption spectroscopy was employed as comparative technique.

Application of cellulose modified with p-aminobenzoic groups in preconcentration system for determination of Cu, Fe, Ni, and Zn in fuel ethanol samples by flame atomic absorption spectrometry

Cellulose chemically modified with p-aminobenzoic groups, abbreviated as Cel-PAB, was used for preconcentration of copper, iron, nickel, and zinc from ethanol fuel, normally used in Brazil as engine fuel. The surface characteristics and the surface area of the cellulose were obtained before and after chemical modification using FT-IR, elemental analysis, and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques.

Flame AAS determination of metal ions in fuel ethanol after preconcentration on acid carboxymethylcellulose (CMCH)

This paper describes the preparation of acid carboxymethylcellulose (CMCH), and the results of a study on the adsorption and preconcentration (using batch and flow-through column methods) of Cd(II), Cu(II), Cr(III), Fe(III), Ni(II) and Zn(II) in ethanol medium. The adsorption capacities for each metallic ion were (in mmol g(-1)) Cd(II) = 0.92; Cu(II) = 1.45; Cr(III) = 1.70; Fe(III) = 1.60; Ni(II) = 1.30; and Zn(II) = 1.10. By means of the flow-through method, a recovery of ca. 100% of the metallic ions adsorbed in a column packed with 2 g of CMCH was found when 5.0 mL of 1.0 mol L-1 hydrochloric acid were used as eluent. An enrichment factor of 20 (100 mt solution containing 50 mu g L-1 of the metallic ions, concentrated to 5.0 mt) was obtained by this preconcentration procedure. The sorption-desorption procedure applied allowed the development of a preconcentration and Flame AAS quantification method of metallic ions in fuel ethanol at trace levels.

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni2+ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni2+ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni2+ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)2 complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 x 10(-9) to 1.0 x 10(-6) mol L-1 with detection limit of 2.0 x 10(-9) mol L-1. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 mu mol L-1 Ni2+ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni2+ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni2+ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step. (c) 2006 Elsevier B.V. All rights reserved.

Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at -0.3 V versus Ag/AgCl(sat) a linear range from 7.5 x 10(-8) to 2.5 x 10(-6) mol L(-1) with detection limit of 3.1 x 10(-8) mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods. (c) 2006 Elsevier B.V. All rights reserved.

Determination of Cu, Ni, and Zn in fuel ethanol by FAAS after enrichment in column packed with 2-aminothiazole-modified silica gel

This work describes the synthesis and characterization of 2-aminothiazole-modified silica gel (SiAT), as well as its application for preconcentration (in batch and column technique) of Cu(II), Ni(II) and Zn(II) in ethanol medium. The adsorption capacities of SiAT determined for each metal ion were (mmol g(-1)): Cu(II)=1.20, Ni(II)=1.10 and Zn(II)=0.90. In addition, results obtained in flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 500 mg of SiAT. The eluent was 2.0 mol L-1 HCl. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in fuel ethanol using flame AAS for their quantification.