Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.

Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.

Study of the emissions from pyrolytic and oxidative thermal decomposition of PVC

Polyvinyl chloride (PVC) is one of the plastics most extensively used due to its versatility. The demand of PVC resin in Europe during 2012 reached 5000 ktonnes1. PVC waste management is a big problem because of the high volume generated all over the world and its chlorine content. End-of-life PVC is mainly mixed with municipal solid waste (MSW) and one common disposal option for this is waste-to-energy incineration (WtE). The presence of plastics such as PVC in the fuel mix increases the heating value of the fuel. PVC has two times higher energy content than MSW ‒around 20 MJ/kg vs 10 MJ/kg, respectively. However, the high chlorine content in PVC resin, 57 wt.%, may be a source for the formation of hazardous chlorinated organic pollutants in thermal processes. Chlorine present in the feedstock of WtE plants plays an important role in the formation of (i) chlorine (Cl2) and (ii) hydrochloric gas (HCl), both of them responsible for corrosion, and (iii) chlorinated organic pollutants2. In this work, pyrolytic and oxidative thermal degradation of PVC resin were carried out in a laboratory scale reactor at 500 ºC in order to analyze the influence of the reaction atmosphere on the emissions evolved. Special emphasis was put on the analysis of chlorinated organic pollutants such as polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and other related compounds like polychlorobenzenes (PCBzs), polychlorophenols (PCPhs) and polycyclic aromatic hydrocarbons (PAHs). Another objective of this work was to compare the results with those of a previous work3 in which emissions at different temperatures in both pyrolysis and combustion of another PVC resin had been studied; in that case, experiments for PCDD/Fs emissions had been performed only at 850 ºC.

Study on the pyrolytic behaviour of xylan-based hemicellulose using TG-FTIR and Py-GC-FTIR

Two sets of experiments, categorized as TG–FTIR and Py–GC–FTIR, are employed to investigate the mechanism of the hemicellulose pyrolysis and the formation of main gaseous and bio-oil products. The “sharp mass loss stage” and the corresponding evolution of the volatile products are examined by the TG–FTIR graphs at the heating rate of 3–80 K/min. A pyrolysis unit, composed of fluidized bed reactor, carbon filter, vapour condensing system and gas storage, is employed to investigate the products of the hemicellulose pyrolysis under different temperatures (400–690 °C) at the feeding flow rate of 600 l/h. The effects of temperature on the condensable products are examined thoroughly. The possible routes for the formation of the products are systematically proposed from the primary decomposition of the three types of unit (xylan, O-acetylxylan and 4-O-methylglucuronic acid) and the secondary reactions of the fragments. It is found that the formation of CO is enhanced with elevated temperature, while slight change is observed for the yield of CO2 which is the predominant products in the gaseous mixture.

Electrochemical Oxidation Of Landfill Leachate In A Flow Reactor: Optimization Using Response Surface Methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99 % of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.

The Influence Of The Buffering Capacity On The Production Of Organic Acids And Alcohols From Wastewater In Anaerobic Reactor.

Some bacteria common in anaerobic digestion process can ferment a broad variety of organic compounds to organic acids, alcohols, and hydrogen, which can be used as biofuels. Researches are necessary to control the microbial interactions in favor of the alcohol production, as intermediary products of the anaerobic digestion of organic compounds. This paper reports on the effect of buffering capacity on the production of organic acids and alcohols from wastewater by a natural mixed bacterial culture. The hypothesis tested was that the increase of the buffering capacity by supplementation of sodium bicarbonate in the influent results in benefits for alcohol production by anaerobic fermentation of wastewater. When the influent was not supplemented with sodium bicarbonate, the chemical oxygen demand (COD)-ethanol and COD-methanol detected in the effluent corresponded to 22.5 and 12.7 % of the COD-sucrose consumed. Otherwise, when the reactor was fed with influent containing 0.5 g/L of sodium bicarbonate, the COD-ethanol and COD-methanol were effluents that corresponded to 39.2 and 29.6 % of the COD-sucrose consumed. Therefore, the alcohol production by supplementation of the influent with sodium bicarbonate was 33.6 % higher than the fermentation of the influent without sodium bicarbonate.

TiO2-Photocatalyzed degradation of phenol in saline media in an annular reactor: hydrodynamics, lumped kinetics, intermediates, and acute toxicity

The photocatalytic degradation of phenol in aqueous suspensions of TiO2 under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen-Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.

Development of a flow through photo-reactor to study degradation of organic compounds by Sequential Injection Analysis (SIA)

This work describes a photo-reactor to perform in line degradation of organic compounds by photo-Fenton reaction using Sequential Injection Analysis (SIA) system. A copper phthalocyanine-3,4',4²,4²¢-tetrasulfonic acid tetrasodium salt dye solution was used as a model compound for the phthalocyanine family, whose pigments have a large use in automotive coatings industry. Based on preliminary tests, 97% of color removal was obtained from a solution containing 20 µmol L-1 of this dye.

The development of an immobilized enzyme reactor containing glyceraldehyde-3-phosphate dehydrogenase from Trypanosoma cruzi: the effect of species' specific differences on the immobilization

Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) plays an important role in the life cycle of the Trypanosoma cruzi, and an immobilized enzyme reactor (IMER) has been developed for use in the on-line screening for GAPDH inhibitors. An IMER containing human GAPDH has been previously reported; however, these conditions produced a T. cruzi GAPDH-IMER with poor activity and stability. The factors affecting the stability of the human and T. cruzi GAPDHs in the immobilization process and the influence of pH and buffer type on the stability and activity of the IMERs have been investigated. The resulting T. cruzi GAPDH-IMER was coupled to an analytical octyl column, which was used to achieve chromatographic separation of NAD+ from NADH. The production of NADH stimulated by D-glyceraldehyde-3-phosphate was used to investigate the activity and kinetic parameters of the immobilized T. cruzi GAPDH. The Michaelis-Menten constant (K-m) values determined for D-glyceraldehyde-3-phosphate and NAD(+) were K-m = 0.5 +/- 0.05 mM and 0.648 +/- 0.08 mM, respectively, which were consistent with the values obtained using the non-immobilized enzyme.

Simplified Mathematical Model for an Anaerobic Sequencing Batch Biofilm Reactor Treating Lipid-Rich Wastewater Subject to Rising Organic Loading Rates

This study proposes a simplified mathematical model to describe the processes occurring in an anaerobic sequencing batch biofilm reactor (ASBBR) treating lipid-rich wastewater. The reactor, subjected to rising organic loading rates, contained biomass immobilized cubic polyurethane foam matrices, and was operated at 32 degrees C +/- 2 degrees C, using 24-h batch cycles. In the adaptation period, the reactor was fed with synthetic substrate for 46 days and was operated without agitation. Whereas agitation was raised to 500 rpm, the organic loading rate (OLR) rose from 0.3 g chemical oxygen demand (COD) . L(-1) . day(-1) to 1.2 g COD . L(-1) . day(-1). The ASBBR was fed fat-rich wastewater (dairy wastewater), in an operation period lasting for 116 days, during which four operational conditions (OCs) were tested: 1.1 +/- 0.2 g COD . L(-1) . day(-1) (OC1), 4.5 +/- 0.4 g COD . L(-1) . day(-1) (OC2), 8.0 +/- 0.8 g COD . L(-1) . day(-1) (OC3), and 12.1 +/- 2.4 g COD . L(-1) . day(-1) (OC4). The bicarbonate alkalinity (BA)/COD supplementation ratio was 1:1 at OC1, 1:2 at OC2, and 1:3 at OC3 and OC4. Total COD removal efficiencies were higher than 90%, with a constant production of bicarbonate alkalinity, in all OCs tested. After the process reached stability, temporal profiles of substrate consumption were obtained. Based on these experimental data a simplified first-order model was fit, making possible the inference of kinetic parameters. A simplified mathematical model correlating soluble COD with volatile fatty acids (VFA) was also proposed, and through it the consumption rates of intermediate products as propionic and acetic acid were inferred. Results showed that the microbial consortium worked properly and high efficiencies were obtained, even with high initial substrate concentrations, which led to the accumulation of intermediate metabolites and caused low specific consumption rates.

Interesterification of milkfat with soybean oil catalysed by Rhizopus oryzae lipase immobilised on SiO(2)-PVA on packed bed reactor

The potential of the lipase from Rhizopus oryzae immobilised on SiO(2)-PVA to catalyse the interesterification of the milkfat with soybean oil in a packed bed reactor running on continuous mode was evaluated. The reactor operated continuously for 35 days at 45 degrees C, and during 12 days, no significant decrease in the initial lipase activity was verified. Interesterification yields were in the range from 35 to 38% wt, which gave an interesterified product having 59% lower consistency in relation to non-interesterified blend. Results showed the potential of the lipase from Rhizopus oryzae to mediate the interesterification of milkfat with soybean oil in packed bed reactor, attaining a more spreadable product under a cool temperature. The biocatalyst operational stability was assessed and an inactivation profile was found to follow the Arrhenius model, revealing values of 34 days and 0.034 day(-1), for half-life and a deactivation coefficient, respectively.

Evaluation of hydrodynamic parameters of a fluidized-bed reactor with immobilized yeast

The fluidized bed reactor has successfully been used to perform biotechnological processes addressed to the production of high added value. The present work evaluates hydrodynamic parameters of a bench-scale fluidized bed reactor with cells of the yeast Candida guilliermondii immobilized either in calcium alginate beads or in polyvinyl alcohol (PVA). The effects of the following variables on cell immobilization were evaluated at 30 degrees C and feeding a synthetic medium containing 50 g L-1 xylose: total particle density (cells plus support), terminal velocity, particle drag force, minimum fluidization velocity and bed porosity. According to the results obtained, the reactor was shown to operate like a fixed-bed bioreactor at xi < 0.5 and a fluidized bed bioreactor at xi > 0.5. The maximum flow rate needed to obtain maximum bed fluidization in the reactor was equal to the terminal velocity of the immobilized cell particles. Particles of cells immobilized within these supports showed values of drag coefficient lower than those reported for other high-density supports. The evaluation of these hydrodynamic characteristics lead to an adequate bed fluidization inside the reactor, thus improving oxygen transference and availability in the fermentation medium, making the process more viable for future scale-up. (c) 2008 Society of Chemical Industry.

Packed-Bed Reactor Running on Babassu Oil and Glycerol to Produce Monoglycerides by Enzymatic Route using Immobilized Burkholderia cepacia Lipase

The aim of this study was the glycerolysis of babassu oil catalyzed by immobilized lipase from Burkholderia cepacia, in a continuous packed-bed reactor. The best reaction conditions were previously established in batchwise via response surface methodology as a function of glycerol-to-oil molar ratio and reaction temperature. The reactor operated continuously for 22 days at 50 A degrees C, and during the first 6 days, no significant decrease on the initial lipase activity was observed. Monoglycerides concentration was in the range from 25 to 33 wt.%. Subsequently, a progressive decrease in the activity was detected, and an inactivation profile described by Arrhenius model estimated values of 50 days and 1.37 x 10(-2) h(-1), for the half-life and deactivation coefficient, respectively.

Full-scale anaerobic sequencing batch biofilm reactor for sulfate-rich wastewater treatment

This paper describes the performance and biofilm characteristics of a full-scale anaerobic sequencing batch biofilm reactor (ASBBR; 20 m(3)) containing biomass immobilized on an inert support (mineral coal) for the treatment of industrial wastewater containing a high sulfate concentration. The ASBBR reactor was operated during 110 cycles (48 h each) at sulfate loading rates ranging from 6.9 to 62.4 kgSO(4)(2-)/cycle corresponding to sulfate concentrations of 0.58-5.2 gSO(4)(2-)/L. Domestic sewage and ethanol were utilized as electron donors for sulfate reduction. After 71 cycles the mean sulfate removal efficiency was 99%, demonstrating a high potential for biological sulfate reduction. The biofilm formed in the reactor occurred in two different patterns, one at the beginning of the colonization and the other of a mature biofilm. These different colonization patterns are due to the low adhesion of the microorganisms on the inert support in the start-up period. The biofilm population is mainly made up of syntrophic consortia among sulfate-reducing bacteria and methanogenic archaea such as Methanosaeta spp.

TOXICITY EVALUATION AS A TOOL TO ASSES THE PERFORMANCE OF AN ANAEROBIC IMMOBILIZED BIOMASS REACTOR

Effluents from pulp mill are usually toxic and mutagenic. This characteristic is mainly a consequence of xenobiotic compounds that are formed during the process. Global parameters such as chemical oxidation demand, total organic carbon and others, do not permit identify whether the toxic potential was remedied by the treatments or not. The objective of this research was to evaluate the performance of an horizontal-flow anaerobic immobilized biomass reactor (HAIB) treating the bleaching effluent from a Kraft pulp mill using toxicological (Daphnia similis - Ceriodaphnia sdvestrii) mutagenicity and citotoxicological assays (Allium cepa L). The results showed high sensibility of the test-organisms and capability of the anaerobic reactor to remove compounds that are exerting toxic and mutagenic effects. The bioassays represented an attractive alternative to water quality analyzes and the performance evaluation of treatments.