Resumo em Inglês:

Abstract Industries engaged in dyeing operation generate coloured effluent due to the presence of spent dyes. Adsorption is among the various treatment processes employed for removal of dyes from effluents. Activated carbon is mostly used as an adsorbent in the treatment process. Attempts have been made by researchers to use non-conventional, low-cost, naturally-occurring biomass as adsorbents, including fruit peals, seeds, leaves, bark, sawdust, straw, ash, sludge and others that are abundantly available. The literature indicates that the dye adsorption capacities of these non-conventional biomasses largely depend on the methods of processing and the types of dyes. This review highlights methods used to prepare the adsorbents, along with their adsorption capacity for removal of different dyes from effluents.

Resumo em Inglês:

Abstract Penicillium echinulatum S1M29 is a mutant with cellulase and xylanase production comparable to the most studied microorganisms in the literature. However, its potential to produce these enzymes has not been fully investigated. This study aimed at optimizing salt and urea concentrations in the mineral solution, employing the response surface methodology. A 25-1 Fractional Factorial Design and a 23 Central Composite Design were applied to elucidate the effect of salts and urea in enzyme production. Lower concentrations of KH2PO4 (2.0 g.L-1), (NH4)2SO4 (1.4 g.L-1), MgSO4.7H2O (0.375 g.L-1) and CaCl2 (0.375 g.L-1) were most suitable for the production of all enzymes evaluated. Nevertheless, higher concentrations of urea (0.525 g.L-1) gave the best results for cellulase and xylanase production. The maximum FPase (1,5 U.m.L-1), endoglucanase (7,2 U.m.L-1), xylanase (30,5 U.m.L-1) and β-glucosidase (4,0 U.m.L-1) activities obtained with the planned medium were, respectively, 87, 16, 17 and 21% higher when compared to standard medium. The experimental design contributed to adjust the concentrations of minerals and urea of the culture media for cellulase and xylanase production by P. echinulatum, avoiding waste of components in the medium.

Resumo em Inglês:

Abstract Glucose production from sugarcane bagasse was investigated. Sugarcane bagasse was pretreated by four different methods: combined acid and alkaline, combined hydrothermal and alkaline, alkaline, and peroxide pretreatment. The raw material and the solid fraction of the pretreated bagasse were characterized according to the composition, SEM, X-ray and FTIR analysis. Glucose production after enzymatic hydrolysis of the pretreated bagasse was also evaluated. All these results were used to develop relationships between these parameters to understand better and improve this process. The results showed that the alkaline pretreatment, using sodium hydroxide, was able to reduce the amount of lignin in the sugarcane bagasse, leading to a better performance in glucose production after the pretreatment process and enzymatic hydrolysis. A good xylose production was also observed.

Resumo em Inglês:

Abstract The production and characterization of cellulase from thermophilic strain Bacillus sp. C1AC5507 was studied. For enzyme production, sugarcane bagasse was used as carbon source. The produced carboxymethyl cellulase (CMCase) had a molecular weight around 55 kDa and its activity varied between 0.14 and 0.37 IU mL-1 in conditions predicted by Response Surface Methodology. The optimum temperature and pH for the CMCase production were 70 °C and 7.0, respectively. The enzyme activity was inhibited mostly by Cu+2 and activated mostly by Co+2, Mn2+, Ca+2 and Fe+3. Our findings provide a contribution to the use of natural wastes such as sugarcane bagasse as substrate for growth and production of thermophilic CMCase. Further optimization to increase the production of cellulase enables the use in industrial applications.

Resumo em Inglês:

Abstract Immobilized metal affinity chromatography (IMAC) was chosen as a method of purification for the recovery of CGTase from E. coli homogenate. E. coli harbouring the Bacillus sp. G1 gene expressed extracellularly secreted CGTase into ampicillin supplied LB broth. Culture was pre-purified using SnakeSkin dialysis tubing (3.5 MWCO) with an enzyme activity of 147.80 U/mL. Three strategies (A, B and C) were employed for the purification of CGTase using column adsorption chromatography with Ni2+-Sepharose resin. Strategy A employed an elution buffer of 50 mM EDTA, pH 7, Strategy B used 0.1 M imidazole, pH 7 and Strategy C employed 45 mM imidazole pH 7 as the elution buffer. Strategy C was found to be most suitable yielding a total CGTase recovery of 87.04% from an initial activity of 147.80 U/mL.

Resumo em Inglês:

Abstract The main goal of this research was the synthesis of enantiopure R(-)-3-aminoisobutyric acid from dihydrothymine with good yield, high stereospecificity and relative simplicity. Seventy two percent yield of the product was obtained in three steps. Step one consisted of dihydrothymine racemization. Step two was a dihydropyrimidinase reaction involving the Pseudomonas aeruginosa 10145 bacterial strain as the biocatalyst. Step three was performed with a diazotization reaction. The bacteria's enzymes determined the stereochemistry of the process since the diazotization reaction did not interfere at this point. The results of this work provide an interesting method for the production of commercial β-amino acids from other substituteddihydrothymines.

Resumo em Inglês:

Abstract Reactor hydrodynamics is important for sulfidogenesis because sulfate reduction bacteria (SRB) do not granulate easily. In this work, the sulfate reduction performance of two continuous anaerobic bioreactors was investigated: (i) an upflow anaerobic sludge blanket (UASB) reactor and (ii) a fluidized bed reactor (FBR). Organic loading, sulfate reduction, and COD removal were the main parameters monitored during lactate and glycerol degradation. The UASB reactor with biomass recirculation showed a specific sulfate reduction rate of 0.089±0.014 g.gSSV-1.d-1 (89% reduction), whereas values twice as high were achieved in the FBR treating either lactate (0.200±0.017 g.gSSV-1.d-1) or glycerol (0.178±0.010 g.gSSV-1.d-1). Sulfate reduction with pure glycerol produced a smaller residual COD (1700 mg.L-1) than that produced with lactate (2500 mg.L-1) at the same COD.sulfate-1 mass ratio. It was estimated that 50% of glycerol degradation was due to sulfate reduction and 50% to fermentation, which was supported by the presence of butyrate in the FBR effluent. The UASB reactor was unable to produce effluents with sulfate concentrations below 250 mg.L-1 due to poor mixing conditions, whereas the FBR consistently ensured residual sulfate concentrations below such a value.

Resumo em Inglês:

Abstract In some operational circumstances a fast evaluation of landfill leachate anaerobic treatability is necessary, and neither Biochemical Methane Potential nor BOD/COD ratio are fast enough. Looking for a fast indicator, this work evaluated the anaerobic treatability of landfill leachate from São Carlos-SP (Brazil) in a pilot scale Anaerobic Sequence Batch Biofilm Reactor (AnSBBR). The experiment was conducted at ambient temperature in the landfill area. After the acclimation, at a second stage of operation, the AnSBBR presented efficiency above 70%, in terms of COD removal, utilizing landfill leachate without water dilution, with an inlet COD of about 11,000 mg.L-1, a TVA/COD ratio of approximately 0.6 and reaction time equal to 7 days. To evaluate the landfill leachate biodegradability variation over time, temporal profiles of concentration were performed in the AnSBBR. The landfill leachate anaerobic biodegradability was verified to have a direct and strong relationship to the TVA/COD ratio. For a TVA/CODTotal ratio lower than 0.20, the biodegradability was considered low, for ratios between 0.20 and 0.40 it was considered medium, and above 0.40 it was considered high.

Resumo em Inglês:

Abstract Thermal treatment is an interesting strategy to dispose of municipal solid waste: it reduces the volume and weight of the material dumped in landfills and generates alternative energy. However, the process emits pollutants, such as dioxins and furans. The present study evaluated MSW gasification-combustion integrated technologies in terms of dioxin and furan emission; and compared the obtained data with literature results on incineration, to point out which operational features differentiate the release of pollutants by these two processes. The results show that the process of integrated gasification and combustion emitted 0.28 ng N-1 m-3, expressed in TEQ (Total Equivalent Toxicity), of PCDD/F, less than the maximum limits allowed by local and international laws, whereas incineration normally affords values above these limits and requires a gas treatment system. The distinct operational conditions of the two thermal processes, especially those related to temperature and the presence of oxygen and fixed carbon, led to a lower PCDD/F emission in gasification.

Resumo em Inglês:

Abstract A Sequencing Batch Reactor (SBR) was combined with heterogeneous photocatalysis (TiO2/UV) as a tertiary treatment for a pencil manufacturer's wastewater. The SBR removed almost all Chemical Oxygen Demand (COD) from the wastewater, although color was barely removed. Photocatalysis was optimized using a factorial design. Final COD, Dissolved Organic Carbon (DOC), and color removals were 95%, 80%, and 93%, respectively. Treated wastewater showed no ecotoxicity towards Lactuca sativa. Color removal kinetics (photocatalysis) followed a pseudo-first order model. The SBR + AOP (Advanced Oxidation Process, TiO2/UV) combination was a feasibility choice for removing both COD and color from this wastewater.

Resumo em Inglês:

Abstract In this study, various water-soluble and oil-soluble demulsifiers were selected for separation of water from crude oil emulsions and their productivity measured using the Bottle-test method at 70 °C and 10 ppm concentration. The best ones among 23 demulsifiers examined through the screening process were fatty alcohol ethoxylate, triethanol amine and urea from the water-soluble group and Basororol E2032, Basorol PDB 9935 and TOMAC from the oil-soluble category. Furthermore, the present study investigated the factors effective for demulsification such as temperature, concentration, pH, salinity and modifiers. It was found that the separation improves with increasing demulsifier concentration, increasing salt content, increasing temperature up to 80 °C, keeping the pH values between 5-9. Adding solvent modifiers proved unnecessary. Two formulations were prepared based on suggested optimal concentrations of demulsifier content by experimental design using Qualitec 4 and these proved to be highly effective in treating real and synthetic emulsions.

Resumo em Inglês:

Abstract 5-Hydroxymethylfurfural (HMF) is a key renewable platform compound for production of fuels and chemical intermediates. The production of 5-hydroxymethylfurfural (HMF) from fructose dehydration was studied using H3PO4 as catalyst, in organic/water system with different solvents (acetone, 2-butanol and ethyl ether). The effect of fructose concentration, temperature and acid concentration was investigated in acetone/water medium. The increase in fructose concentration favors the formation of condensation products and rehydration products are favored at high acid concentration. The solvents exhibited similar performance when the volume ratio of organic to aqueous phase was 1:1, but when this ratio increases to 2:1, the HMF yield obtained with ether was much lower. NaCl addition to the aqueous phase promoted the extraction of HMF to the organic phase, with an HMF yield of 80% in the case of 2:1 acetone/water medium.

Resumo em Inglês:

Abstract The aim of this study was to investigate the interfacial energy involved in the production of water-in-oil (W/O) emulsions composed of water and a Brazilian heavy crude oil. For such purpose an experimental set-up was developed to measure the different energy terms involved in the emulsification process. W/O emulsions containing different water volume fractions (0.1, 0.25 and 0.4) were prepared in a batch calorimeter by using a high-shear rotating homogenizer at two distinct rotation speeds (14000 and 22000 rpm). The results showed that the energy dissipated as heat represented around 80% of the energy transferred to the emulsion, while around 20% contributed to the internal energy. Only a very small fraction of the energy (0.02 - 0.06%) was stored in the water-oil interface. The results demonstrated that the high energy dissipation contributes to the kinetic stability of the W/O emulsions.

Resumo em Inglês:

Abstract This work examines the influence of the residence-time distribution (RTD) of surface elements on a model of cross-flow microfiltration that has been proposed recently (Hasan et al., 2013). Along with the RTD from the previous work (Case 1), two other RTD functions (Cases 2 and 3) are used to develop theoretical expressions for the permeate-flux decline and cake buildup in the filter as a function of process time. The three different RTDs correspond to three different startup conditions of the filtration process. The analytical expressions for the permeate flux, each of which contains three basic parameters (membrane resistance, specific cake resistance and rate of surface renewal), are fitted to experimental permeate flow rate data in the microfiltration of fermentation broths in laboratory- and pilot-scale units. All three expressions for the permeate flux fit the experimental data fairly well with average root-mean-square errors of 4.6% for Cases 1 and 2, and 4.2% for Case 3, respectively, which points towards the constructive nature of the model - a common feature of theoretical models used in science and engineering.

Resumo em Inglês:

Abstract Malachite ore is one of the most important of oxidized copper ores. Copper production can be performed by using this ore. In this work, the leaching kinetics of malachite in ammonium sulfate solutions was investigated, and metallic copper was recovered by a cementation method from the resulting actual leach solution. Copper (II) oxide was prepared by an isothermal oxidation method from the cement copper. In the leaching experiments, the effects of reaction temperature, particle size, and stirring speed on copper leaching from malachite ore were studied. In the cementation experiments, metallic zinc was used as the reductant metal to recover the copper from the solution. Thermal oxidation of cement copper was performed under isothermal conditions. It was found that the leaching rate increased with increasing stirring speed and temperature, and decreased with particle size. It was observed that the leaching reaction fit to diffusion through the product layer. The activation energy of the leaching process was determined to be 25.4 kJ/mol. It was determined that the copper content of the metallic product obtained by the cementation method increased up to 96%. It was found that copper oxide prepared from cement copper had a tenorite structure.

Resumo em Inglês:

Abstract Inhibitors are widely used to prevent corrosion in cooling-water systems, and their protective performance can be enhanced by combination. The aim of this paper is to identify possible synergistic effects between four low toxicity substances used as corrosion inhibitors for mild steel in industrial cooling-water systems. Electrochemical measurements were obtained following a design of experiments (DOE) where the independent variables were the inhibitors concentrations and the response variable the charge transfer resistance estimated from impedance diagrams. Potentiodynamic polarization curves show that all of them act as anodic corrosion inhibitors. Among the tested formulations, only the interaction between sodium molybdate and sodium tungstate showed statistically significant effects, indicating that they can perform better when used together. The results of this work show the importance of using a statistical tool when designing inhibitor mixtures.

Resumo em Inglês:

Abstract In this study polyethersulfone ultrafiltration membrane were prepared with the modifier gelatin at 0, 5, 10, 15 and 20 wt % using DMF as solvent by phase inversion process. Morphologies and characteristics of the membranes were investigated through the methods of SEM, XRD, contact angle measurements. The performance of the modified membrane for the treatment of leather and distillery wastewater through a deadend ultrafiltration process was studied. Morphological investigation showed that the 10% gelatin content in 90% PES results in a two layer structure with a porous top and homogeneous sub-layer with uniform number of pores on the surface. The pure water flux of the modified membrane increases with gelatin concentration, which results in better permeation for both leather and distillery wastewater. In addition to 80-90% reduction in BOD and COD, all modified PES UF membranes showed moderate removal of total suspended and dissolved solids, chlorides, sulphate, oil and grease, potassium, sodium and ammonical nitrogen, apart from color removal.

Resumo em Inglês:

Abstract In miniemulsion polymerization, droplet nucleation is the key factor to ensure the production of polymer particles with a desired composition. The influence of the initiation on droplet nucleation is conflicting and it has not been completely considered. The result of employing different initiator systems on the nucleation mechanism and kinetics in the polymerization of stable styrene/polystyrene miniemulsions with varied droplet size is discussed here. The initiation systems employed provide all combinations between the phase (aqueous or organic) where initiation mainly occurs and the phase affinity of the produced radicals. Latexes with different contributions of droplet nucleation were synthesized according to the employed initiation system and the droplet size of the miniemulsion. The results presented here could be used as a guide for choosing the initiation system to achieve the required contribution of droplet nucleation.

Resumo em Inglês:

Abstract Syngas and hydrogen production by methane reforming of a biogas (CH4/CO2 = 2.85) using carbon dioxide was evaluated in a fixed bed reactor with a Pd-Ag membrane in the presence of a nickel catalyst (Ni 3.31% weight)/γ-Al2O3) at 773 K, 823 K, and 873 K and 1.01×105 Pa. Operation with hydrogen permeation at 873 K increased the methane conversion to approximately 83% and doubled the hydrogen yield relative to operation without hydrogen permeation. A mathematical model was formulated to predict the evolution of the effluent concentrations. Predictions based on the model showed similar evolutions for yields of hydrogen and carbon monoxide at temperatures below 823 K for operations with and without the hydrogen permeation. The hydrogen yield reached approximately 21% at 823 K and 47% at 873 K under hydrogen permeation conditions.

Resumo em Inglês:

Abstract The aim of this study was to determine the kinetic parameters of the oxy-fuel combustion of char from a Brazilian bituminous coal with a high ash content. The char, with a particle diameter of 715 μm, was prepared in a N2 atmosphere at 1173 K. The oxy-fuel combustion assays were performed using a thermobalance at different temperatures and O2/CO2 gas mixtures of different concentrations. According to the unreacted core model, the process is determined by chemical reaction at low temperatures, with an activation energy of 56.7 kJ.kmol-1, a reaction order of 0.5 at 973 K and a reaction order of 0.7 overall. The use of the continuous reaction model did not provide a good fit for the experimental data because the consumption of the particles during the reaction was not constant, as predicted by the model. According to the Langmuir-Hinshelwood model, the activation energy for the first step was 37.3 kJ.kmol-1.

Resumo em Inglês:

Abstract The study of the natural convection flow and heat transfer from hot surfaces in a porous medium has been of considerable interest in energy-related engineering problems. This paper is concerned with the free convection heat transfer over an arbitrary hot surface in a porous medium. It is assumed that the fluid and solid phases are not in local thermal equilibrium and therefore a two-temperature model of heat transfer is applied. The coupled momentum and energy equations are used and transformed into ODE’s. The similar equations obtained are solved numerically and the local heat flux is shown for three types of axisymmetric shapes, i.e., a vertical plate, horizontal cylinder and sphere. The results have also been validated with the available results in the literature; which show that our assumptions and numerical method are accurate. Mathematical derivation of a similarity solution for an arbitrary geometry in the heat transfer analysis is the main novelty of the present study.

Resumo em Inglês:

Abstract Well productivity of gas condensate reservoirs is highly affected by near-wellbore phenomena. Inertial force resulting from convective acceleration of fluid particles in the medium, as well as viscous force, determines the flow of gas through porous media at high velocity. Pressure drop builds up the molar content of water in gas by water vaporization in the near-wellbore region, which means a drop in connate water saturation. Given that the inertial force is a function of the non-Darcy coefficient, β, which itself depends upon connate water saturation, this can ultimately lessen the non-Darcy component of the pressure drop and therefore inertial forces, leading to improvement of well deliverability. Currently, no physically relevant model takes into account the non-Darcian flow coefficient variation due to this phenomenon. This paper utilizes a single-well compositional simulation to exhibit how water vaporization could compensate for the effect of inertia on well productivity of gas condensate reservoirs.

Resumo em Inglês:

Abstract In the past thirty years, the development of compositional reservoir simulators using an equation of state (EOS) has been addressed in the literature. However, the development of compositional thermal simulators in conjunction with the EOS formulation, in particular, has not been addressed extensively. In this work, a fully implicit, thermal, compositional EOS-based simulator in conjunction with unstructured meshes has been developed. In this model, an equation of state is used for equilibrium calculations among phases. Also, the physical properties are calculated based on an EOS, hence obviating the need for using steam tables for calculation of water/steam properties. The governing equations for the model comprise fugacity equations, material balance, pore volume constraint and energy equation. The governing partial differential equations are solved using the EbFVM (Element based Finite Volume Method). Results for several case studies consisting of 2D and 3D reservoirs are presented in order to demonstrate the applicability of the method.

Resumo em Inglês:

Abstract In the production of chemicals from fermentation, the cost of downstream purification constitutes the major portion of the total production cost. Since the bioprocess generally contains a large amount of biochemical separation units, its flowsheets are complex. How to generate the rigorous superstructure of the downstream bioprocess is a primary problem and key step. In this work, a robust combined approach based on the P-graph was proposed to generate the rigorous superstructure of the downstream process of fermentation. This method integrates the hierarchical decomposition of the heuristics with P-graph-based algorithm MSG with the advantages including: (1) Different design flowsheets could be evaluated simultaneously; (2) An unique bipartite graph, P-graph, was introduced, which could represent the maximum structure clearly and intuitively; (3) The rigorous superstructure could be automatically generated. The validity of the present method was verified with two practical bioprocesses. Results show that the effective processes and the adequate operation units could be determined in the beginning stage of the design, and the tedious reforming steps during process synthesis could be avoided.

Resumo em Inglês:

Abstract In this study the influence of the volumetric flow rate and feed concentration was investigated for the adsorption of the reactive dye Blue 5G. Experiments were carried out in a bed packed with retorted shale, at 30 ºC. The ranges investigated were flow rate 2 -10 mL/min and the feed concentration 13-105 mg/L. Mathematical models were used to represent the dynamic sorption. The double resistance model considers the effects of the axial dispersion and the mass transfer resistance of the external film and inside the particles. As a result, the mass transfer coefficient of the external film and the internal mass transfer coefficient were estimated. The Thomas model was used to simulate the experimental data. In this model the fitted parameter was the adsorption kinetic constant. The first model provided an acceptable representation of the dynamic uptake of the reactive dye Blue 5G.

Resumo em Inglês:

Abstract Extractive distillation processes with N-formylmorpholine (NFM) are used industrially to separate benzene from six carbon non-aromatics. In the process studied in this work, the stream of interest consists of nearly 20 different hydrocarbons. A new set of NRTL parameters was correlated based on literature experimental data. Both vapor-liquid equilibrium as well as infinite dilution activity coefficient data were taken into account; missing parameters were estimated with the UNIFAC group contribution model. The extractive distillation process was simulated using ASPEN Plus®. Very good agreement with plant data was obtained. The influences of the main operational parameters, solvent to feed ratio and solvent temperature, were studied. Theoretical optimum operating values were obtained and can be implemented to improve the industrial process. Extreme static sensitivity with respect to reboiler heat was observed, indicating that this can be the source of instabilities.

Resumo em Inglês:

A method for analysis of the electric potential profile in saline solutions was developed for systems with one or two infinite flat plates. A modified Poisson-Boltzmann equation, taking into account nonelectrostatic interactions between ions and surfaces, was used. To solve the stated problem in the steady-state approach the finite-difference method was used. For the formulated pseudo-transient problem, we solved the set of ordinary differential equations generated from the algebraic equations of the stationary case. A case study was also carried out in relation to temperature, solution concentration, surface charge and salt-type. The results were validated by the stationary problem solution, which had also been used to verify the ionic specificity for different salts. The pseudo-transient approach allowed a better understanding of the dynamic behavior of the ion-concentration profile and other properties due to the surface charge variation.

Resumo em Inglês:

Abstract Pressure-density-temperature (p, ρ ,T) data of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][NTF2] at T = (273.15 to 413.15) K and pressures up to p =140 MPa are reported with an estimated experimental relative combined standard uncertainty of Δ ρ / ρ = ±(0.01 to 0.08)% in density. The measurements were carried out with a newly constructed Anton-Paar DMA HPM vibration-tube densimeter. The system was calibrated using double-distilled water, aqueous NaCl solution, methanol, toluene and acetone. An empirical equation of state for fitting the (p, ρ ,T) data of [BMIM][NTF2] has been developed as a function of pressure and temperature. This equation is used for the calculation of the thermophysical properties of the ionic liquid, such as isothermal compressibility, isobaric thermal expansibility, thermal pressure coefficient, internal pressure, isobaric and isochoric heat capacities, speed of sound and isentropic expansibility.