Catalytic conversion of wastes from the bioethanol production into carbon nanomaterials

This work addressed the production of carbon nanomaterials (CNMs) by catalytic conversion of wastes from the bioethanol industry, in the form of either sugarcane bagasse or corn-derived distillers dried grains with solubles (DDGS). Both bagasse and DDGS were pyrolysed at temperatures in the range of 600-1000 degrees C. The pyrolyzate gases were then used as CNM growth agents by chemical vapor deposition on stainless steel meshes, serving as both catalysts and substrates. CNM synthesis temperatures of 750-1000 degrees C were explored, and it was determined that their growth was most pronounced at 1000 degrees C. The nanomaterials produced from pyrolysis of bagasse were in the form of long, straight, multi-wall nanotubes with smooth walls and axially uniform diameters. Typical lengths were circa 50 mu m and diameters were in the range of 20-80 nm. The nanomaterials produced from pyrolysis of DDGS were in the form of long, entangled, rope-like structures with rugged walls, and axially non-uniform diameters. Typical diameters were in the range of 100-300 nm and their lengths were in the tens of microns. This process also produces a bio-syngas byproduct that is enriched in hydrogen. (C) 2011 Elsevier B.V. All rights reserved.

Abrasion and corrosion resistance of new Ni-based coating deposited by HVOF thermal spray process

Coatings based on NiCrAlC intermetallic based alloy were applied on AISI 316L stainless steel substrates using a high velocity oxygen fuel torch. The influence of the spray parameters on friction and abrasive wear resistance were investigated using an instrumented rubber wheel abrasion test, able to measure the friction forces. The corrosion behaviour of the coatings were studied with electrochemical techniques and compared with the corrosion resistance of the substrate material. Specimens prepared using lower O(2)/C(3)H(8) ratios showed smaller porosity values. The abrasion wear rate of the NiCrAlC coatings was much smaller than that described in the literature for bulk as cast materials with similar composition and one order of magnitude higher than bulk cast and heat treated (aged) NiCrAlC alloy. All coatings showed higher corrosion resistance than the AISI 316L substrate in HCl (5%) aqueous solution at 40 degrees C.

Influence of Water Content, Time, and Temperature on the Rheological Behavior of Polyethylene Terephtalate

In this work, the main factors affecting the rheological behavior of polyethylene terephtalate (PET) in the linear viscoelastic regime (water content, time delay before test, duration of experiment, and temperature) were accessed. Small amplitude oscillatory shear tests were performed after different time delays ranging from 300 to 5000 s for samples with water contents ranging from 0.02 to 0.45 wt %. Time sweep tests were carried out for different durations to explain the changes undergone by PET before and during small amplitude oscillatory shear measurements. Immediately after the time sweep tests, the PET samples were removed from the rheometer, analyzed by differential scanning calorimetry and their molar mass was obtained by viscometry analysis. It was shown that for all the samples, the delay before test and residence time within the rheometer (i.e. duration of experiment) result in structural changes of the PET samples, such as increase or decrease of molar mass, broadening of molar mass distribution, and branching phenomena. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3525-3533, 2010

Montmorillonite as a component of polysulfone nanocomposite membranes

Nanocomposite membranes containing polysulfone (PSI) and sodium montmorillonite from Wyoming (MMT) were prepared by a combination of solution dispersion and the immersion step of the wet-phase inversion method. The purpose was to study the MMT addition with contents of 0.5 and 3.0 mass% MMT in the preparation of nanocomposite membranes by means of morphology, thermal, mechanical and hydrophilic properties of nanocomposite membranes and to compare these properties to the pure PSf membrane ones. Small-angle X-ray diffraction patterns revealed the formation of intercalated clay mineral layers in the PSf matrix and TEM images also presented an exfoliated structure. A good dispersion of the clay mineral particles was detected by SEM images. Tensile tests showed that both elongation at break and tensile strength of the nanocomposites were improved in comparison to the pristine PSf. The thermal stability of the nanocomposite membranes, evaluated by onset and final temperatures of degradation, was also enhanced. The hydrophilicity of the nanocomposite membranes, determined by water contact angle measurements, was higher; therefore, the MMT addition was useful to produce more hydrophilic membranes. (C) 2009 Elsevier B.V. All rights reserved.

Characterization of the cold ductility degradation after aging in centrifugally cast 20Cr32Ni+Nb alloy tube

The mechanical properties (yield stress, ultimate tensile stress and elongation) of alloy 20Cr32Ni + Nb subject to isochronal aging at temperatures between 670 and 820 degrees C for 200 h were investigated using samples extracted from a centrifugally cast tube. The results confirm the occurrence of embrittlement in the aged samples, with maximum embrittlement observed around 770 degrees C without significant gain in strength. (C) 2008 Elsevier Ltd. All rights reserved.

Thermal and mechanical characteristics of polyurethane/curaua fiber composites

Polyurethane composites reinforced with curaua fiber at 5, 10 and 20% mass/mass proportions were prepared by using the conventional melt-mixing method. The influence of curaua fibers on the thermal behavior and polymer cohesiveness in polyurethane matrix was evaluated by dynamic mechanical thermal analysis (DMTA) and by differential scanning calorimetry (DSC). This specific interaction between the fibers and the hard segment domain was influenced by the behavior of the storage modulus E` and the loss modulus EaEuro(3) curves. The polyurethane PU80 is much stiffer and resistant than the other composites at low temperatures up to 70A degrees C. All samples were thermoplastic and presented a rubbery plateau over a wide temperature range above the glass transition temperature and a thermoplastic flow around 170A degrees C.

Kinetics and Modeling of Fatty Alcohol Ethoxylation in an Industrial Spray Loop Reactor

The kinetics of the ethoxylation of fatty alcohols catalyzed by potassium hydroxide was studied to obtain the rate constants for modeling of the industrial process. Experimental data obtained in a lab-scale semibatch autoclave reactor were used to evaluate kinetic and equilibrium parameters. The kinetic model was employed to model the performance of an industrial-scale spray tower reactor for fatty alcohol ethoxylation. The reactor model considers that mass transfer and reaction occur independently in two distinct zones of the reactor. Good agreement between the model predictions and real data was found. These findings confirm the reliability of the kinetic and reactor model for simulating fatty alcohol ethoxylation processes under industrial conditions.

Modeling the kinetics of the coalescence of water droplets in crude oil emulsions subject to an electric field, with the cellular automata technique

In this study, the concept of cellular automata is applied in an innovative way to simulate the separation of phases in a water/oil emulsion. The velocity of the water droplets is calculated by the balance of forces acting on a pair of droplets in a group, and cellular automata is used to simulate the whole group of droplets. Thus, it is possible to solve the problem stochastically and to show the sequence of collisions of droplets and coalescence phenomena. This methodology enables the calculation of the amount of water that can be separated from the emulsion under different operating conditions, thus enabling the process to be optimized. Comparisons between the results obtained from the developed model and the operational performance of an actual desalting unit are carried out. The accuracy observed shows that the developed model is a good representation of the actual process. (C) 2010 Published by Elsevier Ltd.

Gas flow analysis in a Kraft recovery boiler

Demands for optimal boiler performance and increased concerns in lowering emission have always been the driving force in the reevaluation and evolution of the Kraft boiler: specifically the air distribution strategies that are directly related to achieving increased residence time of flue gas combustion inside the furnace which in turn lowers atmosphere emission levels and enhances boiler operation. This paper presents the results of a study that analyzes the interaction of the different multilevel air injections have on flue gas flow patterns including various quaternary air supply arrangements. Additionally, this study assesses the performance of the CFD (Computational Fluid Dynamics) model against data available in literature. Simulations were performed considering isothermal and incompressible flows, and did not take into account thermal phenomena or chemical reactions. The numerical solutions generated proved to be coherently related to the data available in literature, and provided proof of the efficiency of tertiary level air injection, as well as revealed that quaternary air injection ports arranged in a symmetrical configuration is most suitable for optimal equipment operation. (C) 2010 Elsevier B.V. All rights reserved.

Hydrolysis of acetic anhydride: Non-adiabatic calorimetric determination of kinetics and heat exchange

A simple calorimetric method to estimate both kinetics and heat transfer coefficients using temperature-versus-time data under non-adiabatic conditions is described for the reaction of hydrolysis of acetic anhydride. The methodology is applied to three simple laboratory-scale reactors in a very simple experimental setup that can be easily implemented. The quality of the experimental results was verified by comparing them with literature values and with predicted values obtained by energy balance. The comparison shows that the experimental kinetic parameters do not agree exactly with those reported in the literature, but provide a good agreement between predicted and experimental data of temperature and conversion. The differences observed between the activation energy obtained and the values reported in the literature can be ascribed to differences in anhydride-to-water ratios (anhydride concentrations). (C) 2010 Elsevier Ltd. All rights reserved.

A mechanistic kinetic model for phenol degradation by the Fenton process

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards. (C) 2009 Elsevier B.V. All rights reserved.

Degradation of Poly(ethylene glycol) in Aqueous Solution by Photo-Fenton and H(2)O(2)/UV Processes

This article reports experimental results obtained in a laboratory-scale photochemical reactor on the photodegradation of poly(ethylene glycol) (PEG) in aqueous solutions by means of the photo-Fenton and H(2)O(2)/UV processes. Dilute water solutions of PEG were fed to a batch reactor, mixed with pertinent reactants, and allowed to react under different conditions. Reaction progress was evaluated by sampling and analyzing the concentration of the total organic carbon (TOC) in solution as a function of the reaction time. Organic acids formed during oxidation were determined by HPLC analyses. The main acids detected in both processes were acetic and formic. Glycolic acid was detected only in the photo-Fenton process, and malonic acid was detected only in the H(2)O(2)/UV treatment, indicating that different reaction paths occur in these processes. The characteristics of both processes are discussed, based on the evolution of the TOC-time curves and the concentration profiles of the monitored organic acids. The experimental results constitute a contribution to the design of industrial processes for the treatment of wastewaters containing soluble polymers with similar properties.

USE OF SOLAR ENERGY IN THE TREATMENT OF WATER CONTAMINATED WITH PHENOL BY PHOTOCHEMICAL PROCESSES

The solar driven photo-Fenton process for treating water containing phenol as a contaminant has been evaluated by means of pilot-scale experiments with a parabolic trough solar reactor (PTR). The effects of Fe(II) (0.04-1.0 mmol L(-1)), H(2)O(2) (7-270 mmol L(-1)), initial phenol concentration (100 and 500 mg C L(-1)), solar radiation, and operation mode (batch and fed-batch) on the process efficiency were investigated. More than 90% of the dissolved organic carbon (DOC) was removed within 3 hours of irradiation or less, a performance equivalent to that of artificially-irradiated reactors, indicating that solar light can be used either as an effective complementary or as an alternative source of photons for the photo-Fenton degradation process. A non-linear multivariable model based on a neural network was fit to the experimental results of batch-mode experiments in order to evaluate the relative importance of the process variables considered on the DOC removal over the reaction time. This included solar radiation, which is not a controlled variable. The observed behavior of the system in batch-mode was compared with fed-batch experiments carried out under similar conditions. The main contribution of the study consists of the results from experiments under different conditions and the discussion of the system behavior. Both constitute important information for the design and scale-up of solar radiation-based photodegradation processes.

Optimal synthesis of Fenton reactor networks for phenol degradation

There is an increasing need to treat effluents contaminated with phenol with advanced oxidation processes (AOPs) to minimize their impact on the environment as well as on bacteriological populations of other wastewater treatment systems. One of the most promising AOPs is the Fenton process that relies on the Fenton reaction. Nevertheless, there are no systematic studies on Fenton reactor networks. The objective of this paper is to develop a strategy for the optimal synthesis of Fenton reactor networks. The strategy is based on a superstructure optimization approach that is represented as a mixed integer non-linear programming (MINLP) model. Network superstructures with multiple Fenton reactors are optimized with the objective of minimizing the sum of capital, operation and depreciation costs of the effluent treatment system. The optimal solutions obtained provide the reactor volumes and network configuration, as well as the quantities of the reactants used in the Fenton process. Examples based on a case study show that multi-reactor networks yield decrease of up to 45% in overall costs for the treatment plant. (C) 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Ultra-thin films of alternating semi-interpenetrating layers of a conducting polymer with thermosetting phenolic resins for sensor application

In this work a new method for crosslinking ultra-thin films with potential applications in sensor systems is proposed. The films were produced by layer-by-layer (LbL) assembly using a conducting polymer, poly(o-ethoxyaniline) (POEA), alternated with a thermosetting resin, novolac-type phenolformaldehyde (PF), crosslinked by a simple thermal treatment. The PF resin served as both alternating and crosslinking agents. The films were characterized by Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, thermogravimetry (TG), desorption, doping/dedoping cycling and electrical measurements. The results showed that film architecture and crosslinking degree can be controlled by the conditions used for film deposition (number of bilayers, polymer concentration, pH, and deposition time), and crosslinking time. Moreover, this approach offers several advantages such as fast curing time and low cost, indicating that these films can be used to produce sensors with improved stability.