Investigation of the mass transfer processes during the desalination of water containing phenol and sodium chloride by electrodialysis

Oxidation processes are used in wastewater treatment when conventional processes are not effective due to the presence of recalcitrant organic contaminants, like phenol. However, the presence of ionic compounds associated with organic pollutants may retard the oxidation. In this work the transport of species contained in an aqueous solution of phenol containing sodium chloride was evaluated in an electrodialysis (ED) system. An experimental study was carried out in which the influence of the process variables on the phenol loss and sodium chloride removal was investigated. Experiments were also performed without current, in order to determine the phenol transfer due to diffusion. The phenol and salt concentration variations in the ED compartments were measured over time, using dedicated procedures and an experimental design to determine the global characteristic parameters. A phenomenological approach was used to relate the phenol, salt and water fluxes with the driving forces (concentration and electric potential gradients). Under ED conditions, two contributions were pointed out for the phenol transport, i.e. diffusion and convection, this latter coming from the water flux due to electroosmosis related to the migration of salts. The fitting of the parameters of the transport equations resulted in good agreement with the experimental results over the range of conditions investigated. (c) 2008 Elsevier B.V. All rights reserved.

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.

Stress cracking and photodegradation behavior of polycarbonate. The combination of two major causes of polymer failure

This work investigates the effects of photodegradation on the environmental stress cracking resistance of polycarbonate (PC). Injection molded samples were exposed to the ultraviolet (UV) light for various times in the laboratory prior to solvent contact. The bars were then stressed with two different loads in a tensile testing machine under the presence of ethanol. During this period, the stress relaxation was monitored and, after unloading, the ultimate properties were evaluated. Complementary tests were done by size exclusion chromatography, UV-visible spectroscopy, scanning electron microscopy, and light microscopy. The results indicated that ethanol causes significant modification in PC, with extensive surface crazing as well as reduction in mechanical properties. The previous degraded samples showed a higher level of stress relaxation and a greater loss in tensile strength in comparison with the undegraded ones. The synergist action of photodegradation and stress cracking in PC may be a consequence of the chemical changes caused by oxidation.

Characterization of the Phenol Monooxygenase Gene from Chromobacterium violaceum: Potential Use for Phenol Biodegradation

In this work, the biodegradation mechanism of phenol and sub products (such as catechol and hydroquinone) in Chromobacterium violaceum was investigated by cloning and molecular characterization of a phenol monooxygenase gene in Escherichia coli. This gene (Cvmp) is very similar (74 and 59% of similarity and identity, respectively) to the ortholog from Ralstonia eutropha, bacteria capable of utilizing phenol as the sole carbon source. The phenol biodegradation ability of E. coli recombinant strains was tested by cell-growth in a minimal medium containing phenol as the sole source of carbon and release of intermediary metabolites (catechol and hydroquinone). Interestingly, during the growth of these strains on phenol, catechol, and hydroquinone accumulated transiently in the medium. These metabolites were further analyzed by HPLC. These results indicated that phenol can be initially orto or para hydroxylated to produce cathecol or hydroquinone, respectively, followed by meta-cleavage of aromatic rings. To verify this information, the metabolites obtained from HPLC were submitted to LC/MS to confirm their chemical structure, thereby indicating that the recombinant strains utilize two different routes simultaneously, leading to different ring-fission substrates for the metabolism of phenol. (C) KSBB

Characterization and spectroscopic analysis of phenol-ethanol hydrogen bonded clusters

Different hydrogen bonded clusters involving phenol and ethanol are studied theoretically using MP2/aug-cc-pVDZ. Nine different 1: 1 clusters are obtained and analyzed according to their stability and spectroscopic properties. Different isomeric forms of ethanol are considered. Attention is also devoted to the spectral shift of the characteristic pi -> pi* transition of phenol. Using TDHF, CIS, CIS(D) and TDB3LYP in aug-cc-pVDZ basis set, all results agree that a red shift is obtained when phenol is the hydrogen donor and a blue shift is obtained in the opposite case. These results are used to rationalize the red shift observed for phenol in liquid ethanol. (C) 2010 Elsevier B.V. All rights reserved.

Immobilization of lutetium bisphthalocyanine in nanostructured biomimetic sensors using the LbL technique for phenol detection

This study describes the development of amperometric sensors based on poly(allylamine hydrochloride) (PAH) and lutetium bisphthalocyanine (LuPc(2)) films assembled using the Layer-by-Layer (LbL) technique. The films have been used as modified electrodes for catechol quantification. Electrochemical measurements have been employed to investigate the catalytic properties of the LuPc(2) immobilized in the LbL films. By chronoamperometry, the sensors present excellent sensitivity (20 nA mu M(-1)) in a wide linear range (R(2) = 0.994) up to 900 mu M and limit of detection (s/n = 3) of 37.5 x 10(-8) M for catechol. The sensors have good reproducibility and can be used at least for ten times. The work potential is +0.3 V vs. saturated calomel electrode (SCE). In voltammetry measurements, the calibration curve shows a good linearity (R(2) = 0.992) in the range of catechol up to 500 mu M with a sensitivity of 90 nA mu M(-1) and LD of 8 mu M. (C) 2011 Elsevier B.V. All rights reserved.

CeO(2)-catalyzed ozonation of phenol

Three different cerium citrate-based precursors were used for synthesizing CeO(2) through thermal treatment. Three morphological types of CeO(2) were obtained. Characterization of these oxides was carried out by XRD patterns, SEM microscopy, N(2) adsorption isotherms, Raman spectroscopy, zeta potential, and UV/Vis luminescence. Ozonation of phenol catalyzed by CeO(2) was studied as a representative reaction of environmental interest. The differences on the catalytic activity showed by these three oxides could be correlated to amounts of Ce(3+) on CeO(2) surface and, consequently, to the demand for oxygen needed to burn each precursor.

Phenol-furfural resins to elaborate composites, reinforced with sisal fibers - Molecular analysis of resin and properties of composites

Resol type resins were prepared in alkaline conditions (potassium hydroxide or potassium carbonate) using furfural obtained by acid hydrolysis of abundant renewable resources from agricultural and forestry waste residues. The structures of the resins were fully determined by H-1, C-13, and 2D NMR spectrometries with the help of four models compounds synthesized specially for this study. MALDI-Tof mass spectrometry experiments indicated that a majority of linear oligomers and a minority of cyclic ones constituted them. Composites were prepared with furfural-phenol resins and sisal fibers. These fibers were chosen mainly because they came from natural lignocellulosic material and they presented excellent mechanical microscopy images indicated that the composites displayed excellent adhesion between resin and fibers. Impact strength measurement showed that mild conditions were more suitable to prepare thermosets. Nevertheless, mild conditions induced a high-diffusion coefficient for water absorption by composites. Composites with good properties could be prepared using high proportion of materials obtained from biomass without formaldehyde. (c) 2008 Wiley Periodicals, Inc.

Removal of phenol in high salinity media by a hybrid process (activated sludge plus photocatalysis)

The degradation of phenol by a hybrid process (activated sludge + photocatalysis) in a high salinity medium (50 g L-1 of chloride) has been investigated. The sludge used from a municipal wastewater facility was adapted to the high salt concentrations prior to use. The photocatalytic conditions were optimized by means of a factorial experimental design. TiO2 P25 from Degussa was used as the photocatalyst. The initial phenol concentration was approximately 200 mg L-1 and complete removal of phenol and a mineralization degree above 98% were achieved within 25 h of treatment (24 h of biological treatment and I h of photocatalysis). From HPLC analyses, five hydroxylated intermediates formed during oxidation have been identified. The main ones were catechol and hydroquinone, followed by 1,2,4-benzenetriol, 2-hydroxy- 1,4-benzoquinone, and pyrogallol, in this order. No formation of organochlorine compounds was observed. Therefore, the proposed hybrid process showed itself to be suited to treat phenol in the presence of high contents of salt. (c) 2007 Elsevier B.V. All rights reserved.

Photodegradation of Folate Sensitized by Riboflavin

Folate is shown to react with singlet-excited state of riboflavin in a diffusion controlled reaction and with triplet-excited state of riboflavin in a somewhat slower reaction with (3)k(q) = 4.8 x 10(8) L mol(-1) s(-1) in aqueous phosphate buffer at pH 7.4, ionic strength of 0.2 mol L(-1), and 25 degrees C. Singlet quenching is assigned as photo-induced reductive electron transfer from ground state folate to singlet-excited riboflavin, while triplet quenching is assigned as one-electron transfer rather than hydrogen atom transfer from folate to triplet-excited riboflavin, as the reaction quantum yield, phi = 0.32, is hardly influenced by solvent change from water to deuterium oxide, phi = 0.37. Cyclic voltammetry showed an irreversible two-electron anodic process for folate, E = 1.14 V versus NHE at a scan-rate of 50 mV s(-1), which appears to be kinetically controlled by the heterogeneous electron transfer from the substrates to the electrode. Main products of folate photooxidation sensitized by riboflavin were pterin-6-carboxylic acid and p-aminobenzoyl-L-glutamic acid as shown by liquid chromatographic ion-trap mass spectrometry (LC-IT-MS).

Thioxanthone Sensitized Photodegradation of Poly(alkyl methacrylate) Films

The thioxanthone-sensitized photodegradation of poly(alkyl methacrylate) films [alkyl = methyl, ethyl, butyl, and hexyl] was studied using near UV-vis light. The photooxidation process continued even after the total consumption of the sensitizer, possibly due to the excitation of the ketyl groups formed during the first stages of the process. The rate of oxidation, as well as the formation of hydroxy, peroxy, and ketyl groups was faster for polymers with larger ester groups. The decrease of the molecular weight of the degradated polymers was also larger for the hexyl substituted polymer. The side-chain size effect was attributed to the larger amount of secondary hydrogens available for abstraction by the triplet state of thioxanthone, present in the larger ester groups. The lower glass transition temperature of the hexyl substituted polymer allows a better diffusion of oxygen to the deeper layers of the films that also contributes to the faster photodegradation rate. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 1283-1288, 2010

Evaluation of iris color stability in ocular prosthesis

Accurate iris reproduction in the fabrication of ocular prosthesis in order to match the remaining eye is a key factor to mask the loss and achieve an esthetic outcome for anophthalmic patients. This study evaluated the stability of acrylic paints used for replicating iris color in ocular prostheses by the analysis of two factors: the temperature of the acrylic resin polymerization cycle during prosthesis fabrication and the incidence of sun light, which is the main photodegrading agent undermining the longevity of ocular prostheses. An accelerated aging assay was used for both analyses. Specimens simulating the prosthetic iris in the colors blue, yellow, black, brown and green were fabricated, and were submitted to a colorimetric reading before and after undergoing the thermal conditions of acrylic resin polymerization. Next, the specimens were submitted to an artificial accelerated aging assay with ultraviolet radiation A and weekly colorimetric readings during a 3-week period. The color change (??*) values for the four specimens painted with the same color paint were averaged and the resulting values were considered for statistical analysis. Levine's test and Student's t-test were used to analyze the influence of the temperature of the polymerization cycle during prosthesis fabrication on the color stability of each acrylic resin paint. Friedman's test for three dependent samples was used for analysis of color photodegradation as function of time. Significance level was set at 0.05 for all analyses. It was observed that, after the action of the temperature of the polymerization cycle, alteration above clinically acceptable level of ??*> 3.3 was observed only for the yellow color. After the accelerated aging assay, there were statistically significant differences (p<0.05) as a function of time in the green, brown, black and blue colors. Changes were clinically acceptable for the brown and black colors; slightly above the clinically acceptable limit for the green color; and significantly high and impracticable from a clinical standpoint for the blue color. There was no statistically significant differences (p>0.05) for the yellow color, which presented color change only a little above the clinically acceptable limit. In conclusion: 1. Only the yellow color presented alterations above the clinically acceptable levels after the polymerization cycle; 2. After accelerated aging, there was no changes in the yellow color above the clinically acceptable levels; 3. For the green color, degradation was significant and slightly above the clinically acceptable levels; 4. The black, brown and blue colors presented significant alterations as function of time; the alterations of the brown and black colors were within acceptable clinical levels, while the blue color presented a more accentuated degradation over time.

Biocompósitos de matriz glioxal-fenol reforçada com celulose microcristalina

Glioxal pode ser obtido a partir de biomassa (como da oxidação de lipídeos) e não é tóxico ou volátil, tendo sido por isso utilizado no presente trabalho como substituto de formaldeído na preparação de resina fenólica do tipo novolaca, sendo usado como catalisador o ácido oxálico, que também pode ser obtido de fontes renováveis. A resina glioxal-fenol foi utilizada na preparação de compósitos reforçados com celulose microcristalina (CM, 30, 50 e 70% em massa), uma celulose com elevada área superficial. As imagens de microscopia eletrônica de varredura (MEV) das superfícies fraturadas demonstraram que os compósitos apresentaram boa interface reforço/matriz, consequência da elevada área superficial da CM e presença de grupos polares (hidroxilas) tanto na matriz como na celulose, o que permitiu a formação de ligações hidrogênio, favorecendo a compatibilidade entre ambas. A análise térmica dinâmico-mecânica (DMTA) demonstrou que todos os compósitos apresentaram elevado módulo de armazenamento à temperatura ambiente. Além disso, o compósito reforçado com 30% de CM apresentou baixa absorção de água, comparável à do termorrígido fenólico, que é utilizado em escala industrial. Os resultados demonstraram que compósitos com boas propriedades podem ser preparados usando elevada proporção de materiais obtidos de biomassa.

Photo-fenton degradation of poly(Ethyleneglycol)

Polyethyleneglycol (PEG) was photooxidized in a photo-Fenton system and results compared with the dark reaction. The products were analysed using GPC and HPLC. In the absence of light, PEG samples needed 490 min to reduce their w by 50%, whereas under UV irradiation, only 10 min were necessary. The exponential decay of w with a concomitant increase in polydispersity and number of average chain scission, characterized a random chain scission mechanism. The degradation products of PEG in both systems showed the presence of lower molecular weight products, including smaller ethyleneglycols and formic acid. The mechanism involves consecutive processes, were the larger ethyleneglycols give rise, successively, to smaller ones. This suggests that the mechanism involves successive scissions of the polymer chain. Irradiated samples decomposed faster than those kept in the dark This study proves that the foto-Fenton method associated with UV-light is a good reactant for PEG photodegradation.

Electrochemical and photocatalytic reactions of polycyclic aromatic hydrocarbons investigated by raman spectroscopy

This paper presents the study of photochemical behavior of polycyclic aromatic hydrocarbons (PAHs), potential pollutants in secondary reactions in aerosols, through Raman spectroscopy compared with its electrochemical behavior. The PAHs studied include pyrene, anthracene, phenanthrene and fluorene. These were adsorbed onto TiO2 and irradiated with ultraviolet light (254 nm). Their electrochemical oxidation was studied by in situ Surface-enhanced Raman Scattering (SERS) and led to the formation of carbonyl-containing products. Oxidized intermediates bearing the C=O group were also formed during photodegradation. The joint analysis of the photodegradation data with those produced by electrochemical means - using spectroscopic techniques for the identification and characterization of the products - revealed the formation of identical products for anthracene, but not for pyrene. A reasonable explanation for this difference in results is that photochemical and electrochemical oxidation reactions proceed via different mechanisms. While photocatalytic degradation over TiO2 is initiated by hydroxyl radicals, electrochemical oxidation is initiated by the direct electron transfer from adsorbed PAH to the electrode, generating PAH cation radicals that undergo subsequent reactions.