Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Oxidation of Aqueous Thiosulfate Solutions by Pulsed Corona Discharge

The aim of this Master’s thesis focused on the oxidation of sodium thiosulfate using non thermal plasma technology as an advance oxidation process (AOP). By using this technology we can degrade certain toxic chemical compounds present in mining wastewaters as pollutants. Different concentrations of thiosulfate and pulse frequencies were used in the PCD experiments and the results in terms of various delivered energies (kWh/m3) and degradation kinetics were compared. Pulsed corona discharge is an energy efficient process compared to other oxidation processes using for the treatment of waste water pollutants. Due to its simplicity and low energy costs make it attractive in the field of waste water treatment processes. This technology of wastewater treatment has been tested mainly on pilot scale level and in future the attempts are to be focus on PCD investigations on larger process scale. In this research work of oxidation of thiosulfate using pulsed corona discharge, the main aim of this research was to study degradation of a studied toxic and not environmental friendly chemical compound. The focus of this research was to study the waste waters coming from the gold mines containing leachate compound thiosulfate. Literature review contained also gold leaching process when cyanide is used as the leachate. Another objective of this work was to compare PCD process with other processes based on their energy efficiencies. In the experimental part two concentrations of sodium thiosulfate, 1000ppm and 400ppm, were used. Two pulse generator frequencies of 833 and 200 pulses per second (pps) were used. The chemical analyses of the samples taken during semi-batch PCD oxidation process were analyzed by ion chromatographic (IC). It is observed after the analyses that among different frequencies and concentrations, the most suitable ones for the process is 200pps and 1000ppm respectively because the pollutants present in the waste water has more time to react with the OH radicals which are the oxidants and the process is energy efficient compared to other frequencies.

Anodic oxidation of wastewater containing the Reactive Orange 16 Dye using heavily boron-doped diamond electrodes

Boron-doped diamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 x 10(21) atoms cm(-3), respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman`s spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 00). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process. (C) 2011 Elsevier B.V. All rights reserved.

Toxicity assessment and degradation of disperse azo dyes by photoelectrocatalytic oxidation on Ti/TiO2 nanotubular array electrodes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrode

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(ap)p close to 3.2 x 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities >= 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition. (C) 2012 Elsevier Ltd. All rights reserved.

Hybrid magnetic graphitic nanocomposites for catalytic wet peroxide oxidation applications

Hybrid magnetic graphitic nanocomposites (MGNC) prepared by inclusion of magnetite nanoparticles (obtained by coprecipitation) into an organic-organic self-assembly system, followed by calcination, revealed high activity for the catalytic wet peroxide oxidation (CWPO) of 4-nitrophenol solutions (5 g L-l), with pollutant removais up to 1245 mg g-' h-l being obtained when considering the mass ratio [pollutant]/[catalyst] =10. The stability of the MGNC catalyst against metal leaching was ascribed to the confinement effect of the carbon based material. These observations, together with the magnetically recoverable characteristics of MGNC, open new prospects for the wide use of this catalyst in highly efficient CWPO applications.

The investigation of photocatalysts and iron based materials in the oxidation and adsorption of toxic organic and chromium materials

The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.

Trends and strategies of ozone application in environmental problems

Efforts presented by the scientific community in recent years towards the development of numerous green chemical processes and wastewater treatment technologies are presented and discussed. In the light of these approaches, environmentally friendly technologies, as well as the key role played by the well-known advanced oxidation processes, are discussed, giving special attention to the ones comprising ozone applications. Fundamentals and applied aspects dealing with ozone technology and its application are also presented.

Degradação de corantes ácidos por processos oxidativos avançados usando um reator com disco rotatório de baixa velocidade

Three technologies were tested (TiO2/UV, H2O2/UV, and TiO2/H2O2/UV) for the degradation and color removal of a 25 mg L-1 mixture of three acid dyes: Blue 9, Red 18, and Yellow 23. A low speed rotating disc reactor (20 rpm) and a H2O2 concentration of 2.5 mmol L-1 were used. The dyes did not significantly undergo photolysis, although they were all degraded by the studied advanced oxidation processes. With the TiO2/H2O2/UV process, a strong synergism was observed (color removal reached 100%). Pseudo first order kinetic constants were estimated for all processes, as well as the respective apparent photonic efficiencies.

Photolysis of ferric ions in the presence of sulfate or chloride ions: implications for the photo-Fenton process

The photo-Fenton process (Fe(2+)/Fe(3+), H(2)O(2), UV light) is one of the most efficient and advanced oxidation processes for the mineralization of the organic pollutants of industrial effluents and wastewater. The overall rate of the photo-Fenton process is controlled by the rate of the photolytic step that converts Fe(3+) back to Fe(2+). In this paper, the effect of sulfate or chloride ions on the net yield of Fe(2+) during the photolysis of Fe(3+) has been investigated in aqueous solution at pH 3.0 and 1.0 in the absence of hydrogen peroxide. A kinetic model based on the principal reactions that occur in the system fits the data for formation of Fe(2+) satisfactorily. Both experimental data and model prediction show that the availability of Fe(2+) produced by photolysis of Fe(3+) is inhibited much more in the presence of sulfate ion than in the presence of chloride ion as a function of the irradiation time at pH 3.0.

Treatment of wastewater from a cotton dyeing process with UV/H(2)O(2) using a photoreactor covered with reflective material

Wastewater containing several dyes, including sulfur black from the dyeing process in a textile mill, was treated using a UV/H(2)O(2) process. The wastewater was characterized by a low BOD/ COD ratio, intense color and high acute toxicity to the algae species Pseudokirchneriella subcaptata. The influence of the pH and H(2)O(2) concentration on the treatment process was evaluated by a full factorial design 2(2) with three replicates of the central experiment. The removal of aromatic compounds and color was improved by an increase in the H(2)O(2) concentration and a decrease in pH. The best results were obtained at pH 5.0 and 6 g L(-1). With these conditions and 120 min of UV irradiation, the removal of the color, aromatic compounds and COD were 74.1, 55.1 and 44.8%, respectively. Under the same conditions, but using a photoreactor covered with aluminum foil, the removal of the color, aromatic compounds and COD were 92.0, 77.6 and 59.4%, respectively. Moreover, the use of aluminum foil reduced the cost of the treatment by 40.8%. These results suggest the potential application of reflective materials as a photoreactor accessory to reduce electric energy consumption during the UV/H(2)O(2) process.

Treatment of industrial effluents of recalcitrant nature using ozone, hydrogen peroxide and ultraviolet radiation

Currently diverse industries have high pollution potential because their productive processes generate great volumes of refractory effluents. These effluents are problematic, mainly due to the presence of recalcitrant compounds that are detrimental in wastewater treatment plants using biological systems in their processes. In general, biological treatments do not remove refractory elements. Also, in most cases these compounds can inhibit the yield or are toxic for biota responsible to remove the polluting agents. The Advanced Oxidative Processes (AOPs) represent a technological alternative with a great potential for treatment of no biodegradable effluents. In this paper a review of the use of advanced oxidatives processes: Ozone (O(3)), peroxide of hydrogen (H(2)O(2)) and ultraviolet radiation (UV) is presented applied to the treatment of recalcitrant effluents.

Combination of an anaerobic process with O(3), UV and O(3)/UV for cellulose pulp bleaching effluent treatment

Recent studies have shown that partial oxidation by advanced oxidation processes (AOP) is able to transform hard-to-degrade compounds and increase their biodegradability. In this work, anaerobic treatment was followed by ozonation, UV radiation and ozonation in the presence of UV radiation, to treat bleaching effluents from a cellulose kraft Pulp plant. The anaerobic reactor (horizontal anaerobic immobilized Sludge bed, HAISB) was Used as a pretreatment to reduce the efficient organic load before applying ACIP. The ozone treatments were applied in three different pH environments (3, 8 and 10) with retention times of 10, 30, 45 and 60 min. COD and adsorbable organic halogens (AOX) removal efficiencies at the HAISB were approximately 50%, while the BOD removal efficiency reached 80%. Ozonation promoted further removal of AOX and COD so that the combined efficiency reached 96% for AOX and 70% for COD. In the oxidation process, BOD was either removed in small quantities or actually increased, as intended, so that a second biological treatment would be able to complete the treatment. The maximum increase in the BOD(5)/COD ratio (biodegradability indicator) Occurred at pH 8, reaching 104% for ozonation at a dosage of 1540 mg(O3).L(-1). Applying UV radiation alone resulted in lower values: a 34% increase ill the BOD(5)/COD ratio and a 76% AOX removal efficiency. These results indicate that the combination of anaerobic treatment with ozonation or ozonation/UV radiation improves the treatability of cellulose pulp bleaching efficients and that the resulting wastewater is suitable for further biological treatment under aerobic conditions with a low level of toxic compounds from the halogenated family.

MODELING ELECTRODIALYSIS AND A PHOTOCHEMICAL PROCESS FOR THEIR INTEGRATION IN SALINE WASTEWATER TREATMENT

Oxidation processes can be used to treat industrial wastewater containing non-biodegradable organic compounds. However, the presence of dissolved salts may inhibit or retard the treatment process. In this study, wastewater desalination by electrodialysis (ED) associated with an advanced oxidation process (photo-Fenton) was applied to an aqueous NaCl solution containing phenol. The influence of process variables on the demineralization factor was investigated for ED in pilot scale and a correlation was obtained between the phenol, salt and water fluxes with the driving force. The oxidation process was investigated in a laboratory batch reactor and a model based on artificial neural networks was developed by fitting the experimental data describing the reaction rate as a function of the input variables. With the experimental parameters of both processes, a dynamic model was developed for ED and a continuous model, using a plug flow reactor approach, for the oxidation process. Finally, the hybrid model simulation could validate different scenarios of the integrated system and can be used for process optimization.

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.