Eletrólise de resíduos poluidores: I - Efluente de uma indústria liofilizadora de condimentos

Wastewater from a seasoning freeze-drying industry was electrolysed to increase its biodegradability. Stainless-steel electrodes were used at 9.09 A/m², for up to 80 min. Conductivity, pH, biochemical (BOD) and chemical (COD) oxygen demands, Daphnia similis acute toxicity bioassays, and bacteria counting through the plate count agar method were determined after different times of electrolysis. The results (e.g. higher BOD and lower COD) showed that the biodegradability of the wastewater was significantly increased; furthermore, Fe2+ ions liberated by the electrodes cause microorganisms to die and, when oxidised to Fe3+, contribute for the flocculation and sedimentation of solid residues.

High voltage discharge for degradation of organic contaminants in water

The pulsed dielectric barrier discharge (PDBD) and pulsed corona discharge (PCD) were compared for their efficiency to degrade phenol in water solution. Results show that PCD has higher efficiency than PDBD to degrade phenol. When initial pH of water solution was elevated, phenol degradation in the PCD reactor was significantly enhanced, although no considerable effect was seen in the PDBD reactor. The PCD reactor was also able to degrade lignin significantly, both in synthetically prepared solution and in pulp and paper mill wastewater. Water temperature did not affect phenol degradation; however, lignin was better oxidized at lower temperature.

Utilização do resíduo líquido de indústria de processamento de suco de laranja como meio de cultura de Penicillium citrinum: depuração biológica do resíduo e produção de enzima

Penicillium citrinum grown in orange juice processing wastes medium under continuous agitation was studied in order to establish optimal conditions (incubation period, incubation temperature, initial pH and nitrogen addition) for biomass and ribonuclease production, as well as, biological depuration of the wastes. Nitrogen addition to wastes medium increased the biomass and ribonuclease production and provides COD reduction. The soy meal shows to be the best nitrogen source. The conditions for a more favorable enzyme and biomass production and COD reduction were initial pH 6.0 and temperature of 27°C. The maximum value obtained for these parameters on optimal conditions of cultivation was 11 U/mL of enzyme, 4 mg/mL of biomass (dry matter) and 55% of COD reduction, in 96 hours of incubation.

Laitepuhdistamon ylijäämäliete ja sen kuiva-ainepitoisuuden nostaminen

Työssä tutkittiin pienpuhdistamon ylijäämälietteen ominaisuuksia ja käyttäytymistä pienpuhdistamon ylijäämälietteen tiivistys- tai kuivausmenetelmän kehittämisen teoriapohjaksi. Työ sisältää myös lietteiden tiivistysmenetelmien kustannustarkastelua. Kokeellisessa osuudessa käytettiin työn teettäjän Oy KWH Pipe Ab:n valmistamien pienpuhdistamojen ylijäämälietettä. Tutkittava ylijäämäliete oli peräisin asukasvastineluvultaan 5–95 pienistä aktiivilietelaitepuhdistamoista. Tiivistys- tai kuivausmenetelmän kehittämisen tarkoituksena on saavuttaa kustannussäästöjä pienpuhdistamon ylijäämälietteen kuljetusmatkojen vähentämisen kautta. Soveltuvia vertailtavia sovelluksia ovat staattiseen laskeuttamiseen perustuvat menetelmät, mekaaniset ruuvi- ja linkokuivaimet, kuivauslava ja flotaatio. Tarkasteltavien menetelmien tuli olla käytöltä ja huollolta sekä käyttökuluiltaan edullisia ja yksinkertaisia. Ylijäämälietteiden ominaisuuksia ja käyttäytymistä tutkittiin kirjallisuuslähteistä ja käytännön kokein. Kokeissa tarkasteltiin ylijäämälietteen laskeutumis- ja nousuominaisuuksia, redox-potentiaalin vaihtelua seisovassa näytteessä ja flotaation onnistumista testattavalle lietteelle. Kokeet tehtiin kullakin kerralla eri ajankohtana otetuille lietenäytteille, käytettyjä puhdistamoja oli useita ja mitoitus, kuormitus sekä jäteveden laatu vaihteli paljon.

Catalytic Wet Oxidation of Paper Mill Debarking Water

The objective of the research was to study the influence of temperature, oxygen pressure, catalysts loading and initial COD concentration of debarking wastewater on the pollutants during the catalytic oxidation. More importantly, how the addition of catalyst affects the wet oxidation process. The whole work was divided into two main sections, theoretical and experimental parts. The theoretical part reviews the pulp and paper industry from wood processing to paper production as well as operations that generate wastes. Treatment methods applicable for industrial pulp and paper mill effluents were also discussed. Wet oxidation and catalytic wet oxidation processes including mechanism, reactions, kinetics and industrial applications were previewed. In the experimental part, catalytic wet oxidation process were studied at 120-180°C, 0-10 bar oxygen pressure, 0-1 g/L catalyst concentration and 1000-3000 mg/L initial COD concentration. Responses, such as Chemical oxygen demand (COD), Total organic carbon (TOC), colour, lignin/tannin, Biochemical oxygen demand (BOD) and pH were measured. In the experiment, the best conditions occurred at 180°C, 10 bar, l g/L catalyst concentration and 3000mg/L initial COD. At these conditions; 74% COD, 97% lignin/tannin, 54% TOC, 90% colour were removed from the wastewater. pH was greatly reduced from 7 to 4.6. Lignin/tannin was removed most. Lignin/tannin showed linear dependency with colour during oxidation. Temperature made the most impact in reducing contaminants in debarked wastewater.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Integration of a Bioethanol Process to a Pulp Mill

Tässä diplomityössä tutkittiin puuhakkeen esihydrolyysi- ja hakkuujätteen hydrolyysiprosessien integroimista sellutehtaaseen bioetanolin tuottamiseksi. Tällaisesta ns. biojalostamosta luotiin WinGEMS-simulointiohjelmalla simulointimalli, jonka avulla tutkittiin bioetanoliprosessin vaikutusta sellutehtaan massa- ja energiataseisiin sekä alustavaa biojalostamon kannattavuutta. Simuloinnissa tarkasteltiin kolmea eri tapausta, joissa mäntysellun tuotannon ajateltiin olevan 1000 tonnia päivässä ja hakkuujätettä käytettävän 10 % tarvittavan kuitupuun määrästä: 1) Puuhakkeen esihydrolyysi ja hakkuujätteen hydrolyysi etanolin tuottamiseksi 2) Puuhakkeen esihydrolyysi, hakkuujäte kuorikattilaan poltettavaksi 3) Ei esihydrolyysiä, hakkuujäte kuorikattilaan poltettavaksi Verrattuna tapaukseen 3, puun kulutus kasvaa 16 % esihydrolysoitaessa puuhake ennen keittoa tapauksissa 1 ja 2. Kasvaneella puun kulutuksella tuotetaan tapauksessa 1 149 tonnia etanolia ja 240 MWh enemmän ylimääräsähköä päivässä. Tapauksessa 2 tuotetaan 68 tonnia etanolia ja 460 MWh enemmän ylimääräsähköä päivässä. Tämä tuottaisi vuotuista lisäkassavirtaa 18,8 miljoonaa euroa tapauksessa 1 ja 9,4 miljoonaa euroa tapauksessa 2. Hydrolyysin tuoteliuoksen, hydrolysaatin, haihduttaminen sekä hydrolyysiprosessien orgaanisten jäännöstuotteiden haihduttaminen ja polttaminen kasvattavat haihduttamon ja soodakattilan kuormitusta. Verrattuna tapaukseen 3, tapauksissa 1 ja 2 haihduttamon vaiheiden määrä on kasvatettava viidestä seitsemään ja tarvittavat lämmönsiirtopinta-alat lähes kaksinkertaistettava. Soodakattilan kuormitus kasvaa 39 % tapauksessa 1 ja 26 % tapauksessa 2.

Utilização de regressão multivariada para avaliação espectrofotométrica da demanda química de oxigênio em amostras de relevância ambiental

In this work, a partial least squares regression routine was used to develop a multivariate calibration model to predict the chemical oxygen demand (COD) in substrates of environmental relevance (paper effluents and landfill leachates) from UV-Vis spectral data. The calibration models permit the fast determination of the COD with typical relative errors lower by 10% with respect to the conventional methodology.

Tratamento de chorume de aterro sanitário por fotocatálise heterogênea integrada a processo biológico convencional

The chemical and microbiological decomposition of the garbage deposited in landfills leads to the generation of a dark and malodorous liquid residue that shows a chemical composition of extreme variability and complexity. When matured, the leachates show low biodegradability, which makes it difficult to treat by conventional biological processes. In this work a new strategy for the treatment of landfill leachates is proposed, involving a preliminary treatment by heterogeneous photocatalysis followed by an activated sludge system. The results demonstrate that photochemical treatments of 60 and 90 min significantly enhance the leachates' biodegradability favoring subsequent biological treatment. The biodegradability rate (BOD/COD) was also greatly enhanced.

Influence of EfOM on the oxidation of micropollutants by Ozone and UV/H2O2 in secondary effluents

The aim of this work was to study the influence of effluent organic matter (EfOM) on micropollutants removal by ozone and UV/H2O2. To perform the experiments, deionized water and municipal secondary effluents (SE) were artificially contaminated with atrazine (ATZ) and treated by the two proposed methods. ATZ concentration, COD and TOC were recorded along the reaction time and used to evaluate EfOM effect on the system efficiency. Results demonstrate that the presence of EfOM can significantly reduce the micropollutant removal rate due to competition of EfOM components to react with radicals and/or molecular ozone. The hydroxyl radical scavenging caused by EfOM was quantified as well as the contribution of molecular ozone and �OH radicals during the ozonation of SE. EfOM components promoted higher inhibition of ATZ oxidation by hydroxyl radicals than by molecular ozone.

Aplicação de radiação UV artificial e solar no tratamento fotocatalítico de efluentes de curtume

Tannery effluents are very dangerous for the environment since they contain large amounts of dangerous and biorecalcitrant contaminants (organic matter and Cr(VI)). This paper reports the efficiency of heterogeneous photocatalysis, based on the application of solar and artificial radiation, furnished by UV lamps, using TiO2 fixed on a flat plate, in the treatment of synthetic effluents. The results of COD and Cr(VI) demonstrate that the use of solar radiation is the most efficient way to perform the photocatalytic treatment of these effluents since a minimum removal of 62 and 61% was observed for Cr(VI) and organic matter, respectively.

The effect of pulp washing on bleaching efficiency

The main aim of this study was to inspect the influence of the ultrafiltration implementation on the washing and on bleaching efficiency. Four cases corresponding to four washing stages were observed: two with hardwood pulp and two with softwood pulp; each case had a reference and a trial experiment. The experiments with hardwood pulp were arranged in a manner to explore predominantly the possibility of bleaching performance improvement by applying for washing instead of untreated filtrate (reference case) the same treated one (trial case). Despite that the ultrafiltration reduced the COD of the wash filtrates allowing the decreasing of COD carry-over to the bleaching stage it didn’t affect the bleaching performance. Another set was used in the experiments with softwood pulp. It implied the ultrafiltration and recirculation of the filtrate to the same washing stage with the purpose to reduce the volumes and pollution of the bleaching effluents. In one case the negative result was obtained which was expressed by worse parameters of the pulp after bleaching. Another case showed the opportunity to replace hot water with the filtrate and reduce the fresh water consumption.

Predição da demanda química de oxigênio em chorume maduro contendo reagente de Fenton, por meio de modelo matemático empírico gerado com planejamento fatorial completo

COD is an important parameter to estimate the concentration of organic contaminants. The closed system technique with the use of K2Cr2O7 is the most important one, however, it has the inconvenience to suffer positive chemical interferences from inorganic compounds such as Fe2+ and H2O2 (not enough reported in the literature). This paper considers a statistical-experimental set capable to validate a empirical mathematical model generated from a 23 experimental design, in the presence of Fe2+ and H2O2. The t test shows that mathematical model has 99,99999% confidence degree and the experimental validation test indicates absolute mean error of 4,70%.

Degradação fotoeletroquímica de corantes dispersos em efluente têxtil utilizando fotoanodos de Ti/TiO2

The degradation of disperses dyes in aqueous solution and in effluents from textile industry has been investigated by photoelectrocatalytic oxidation using nanoporous thin films electrodes of Ti/TiO2. Samples of dispersil black dye and dispersil blue dye after 300 min of photoelectrolyzed at applied potential of +1.0 V and UV irradiation exhibited 100% of discoloration and 90% and 64% reduction total organic carbon, respectively. The proposed method was applied with success in a textile industry effluent containing residues of these dyes, which after 300 min of treatment leads to reduction of 60% of COD and 64% removal of TOC.

Estudo da degradação de ranitidina via H2O2 eletrogerado/Fenton em um reator eletroquímico com eletrodos de difusão gasosa

The study of the electrochemical degradation of the ranitidine was developed using an electrochemical reactor with a gas diffusion electrode (GDE) as cathode. The electrolysis experiments was performed at constant current (1 < A < 10) and flow rate of 200 L h-1. The process of drug degradation, chemical/electrochemical and electro-Fenton ways, using electrochemical reactor showed best efficiency at current values of > 4 A. The process reached a production of 630 mg L-1 of the H2O2 at 7 A. The ranitidine concentrations was reduced in 99.9% (HPLC) and chemical oxygen demand (COD) was reduced in 86.7% by electro-Fenton.