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1.
J Environ Manage ; 339: 117951, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37080096

RESUMO

In this investigation, a sustainable and low-cost method to capture CO2 generated from the treatment of urban wastewater was evaluated. We studied the adsorption of CO2 on olive pomace biochar. The experiments of degradation of synthetic wastewater mimicking effluents of municipal wastewater treatment plant (WWTP) with an initial Total Organic Carbon (TOC) concentration of 10 mg L-1 were conducted by using the UV-C/H2O2 process in the absence or presence of biochar. The biochar was placed in a fixed bed column through which air from the UV reactor was circulated. First, the effects of different parameters such as H2O2 initial concentration and pH on wastewater mineralization efficiency were determined. Total Organic Carbon (TOC) removal was 87% in 2 h under optimal degradation conditions. The maximal concentration of CO2(gas) in air, in a closed system (air volume: 7.3 10-4 m3), after 11 h was 12,500 µmol mol-1 in the absence of biochar and only 150 µmol mol-1 when 10 g biochar were used. The results proved that by combining biochar with oxidative degradation of organic compounds, it is possible to mineralize organic compounds and reduce the requisite CO2 emissions by about 99%. The experimental equilibrium results were fit well with both Langmuir and Freundlich isotherms models concluding that CO2 adsorption on biochar followed both chemisorption and physisorption and both monolayer and multi-layer CO2 adsorption could occur. The total desorption of CO2 from biochar was reached in 120 min by simultaneously increasing the temperature to 150 °C and introducing a purge N2(gas).


Assuntos
Olea , Purificação da Água , Águas Residuárias , Dióxido de Carbono , Adsorção , Peróxido de Hidrogênio , Carvão Vegetal/química , Purificação da Água/métodos
2.
J Environ Manage ; 210: 122-130, 2018 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-29339330

RESUMO

The aim of this work was to evaluate the performance of a novel self-autonomous reactor technology (capable of working with solar irradiation and artificial UV light) for water treatment using aniline as model compound. This new reactor design overcomes the problems of the external mass transfer effect and the accessibility to photons occurring in traditional reaction systems. The UV-light source is located inside the rotating quartz drums (where TiO2 is immobilized), allowing light to easily reach the water and the TiO2 surface. Several processes (UV, H2O2, Solar, TiO2, Solar/TiO2, Solar/TiO2/H2O2 and UV/Solar/H2O2/TiO2) were tested. The synergy between Solar/H2O2 and Solar/TiO2 processes was quantified to be 40.3% using the pseudo-first-order degradation rate. The apparent photonic efficiency, ζ, was also determined for evaluating light utilization. For the Solar/TiO2/H2O2 process, the efficiency was found to be practically constant (0.638-0.681%) when the film thickness is in the range of 1.67-3.87 µm. However, the efficiency increases up to 2.67% when artificial UV light was used in combination, confirming the efficient design of this installation. Thus, if needed, lamps can be switched on during cloudy days to improve the degradation rate of aniline and its mineralization. Under the optimal conditions selected for the Solar/TiO2/H2O2 process ([H2O2] = 250 mg/L; pH = 4, [TiO2] = 0.65-1.25 mg/cm2), 89.6% of aniline is degraded in 120 min. If the lamps are switched on, aniline is completely degraded in 10 min, reaching 85% of mineralization in 120 min. TiO2 was re-used during 5 reaction cycles without apparent loss in activity (<2%). Quantification of hydroxyl radicals and dissolved oxygen allows a chemical-based explanation of the process. Finally, the UV/Solar/TiO2/H2O2 process was found to have lower operation costs than other systems described in literature (0.67 €/m3).


Assuntos
Compostos de Anilina/química , Poluentes Químicos da Água/química , Catálise , Peróxido de Hidrogênio , Fotoquímica , Luz Solar , Titânio , Raios Ultravioleta
3.
J Environ Manage ; 187: 504-512, 2017 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-27856036

RESUMO

The photo-degradation of the emerging contaminant antipyrine (AP) was studied and optimized in a novel photocatalytic spinning disc reactor (SDR). A heterogeneous process (UV/H2O2/TiO2) was used. TiO2 was immobilized on the surface of a glass disc using a sol-gel method. A factorial design of experiments followed by a Neural Networks fitting allowed the optimal conditions to be determined for treating 50 mg/L of AP. Under these conditions (pH = 4; [H2O2]0 = 1500 mg/L; disc speed = 500 rpm; flowrate = 25 mL/s), AP was completely degraded in 120 min and regeneration of the disc allowed 10 cycles with no loss in efficiency. The value of the apparent volumetric rate constant was found to be 6.9·10-4 s-1 with no apparent mass transfer limitation. Based on the main intermediates identified, a mechanism is proposed for antipyrine photodegradation: Firstly, cleavage of the NN bond of penta-heterocycle leads to the formation of two aromatic acids and N-phenylpropanamide. An attack to the CN bond in the latter compound produces benzenamine. Finally, the phenyl ring of the aromatic intermediates are opened and molecular organic acids are formed.


Assuntos
Antipirina/química , Titânio/química , Poluentes Químicos da Água/química , Purificação da Água , Catálise , Humanos , Fotólise , Raios Ultravioleta , Purificação da Água/métodos
4.
J Environ Manage ; 141: 61-9, 2014 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-24768835

RESUMO

The mineralization of pharmaceutical wastewater containing chloride ions using a UV/H2O2/Fe(II) process was studied. The addition of Fe(II) to the UV/H2O2 system did not improve the degradation efficiency due to inhibition of the photo-Fenton reaction, at acid pH, in the presence of chloride ions in these wastewaters. The increase of pH from 2 to 7 increased the degree of mineralization under UV photolysis of H2O2 because more HO radicals are available by HOCl dissociation reaction. Under the selected operation conditions ([H2O2]o = 11,500 ppm, [Fe(II)] = 0 ppm, [TOC]o = 125 ppm and pH = 7), 100% of TOC removal was attained in 120 min. A significant synergistic effect of combining photolysis (UV/H2O2) and sonolysis was observed. Sonophotolysis (UV/H2O2/ultrasound) technique significantly increased the degree of mineralization (100% TOC removal in 90 min using 6500 ppm H2O2) when compared with each individual process. Sonochemical reaction was favored by the presence of chloride ions since the concentration of contaminants at the gas-liquid interface increased. Free radicals reaction was the controlling mechanism in the UV/H2O2/ultrasound system. HO radicals were the main oxidative intermediate species in the process, although hydroperoxyl radicals (HO2) also played a role. The contribution of thermal-pyrolytic reaction (in gas-phase) to sonophotolysis process was negligible.


Assuntos
Indústria Farmacêutica , Compostos Ferrosos/efeitos da radiação , Peróxido de Hidrogênio/efeitos da radiação , Raios Ultravioleta , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Cloretos/química , Compostos Ferrosos/química , Peróxido de Hidrogênio/química , Radical Hidroxila/química , Oxirredução , Fotólise , Ultrassom , Águas Residuárias/química
5.
J Environ Manage ; 130: 64-71, 2013 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-24064141

RESUMO

The mineralization of an aqueous solution of antipyrine (C11H12N2O), an emerging contaminant, using a solar photocatalytic oxidation process assisted with ferrioxalate was evaluated in a compound parabolic collector (CPC) pilot plant. Under the selected operating conditions ([H2O2] = 250 ppm, [Fe] = 14 ppm, pH = 2.7, and [(COOH)2·2H2O] = 80 ppm), 60% of TOC is removed just 5 min after treating an aqueous solution containing 50 ppm of antipyrine. The addition of oxalic acid up to a maximum concentration of 80 ppm significantly increases the mineralization rate during the first 15 min of the reaction. The synergism between the solar and dark H2O2/ferrioxalate process was quantified at 79%, calculated from the pseudo first-order mineralization rate constants. The operational costs due to the consumption of electrical energy, reagents and catalysts were calculated from the optimal conditions and compared with a novel sono-photocatalytic process using artificial UV-light. The results showed that the ferrioxalate-assisted solar photo-Fenton process was economically feasible, being able to achieve up to 60% mineralization with a total cost of 4.5 cent €/g TOC removed (1.1 €/m(3)).


Assuntos
Antipirina/química , Oxirredução , Poluentes Químicos da Água/química , Antipirina/efeitos da radiação , Redes Neurais de Computação , Oxalatos/química , Oxidantes Fotoquímicos , Projetos Piloto , Raios Ultravioleta , Poluentes Químicos da Água/efeitos da radiação , Poluição da Água/análise , Poluição da Água/prevenção & controle , Purificação da Água/métodos
6.
J Environ Manage ; 128: 210-9, 2013 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-23764505

RESUMO

The degradation of a pharmaceutical wastewater using a ferrioxalate-assisted solar/photo-Fenton system has been studied. The photochemical reaction was carried out in a pilot plant consisting of a compound parabolic collector (CPC) solar reactor. An optimization study was performed combining a multivariate experimental design and Neuronal Networks that included the following variables: initial concentrations of H2O2, catalyst Fe (II) and oxalic acid (H2C2O4), temperature and solar power. Under optimal conditions, 84% TOC (Total Organic Carbon) removal was achieved in 115 min. Oxalic acid had a positive effect on mineralization when solar power was above 30 W m(-2). The minimum amount of H2O2 to degrade 1 mol of TOC was found to be 3.57 mol. Both the H2O2 conversion efficiency and the degree of mineralization were highest when the oxalic/Fe(II) initial molar relation was close to 3. HO radicals were the main oxidative intermediate species in the process, although hydroperoxyl radicals (HO(2)(·)) also played a role.


Assuntos
Indústria Farmacêutica , Oxalatos/química , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/química , Catálise , Custos e Análise de Custo , Desenho de Equipamento , Peróxido de Hidrogênio/química , Resíduos Industriais , Redes Neurais de Computação , Ácido Oxálico/química , Oxirredução , Fotoquímica/métodos , Energia Solar , Luz Solar , Temperatura , Eliminação de Resíduos Líquidos/economia , Eliminação de Resíduos Líquidos/instrumentação
7.
J Environ Manage ; 98: 1-4, 2012 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-22325636

RESUMO

The aim of this work was to study the operation costs of treating a real effluent from an integrated gasification combined cycle (IGCC) power station located in Spain. The study compares different homogeneous photocatalytic processes on a pilot plant scale using different types of radiation (artificial UV or solar UV with a compound parabolic collector). The efficiency of the processes was evaluated by an analysis of the total organic carbon (TOC) removed. The following processes were considered in the study: (i) a photo-Fenton process at an artificial UV pilot plant (with the initial addition of H(2)O(2)), (ii) a modified photo-Fenton process with continuous addition of H(2)O(2) and O(2) to the system and (iii) a ferrioxalate-assisted solar photo-Fenton process at a compound parabolic collector (CPC) pilot plant. The efficiency of these processes in degrading pollutants has been studied previously, and the results obtained in each of those studies have been published elsewhere. The operational costs due to the consumption of electrical energy, reagents and catalysts were calculated from the optimal conditions of each process. The results showed that the solar photo-Fenton system was economically feasible, being able to achieve up to 75% mineralization with a total cost of 6 €/m(3), which can be reduced to 3.6 €/m(3) by subtracting the electrical costs because the IGCC plant is self-sufficient in terms of energy.


Assuntos
Peróxido de Hidrogênio/química , Resíduos Industriais , Ferro/química , Fotólise , Raios Ultravioleta , Eliminação de Resíduos Líquidos/métodos , Projetos Piloto , Eliminação de Resíduos Líquidos/economia
8.
Sci Total Environ ; 790: 148136, 2021 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-34102438

RESUMO

The capture of ambient air CO2(gas) from synthetic urban wastewater mineralization reaction was studied. An ion exchange membrane was used as sorbent, which adsorbs CO2 when dry and releases it when wet. The UV/H2O2 degradation process was chosen to convert Total Organic Carbon (TOC) to carbon dioxide due to its advantages of convenience and fast kinetics over the conventional biological treatment that is usually used in urban wastewater treatment plants. In the first phase, experiments combining UV-C light and H2O2 were carried out to select the optimal values of the following parameters: pH, the dose of H2O2 and temperature. In the second stage, the CO2(gas) emission into the air from the degradation of organic compounds present in wastewater during UV/H2O2 process in the absence or presence of ion exchange membranes was evaluated. The effects of parameters such as temperature or air humidity were studied. A qualitative study of desorption was carried out to check the viability of reuse CO2 captured in the membrane. Finally, a similar CO2(gas) adsorption capacity after five cycles of adsorption and regeneration of the membranes was observed, being percentage loss of around 4%.


Assuntos
Dióxido de Carbono , Águas Residuárias , Adsorção , Peróxido de Hidrogênio , Troca Iônica
9.
J Environ Manage ; 91(9): 1840-6, 2010 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-20510498

RESUMO

The aim of this work was to study the mineralization of wastewater effluent from an integrated-gasification combined-cycle (IGCC) power station sited in Spain to meet the requirements of future environmental legislation. This study was done in a pilot plant using a homogeneous photo-Fenton oxidation process with continuous addition of H(2)O(2) and air to the system. The mineralization process was found to follow pseudo-first-order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The NNs model reproduced the experimental data to within a 90% confidence level and allowed the simulation of the process for any values of the parameters within the experimental range studied. At the optimum conditions (H(2)O(2) flow rate=120 mL/h, [Fe(II)]=7.6 mg/L, pH=3.75 and air flow rate=1 m(3)/h), a 90% mineralization was achieved in 150 min. Determination of the hydrogen peroxide consumed and remaining in the water revealed that 1.2 mol of H(2)O(2) was consumed per each mol of total organic carbon removed from solution. This result confirmed that an excess of dissolved H(2)O(2) was needed to achieve high mineralization rates, so continuous addition of peroxide is recommended for industrial application of this process. Air flow slightly improved the mineralization rate due to the formation of peroxo-organic radicals which enhanced the oxidation process.


Assuntos
Peróxido de Hidrogênio/química , Resíduos Industriais/análise , Ferro/química , Eliminação de Resíduos Líquidos/métodos , Poluição Química da Água/prevenção & controle , Ar , Concentração de Íons de Hidrogênio , Redes Neurais de Computação , Projetos Piloto , Centrais Elétricas , Raios Ultravioleta
10.
Chemosphere ; 71(1): 161-7, 2008 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-18078669

RESUMO

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.


Assuntos
Resíduos Industriais , Centrais Elétricas , Luz Solar , Titânio/química , Catálise , Concentração de Íons de Hidrogênio , Fotoquímica
11.
J Hazard Mater ; 342: 597-605, 2018 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-28892797

RESUMO

The intensification of the solar photo-Fenton system with ferrioxalate photoactive complexes and ultrasound applied to the mineralization of 15mg/L carbamazepine aqueous solution (CBZ) was evaluated. The experiments were carried out in a solar compound parabolic collector (CPC) pilot plant reactor coupled to an ultrasonic processor. The dynamic behavior of hydroxyl radicals generated under the different studied reaction systems was discussed. The initial concentrations of hydrogen peroxide and ferrous/oxalic acid and pH were found to be the most significant variables (32.79%, 25.98% and 26.04%, respectively). Under the selected optimal conditions ([H2O2]0=150mg/L; [Fe2+]0=2.5mg/L/[(COOH)2]0=12.1mg/L; pH=5) CBZ was fully degraded after 5min and 80% of TOC was removed using a solar photo-Fenton system intensified with ferrioxalate (SPFF). However, no improvement in the mineralization using SPFF process combined with ultrasound was observed. More mild pH conditions could be used in the SPFF system if compared to the traditional photo-Fenton (pH 3) acidic systems. Finally, a possible reaction pathway for the mineralization of CBZ by the SPFF system was proposed and therein discussed.

12.
J Hazard Mater ; 357: 457-465, 2018 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-29935458

RESUMO

Degradation of a diclofenac aqueous solution was performed using persulfate anions activated by ultrasound. The objective of this study was to analyze different parameters affecting the diclofenac (DCF) removal reaction by the ultrasonic persulfate (US/PS) process and to evaluate the role played by various intermediate oxidative species such as hydroxyl- and sulfate radicals, superoxide radical anion or singlet oxygen in the removal process as well as to determine a possible reaction pathway. The effects of pH, initial persulfate anion concentration, ultrasonic amplitude and temperature on DCF degradation were examined. Sulfate and hydroxyl radicals were involved in the main reaction pathway of diclofenac. Diclofenac amide and three hydroxy-diclofenac isomers (3´-hydroxy diclofenac, 4´-hydroxy diclofenac and 5-hydroxy diclofenac) were identified as reaction intermediates.

13.
Water Res ; 41(3): 690-8, 2007 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-17011017

RESUMO

The heterogeneous photocatalytic degradation of reactive blue 4 dye (RB4) solutions under Fenton reagent and TiO(2) assisted by concentrated solar light irradiation using a Fresnel lens has been studied. Multivariate experimental design was applied to study the kinetic process. The efficiency of photocatalytic degradation was determined from the analysis of color and total organic carbon (TOC) removal. Factorial experimental design allowed to determine the influence of four parameters (pH and initial concentrations of TiO(2), Fe(II) and H(2)O(2)) on the value of the decoloration kinetic rate constant. Experimental data were fitted using neural networks (NNs). The mathematical model reproduces experimental data within 86% of confidence and allows the simulation of the process for any value of parameters in the experimental range studied. Also, a measure of the saliency of the input variables was made based upon the connection weights of the neural networks, allowing the analysis of the relative relevance of each variable with respect to the others. Results showed that acidic pHs (pH=3.6) are preferred for the complete dye decoloration. The optimum catalyst concentration is 1.2g TiO(2)/l. The use of a low cost catalyst and its activation using a Fresnel lens to concentrate solar energy significantly accelerates the degradation process when compared with direct solar radiation alone and can offer an economical and practical alternative for the destruction of environmental organic compounds.


Assuntos
Fotoquímica/métodos , Luz Solar , Triazinas/química , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Ferro/química , Fotoquímica/instrumentação , Triazinas/efeitos da radiação , Poluentes Químicos da Água/química , Poluentes Químicos da Água/efeitos da radiação , Purificação da Água/métodos
14.
J Hazard Mater ; 144(1-2): 132-9, 2007 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-17118539

RESUMO

The aim of this work is to improve the quality of water effluents coming from Elcogas IGCC power station (Puertollano, Spain) with the purpose of fulfilling future more demanding normative, using heterogeneous photocatalytic oxidation processes (UV/H(2)O(2)/TiO(2) or ZnO). The efficiency of photocatalytic degradation for the different catalysts (TiO(2) and ZnO) was determined from the analysis of the following parameters: cyanides, formates and ammonia content. In a first stage, the influence of two parameters (initial concentration of H(2)O(2) and amount of catalyst) on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. pH was always kept in a value >9.5 to avoid gaseous HCN formation. The degradation of cyanides and formates was found to follow pseudo-first order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The mathematical model reproduces experimental data within 90% of confidence and allows the simulation of the process for any value of parameters in the experimental range studied. Moreover, a measure of the saliency of the input variables was made based upon the connection weights of the neural networks, allowing the analysis of the relative relevance of each variable with respect to the others. Results showed that the photocatalytic process was effective, being the degradation rate of cyanides about five times higher when compared to removal of formates. Finally, the effect of lowering pH on the degradation of formates was evaluated after complete cyanides destruction was reached (10 min of reaction). Under the optimum conditions (pH 5.2, [H(2)O(2)]=40 g/l; [TiO(2)]=2g/l), 100% of cyanides and 92% of initial NH(3) concentration are degraded after 10 min, whereas 35 min are needed to degrade 98% of formates.


Assuntos
Cianetos/química , Formiatos/química , Poluentes Químicos da Água/química , Catálise , Cianetos/efeitos da radiação , Formiatos/efeitos da radiação , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Resíduos Industriais , Redes Neurais de Computação , Fotoquímica , Centrais Elétricas , Titânio/química , Raios Ultravioleta , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/efeitos da radiação , Purificação da Água/métodos , Óxido de Zinco/química
15.
Ultrason Sonochem ; 34: 496-503, 2017 01.
Artigo em Inglês | MEDLINE | ID: mdl-27773274

RESUMO

The photo-Fenton degradation of carbamazepine (CBZ) assisted with ultrasound radiation (US/UV/H2O2/Fe) was tested in a lab thin film reactor allowing high TOC removals (89% in 35min). The synergism between the UV process and the sonolytic one was quantified as 55.2%. To test the applicability of this reactor for industrial purposes, the sono-photo-degradation of CBZ was also tested in a thin film pilot plant reactor and compared with a 28L UV-C conventional pilot plant and with a solar Collector Parabolic Compound (CPC). At a pilot plant scale, a US/UV/H2O2/Fe process reaching 60% of mineralization would cost 2.1 and 3.8€/m3 for the conventional and thin film plant respectively. The use of ultrasound (US) produces an extra generation of hydroxyl radicals, thus increasing the mineralization rate. In the solar process, electric consumption accounts for a maximum of 33% of total costs. Thus, for a TOC removal of 80%, the cost of this treatment is about 1.36€/m3. However, the efficiency of the solar installation decreases in cloudy days and cannot be used during night, so that a limited flow rate can be treated.


Assuntos
Carbamazepina/química , Carbamazepina/isolamento & purificação , Custos e Análise de Custo , Fotólise , Ondas Ultrassônicas , Peróxido de Hidrogênio/química , Ferro/química , Projetos Piloto , Raios Ultravioleta
16.
Ultrason Sonochem ; 35(Pt A): 185-195, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-27692667

RESUMO

The aim of this study was to examine the kinetics of the different mechanisms (radical pathway, photolysis, molecular reaction with H2O2 and reaction with ultrasonically generated oxidative species) involved in the homogeneous sono-photoFenton (US/UV/H2O2/Fe) mineralization of antipyrine present in a synthetic municipal wastewater effluent (ASMWE). The dynamic behavior of hydroxyl (HO) radical generation and consumption in mineralization reaction under different systems was investigated by measuring hydroxyl radical concentration during the reaction. The overall mineralization process was optimized using a Central-Composite Experimental Design (CCED) with four variables (initial concentrations of H2O2 and Fe(II), amplitude and pulse length). The response functions (pseudo-first order mineralization kinetic rate constants) were fitted using neural networks (NNs). Under the optimal conditions ([H2O2]o=500mgL-1, [Fe(II)]o=27mgL-1, Amplitude (%)=20andPulse length=1), the TOC removal was 79% in 50min. The radical reaction in the bulk solution was found be the primary mineralization pathway (94.8%), followed by photolysis (3.65%), direct reaction with H2O2 (0.86%), and reaction by ultrasonically generated oxidative species (0.64%). The role of the Fe catalyst on the radical reaction and the presence of refractory intermediates towards hydroxyl radical were also studied.


Assuntos
Antipirina/química , Cidades , Peróxido de Hidrogênio/química , Radical Hidroxila/química , Ferro/química , Minerais/química , Sonicação , Águas Residuárias/química , Catálise , Processos Fotoquímicos
17.
Chemosphere ; 186: 177-184, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-28778015

RESUMO

The aim of this work is to study the applicability of a UV/H2O2 process intensified with persulfate (PS) as a source of SO4- radicals to efficiently mineralize a synthetic effluent containing aniline in a glass reactor arranged in a cascade configuration. pH conditions were studied and the concentration of PS was optimized. The synergism for aniline mineralization between the UV/H2O2 process and the combined UV/H2O2/PS process was quantified in 10.1%. Aniline degradation reached 100% under the UV/H2O2/PS process after 20 min. Its mineralization is favored under acidic conditions and with the presence of persulfate (optimal conditions: 49% in 90 min; pH = 4; [PS] = 250 ppm). On the contrary, the worst conditions were found at pH = 11, since hydrogen peroxide decomposes and carbonates were formed increasing the scavenging effect. The different mechanisms involved (formulated from intermediates identified by mass spectrometry) confirm these results. Aniline was found to follow a degradation pathway where phenol is the main intermediate. The presence of sulfate radicals increases phenol degradation rate leading to a higher mineralization extent. Benzoquinone was identified as the main aromatic oxidation product of phenol, whereas succinic, 4-oxo-pentanoic, fumaric and oxalic acids were detected as aliphatic oxidation products for both UV/H2O2 and UV/H2O2/PS oxidation processes.


Assuntos
Sulfatos/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Compostos de Anilina , Carbonatos/química , Compostos Ferrosos , Peróxido de Hidrogênio/química , Radical Hidroxila/química , Oxirredução , Fenol/química , Fenóis , Raios Ultravioleta
18.
Chemosphere ; 65(7): 1242-8, 2006 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-16762397

RESUMO

The decoloration and mineralization of the azo dye orange II under conditions of artificial ultraviolet light and solar energy concentrated by a Fresnel lens in the presence of hydrogen peroxide and TiO(2)-P25 was studied. A comparative study to demonstrate the viability of this solar installation was done to establish if the concentration reached in the focus of the Fresnel lens was enough to improve the photocatalytic degradation reaction. The degradation efficiency was higher when the photolysis was carried out under concentrated solar energy irradiation as compared to UV light source in the presence of an electron acceptor such us H(2)O(2) and the catalyst TiO(2). The effect of hydrogen peroxide, pH and catalyst concentration was also determined. The increase of H(2)O(2) concentration until a critical value (14.7 mM) increased both the solar and artificial UV oxidation reaction rate by generating hydroxyl radicals and inhibiting the (e(-)/h(+)) pair recombination, but the excess of hydrogen peroxide decreases the oxidation rate acting as a radical or hole scavenger and reacting with TiO(2) to form peroxo-compounds, contributing to the inhibition of the reaction. The use of the response surface methodology allowed to fit the optimal values of the parameters pH and catalyst concentration leading to the total solar degradation of orange II. The optimal pH range was 4.5-5.5 close to the zero point charge of TiO(2) depending on surface charge of catalyst and dye ionization state. Dosage of catalyst higher than 1.1 gl(-1) decreases the degradation efficiency due to a decrease of light penetration.


Assuntos
Compostos Azo/efeitos da radiação , Benzenossulfonatos/efeitos da radiação , Corantes/efeitos da radiação , Luz Solar , Raios Ultravioleta , Poluentes Químicos da Água/efeitos da radiação , Compostos Azo/química , Benzenossulfonatos/química , Carbono/análise , Catálise , Cor , Corantes/química , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Lentes , Fotoquímica , Energia Solar , Titânio/química , Eliminação de Resíduos Líquidos , Poluentes Químicos da Água/química , Purificação da Água/métodos
19.
J Hazard Mater ; 306: 77-86, 2016 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-26698672

RESUMO

Complete mineralisation of reaction intermediates refractory towards hydroxyl radical, generated from a previous ineffective degradation of urban wastewater containing antipyrine by HO-mediated sono-photo-Fenton reaction, has been attained using persulfate anions simultaneously activated by heat energy (thermally, ultrasound) and UV-C light. The SO4(-)-based mineralisation process enables another reaction pathway generating more easy degradable derivatives. The influences of the initial concentration of persulfate, ultrasound amplitude, temperature and the reaction time in the previous HO-based previous oxidation on the mineralisation degree were studied by using a Central-Composite Experimental Design. Under optimal conditions ([S2O8(2-)]o=1200mgL(-1), temperature=50°C, amplitude=10%, pH 2.8, HO-based reaction time=25min) practically complete degradation was achieved in approximately 120min. The contribution of HO and SO4(-) radicals in this system was also evaluated. The presence of chloride ion in urban wastewater can benefit the oxidation of acetate by sulfate radical. Results demonstrated that this activated persulfate-based oxidation system is a potential alternative to degrade intermediate compounds, which are refractory against hydroxyl radicals, generated in Advanced Oxidation Processes used to treat wastewater containing emerging contaminants such as antipyrine.

20.
J Agric Food Chem ; 53(26): 10097-104, 2005 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-16366701

RESUMO

The oxidation of protocatechuic acid (PA), a typical phenol-type compound present in food processing wastewater, has been carried out by means of Fenton's reagent. Both the H2O2 and Fe(II) initial concentrations increase the PA degradation rate. Temperature also enhances the PA conversion when raised from 283 to 313 K, a further increase to 323 K results in a lower PA removal. Increasing the PA initial concentration leads to a decrease of conversion values but an opposite effect in terms of removal rate. pH values in the range 3-4 resulted in the total inhibition of the oxidation process. Similar PA depletion rates were experienced regardless of the oxidation state of the catalyst (ferrous or ferric iron). Additionally, an attempt based on the classic Fenton's chemistry plus some other stages accounting for the Fe(II) regeneration from Fe(III) and the inefficient H2O2 decomposition was conducted to model the process.


Assuntos
Indústria Alimentícia , Hidroxibenzoatos/química , Resíduos Industriais/análise , Catálise , Peróxido de Hidrogênio/química , Ferro , Cinética , Oxirredução , Temperatura
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