Analysis of the Capacity of the Fenton Process for the Treatment of Polluted Wastewater from the Leather Dyeing Industry.

In this work, the capacity of the Fenton oxidation process for the degradation of color and organic matter contained in the wastewater generated in the leather dyeing stage (WWDS) of an industrial tannery was evaluated. The wastewater characteristics included, among others, high toxicity (lethal concentration for Artemia salina, 24 h test, 50% of population = 93.71 ppm), high dye concentration (36 mg/L, yellow color), high chromium concentration (3.34 mg/L), and low biodegradability index (BOD5/COD ratio = 0.083). From an experimental design, the response surface methodology, and the multiobjective optimization analysis, the following optimal operating conditions were established: initial pH = 3.15, [Fe2+] = 0.981 mM, and [H2O2] = 5.38 mM. After 10 min of oxidation (determined from kinetic studies), it reached approximately 97% decolorization, COD reduction of approximately 82%, and TOC mineralization of approximately 92%. A synergistic effect of Fenton's reagents for TOC removal (S TOC = 0.8) and decolorization (S CN = 0.28) of the WWDS under study was confirmed experimentally. An increase in the biodegradability index, to a value of approximately 0.3, was confirmed. The cost of the treatment was estimated at 0.0112 USD/m3. Thus, the Fenton oxidation process allowed compliance with current Colombian environmental regulations and considerably improved the biodegradability and toxicity characteristics of the studied industrial effluent. It can be considered as an efficient alternative, easy to carry out on an industrial batch scale, and economically viable for the treatment of wastewater from the leather dyeing stage of an industrial tannery.

Integration of environmental and economic performance of Electro-Coagulation-Anodic Oxidation sequential process for the treatment of soluble coffee industrial effluent.

This study examined a sequential Electro-Coagulation-Anodic Oxidation (EC-AO) process, using low-cost electrodes (EC: iron/stainless steel and AO: graphite/stainless steel), as an alternative for the treatment of soluble coffee industrial effluent (a complex mixture of organic macromolecules). Process operational parameters were optimized using experimental design, ANOVA, the response surface methodology, and a constrained nonlinear optimization algorithm. Experimental results allow discussing the role of graphite electrode, the mineralization via hydroxyl radicals and chlorine species (mainly as HClO and ClO- as defined from pH conditions and equilibrium calculations). EC-AO treatment allows achieving ca. 97% decolorization, as well as 72% and 65% of COD and TOC removal, respectively, with total operation costs of 10.81 USD/m3. The Molecular Weight Distribution (MWD) analysis showed that during the EC step, contaminants with molecular weight > 30 kDa were effectively decomposed. In contrast, AO was quite efficient in the mineralization of contaminants with MW in the range of 5 to 10 kDa. A kinetic analysis of EC-AO allowed defining the operation time of ca. 160 min required to meet permissible discharge limits for soluble coffee effluents, established by Colombian legislation; and obtaining COD and TOC degradation rate laws for upcoming studies on process conceptual design. Finally, the EC-AO process yielded an oxidized (AOS = 0.687), biocompatible (BOD5/COD = 0.41) not toxic effluent.

Optimization and toxicity assessment of a combined electrocoagulation, H2O2/Fe2+/UV and activated carbon adsorption for textile wastewater treatment.

In this study, the potential application of sequential Electrocoagulation + Fenton (F) or Photo-Fenton (PF) + Active carbon adsorption (EC + F/PF + AC) processes were analyzed as alternatives for the treatment of an industrial textile wastewater resulting from an industrial facility located in Medellín (Colombia). In order to maximize the organic matter degradation, each step of the treatment was optimized using the Response Surface Methodology. At first, the optimal performance of EC was achieved with Fe electrodes operating at pH = 7, jEC = 10 mA/cm2 and 60 rpm, during 10 min of electrolysis. At these conditions, EC let to remove 94% of the dye's color, 56% of the COD and 54% of the TOC. Next, sequentially applied Fenton or photo-Fenton process (i.e., EC + F/PF), operating at the optimized conditions (pH = 4.3, [Fe2+] = 1.1 mM, [H2O2] = 9.7 mM, stirring velocity = 100 rpm and reaction time = 60 min.), improved the quality of the treated effluent. The EC + F let to achieve total color reduction, as well as COD and TOC removals of 72 and 75%, respectively. The EC + PF reached 100% of color, 76% of COD and 78% of TOC reductions. The EC + F/PF processes were more efficient than EC in elimination of low molecular weight (<5 kDa) compounds from wastewater. Moreover, the BOD5/COD ratio increased from 0.21 to 0.42 and from 0.21 to 0.46 using EC + F and EC + PF processes, respectively. However, EC + F/PF were not fully effective for the removal of acute toxicity to Artemia salina: 20% and 60% of reduction in toxicity using EC + F and EC + PF, respectively, comparing to very toxic (100%) raw textile wastewater. Thus, activated carbon adsorption was applied as an additional step to complete the treatment. After AC adsorption, the acute toxicity decreased to 10% and 0% using EC + F and EC + PF, respectively. The total operational costs, including chemical reagents, electrodes, energy consumption and sludge disposal, were of 1.65 USD/m3 and 2.3 USD/m3 for EC + F and EC + PF, respectively.

Integrated electrocoagulation-electrooxidation process for the treatment of soluble coffee effluent: Optimization of COD degradation and operation time analysis.

Soluble coffee production generates wastewater containing complex mixtures of organic macromolecules. In this work, a sequential Electrocoagulation-Electrooxidation (EC-EO) process, using aluminum and graphite electrodes, was proposed as an alternative way for the treatment of soluble coffee effluent. Process operational parameters were optimized, achieving total decolorization, as well as 74% and 63.5% of COD and TOC removal, respectively. The integrated EC-EO process yielded a highly oxidized (AOS = 1.629) and biocompatible (BOD5/COD ≈ 0.6) effluent. The Molecular Weight Distribution (MWD) analysis showed that during the EC-EO process, EC effectively decomposed contaminants with molecular weight in the range of 10-30 kDa. In contrast, EO was quite efficient in mineralization of contaminants with molecular weight higher than 30 kDa. A kinetic analysis allowed determination of the time required to meet Colombian permissible discharge limits. Finally, a comprehensive operational cost analysis was performed. The integrated EC-EO process was demonstrated as an efficient alternative for the treatment of industrial effluents resulting from soluble coffee production.

Coagulation-flocculation sequential with Fenton or Photo-Fenton processes as an alternative for the industrial textile wastewater treatment.

In this study, the industrial textile wastewater was treated using a chemical-based technique (coagulation-flocculation, C-F) sequential with an advanced oxidation process (AOP: Fenton or Photo-Fenton). During the C-F, Al2(SO4)3 was used as coagulant and its optimal dose was determined using the jar test. The following operational conditions of C-F, maximizing the organic matter removal, were determined: 700 mg/L of Al2(SO4)3 at pH = 9.96. Thus, the C-F allowed to remove 98% of turbidity, 48% of Chemical Oxygen Demand (COD), and let to increase in the BOD5/COD ratio from 0.137 to 0.212. Subsequently, the C-F effluent was treated using each of AOPs. Their performances were optimized by the Response Surface Methodology (RSM) coupled with a Box-Behnken experimental design (BBD). The following optimal conditions of both Fenton (Fe2+/H2O2) and Photo-Fenton (Fe2+/H2O2/UV) processes were found: Fe2+ concentration = 1 mM, H2O2 dose = 2 mL/L (19.6 mM), and pH = 3. The combination of C-F pre-treatment with the Fenton reagent, at optimized conditions, let to remove 74% of COD during 90 min of the process. The C-F sequential with Photo-Fenton process let to reach 87% of COD removal, in the same time. Moreover, the BOD5/COD ratio increased from 0.212 to 0.68 and from 0.212 to 0.74 using Fenton and Photo-Fenton processes, respectively. Thus, the enhancement of biodegradability with the physico-chemical treatment was proved. The depletion of H2O2 was monitored during kinetic study. Strategies for improving the reaction efficiency, based on the H2O2 evolution, were also tested.

Prediction of acid hydrolysis of lignocellulosic materials in batch and plug flow reactors.

This study unifies contradictory conclusions reported in literature on acid hydrolysis of lignocellulosic materials, using batch and plug flow reactors, regarding the influence of the initial liquid ratio of acid aqueous solution to solid lignocellulosic material on sugar yield and concentration. The proposed model takes into account the volume change of the reaction media during the hydrolysis process. An error lower than 8% was found between predictions, using a single set of kinetic parameters for several liquid to solid ratios, and reported experimental data for batch and plug flow reactors. For low liquid-solid ratios, the poor wetting and the acid neutralization, due to the ash presented in the solid, will both reduce the sugar yield. Also, this study shows that both reactors are basically equivalent in terms of the influence of the liquid to solid ratio on xylose and glucose yield.

Decolorization and mineralization of Diarylide Yellow 12 (PY12) by photo-Fenton process: the Response Surface Methodology as the optimization tool.

The Response Surface Methodology (RSM) was applied as a tool for the optimization of the operational conditions of the photo-degradation of highly concentrated PY12 wastewater, resulting from a textile industry located in the suburbs of Medellin (Colombia). The Box-Behnken experimental Design (BBD) was chosen for the purpose of response optimization. The photo-Fenton process was carried out in a laboratory-scale batch photo-reactor. A multifactorial experimental design was proposed, including the following variables: the initial dyestuff concentration, the H(2)O(2) and the Fe(+2) concentrations, as well as the UV wavelength radiation. The photo-Fenton process performed at the optimized conditions resulted in ca. 100% of dyestuff decolorization, 92% of COD and 82% of TOC degradation. A kinetic study was accomplished, including the identification of some intermediate compounds generated during the oxidation process. The water biodegradability reached a final DBO(5)/DQO = 0.86 value.

The Box-Benkhen experimental design for the optimization of the electrocatalytic treatment of wastewaters with high concentrations of phenol and organic matter.

In this work, the Box-Benkhen experimental Design (BBD) was applied for the optimization of the parameters of the electrocatalytic degradation of wastewaters resulting from a phenolic resins industry placed in the suburbs of Medellin (Colombia). The direct and the oxidant assisted electro-oxidation experiments were carried out in a laboratory scale batch cell reactor, with monopolar configuration, and electrodes made of graphite (anode) and titanium (cathode). A multifactorial experimental design was proposed, including the following experimental variables: initial phenol concentration, conductivity, and pH. The direct electro-oxidation process allowed to reach ca. 88% of phenol degradation, 38% of mineralization (TOC), 52% of Chemical Oxygen Demand (COD) degradation, and an increase in water biodegradability of 13%. The synergetic effect of the electro-oxidation process and the respective oxidant agent (Fenton reactant, potassium permanganate, or sodium persulfate) let to a significant increase in the rate of the degradation process. At the optimized variables values, it was possible to reach ca. 99% of phenol degradation, 80% of TOC and 88% of COD degradation. A kinetic study was accomplished, which included the identification of the intermediate compounds generated during the oxidation process.

Treatment of automotive industry oily wastewater by electrocoagulation: statistical optimization of the operational parameters.

An electrocoagulation process was used for the treatment of oily wastewater generated from an automotive industry in Medellín (Colombia). An electrochemical cell consisting of four parallel electrodes (Fe and Al) in bipolar configuration was implemented. A multifactorial experimental design was used for evaluating the influence of several parameters including: type and arrangement of electrodes, pH, and current density. Oil and grease removal was defined as the response variable for the statistical analysis. Additionally, the BOD(5), COD, and TOC were monitored during the treatment process. According to the results, at the optimum parameter values (current density = 4.3 mA/cm(2), distance between electrodes = 1.5 cm, Fe as anode, and pH = 12) it was possible to reach a c.a. 95% oils removal, COD and mineralization of 87.4% and 70.6%, respectively. A final biodegradability (BOD(5)/COD) of 0.54 was reached.

Multifactorial optimization of the decolorisation parameters of wastewaters resulting from dyeing flowers.

This work deals with the treatment of the wastewaters resulting from the process of dyeing flowers. In some local cases for growing flowers near to Medellín (Colombia), wastewater color was found to be one of the main problems in meeting local effluent standards. Wastewaters were treated by photodegradation process (which includes photocatalysis) to achieve the degradation of dyes mixture and organic matter in the wastewater. A multifactorial experimental design was proposed, including as experimental factors the following variables: pH, and the concentration of both catalyst (TiO(2)) and hydrogen peroxide (H(2)O(2)). According to the obtained results, at the optimized variables values, it is possible to reach a 99% reduction of dyes, a 76.9% of mineralization (TOC) and a final biodegradability of 0.834. Kinetic analysis allows proposing a pseudo first order reaction for the reduction, the mineralization, and the biodegradation processes.

Removal of NOx from lean exhaust gas by storage/reduction on H3PW12O40 x 6H2O supported on Ce(x)Zr4-xO8.

We have demonstrated the interest of using Zr-Ce mixed oxides as supports for the system H3PW12O40 x 6H2O (HPW) and Pt for the storage (absorption into HPW and adsorption on Zr-Ce support)-reduction of NOx. Zr-Ce oxides adsorb NOx (mainly NO2) as nitrates, which are desorbed thermally as NO2 and NO (12 mg of NOx x g(-1)). On (HPW-Pt)/Zr-Ce system, NO and NO2 are stored equimolarly by substitution of water molecules of the HPW structure. The Zr/Ce support molar ratio has an important influence on the quantity of NOx stored with a maximum for the system Zr/Ce = 0.5. The presence of Pt has no influence on storage capacity but rather on its efficiency, and it is essential when reducing. Pt strongly accelerates both NOx desorption and reduction processes. Reduction of NOx occurs with H2, CO, or an H2/CO mixture. With H2, NO2 is reduced to NO. With CO, it seems reasonable that the mechanism of NO2 reduction concerns its reaction with CO to produce CO2 and NO. Addition of H2 to CO accelerates the reduction process. However, the difference between NOx stored and desorbed implies also the presence of another reduction step. This could be related to an NO interaction with an active site which produces its decomposition with nitrogen as product. The catalytic system proposed is highly selective since no N2O formation was detected.