An optimization and modeling approach for H2O2/UV‐C oxidation of a commercial non‐ionic textile surfactant using central composite design

BACKGROUND: Industrial surfactants are biologically complex organics that are difficult to degrade and may cause ecotoxicological risks in the environment. Until now, many scientific reports have been devoted to the effective treatment of surfactants employing advanced oxidation processes, but there is no available experimental study dealing with the optimization and statistical design of surfactant oxidation with the well‐established H₂O₂/UV‐C process. RESULTS: Considering the major factors influencing H₂O₂/UV‐C performance as well as their interactions, the reaction conditions required for the complete oxidation of a commercial non‐ionic textile surfactant, an alkyl ethoxylate, were modeled and optimized using central composite design‐response surface methodology (CCD‐RSM). Experimental results revealed that for an aqueous non‐ionic surfactant solution at an initial chemical oxygen demand (COD) of 450 mg L^?1, the most appropriate H₂O₂/UV‐C treatment conditions to achieve full mineralization at an initial pH of 10.5 were 47 mmol L^?1 H₂O₂ and a reaction time of 86 min (corresponding to a UV dose of 30 kWh m^?3). CONCLUSION: CCD allowed the development of empirical polynomial equations (quadratic models) that successfully predicted COD and TOC removal efficiencies under all experimental conditions employed in the present work. The process variable treatment time, followed by the initial COD content of the aqueous surfactant solution were found to be the main parameters affecting treatment performance, whereas the initial H₂O₂ concentration had the least influence on advanced oxidation efficiencies. The H₂O₂ concentration and surfactant COD were found to be more important for TOC abatement compared with COD abatement. Copyright © 2009 Society of Chemical Industry     

Advanced oxidation of cork‐processing wastewater using Fenton's reagent: kinetics and stoichiometry

This work evaluates Fenton oxidation for the removal of organic matter (COD) from cork‐processing wastewater. The experimental variables studied were the dosages of iron salts and hydrogen peroxide. The COD removal ranged from 17% to 79%, depending on the reagent dose, and the stoichiometric reaction coefficient varied from 0.08 to 0.43 g COD (g H₂O₂)^?1 (which implies an efficiency in the use of hydrogen peroxide varying from 17% to 92%). In a study of the process kinetics, based on the initial rates method, the COD elimination rate was maximum when the molar ratio [H₂O₂]_o:[Fe²⁺]_o was equal to 10. Under these experimental conditions, the initial oxidation rate was 50.5 mg COD dm^?3 s^?1 with a rate of consumption of hydrogen peroxide of 140 mg H₂O₂ dm^?3 s^?1, implying an efficiency in the use of the hydrogen peroxide at the initial time of 77%. The total amount of organic matter removed by Fenton oxidation was increased by spreading the H₂O₂ and ferrous salt reagent over several fractions by 15% for two‐fractions and by 21% for three‐fractions. Copyright © 2004 Society of Chemical Industry     

Preparation of poly(ether sulfone) hollow fiber UF membrane for removal of NOM

In this study, a high performance poly(ether sulfone) (PES) hollow fiber ultrafiltration (UF) membrane has been prepared for removal of natural organic matter (NOM). The membrane was spun from a dope solution containing PES/poly (vinyl pyrrolidone) (PVP 40K)/N‐methyl‐2‐pyrrolidone (NMP) by using a wet‐spinning process. Characterization of the membrane in terms of pure water flux, molecule weight cut‐off (MWCO), and retention for a model humic acid (HA) were conducted, and the fouling resistance was analyzed. The experimental results showed that the membrane had a pure water permeability of 20 × 10^?5 L m^?2 h^?1 Pa^?1 and a nominal MWCO of 6000 Da. The results also showed that the membrane retention for humic acid was over 97% and both productivity and selectivity for HA increased with increasing feed velocity. The PES membrane in this study exhibited a much lower fouling tendency than the commercial polysulfone membrane. SEM images revealed that the membrane had an outer dense skin and a porous inner surface. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 430–435, 2006     

Evaluation of membrane fouling and flux decline related with mass transport in nanofiltration of tartrazine solution

BACKGROUND: This work was carried out to investigate and analyze the interrelated dynamics of mass transport, membrane fouling and flux decline during nanofiltration of tartrazine. A combined application including pore diffusion transport model and a material balance approach was used to model an experimental flux data obtained from different values of pH (3, 5, 7 and 10), feed‐dye concentration (25, 100 and 400 mg L^?1), and transmembrane pressure (1200, 1800 and 2400 kPa). RESULTS: Almost 100% dye solution removal and a permeate flux of 135 L m^?2 h^?1 were obtained for 25 mg L^?1 and 1200 kPa at pH 10. At pH 10, lower membrane fouling was obtained due to the increase of electrostatic repulsion between anionic dye molecules and the more negatively charged membrane surface. Flux decline and membrane fouling increased together with transmembrane pressure and dye concentration. Fouling was found to be directly related to proportional‐permeation coefficient (k_O′) of dye which was identified as the solute passing into the permeate with respect to the amount transported into the membrane from the feed. CONCLUSIONS: For a decrease of pH (10 to 3) and transmembrane pressure (2400 to 1200 kPa) or an increase of feed‐dye concentration (25 to 400 mg L^?1), fewer dye molecules passed into the permeate with respect to the amount transported into the membrane from the feed. This situation depended mainly on the combined influences of the gel layer and fouling in the membrane. Copyright © 2010 Society of Chemical Industry     

Ozone/H2O2 Performance on the Degradation of Sulfamethoxazole

This work aims to analyze the contribution of H₂O₂ on ozonation of Sulfamethoxazole (SMX). A single ozonation was able to totally remove SMX. TOC and COD depletion rates after a transferred ozone dose of 60 mg/L was related to the formation and decomposition of H₂O₂. An increase on O₃ gas inlet concentration from 10 g/m³ to 20 g/m³ improved COD abatement from 11% to 36%. When the presence of H₂O₂ at the beginning of ozonation was tested, it was verified that COD and TOC degradation were enhanced, attaining maximum values of 76% and 32%, respectively, when compared with 35% and 15% reached in a single ozonation.     

Electrolytic reduction improves treatability of humic acids containing water streams

BACKGROUND: An understanding of the structure of humic acids is essential for their degradation or physical removal from wastewaters. This work aims at targeting the reactivity of these molecules by modifying their properties. Structural alterations were carried out by electrolytically reducing the solution containing humic acid in an electrolytic cell to convert them into less polar structures. RESULTS: Overall it was observed that electrolytic reduction of humic acids strongly facilitated their further treatability. First, the reduced forms of humic acids exhibited improved adsorption on activated carbon. For 1 kW h of electrical energy consumed during electrolytic reduction, the additional chemical oxygen demand (COD) adsorbed was 60 g for a synthetic humic acid solution. Similarly, the additional COD adsorbed (kW h)^?1 was found to be 35 g and 112 g for humic acid‐rich effluent and landfill leachate, respectively. In comparison with non‐reduced control samples, a 200‐fold decrease in the chloroform formation was observed when electrolytically reduced drinking water samples were supplemented with a chlorine dosage of 150 mg L^?1. Moreover, an enhanced membrane flux was obtained with electrically reduced samples, indicating their improved membrane filterability. CONCLUSION: The electrolyzed humus species were characterized by analyzing their surface tension and particle size. This work addresses an alternative technology for the treatment of water streams containing humic acids. Copyright © 2007 Society of Chemical Industry     

Study on the cleaning of new ultrafiltration spiral-woundmodules to prevent membrane fouling (including biological fouling)

A study of cleaning a Bulgarian OF 60 PAN spiral-wound module was carried out on an ultrafiltration unit(Millipore, USA). Chemical cleaning of the membrane with a 0.25% solution of sodium metabisulfite did not prevent biological fouling. When treated with a 1% solution of formaldehyde, membrane fouling was diminished and the ultrafiltrate obtained contained a significantly lower number of microorganisms and colloid formations including iron and humic acids. After treatment with the two cleaning agents, the membrane maintained its flux for the water studied within a range of 1.58 to 1.64 m³/m²/d. The effect on the contaminants to be removed was also found to be comparatively constant. Membrane selectivity remained constant at different permeate yields.     

Removal of ampicillin sodium in solution using activated carbon adsorption integrated with H2O2 oxidation

BACKGROUND: The removal of antibiotic ampicillin sodium using H₂O₂ and modified granular activated carbon (GAC) is discussed. Two types of modified activated carbons were used in experiment to catalyze ·OH production from H₂O₂. One was modified with base (NaOH; called B‐GAC), the other was modified with Fe(NO₃)₃ (Fe‐GAC) and the nominal Fe metal loading was 5 wt%. In the experiment, pH, contact time, dosage of activated carbon and H₂O₂ and initial concentration of ampicillin sodium were investigated to determine their influence on the removal efficiency. The stability of Fe‐GAC was also evaluated. RESULTS: With an initial ampicillin sodium concentration of 200 mg L^?1, 85.2% of chemical oxygen demand (COD) and 76.4% of total organic carbon (TOC) can be removed with 8.0 g L^?1 of B‐GAC and 80 mg L^?1 of H₂O₂ (at pH 5.0). For the Fe‐GAC/H₂O₂ process, with 5.0 g L^?1 of activated carbon and 80 mg L^?1 of H₂O₂, COD and TOC removal can be elevated to 91.2% and 79.5% (at pH 3.0), respectively. CONCLUSION: The integration of activated carbon and H₂O₂ treatment was more effective for the removal of ampicillin from aqueous solution than using activated carbon alone. In the process, adsorption played a dominant role and the addition of a small amount of H₂O₂ accelerated the reaction rate and improved the removal efficiency. pH also greatly affected removal efficiency. Copyright © 2011 Society of Chemical Industry     

Stable equilibrium shift of methane steam reforming in membrane reactors with hydrogen‐selective silica membranes

Equilibrium shifts of methane steam reforming in membrane reactors consisting of either tetramethoxysilane‐derived amorphous hydrogen‐selective silica membrane and rhodium catalysts, or hexamethyldisiloxane‐derived membrane and nickel catalysts is experimentally demonstrated. The hexamethyldisiloxane‐derived silica membrane showed stable permeance as high as 8 × 10^?8 mol m^?2 s^?1 Pa^?1 of H₂ after exposure to 76 kPa of vapor pressure at 773 K for 60 h, which was a much better performance than that from the tetramethoxysilane‐derived silica membrane. Furthermore, the better silica membrane also maintained selectivity of H₂/N₂ as high as 10³ under the above hydrothermal conditions. The degree of the equilibrium shifts under various feedrate and pressure conditions coincided with the order of H₂ permeance. In addition, the equilibrium shift of methane steam reforming was stable for 30 h with an S/C ratio of 2.5 at 773 K using a membrane reactor integrated with hexamethyldisiloxane‐derived membrane and nickel catalyst. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Separation of Humic Substances by Porous Ion-Exchange Membranes from Sulfonated Polysulfone

Abstract

Ultrafiltration involving sulfonated polysulfone membranes provides high efficiency for humic matter removal from water. The increase in ion-exchange capacity of the polymer matrix from 0.24 to 0.96 mmol SO₃H groups per 1 g of dry membrane increases the membrane pore diameter and its hydrophilicity, and thus the permeate flux from 0.05 to 3.69 m³/m²·d. In order to decrease the manufacturing cost, membranes from polysulfone and sulfonated polysulfone blends were investigated. It was shown that a one-to-one blend resulted in a membrane having similar antifouling properties to pure sulfonated polysulfone. Both membranes reject humic matter in the 91–98% range and show a flux decline of 5–30% as a result of surface fouling.     

Photo Assisted Fenton in a Batch and a Membrane Reactor for Degradation of Drugs in Water

Abstract

Some advanced oxidation processes (AOP's) such as Fenton H₂O₂/Fe²⁺, photo assisted Fenton UV/H₂O₂/Fe²⁺, UV photolysis, and photo assisted Fenton—like UV/O₂/Fe²⁺ have been tested for the degradation of Gemfibrozil in aqueous solution in a batch system and then in a membrane reactor. A nanofiltration/reverse osmosis type cross‐linked polyamide, UTC‐60 (Toray) membrane (19 cm²) was used. In the batch degradation tests, the gemfibrozil, used at 5 mg/L, was degraded by employing the four AOP's but numerous peaks of intermediates were observed at the HPLC. Indeed DOC analyses showed poor mineralization in the case of photolysis (3.1%) and UV/O₂/Fe (10%), while it was 62% using the photo assisted Fenton and 24% using the Fenton. Thus in the membrane reactor only the Fenton and the photo assisted Fenton were tested. Obtained results showed a drug degradation higher than 92%, a mineralization higher than 55%, and a membrane retention of the catalyst in solution higher than 95%.     

The Effect Of Preozonation,Ozone/Hydrogen Peroxide Treatment,And Nanofiltration On The Removal Of Organic Matter From Drinking Water

Pilot scale experiments were performed to evaluate the ability of ozonation, ozone/hydrogen peroxide treatment and nanofiltration to reduce levels of organic matter, mutagenicity, total adsorbable halogens, color and turbidity from purified and bank-filtered surface water rich with humic material.

Ozonation and ozone/hydrogen peroxide decreased the amount of organic material from drinking water by about 20 percent measured as TOC and COD_Mn. Color and turbidity level reductions were 49 and 11 percent, respectively. Ozonation reduced the AOX concentrations formed during postchlorination from 150 μgL^?1 to 75 μgL^?1. The addition of hydrogen peroxide further improved the removal to 37 and 26 μgL^?1 depending on the ratio of H₂O₂/O₃. The mutagenicity reduction followed the same pattern: without ozonation the chlorination-derived mutagenicity was 1,450 net revertant L^?1 after the ozonation 700 and after the H₂O₂/O₃ treatment from <100 to 400 net revertant L^?1 depending on the H₂O₂/O₃ ratio. Nanofiltration appeared to be the most effective way to remove organic material. The removal of TOC was 68%, COD_M 72%, color 90%, turbidity 68%, AOX 88%, and mutagenicity 85%.     

Effect of rheological properties of AlOOH sol on the preparation of Al2O3 nanofiltration membrane by sol-gel method

In order to directly prepare an High Flux Al₂O₃ nanofiltration membrane on an Al₂O₃ support with an average pore size of 4 μm, AlOOH sol was prepared with aluminum isopropoxide as the precursor, The effect of rheology on the dip-coating of AlOOH sol and the effect of viscoelasticity on the heat treatment of AlOOH gel film to prepare defect-free Al₂O₃ nanofiltration membrane were studied. The results indicate that AlOOH sol will increase its viscosity with the increase of the standing time. When the viscosity increases to a certain extent, the colloidal particles will gradually transform into gels, and change from Bingham fluid to Herschel-Bulkley pseudoplastic fluid. The thickness of the AlOOH gel film is related to the viscosity of the AlOOH sol. The flow viscosity of AlOOH sol should be about 0.0025～0.005 Pa·s, while the thickness of the AlOOH gel film after dip-coating is about 6.5～12 μm. The storage modulus and loss modulus of AlOOH gel film increase with the increase of aging time. Only when the storage modulus of the AlOOH gel is greater than the saturated vapor pressure of the solvent under normal pressure (0.1 MPa), it will not crack due to the evaporation of the sol during the heat treatment process. After the storage modulus exceeds 0.1 MPa, the surface of the heat-treated Al₂O₃ ceramic membrane is smooth and crack-free, the rejection rate for crystal violet dye is 99.8%, and its average pore size is 2.75 nm, that has the capability of nanofiltration. Due to the lack of intermediate layer, the pure water flux of the Al₂O₃ nanofiltration membrane is as high as 201.7 l.m^-2bar^-1h^-1, and the steady-state filtration flux is 48.7 l.m^-2bar^-1h^-1 when filtering 20 mg/l crystal violet solution. By controlling the rheological properties of AlOOH sol, a high flux Al₂O₃ nanofiltration membrane was prepared.     

Humic acid fouling in the membrane distillation process

This work investigates the extent of humic acid fouling during the membrane distillation process for water treatment. The effects of pH, ionic strength, and divalent ion on fouling were studied. The experiments were performed with a 0.22-μm PVDF flat-sheet membrane in a direct contact membrane distillation unit. Flux declines were negligible (less than 6%) for the ranges of humic acid concentration, ionic strength, and pH studied. The examination of the membrane surface by SEM revealed a thin deposit layer. The addition of divalent cations (Ca²⁺) into the solution considerably reduced flux when Ca²⁺ concentration exceeded the critical coagulation concentration. Ca²⁺ affected flux by forming complexes with humic acids and resulted in coagulation on the membrane surface. The normalized flux, J/J₀, was 0.57 after 18 h of operation when the CaCl₂ concentration was 3.775 mM. However, the deposit of humic acid coagulate on the membrane surface was loosely packed, and was rather easily removed. Rinsing of the fouled membrane with clean water and a 0.1 M NaOH solution gave 100% of flux recovery.     

Development of an All-ceramic Module with Silica Membrane Tubes for High Temperature Hydrogen Separation

Abstract

Heat resistant hydrogen selective membranes are desired for use as membrane reactors in low-temperature hydrogen production via the steam reforming of hydrocarbons, which are usually operated over 1000 K. In addition, developing a multi-tubular type of membrane unit that can process more reactants is becoming more and more important in order to realize the practical use of membrane reactors.

In this study, an all-ceramic module consisting of 6 silica membrane tubes with a comparatively large membrane area of around 0.04 m² was fabricated by a counter-diffusion chemical vapor deposition technique. As a result, the H₂/N₂ ideal separation factor and the H₂ permeance of the module were 1300 and 1.9 × 10^?7 mol·m^?2s^?1Pa^?1 at 873 K, respectively. In a 1000-hour thermal stability test for the silica membrane module, it was found that the H₂ permeance initially decreased by about 30% and then became steady under ΔP = 0.95 MPa at 773 K.     

Removal of Natural Organic Matter from Groundwater Using Advanced Oxidation Processes at a Pilot Scale Drinking Water Treatment Plant in the Central Banat Region (Serbia)

To improve water quality, a pilot-scale evaluation into upgrading the conventional treatment process was conducted. By following DOC content, UV₂₅₄ absorbance, SUVA and by-products formation, three oxidative pre-treatments were evaluated: pre-ozonation (2.2 g O₃/m³); O₃/H₂O₂ process (2.2 g O₃/m³; H₂O₂:O₃ = 1:2) and O₃/H₂O₂ process (2.2 g O₃/m³; H₂O₂:O₃ = 2:1). The second pre-treatment gave the best results, with a final average DOC content of 0.9 mg C/L, UV₂₅₄ absorbance of 0.06 cm^?1 and the lowest THMFP of 130 μg/L. UV₂₅₄ absorbance can serve as a proper indicator for predicting THM and HAA formation, yielding a correlation coefficient ≥ 0.90.     

Effect of dodeca‐tungstophosphric acid on morphology and performance of polyvinyl alcohol membrane for gas separation

In this article, organic/inorganic membrane was prepared for gas separation by incorporating dodeca‐tungstophosphric acid (PWA) into the base polymer. Flat‐sheet composite membranes were produced via dry‐phase inversion method. In the first stage, the effects of PWA concentration on morphology and performance of polyvinyl alcohol (PVA) membranes were elucidated. For this stage, the preparation of membranes was carried out at constant temperature of 40°C. The porosity of the prepared membrane was slightly increased with addition of PWA. By increasing the PWA concentration up to 6 wt % in the membrane recipe, the permeability of N₂, O and air was improved from 50,000 (for no addition of PWA) to around 160,000, 140,000, and 80,000 L m^?2 h^?1, respectively. For H this was enhanced from 110,000 to 230,000 L m^?2 h^?1. The ideal selectivity of the membrane was slightly improved for N₂/air (from 1 to 1.2). For N₂/O₂ pair, the initial drop (from 2.5 to 1.5) was followed by a slight increase (1.5–1.9). Moreover, the selectivity was decreased for H₂/air (from 2.8 to 1.8) and H₂/N₂ (from 2.2 to 1.7) by increasing the PWA concentration. The 10 wt % PVA membrane with 6 wt % PWA demonstrated superior performance compared with the other compositions. In summary, the presence of PWA in the casting solution results in lower flux for O₂ and higher selectivity for H₂/O₂ pair. In the second stage, the effects of solvent evaporation temperature (10, 27, 40, and 80°C) on morphology and performance of the membranes were studied. By increasing the temperature, the number and size of voids were increased. The permeation of gases was improved from 100,000 L m^?2 h^?1 (at 10°C) to 150,000 (O₂), 250,000 (air), 380,000 (N₂), and 600,000 L m^?2 h^?1 (H₂) by increasing the temperature up to 80°C. This increment resulted in selectivity alteration either increment or diminishment. The selectivity was changed from 1.3 to 3.2 (H₂/O₂), 0.8–2.5 (N₂/O₂), 1.2–2.4 (H₂/air), 0.6–1.5 (N₂/air) and 2.0–1.5 (H₂/N₂). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

钯复合膜的制备及其在氢气氮气分离中的应用

Thin palladium composite membranes were prepared by modified electroless plating method on a-alumina supports and a dense Pd/α-Al2O3 composite membrane with high hydrogen flux, good selectivity for hydrogen was obtained. It was tested in a single gas permeation system for hydrogen permeance and hydrogen selectivity over mtrogen. The hydrogen permeance of the corresponding membrane was ashigh as 2.45×10^-6mol·m^-2·s^-1.Pa^-1 and H2/N2 selectivityover700 at 623K and a pressure difference of 0.1MPa. The-main resistance of the composite membrane to H2 permeation lies in the aluminum ceramic support rather than the thin Pd layer.     

Oxidation of Parachloronitrobenzene in Dilute Aqueous Solution by O3 + UV and H2O2 + UV : A Comparative Study

This laboratory study was designed to investigate the degradation of 4-chloronitrobenzene ([CNB] = 2.4 × 10^?6 mol L^?1; pH = 7.5) by H₂O₂/UV and by O₃/UV oxidation processes which involve the generation of very reactive and oxidizing hydroxyl free radicals. The effects of the oxidant doses (H₂O₂ or aqueous O₃), liquid flow rate (or the contact time), and bicarbonate ions acting as OH· radical scavengers on the CNB removal rates were studied. For a constant oxidant dose, the results show that the O₃/UV system appears to be more efficient than the H₂O₂/UV system to remove CNB because of the greatest rate of OH· generation by ozone photodecomposition compared to H₂O₂ photolysis. However, for a given amount of oxidant decomposed, the H₂O₂/UV oxidant system was found to be more efficient than O₃/UV. Moreover, high levels of bicarbonate ions in solution (4 × 10^?3 mol L^?1) significantly decrease the efficiency of CNB removal by H₂O₂/UV and by O₃/UV oxidation processes.     

Fenton oxidation and adsorption pretreatment for superior biogas recovery from biomethanated spent wash

Abstract

A key task in alcohol distilleries is the effective treatment of biomethanated spent wash after biogas recovery. This colored washwater exhibits low biodegradability index (BI?<?0.2), high chemical oxygen demand (30,000?<?COD?<?40,000?mg/L), and recalcitrance to aerobic treatment. In this work, pretreatment of biomethanated distillery wastewater by Fenton oxidation was proposed for improved biogas recovery. The effects of temperature, solution pH, and H₂O₂ dosage on the efficacy of the oxidation process were studied. Using ferrous sulfate catalyst (36?mg/L) for diluted wastewater (BOD₅?=?81; COD?=?400?mg/L), 54% reduction in COD was achieved within 1?h in acidic medium (pH?=?3) at ambient temperature (T?=?30?°C). Post-oxidation, the BI value improved (0.33). After subsequent adsorption over activated carbon (loading 5%) for 1?h, COD reduction (70%), and BI value (0.43) improved further. Upon anaerobic treatment with 1% acclimatized biomass, 1?Nm³ of biogas (47% CH₄) was additionally formed per m³ of treated wastewater; without pretreatment, this value was 0.9?Nm³ (just 11% CH₄). Lastly, aerobic treatment was performed and the results were encouraging: BI?=?0.51 and COD reduction?=?94%. Many oxidation products were identified and first-order kinetic plots were made to describe COD conversion kinetics. In this way, useful insight on a plausible technique for valorization of biomethanated washwater was provided.