OXIDATION OF C.I. ACID ORANGE 7 WITH OZONE AND HYDROGEN PEROXIDE IN A HOLLOW FIBER MEMBRANE REACTOR

The degradation of C.I. Acid Orange 7 by ozone combined with hydrogen peroxide was carried out in a hollow fiber membrane reactor, and batch recirculation mode of aqueous phase was employed. The effect of initial pH, hydroxyl radical scavenger, hydrogen peroxide concentration, liquid recirculation rate, gas flow rate, and gaseous ozone concentration on the decolorization of C.I. Acid Orange 7 was investigated. The results showed that the decolorization of C.I. Acid Orange 7 fits the pseudo-half-order kinetic model. The rate constant increased with the increase of initial pH, hydrogen peroxide concentration, liquid recirculation rate, gas flow rate, and gaseous ozone concentration. The presence of hydroxyl radical scavenger inhibited the decolorization rate by over 50%. The combination of ozone with hydrogen peroxide achieved a higher COD removal efficiency than ozone alone in the membrane reactor.     

US/O3降解对硝基苯酚的影响因素及机理

研究了US（超声波）/O₃（臭氧）体系中气速、温度、pH值、对硝基苯酚初始质量浓度以及超声声强对对硝基苯酚降解速率的影响.研究结果表明：对硝基苯酚降解速率随着气速、超声声强及pH值（pH≤6时）的提高而提高,随着对硝基苯酚初始质量浓度的提高而下降,而反应温度及在pH>6时影响不明显.对硝基苯酚在US/O₃、US及O₃体系中的降解均遵循拟一级反应动力学规律,其反应速率常数分别为1.50×10^-3 s^-1、3.27×10^-5 s^-1和6.63×10^-4 s^-1,增强因子为216％,具有明显的协同效应,其协同效应主要是由臭氧在空化泡内热解产生•OH引起的.采用液相色谱（HPLC）、离子色谱(IC)、GC-MS等方法测定出对硝基苯酚降解的主要中间产物有邻苯二酚、邻苯醌、对苯二酚、对苯醌、苯酚、反丁烯二酸、顺丁烯二酸、草酸和甲酸等,并依此推导出对硝基苯酚的降解机理.     

Sequential Treatment of Tequila Industry Vinasses by Biopolymer-based Coagulation/Flocculation and Catalytic Ozonation

This article describes the study of the treatment of tequila industry vinasses based on the sequential application of coagulation-flocculation and heterogeneous catalytic ozonation. Coagulation-flocculation treatment used biopolymers to reduce the nondissolved organic matter and to reduce the degree of color units in effluent. Among six different substances, chitosan was the most efficient biopolymer to remove the highest chemical organic demand (COD) concentration (84.0%). The response surface technique was used to obtain the best attainable operation conditions of coagulation-flocculation process. The initial organic matter concentration, the reaction period and biopolymer concentration were selected as the independent variables. Two levels of analysis were performed: optimally and sensibility. The best reaction conditions were 3.23 × 10⁴ mg L^?1 of initial COD, 125.4 mg L^?1 of chitosan concentration, and 60.0 min of reaction. Ozonation process was performed on the effluent of coagulation-flocculation treatment. A batch reaction with 30 mg L^?1 of ozone in gaseous phase and a flow of 0.1 L min^?1 was implemented. Nickel oxide (100 mg L^?1) was used as the catalyst of the ozonation reaction. Twice larger COD concentration removal was obtained when the catalyst participated in the reaction compared to the so-called conventional ozonation (12.00% in conventional case vs 26.70% in catalyst presence). An ultraviolet-visible (UV-Vis) spectroscopy study was conducted to obtain a preliminary evaluation of organic compounds removal by effect of the sequential method proposed in this study. A significant total organics removal from the tequila industry wastewater (measured as the integral of UV-Vis spectrum) of 398.6 conditional units was obtained when the conventional ozonation was used after coagulation-flocculation, but that value was increased up to 1609.12 conditional units when the catalyst was inserted into the reaction.     

ELECTROCHEMICAL RECOVERY OF CHLORINE AND HYDROGEN FROM HYDROGEN CHLORIDE BY-PRODUCT PRODUCED IN THE PETROCHEMICAL INDUSTRY

Simultaneous production of hydrogen as an energy carrier and chlorine as a valuable chemical from recycled hydrogen chloride was investigated employing a lab-scale membrane electrolysis setup. The effects of various process parameters including current density (1–4 kA m^?2), cell temperature (45°–75°C), flow rate of hydrochloric acid feed (200–500 mL min^?1), and concentration of acid (18–21 wt.%) on the cell voltage and chlorine current efficiency (ChCE) were studied. The Taguchi design of experiments (L₁₆ array) was employed to design the minimum number of experiments necessary to fully study the process. A filter press type cell of 10 cm² surface area comprising a DSA anode, an alloy of predominantly nickel cathode and Nafion 115 membrane, was used. It was observed that increasing anolyte flow rate, anolyte concentration, or cell temperature caused a decrease in cell voltage and an increase in ChCE, while increasing current density linearly increased cell voltage and decreased ChCE.     

Biosorption of Direct Red 28 (Congo Red) from Aqueous Solutions by Eggshells: Batch and Column Studies

The feasibility of using eggshells as a low-cost biosorbent for the removal of Direct Red 28 (DR 28) from aqueous solutions was studied in batch and dynamic flow modes of operation. The effect of biosorption process variables such as particle size, solution pH, initial dye concentration, contact time, temperature, feed flow rate, and bed height were investigated. Both the Langmuir and Freundlich isotherm models exhibited excellent fit to the equilibrium biosorption data. Optimum pH (6.0), particle size (<250 µm), initial dye concentration (50 mg g^?1), temperature (313 K), and contact time (240 min) gave maximum monolayer biosorption capacity of 69.45 mg g^?1 which was higher than those of many sorbent materials. Pseudo-second-order kinetic model depicted the biosorption kinetics accurately. Thermodynamic study confirmed the spontaneous and endothermic nature of the biosorption process. Breakthrough time increased with increase in the bed height but decreased with increase in flow rate. Overall, batch and continuous mode data suggest the applicability of eggshells as an environment friendly and efficient biosorbent for removal of DR 28 from aqueous media.     

Removal of Rhodamine B Dye Using Activated Carbon Prepared from Palm Kernel Shell and Coated with Iron Oxide Nanoparticles

The efficacy of activated carbon prepared from Palm Kernel Shell (PKSAC) from agriculture biomass and coated with magnetic nanoparticle (Fe₃O₄) in the removal of Rhodamine B dye was investigated. Adsorption experiments were carried out at various initial pH, adsorbent dosage, initial dye concentration, particle size, and temperature. Kinetic analyses were conducted using pseudo first order, pseudo second order and intra particle diffusion models. However, the regression results showed that the adsorption kinetics was represented more accurately by the pseudo second order model. The pseudo second order kinetic constant obtained was 1.7 × 10^?4 min^?1 at 323 K when 200 mg L^?1 dye concentration was used. The equilibrium data were well described by both Langmuir and Freundlich isotherm models. The Langmuir adsorption capacity was 625 mgg^?1. The rate of adsorption improved with increasing temperature and the process was endothermic with ΔH value assessed at 80 kJmol^?1. Results obtained reveal that activated carbon prepared from Palm Kernel Shell coated with magnetic nanoparticle from agriculture biomass can be an attractive option for dye removal from industrial effluent.     

Extraction separation of toluene/cyclohexane with hollow fiber supported ionic liquid membrane

A supported liquid membrane with ionic liquid was used for the separation of toluene/cyclohexane. The interactions of ionic liquid with toluene and cyclohexane were calculated and experimentally studied by quantum chemical calculation and liquid-liquid extraction process. The results showed [BPy][BF₄] have stronger interaction with toluene than that with cyclohexane. The selectivity of SILM processes was larger than 10 at the temperature of 323 K and the flow rate of 13.5 mL·min^?1 on both shell side and lumen side. Due to the higher viscosity of IL, SILM process had good long-term stability. As the effects of mass transfer driving force of SILM process, the flux and removal efficiency increased with increase of initial toluene concentration, while the selectivity decreased because of the competitive transport. Base on the resistance in-series model and experimental results, the mass transfer resistance was mainly lay liquid membrane phase. The influence of flow rates on both sides was slight. The higher temperature could enhance the mass transfer performance significantly. The removal efficiency increased from 28.2% to 45.1% with the increasing of operation temperature from 298 K to 323 K.     

Rapid Removal of Nitrobenzene in a Three-Phase Ozone Loaded System with Gas–Liquid–Liquid

This study explores the removal rate of nitrobenzene (NB) using a new gas–liquid–liquid (G–L–L) three-phase ozone-loaded system consisting of a gaseous ozone, an aqueous solvent phase, and a fluorinated solvent phase (perfluorodecalin, or FDC). The removal rate of NB was quantified in relation to six factors including (1) initial pH, (2) initial NB dosage, (3) gaseous ozone dosage, (4) free radical scavenger, (5) FDC pre-aerated gaseous ozone, and (6) reuse of FDC. NB removal rate is positively affected by the first three of these factors. Compared with the conventional gas–liquid (water) (G–L) two-phase ozonation system, the free radical scavenger (tertiary butyl alcohol) has much less influence on the removal rate of NB in the G–L–L system. The FDC-loaded ozone acts as an ozone reservoir and serves as the main reactive phase in the G–L–L three-phase system. The reuse of FDC has little influence on the removal rate of NB. These experimental results suggest that the oxidation efficiency of ozonation in the G–L–L three-phase system is better than that in the conventional G–L two-phase system.     

Enhancement of Ozone Mass Transfer by Stainless Steel Wire Mesh and Its Effect on Hydroxyl Radical Generation

ABSTRACT

In order to improve the mass transfer efficiency of ozone in water, stainless steel wire mesh (SSWM) corrugated structure was packed into a microbubble ozone reactor to enhance the mass transfer efficiency. The results showed that the SSWM/O₃ system could effectively improve the mass transfer efficiency. When the concentration of ozone in the liquid phase reached a stable state, it was about 21 mg/L, which was about 14% higher than that of ozone alone; the apparent mass transfer coefficient (K_La) was 0.7255 min^?1, which was about 51% higher than that by ozone alone systems. The hydroxyl radicals in the SSWM/O₃ system were more generated than that of ozone alone. After 6 min of operation, the concentration of hydroxyl radicals increased by 60 µmol/L compared with that in ozone alone system. The Chemical Oxygen Demand (COD) removal efficiency of biologically treated leachate by SSWM/O₃ system was about 10% higher than that of ozone alone system after 120 min of reaction. The effects of pressure, temperature, ozone inlet concentration, and flow rates on the ozone concentration in the liquid phase and the generation of hydroxyl radicals were also investigated. The results indicated that reactor pressure has little effect on ozone concentration in liquid phase, but increasing pressure helps to generate ·OH; ozone concentration and ·OH generation in liquid phase increase with the increase of inlet ozone concentration and flow rate; ozone concentration in the liquid phase decreases with the increase of temperature, but ·OH generation increases with the increase of temperature. Our results indicate that the system consisting of SSWM and microbubble column reactor is an efficient process for the intensification of ozone-based advanced oxidation processes.     

PHENOLIC WASTEWATER TREATMENT BY SUPPORTED LIQUID MEMBRANE USING DIFFERENT COOKING OILS AS LIQUID MEMBRANE

Transport of phenol through a flat sheet supported liquid membrane (SLM) containing cooking oil as liquid membrane (LM) was investigated. Factors affecting permeation of phenol such as membrane phase, support material, feed phase pH, stripping phase concentration, stirring speed, and initial concentration of phenol were studied. It was found that these parameters strongly influence phenol removal efficiency; PTFE membrane as support material, grape seed oil as liquid membrane, feed pH of 2.0, initial phenol concentration of 100 mg/L, stirring speed of 350 rpm, and 0.2 M sodium hydroxide as effective stripping agent were found as the best conditions for greater phenol transport. Under these conditions, permeability was found to be 7.46 × 10^?6 m/s. After 10.5 h, phenol was completely removed from the feed phase to strip phase. According to stability experiments, it was observed that the SLM is stable after 22 h. Thus, the use of cheap, nontoxic, and naturally oil as a novel and green membrane for recovery of phenol from wastewater was demonstrated.     

Ozonolysis Post-Treatment of Anaerobically Digested Distillery Wastewater Effluent

ABSTRACT

In this study, the ozonolysis of real anaerobically digested distillery wastewater (DWW) was carried out. The effect of operating parameters, such as pH, initial concentration, and ozone dosage, on the efficiency of ozone utilization, color removal, and sludge solubilization was studied. The highest ozone utilization of 99% was observed at the highest initial concentration (COD of 3000 mg/L) and lowest ozone flowrate (22.5 mg O₃/L/min), but with a very low color reduction of 20%, after 60 minutes of ozonolysis. To achieve a higher color reduction >80% and at ozone utilization >95%, the DWW had to be diluted twice (COD 1500 mg/L), and the flowrate doubled to 45 mg O₃/L/min. The reduction in color signified the oxidation of the color causing biorecalcitrant aromatic melanoidin compounds. This was confirmed by the 47% reduction in ultraviolet absorbance at 254 nm indicating the breakdown of the complex aromatic compounds into low molecular weight organics. Moreover, increases in average oxidation state from ?0.6 to ?0.2 suggested a decline in aromaticity and formation of easily biodegradable aliphatic compounds. The ozonolysis process was found to follow the first-order reaction kinetic model with the highest rate constant of 0.0326 min^?1 obtained. A reduction in suspended COD by 88% indicated solubilization of the sludge contained in the effluent.     

Determination of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) Ions by FAAS after Separation/Preconcentration using Amberlite XAD‐1180 Chelating Resin Chemically Modified with o‐Aminophenol

Abstract

The use of a newly synthesized chelating resin with an o‐aminophenol–type functional groups and Amberlite XAD‐1180–type supporting material for separation/preconcentration of trace metal ions from various water samples was described. Amberlite XAD‐1180‐o‐aminophenol chelating resin (XAD‐o‐AP) was synthesized using Amberlite XAD‐1180 resin as solid support and o‐aminophenol as the chelating ligand. The determination of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) ions was made by flame atomic absorption spectrometry (FAAS). Studying with model solutions for the optimization of the method was based on the measurement of recovery values (between 92–106%) of the analyte elements. Some analytical parameters such as pH (6.0), volume of the sample (～250 mL), effect of matrix ions, flow rates of the sample (2.5 mL min^?1) and elution solutions (2.5 mL min^?1), concentration, type and volume of the eluent (4 mol L^?1 HNO₃, 20 mL) were investigated. The detection limit (3s/b, n=20) and the relative standard deviation (n=7) of the method were found to be in the range 0.9–4.3 µg L^?1 and 4.4–5.5%, respectively. The proposed method was successfully applied to the real samples such as wastewater, boiler feeding water and a certified reference material (Estuarine water, LGC 6016).     

Vapor and Liquid Phase Ozonation of Benzene

A comparative study is made of the benzene-ozone reaction in the gaseous and aqueous phase reactors at atmospheric pressure and 25°C. The vapor phase ozonation of benzene is first order in ozone and independent of benzene concentration. In distilled water (pH ranging from 5.2 to 5.4), the reaction is one-half order with respect to both concentrations of dissolved benzene and ozone. The overall rate constants are 0.0011 and 2.67 s^?1, respectively, in the vapor and liquid phase reactions. Results of this study suggest that it is technically feasible to remove benzene from a gas stream by the ozonation process, although the reaction rate is slow.     

Abatement of 4-Chlorophenol in Aqueous Phase by Ozonation Coupled with a Sequencing Batch Biofilm Reactor (SBBR)

The aim of this work was to assess the mineralization of 100 and 200 mg L^?1 4-chlorophenol (4-CP) solutions by ozonation-biological treatment. The results show that starting from a 4-CP initial concentration from 100 to 500 mg L^?1 and using an ozone flow rate of 5.44 and 7.57 g h^?1, 4-CP was completely removed. A kinetic constant around 9·10^?2 min^?1 was calculated for the ozone direct attack. The biodegradability (BOD₅/COD) of the pre-ozonated solutions increased from 0 until a range between 0.2–0.37. The combination of the ozonation and aerobic biological treatment in an aerobic sequencing batch biofilm reactor (SBBR) gave an abatement of more than 90% of the initial TOC.     

Removal of Cyanide from Liquid Waste by Electrochemical Oxidation in a New Cell Design Employing a Graphite Anode

Removal of CN^? from liquid solutions was studied experimentally by an anodic oxidation technique under various operating conditions. A new cell configuration was used, the cell consists of four vertical graphite rod anodes distributed at 90° on the circular circumference at a distance of 3 cm from the wall and surrounded by two cylindrical stainless steel screen cathodes from the inner and the outer side. Parameters investigated are the initial concentration of cyanide ions, applied current density, initial pH of the electrolyte, and electrolyte conductivity. All parameters were investigated at an operating time of 3 h. The % removal increased upon increasing the applied current density, increasing the electrolyte conductivity, and decreasing the initial concentration of CN^?. Increasing initial pH from 4 to 8 increased the % removal by a factor ranging from 55 to 73%, further increase of pH up to 12 slightly increased the % removal (3–8%).

Application of the present electrochemical reactor in treating cyanide containing effluents from different industries was highlighted.     

Enhancing Biodegradability of Textile Wastewater by Ozonation Processes: Optimization with Response Surface Methodology

ABSTRACT

In this study, an ozonation process was used to increase biodegradability of textile wastewater by considering chemical oxygen demand (COD) and color removal. Response surface methodology was applied in order to determine the significance of independent variables which are initial pH, reaction time and ozone dose. While a biological oxygen demand (BOD)/COD rate of 0.315 was obtained at optimum conditions, which are pH 9, 75 min of reaction time and 26 mg/L ozone dose, color and COD removal was obtained at 74% and 39%, respectively. BOD/COD ratio value increased from 0.18 to 0.32 by ozonation process. In addition, k coefficient for BOD also increased from 0.21 to 0.30 d^?1.     

Production of the fungal exopolysaccharide scleroglucan by cultivation of Sclerotium glucanicum in an airlift reactor with an external loop

Sclerotium glucanicum NRRL 3006 was cultivated in a 120 dm³ working volume airlift reactor with external recirculation loop for the production of the exopolysaccharide (EPS), scleroglucan. When culture pH was not controlled EPS production, at a range of air flow rates, was poor (<2 kg m^?3). Biomass formation generally increased with increasing aeration rate. When culture pH was controlled at 4·5 ± 0·2 EPS production was maximal at an air flow rate of 100 dm³ min^?1 and fell as air flow rate decreased. Operation of the reactor at a high (100 dm³ min^?1) air flow rate for the early part of the process (up to 96 h), followed by a low air flow rate (20 dm³ min^?1), led to reduced biomass and oxalate formation, and a slight increase in EPS concentration relative to operation at a constant air flow rate of 100 dm³ min^?1. EPS production in this pneumatically-agitated reactor was equal to the highest levels reported in small-scale stirred tank reactors.     

Efficiency and Mechanism of Ciprofloxacin Hydrochloride Degradation in Wastewater by Fe3o4/Na2S2O8

ABSTRACT

The nanosized Fe₃O₄ catalyst was synthesized via a modified reverse coprecipitation method and characterized by means of a scanning electron microscope (SEM) and an X-ray diffraction (XRD) analysis instrument. The degradation efficiency and reaction rate of Fe₃O₄ in activating sodium persulfate used to degrade ciprofloxacin were determined from the catalyst dosage, oxidant concentration, and initial pH. The results showed that under the optimum conditions of a catalyst dosage of 2.0 g·L^?1, a sodium persulfate concentration of 1.0 g·L^?1, and an initial pH of 7, the degradation rate of ciprofloxacin was 93.73%, the removal rate of total organic carbon was 78%, and the first-order reaction constant was 0.06907 min^?1 within 40 min. It was also demonstrated that the reactive oxygen species in the Fe₃O₄/sodium persulfate catalytic system were mainly composed of SO₄^– and supplemented by OH· and HO₂· using probe compounds such as ethanol, tertiary butanol, and benzoquinone.     

Ozonation of Reactive Orange 122 Using La3+-Doped WO3/TiO2/Sep Photocatalyst

La³⁺/WO₃/TiO₂/sep composites have been prepared by the sol–gel method. The degradation of dye was studied under the influence of various operational parameters such as initial pH, amounts of catalyst, concentrations of the dye, and ozone flow rate. The mineralization of Reactive Orange 122 has been confirmed by chemical oxygen demand measurements. The color removal of dye was found to follow a pseudo–first-order kinetics. Maximum color and chemical oxygen demand removal were 99.9% and 90% respectively, at a dye concentration of 200 mg/L, ozone flow rate of 2.0 L/min., 0.05 g/L weight of catalyst, and pH of 6.9 in 4 h. In addition, the catalyst was characterized by X-ray diffraction spectra, Fourier-Transform Infrared Spectroscopy, scanning electron microscopy, and a transmission electron microscope. This work could be a good candidate as a practical application for photocatalytic dye degradation.     

Facilitated Transport of Cd(II) Through a Supported Liquid Membrane with Aliquat 336 as a Carrier

Selective removal of cadmium from wastewaters is very important, because cadmium is toxic for the environment and for human health. This work is a comprehensive study on the selective removal of Cd(II) from aqueous solutions by using a co-current flow flat sheet supported liquid membrane system. 4.4 × 10^?4 M Cd(II) concentration was used as a feed solution in the experiments. Toluene containing Aliquat 336 was used as the membrane liquid in the membrane system. Parameters such as the properties of feed and stripping solutions, carrier concentration, and flow rate, which have roles in transport of Cd(II) ions, were optimized. The efficiency of the system is expressed in terms of permeability and flux values, and transport efficiency. The optimum process conditions for the Cd(II) transport are experimentally found as follows: The feed solution as 2 M HCl, the carrier concentration as 0.1 M Aliquat 336, the stripping solution as 0.06 M EDTA, and the flow rates for the feed and stripping solutions as 50 mL/min and 80 mL/min, respectively. Under these conditions, the Cd(II) transport efficiency is found to be 82%.