Decolorization and degradation of acid dye with immobilized titania nanoparticles

This paper addresses the decolorization and degradation of acid dye by a heterogeneous photocatalytic process using immobilized nano-sized TiO₂ particles as the photocatalyst. Sackcloth fiber was used as a support to immobilize the nano-sized TiO₂ photocatalyst. The structural properties of the immobilized photocatalyst were characterized by XRD, SEM and EDX. UV–Vis absorption spectroscopy and the measurement of the chemical oxygen demand (COD) were also used for the process performance studies. The XRD results did not show significant changes in the structure of P25 as a consequence of the immobilization procedure. The formation of titania crystallites in the sackcloth fiber was confirmed by SEM/EDX. The photocatalytic activities of TiO₂-coated sackcloth fiber catalyst were evaluated using Acid Black 26 as a model organic contaminant and using UV-A radiation. Experimental results showed that after 60 min, the degradation of Acid Black 26 with the immobilized TiO₂ particles was higher than that with plain TiO₂. Based on the COD results, after 3 h, the TiO₂-coated sackcloth fiber effectively decomposed all of the organic compounds present in dye solution under the studied experimental conditions. The effects of the oxidant H₂O₂, initial dye concentration and pH on the photocatalytic degradation were also investigated. The presence of CO₃^2? as a dissolved inorganic anion had the highest inhibitory effect on the decolorization of the dye, when compared with the other anions investigated. Kinetics analysis indicates that the photocatalytic decolorization rate of Acid Black 26 can be described by a pseudo-first-order model.     

Modeling and optimization of a sono-assisted photocatalytic water treatment process via central composite design methodology

This work focuses on modeling and optimization of a sono-assisted photocatalytic decolorization process of a model pollutant, azo dye C.I. direct red 16 (DR16). In the process, a high temperature thermal decomposition nano synthesized titanium dioxide (TD-TiO₂) was applied as photocatalyst. Central composite design (CCD) methodology was used for designing the experiments, modeling and optimization of the process. A quadratic model was established to describe dependency of the decolorization efficiency (DE), as the model response, to some effective operational parameters, i.e. the catalyst dosage, pH and the dye initial concentration. The ANOVA analysis confirmed that all of the variables have significant influence on the model response. Under the established optimum conditions, 92.4% DE was achieved after 45 min; however, to access desirable mineralization efficiency, the process should be continued up to 120 min. All withdrawn samples from the reaction media during the process showed no antibacterial activity, which indicates safety of the treated effluent for disposal into the environment. Also studies showed that the process proceeds via two parallel branches of photolysis and photocatalysis, where propagation of the ultrasonic waves into the reaction media plays a vital promoting role on the latter branch.     

TiO2悬浆体系光催化降解酸性红B动力学分析

采用TiO2悬浆体系, 以高硼紫外灯为光源, 考察了酸性红B 光催化降解中溶液初始质量浓度、催化剂投加量、无机盐、空气通入量、pH 值对光催化降解速率影响.用Langmuir-hinshelwood 方程描述酸性红B光催化动力学行为. 结果表明:初始质量浓度增加, 反应由一级向零级过渡; 催化剂投加量在0.5～2.5 g/L时, 30 mg/L酸性红B一级反应速率常数与投加量成线性关系; 5种溶解性无机盐对光催化降解酸性红B存在抑制作用, 阴离子影响大于阳离子; 通入空气影响动力学行为, 改变反应级数.本实验在pH 值为3时光催化降解效果最佳, 且酸性条件下比碱性下条件效果更好;TiO2表面吸附能力随pH 值增大而减弱,光催化过程控制步骤在酸性和碱性条件不同.     

Use of advance oxidation process to improve the biodegradability of olive oil mill effluents

In this study, recalcitrant total phenol (TPh) and organic matter removal were investigated at olive mill wastewater (OMW) in sequential Coagulation and Fenton system. This study focused on different operational parameters such as pH, H₂O₂, and Fe²⁺ dosages, and [Fe²⁺]/[H₂O₂] ratios. The optimum conditions were determined as; pH = 3; [Fe²⁺] = 2.5 g/L; [Fe²⁺]/[H₂O₂] = 2.5. A higher treatment efficiency was achieved at sequential Coagulation and Fenton system (COD, 65.5%) and TPh, 87.2%), compared to coagulation process (COD, 51.4%; total organic carbon (TOC), 38.6% and total nitrogen (TN) 52.1%). This study demonstrated that the Coagulation and Fenton process has a potential for efficient removal of phenolic pollutants from wastewater.     

A novel pretreatment process of mature landfill leachate with ultrasonic activated persulfate: Optimization using integrated Taguchi method and response surface methodology

A novel advanced oxidation process (AOP) using ultrasonic activated persulfate oxidation was used to pretreat mature landfill leachate. The effects of different operating variables (e.g., the initial S₂O₈²⁻ concentration, pH, temperature, ultrasonic power and reaction time) on the oxidation performance were investigated regarding the total organic carbon (TOC) removal efficiency, and the variables were optimized using the integrated Taguchi method and response surface methodology (RSM). Based on the Taguchi method under L₁₆ (4⁵) arrays and a grey relational analysis, the most significant variables included the initial S₂O₈²⁻ concentration, temperature and reaction time. The concentrations of these variables were further optimized using RSM. Using the integrated optimization method, the optimal conditions included an initial S₂O₈²⁻ concentration of 8.5 mM, a reaction temperature of 70 °C and a reaction time of 2.46 h, which resulted in a TOC removal efficiency of 77.32%. The experimental results showed that the enhanced TOC removal from mature landfill leachate by sono-activated persulfate oxidation could be attributed to the combined effects of ultrasonic catalysis and sulfate radical-AOP. Overall, ultrasonic activated persulfate oxidation is a promising method for the pretreatment of landfill leachate.     

Feasibility study of decomposing methane with hydroxyl radicals

Coal-mine gas disaster is one of the most serious coal-mine disasters in China. The main component of coal-mine gas, methane is chemically stable and very difficult to be degraded by conventional methods. Hydroxyl radical (OH), due to strong oxidizing ability and high electro-negativity, is the primary degradation source of atmospheric methane. In the present study, methane degradation using hydroxyl radicals generated by Fenton’s reagent, Fe²⁺/H₂O₂, has been carried out in the self-designed bubbling reactor. The effects of H₂O₂ concentration, dosage of FeSO₄·7H₂O and initial pH value on methane removal efficiency were investigated respectively. It has been found that the optimal reaction conditions were 100 mM of hydrogen peroxide, 2.00 mM of ferrous ion and initial pH value of 2.5. Under optimal conditions, the removal efficiency of methane reached 25% after 30 min. The preliminary experimental results unambiguously demonstrate that the degradation of methane using hydroxyl radicals generated by Fenton’s reagent is feasible.     

On–off control of aeration time in the simultaneous removal of ammonia and manganese using a biological aerated filter system

The biological aerated filter (BAF) system, a new alternative in drinking water treatment, was designed to remove NH₄⁺–N and Mn²⁺ simultaneously. This study aimed to control the aeration time in the BAF system for simultaneous NH₄⁺–N and Mn²⁺ removal to achieve the Malaysian effluent quality regulation for drinking water. The experiment was conducted under four strategies of S1, S2, S3 and S4. The results demonstrated that acceptable levels of NH₄⁺–N and Mn²⁺ were achieved over a 6 h aeration period (S1), producing effluent concentrations of 0.7 mg/L (93.2% removal) and 0.08 mg/L (79.6% removal), respectively. At the initial treatment of S1 and S2, the dissolved oxygen (DO) level rapidly increased until it reached a saturated concentration (6.8 mg/L DO) after 2 h period. Automatic on–off aeration time to maintain 3 mg/L DO set point (S4) resulted with a good effluent quality of NH₄⁺–N and Mn²⁺ compared with the 2 mg/L DO set point (S3) which did not meet the regulated standard limits. Through the automatic on–off aeration time, the saturated and excessive DO levels in the BAF system can be avoided consequently reduce the wastage of energy and electrical consumption for simultaneous NH₄⁺–N and Mn²⁺ removal from drinking water treatment.     

Growing Carbon Nanotube on Aluminum Oxides: An Inherently Safe Approach for Environmental Applications

Using micron-sized Al₂O₃ particles as carriers to grow carbon nanotubes (CNTs) under 700°C atmosphere of methane and hydrogen after pre-planted catalysts of Fe–Ni nanoparticles, those composite CNTs (CCNTs) have demonstrated several unique properties compared to CNTs—medium specific surface area and zeta potential, high adsorption capacity for metal ions, high recovery rate by acids, low decomposition heat for exothermal reaction, and so on. The adsorption behaviours of Pb²⁺, Cu²⁺ and Cd²⁺ in aqueous solutions by CCNTs are in good agreement with the Langmuir adsorption isotherm and second order kinetic model with maximum individual adsorption capacities of 67.11, 26.59 and 8.89 mg g⁻¹. The individual and competitive adsorption behaviours indicated that the preference order of adsorption were Pb²⁺ > Cu²⁺ > Cd²⁺ for aluminum oxides, activated carbon, commercial CNTs, and CCNTs as well as other researchers’ CNTs. We suggest that future development of CNTs to combine with metals and/or other materials, such as TiO₂, should consider attached to carriers or surface in order to avoid concerns on environment, health and safety. Thus, growing CNTs on Al₂O₃ particles to form CCNTs is an inherently safe approach for many promising environmental applications.     

Zero valent nano-sized iron/clinoptilolite modified with zero valent copper for reductive nitrate removal

Nitrates constitute one of the main toxic contaminants of groundwater. On the other hand, groundwater may be considered anoxic (oxygen concentration less than 9 μg L^?1). This fact justifies the use of nano zero valent metals for nitrate removal. In such conditions, zero valent metals are quite stable against oxidation due to the very low level of dissolved oxygen concentration. It has been shown that the performance of zero valent iron coated clinoptilolite zeolite for the reduction of nitrate anion in un-buffered conditions may be enhanced by coating small amounts of Cu⁰ onto the freshly prepared Fe⁰/zeolite composite. An optimum loading of Cu⁰ exists for which the rate of nitrate removal is maximal. For this optimal composition, the nitrite anion production curve with time passes through a maximum. Nitrite production, however, is slightly higher for the Cu modified zeolite. It has been shown that the nitrate removal process is only slightly dependent on the initial solution pH. In the temperature range of 20–60 °C, the process is controlled by both the liquid phase mass transfer and intrinsic reaction rate resistances. FESEM analysis of the zero valent metal/zeolite composite showed that upon the metal reduction reaction, an egg-shell distribution of zero valent metal in the zeolite agglomerate particle is produced.     

Equilibrium study and kinetics of Cu removal from water by zeolite prepared from oil shale ash

Engineered zeolite was produced from oil shale ash by reaction with sodium hydroxide in a closed vessel reactor. This adsorbent was used for removal of copper ions from aqueous solution. The maximum adsorption capacity was 504.6 mg Cu²⁺/g zeolite. Kinetic studies showed that the rate of adsorption of copper is increased with increasing the solution pH and temperature, quantity of the zeolite and agitation speed. The kinetic data were fitted to homogeneous micropore model and found that the mass transfer coefficient and diffusivity of the Cu²⁺ are directly affected by the kinetic parameters. The increase in solution concentration will decrease the mass transfer coefficient while diffusivity is increased.     

Removal of humic substances from landfill leachate by Fenton oxidation and coagulation

In this study, chemical oxygen demand (COD) was characterized as total organic constituents and the isolated humic substances (HS) were characterized as an individual organic contaminant in landfill leachate. It was found that the HS content of landfill leachate was 83.3%. The results of laboratory tests to determine the roles of HS in reducing the organic content of landfill leachate during Fenton process are presented. Furthermore, the performances of oxidation and coagulation of Fenton reaction on the removal of HS and COD from leachate were investigated. The change curves of HS removal were similar to those of COD. The HS removal was 30% higher than COD removal, which indicated that HS were mostly degraded into various intermediate organic compounds but not mineralized by Fenton reagent. The oxidation removal was greatly influenced by initial pH relative to the coagulation removal. The oxidation and coagulation removals were linear dependent with hydrogen peroxide and ferrous dosages, respectively. Ferrous dosage greatly influenced the coagulation removal of COD at low ratio ([H₂O₂]/[Fe²⁺] < 3.0), but not at extremely high ratio ([H₂O₂]/[Fe²⁺] > 6.0). The coagulation removal of HS was not affected obviously by oxidation due to both Fenton oxidation and coagulation remove high molecular weight organics preferentially. Higher temperature gave a positive effect on oxidation removal at low Fe²⁺ dosage, but this effect was not obvious at high Fe²⁺ dosage.     

Disintegration of waste activated sludge by different applications of Fenton process

Oxidative disintegration of municipal waste activated sludge (WAS) using conventional Fenton (Fe²⁺ + H₂O₂, CFP) and Fenton type (Fe⁰ + H₂O₂, FTP) processes was investigated and compared in terms of the efficiency of sludge disintegration and enhancement of anaerobic biodegradability. The influences of different operational variables namely sludge pH, initial concentration of Fe²⁺ or Fe⁰, and H₂O₂ were studied in detail. The optimum conditions have been found as catalyst iron dosage = 4 g/kg TS, H₂O₂ dosage = 40 g/kg TS and pH = 3 within 1 h oxidation period for both CFP and FTP. Kinetics studies were performed under optimal conditions. It was determined that the sludge disintegration was happened in two stages by both processes: rapid and subsequent slow disintegration stages and rapid sludge disintegration stage can be described by a zero-order kinetic model. The effects of oxidative sludge disintegration under the optimum conditions on anaerobic digestion were experienced with biochemical methane potential (BMP) assay in batch anaerobic reactors. Total methane production in the CFP and FTP pre-treated reactors increased by 26.9% and 38.0%, relative to the untreated reactor (digested the raw WAS). Furthermore, the total chemical oxygen demand reductions in the pre-treated reactors were improved as well.     

Application of Modified Carbon Anodes in Microbial Fuel Cells

The effect of different carbon anodes was examined in a new design of single chambered microbial fuel cell (SCMFC). The new cell design used a low-cost hydrophilic membrane to replace costly proton exchange membranes and carbon felt and a range of carbon and modified carbon anodes were investigated. The fuel for the SCMFC was brewery wastewater which was diluted with domestic wastewater and the presented microflora acts as a source of electro-active bacteria. The membrane acts as a separator between the anode chamber and an air cathode and allows the transfer of ions based on the wastewater's natural conductivity. The air cathode was carbon black (Ketjen Black EC 300J) which was deposited (1 mg cm⁻² concentration) directly onto the surface of the separator (one side of the membrane). Steady state polarization demonstrated maximum power densities of up to 30 mW m⁻² and a steady state power density of 20 mW cm⁻² at a current density of 110 mA m⁻² was achieved. The best performing anodes were made from carbon modified with quinone/quinoid groups. With unmodified graphite felt (the control anode material) as anode, the maximal power density obtained was 9.5 mW m⁻².     

Kinetics of nitrate reductive denitrification by nanoscale zero-valent iron

Nanoscale zero-valent iron (Fe⁰) was synthesized for nitrate denitrification. The reduction efficiency of nitrate decreased quickly with increasing initial pH value, increased considerably with the increasing dosage of nanoscale Fe⁰, and did not vary much with initial nitrate concentrations changing from 20 to 50 mg l^?1 when the excessive amount of nanoscale Fe⁰ was utilized. With reductive denitrification of nitrate by nanoscale Fe⁰, the removal rate of nitrate reached 96.4% in 30 min with nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7, and more than 85% of the nitrate was transformed into ammonia. Kinetics analysis in batch studies demonstrates that the denitrification of nitrate by nanoscale Fe⁰ involves reaction on the metal surface, which fits well the pseudo-first order reaction with respect to nitrate concentration. The observed reaction rate constant of reductive denitrification of nitrate was determined to be 0.086 min^?1 with a nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7. Fast and highly effective denitrification can be achieved by nanoscale Fe⁰ compared with commercial Fe⁰ powder, this is due to the extremely high surface area and high reactivity for nanoscale Fe⁰, which can enhance the denitrification efficiencies remarkably.     

铝阳极电凝聚处理活性黑KN-B染料模拟废水

对铝阳极电凝聚处理活性黑KN-B模拟废水进行了初步的实验研究.考察了电流密度、初始pH值、电解质浓度及种类、温度、染料浓度等因素的影响.结果表明,在一定实验条件下,活性黑KN-B模拟废水的脱色效率可达到88%;电流强度、染料浓度、电解液初始pH值、氯化钠电解质浓度、温度对染料溶液脱色效率的影响明显,而硫酸钠电解质浓度对脱色效率的影响不显著;在电凝聚处理过程中,主要作用机理是吸附网捕占主导地位;活性黑KN-B在阴极上发生了还原反应.     

Adsorption of copper and nickel on Na-bentonite

The removal of copper and nickel from aqueous solution on the Na-bentonite has been studied under static conditions. Experiments were carried out as a function of solution pH, dosage of Na-bentonite, contact time and temperature. The adsorption equilibrium for nickel and copper onto Na-bentonite is reached in 200 min. The adsorption of copper and nickel is pH dependent in the pH range 2–9. The kinetic process of adsorption can be described by the pseudo-second-order kinetic equation excellently and the adsorption isotherm be fitted to the Langmuir model by means of regression analyses very well. The adsorption capacities follow the order of Cu²⁺ > Ni²⁺ in single-component systems and competitive adsorption capacities in order decreasing is Cu²⁺ > Ni²⁺ in binary-component systems.     

Study on decomposition of hydroxylamine/water solution

The risk evaluation of decomposition of hydroxylamine(HA)/water solution was studied experimentally. The thermal property of HA/water solution was studied from the calorimetric data obtained using the differential thermal analysis (DTA). The intensity of decomposition was studied on the basis of the results of the mini closed pressure vessel test (MCPVT) and the pressure vessel test (PVT) in addition to the steel tube test.The thermal property of HA/water solution was evaluated on the basis of results of the DTA. The heat-release onset temperatures using the no-treated stainless steel cells were more than 70 K below those measured using the GSC. This result implies that the heat-release onset temperature depends on the materials of sample cell. On the other hand, the heat of reaction did not depend on the materials of sample cell.The intensity of the thermal decomposition was investigated on the basis of results of the MCPVT, the PVT and the steel tube test. The intensity of the thermal decomposition increased as the HA concentration increased in the MCPVT. The intensity of the thermal decomposition increased greatly when the HA concentration was beyond 80wt.% in the MCPVT. It was elucidated that the thermal decomposition of HA 70wt.%/water solutions was very violent in the PVT. In addition, HA/water solutions of more than 80wt.% concentration could detonate in the steel tube test. HA 80 wt.% water/solution was easily detonated by a detonator without RDX in the steel tube test.In addition, the decomposition hazard of HA/water solution by the metal ion and the iron powder was studied in this paper. The thermal stability of HA85%/water solution with the iron ion or the iron powder was discussed on the basis of the heat-release onset temperature by the DTA. The heat-release onset temperatures decreased when the concentration of the iron ion or the iron powder increased in the DTA measurements. The reactiveness of HA/water solution with the metal ion of iron, manganese, nickel, chromium and copper was examined by measuring the mass loss of HA/water solution after the metal ion was added to HA/water solution at room temperature. The reactiveness of HA/water solution with the iron powder was also studied in this paper. The ferrous ion, the ferric ion and the iron powder reacted with HA/water solution. Ignition automatically began when the 0.2wt.% ferric ion solution was added to HA85wt.%/water solution. The mass loss rate depended on the HA concentration greater than the iron ion concentration. The mass loss rate increased when an amount of the iron powder increased. On the other hand, the decomposition reaction of HA85wt.%/water solution with Cu²⁺ was calm compared to that of the iron ion. HA/water solution did not react with Mn²⁺, Ni²⁺ and Cr³⁺ at room temperature.     

铜铁共掺杂TiO2/膨润土光催化剂的制备及光催化性能

以溶胶-凝胶法、液相沉淀法和机械混合法制备了Cu-Fe双金属掺杂的TiO2/膨润土复合光催化剂,采用XRD、FTIR对其进行了结构表征,以紫外光和可见光催化降解直接天蓝染料废水为模型,考察了制备方法对催化剂光催化性能的影响。结果表明:各催化剂中均有锐钛矿型TiO2生成,且部分TiO2进入了膨润土的蒙脱石层间,改变了其层间的有序性,生成了Ti—O—Si键,实现了TiO2粒子与膨润土的复合。溶胶-凝胶法制备的催化剂中TiO2与膨润土的复合程度最高,Cu2+和Fe3+成功掺入了TiO2晶格,形成了复合半导体,拓宽了TiO2的光谱响应范围,使该催化剂表现出最优的光催化活性,并且该催化剂性能稳定,易于沉降分离,经高温活化再生后仍具有良好的催化活性,可重复多次使用,表现出良好的再生性能。     

Evaluating the efficacy of alumina/carbon nanotube hybrid adsorbents in removing Azo Reactive Red 198 and Blue 19 dyes from aqueous solutions

Concerning the high volume of wastewater containing dye in Iran and its adverse effects, it is necessary to develop scientific solutions for treating these wastewaters. The aim of this study was to evaluate the efficiency of the alumina-coated multi-walled carbon nanotubes in removing the Reactive Red 198 (RR 198) and Blue 19 (RB 19) dyes. Synthetic samples including dye with different concentrations were prepared. These samples were put in contact with different contents of alumina/multi-walled carbon nanotubes, in different pH values, in different contact times, different temperatures and the presence of sodium sulfate or sodium carbonate. The optimum pH, dye concentration and temperature for removal of the two dyes was 3, 50 mg l⁻¹ and 25 °C, respectively. The optimum adsorbent dose for removal the RR 198 dye was 0.5 g l⁻¹ and for Blue 19 was 0.4 g l⁻¹. The optimum contact time for RR 198 was 150 min and RB 19 was 180 min. In this condition, maximum removal efficiency for RR 198 and RB 19 was 91.54% and 93.51%, respectively. The adsorption study was analyzed kinetically, and the results revealed that the adsorption fitted a pseudo-second order kinetic model. According to these results alumina/multi-walled carbon nanotubes can effectively remove RR 198 and RB 19 from aqueous solutions.     

Evaluation of Abelmoschus esculentus (lady's finger) seed as a novel biosorbent for the removal of Acid Blue 113 dye from aqueous solutions

The use of a new biosorbent derived from Abelmoschus esculentus (A. esculentus) seed for the removal of Acid Blue 113 (AB113) in aqueous solutions was investigated in batch mode. Biosorption studies were carried out under varying operational parameters including initial pH, biosorbent dosage, contact time, initial dye concentration and temperature. The results indicated that the biosorption properties were strongly dependent on initial pH. Fourier transform infrared spectroscopy analysis revealed that hydroxyl, carboxylic and amide functional groups present on the biosorbent surface were involved in the dye removal process. Equilibrium data were best fitted by the Langmuir model. The maximum biosorption capacity was 169.9 ± 3.1 mg g⁻¹ at 25 °C and initial pH 5.5. The kinetic data were in good agreement with the pseudo-second-order kinetic model. The process was controlled by diffusion through boundary layer at the initial stage followed by intra-particle diffusion at the later stage. Thermodynamic evaluation showed that the process was endothermic and spontaneous. The present study suggests that A. esculentus seed with maximum biosorption capacity which compared well with values reported in the literature can be a potential biosorbent for AB113 dye removal.