Impact of Fenton and ozone on oxidation of wastewater containing nitroaromatic compounds

Fenton and ozone treatment was investigated at laboratory scale for the degradation of aqueous solutions of nitrobenzene (NB).Effects of reactants concentration (O3,H2O2,and Fe(II)),temperature,and pH on NB degradation were monitored.Reaction kinetic of these processes was also assessed.A rapid reaction took place for Fenton process at higher initial concentration of H2O2,higher temperatures,and more acidic conditions(pH 3).Similarly, ozonation reaction exhibited rapid rates for higher ozone dose,higher temperatures,and more basic conditions(pH 11).Complete NB degradation in 65 min Was achieved using Fenton process.The conditions of complete elimination of 100 mg/L of initial NB concentration,were 250 mg/L of H2O2 concentration,pH 3,and 10 mg/L of Fe(Ⅱ) concentration.Under these conditions,55% organic carbon elimination Was achieved.Total organic carbon mineralization Was attained in 240 min reaction time by Fenton process with 900 mg/L of H2O2 concentration,and 30 mg/L of Fe(II) concentration.Fenton reaction showed a pseudo-first order kinetic;the reaction rate constant Was ranged from 0.0226 to 0.0658 min-1.Complete NB degradation wag also achieyed for an ozone dose of the order of 2.5 g/L.The ozonation Was studied at different ozone doses.different initial pH(7-11)and at difierent temperatures(15-35℃).NB ozonation kinetic Was represented by a bi-molecular kinetic model which was reduced to pseudo-first order kinetic.The pseudo-first order reaction rate constant was determined to increase at 20℃ from 0.004 to 0.020 min-1 as the used ozone increased from 0.4 to 1.9g/L.     

Degradation kinetics and mechanism of trace nitrobenzene by granular activated carbon enhanced microwave/hydrogen peroxide system

The kinetics of the degradation of trace nitrobenzene (NB) by a granular activated carbon (GAC) enhanced microwave (MW)/hydrogen peroxide (H₂O₂) system was studied. Effects of pH, NB initial concentration and tert-butyl alcohol on the removal efficiency were examined. It was found that the reaction rate fits well to first-order reaction kinetics in the MW/GAC/H₂O₂ process. Moreover, GAC greatly enhanced the degradation rate of NB in water. Under a given condition (MW power 300 W, H₂O₂ dosage 10 mg/L, pH 6.85 and temperature (60±5)℃), the degradation rate of NB was 0.05214 min^-1 when 4 g/L GAC was added. In general, alkaline pH was better for NB degradation; however, the optimum pH was 8.0 in the tested pH value range of 4.0-12.0. At H₂O₂ dosage of 10 mg/L and GAC dosage of 4 g/L, the removal of NB was decreased with increasing initial concentrations of NB, indicating that a low initial concentration was beneficial for the degradation of NB. These results indicated that the MW/GAC/H₂O₂ process was effective for trace NB degradation in water. Gas chromatography-mass spectrometry analysis indicated that a hydroxyl radical addition reaction and dehydrogenation reaction enhanced NB degradation.     

Effect of electron beam irradiation on the degradation of monochlorophenols in aqueous solution

Electron beam was successfully used for the degradation of 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP) in aqueous solutions in this research. The effect of radiation dose on substrate degradation and dechlorination of solutions with concentration of 50mg/L was investigated. The effect of initial concentration, pH and presence of oxygen was also investigated. The concentration of 2-CP and 4-CP remaining in solution after irradiation were measured by HPLC. The results showed that increased radiation dose led to increased degradation of the chlorophenols and increased CI^- yield. Deaeration was also found to significantly increase the rate of degradation of chlorphenols in water while degradation and dechlodnation under alkaline condition was lower than at low to neutral pH.     

Photodegradation of nitroaromatic compounds in aqueous solutions in the UV/H2O2 process

Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irradiated NB aqueous solutions. The distribution of nitrophenol isomers follows the order p-〉 m-〉 o-nitrophenol. Other intermediates detected include nitrohydroquinone, nitrocatechol, catechol, benzoquinone, phenol, nitrate/nitrite ions, formic acid, glyoxylic acid, maleic acid, oxalic acid and some aliphatic ketones and aldehydes. The degradation of nitrobenzene and nitrophenols at initial stages follows the first-order kinetics and the decay rate constants for nitrobenzene（NB） are around l0^-3-10^-2 s^-1 and for nitrophenols are around 10^-2 s^-1. The decomposition of H2 O2 in the presence of NB and each nitrophenol isomers follows zero-order kinetics. The quantum yields at initial stages for NB decay were estimated around 0.30 to 0.36, and for NPs decay is around 0.31-0.54.     

Radiolysis of pentachlorophenol (PCP) in aqueous solution by gamma radiation

Steady-state radiolysis experiments were performed to investigate the γ-irradiation treatment of pentachlorophenol (PCP) in aqueous solution. The e?ect of initial concentration on the PCP degradation was also investigated. The experimental results showed that γirradiation was able to degrade PCP in aqueous solution successfully, and the radiolytical degradation process of PCP could be described by the first-order kinetic model. When the initial concentration of PCP was 25 and 50 mg/L and the radiation dose ...     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.     

Formaldehyde degradation by UV/TiO2/O3process using continuous flow mode

The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.     

Destruction of 4-phenolsulfonic acid in water by anodic contact glow discharge electrolysis

Destruction of 4-phenolsulfonic acid (4-PSA) in water was carried out using anodic contact glow discharge electrolysis. Accompanying the decay of 4-PSA, the amount of total organic carbon (TOC) in water correspondingly decreased, while the sulfonate group of 4- PSA was released as sulfate ion. Oxalate and formate were obtained as minor by-products. Additionally, phenol, 1,4-hydroquinone, hydroxyquinol and 1,4-benzoquinone were detected as primary intermediates in the initial stages of decomposition of 4-PSA. A reaction pathway involving successive attacks of hydroxyl and hydrogen radicals was assumed on the basis of the observed products and kinetics. It was revealed that the decay of both 4-PSA and TOC obeyed a first-order rate law. The effects of different Fe ions and initial concentrations of 4-PSA on the degradation rate were investigated. It was found that the presence of Fe ions could increase the degradation rate of 4-PSA, while initial concentrations lower than 80 mmol/L had no significant effect on kinetic behaviour. The disappearance rate of 4-PSA was significantly affected by pH.     

Toxicity of the xenoestrogen nonylphenol and its biodegradation by the alga Cyclotella caspia

Alkylphenols (APs), the breakdown products of alkylphenol polyethoxylates that are widely used as surfactants, have been proven to exert estrogenic effects. With industrial development, higher concentrations of APs are discharged into aquatic environments. Nonylphenol (NP), the most noxious AP, is included in the blacklist of several countries. The toxicity of NP to the alga Cyclotella caspia and the biodegradation of NP by C. caspia were studied in the laboratory. The median effective concentration at 96 hr (96 hr EC50 ) of NP for C. caspia was found to be 0.18 mg/L. Five toxicity and three degradation indices were selected for toxicity and biodegradation experiments, respectively, in five or three concentrations of NP set by the 96 hr EC50 of NP. The algal growth rate and chlorophyll a contents decreased as NP concentration increased. The main manifestations of morphological deformity of the cells included volume expansion and the presence of cytoplasmic inclusions (lipid droplets). The abnormality rate of the cells increased with NP concentration and time, and was 100% at 0.22 and 0.26 mg/L of NP after 192 hr of culture. Superoxide dismutase activity initially increased and then declined at a higher NP toxicity of greater than 0.18 mg/L. After 192 hr of culture, the biodegradation rates of NP by C. caspia with initial concentrations of 0.14, 0.18, and 0.22 mg/L were 37.7%, 31.7%, and 6.5%, respectively. The kinetic equation of C. caspia biodegradation on NP was correlated with algal growth rate and initial NP concentration.     

Enhanced photodegradation of phenolic compounds by adding TiO2 to soil in a rotary reactor

Photodegradation ofpentachlorophenol （PCP） and p-nitrophenol （PNP） in soil was carried out in a designed rotary reactor, which can provide the soil particles with continually uniform irradiation, and on a series of thin soil layers. TiO2, as a kind of environmental friendly photocatalyst, was introduced to the soil to enhance the processes. Compared with that on the soil layers, photodegradation of PCP at initial concentration of 60 mg/kg was improved dramatically in the rotary reactor no matter whether TiO2 was added, with an increase of 3.0 times in the apparent first-order rate constants. The addition of 1 wt% TiO2 furthered the improvement by 1.4 times. Without addition of TiO2, PNP （initial concentration of 60 mg/kg） photodegradation rate in the rotary reactor was similar to that on the soil layers. When 1 wt% additional TiO2 was added, PNP photodegradation was enhanced obviously, and the enhancement in the rotary reactor was 2 times of that on the soil layers, which may be attributed to the higher frequency of the contact between PNP on soil particles and the photocatalyst. The effect of soil pH and initial concentrations of the target compounds on the photodegradation in the rotary reactor was investigated. The order of the degradation rate at different soil pH was relative to the aggregation of soil particles during mixing in the rotary reactor. Photodegradation of PCP and PNP at different initial concentrations showed that addition of TiO2 to enhance the photodegradation was more suitable for contaminated soil with higher concentration of PCP, while was effective for contaminated soil at each PNP concentration tested in our study.     

Degradation of nitrobenzene in wastewater by γ-ray irradiation

The degradation of nitrobenzene(NB) by γ-ray irradiation was studied. The influences of dose rate and initial NB concentration were investigated in details. At a dose rate of 55 Gy/min, the degradation kinetics was pseudo-first-order at NB concentrations from 0.2 mmol/L to 4.0 mmol/L. At an initial NB concentration of 0.8 mmol/L, the degradation of NB at various dose rates also followed pseudo-first-order kinetics. Dissolved oxygen was found to have a positive effect on NB degradation. The degradation products were identified as nitrophenol, nitrosobenzene, and hydroquinone, and so on. Based on the product analysis, possible degradation pathways of nitrobenzene were proposed.     

工业铁屑(零价铁)还原硝基苯影响因素研究

通过静态试验,研究了初始硝基苯浓度、零价铁含量和pH值对零价铁还原硝基苯的影响.结果表明,在pH值为7,硝基苯初始浓度为311.25mg/L条件下,零价铁含量分别是100、50和25g/L时,硝基苯的降解速率常数分别是-0.02991、-0.0165和-0.00783min-1,零价铁含量越大硝基苯的降解速率越大;在pH值为7,零价铁含量为50g/L条件下,硝基苯的初始浓度分别是127.5,311.25,467.01mg/L时,硝基苯的降解速率常数分别是-0.01532、-0.01235和-0.00891min-1;在硝基苯初始浓度为311.5mg/L,零价铁含量为50g/L条件下,pH值为2.94时,硝基苯的降解速率最大,pH值为7其次,pH值为11.89时的降解速率最小,酸性环境利于零价铁还原硝基苯的进行.由此可见,硝基苯浓初始浓度、零价铁含量和pH值对硝基苯的还原具有重大影响.     

臭氧/沸石工艺处理水中硝基苯的效能研究

在连续反应器中,考察了臭氧/沸石工艺在不同条件下去除硝基苯的效果.结果表明,臭氧/沸石工艺对硝基苯的去除效率明显高于单纯臭氧氧化,反应7 min后,硝基苯去除率达到100％,并且该反应符合假一级反应动力学.叔丁醇能抑制臭氧/沸石工艺对硝基苯的去除效率,表明在氧化去除硝基苯过程中羟基自由基起主导作用.增加沸石投量和臭氧浓度均能有效地提高臭氧/沸石工艺对硝基苯的去除效率,并且臭氧/沸石工艺对硝基苯的去除速率与沸石投量之间存在1个最优值,与臭氧浓度呈线性关系.臭氧/沸石工艺对硝基苯的去除速率与初始硝基苯浓度无关.离子强度对臭氧/沸石工艺降解硝基苯的效率影响较大,当离子强度从0增加到1×10^-3　mol/L时,臭氧/沸石工艺对硝基苯的去除率从81.2％降低至31.6％.pH值主要影响臭氧的分解能力,随着溶液pH降低,臭氧/沸石工艺对硝基苯的去除效率逐渐下降.沸石具有较长的使用寿命.     

超声波/零价铁协同降解三氯甲烷特性研究

研究三氯甲烷在单独超声(US)、单独零价铁(Fe0)及超声波/零价铁协同体系(US/Fe0)中的降解发现,拟一级动力学能很好地拟合降解过程,协同体系中三氯甲烷一级降解速率常数(K_US/Fe0)为0.010　3 min-1,约为同等条件下零价铁体系所得K_Fe0的3倍,且大于K_Fe0与K_US之和,说明二者之间存在协同效应.考察零价铁投加量〔ρ(Fe0)〕,初始pH,初始三氯甲烷浓度(c₀),超声功率,溶液离子强度等控制参数对三氯甲烷降解速率(K_US/Fe0)的影响,结果表明,其拟一级速率常数分别在ρ(Fe0)为6 g/L,初始pH为6.0,c0为5 mmol/L以及0.5 mol/L　Na₂SO₄当量离子强度下达最大值,并且随着超声功率的增大而增大.      

S-NZVI/PS凝胶反应带修复硝基苯污染地下水

采用前置硫化法合成制备硫化纳米铁,研究其与过硫酸盐对硝基苯的联合降解效果,检测反应前后溶液中铁离子和TOC浓度变化,对反应前后的S-NZVI进行表征,分析S-NZVI和PS对NB的联合降解机制.以纳米硅胶溶液为胶结剂,以PS为活性成分,制备缓释PS溶胶,注入砂柱中扩散形成凝胶,与S-NZVI构成S-NZVI/PS组合反应带,研究其对模拟硝基苯污染地下水的原位修复效果.结果表明,S-NZVI能够高效去除NB并生成大量苯胺（AN）,S-NZVI被PS氧化产生的Fe²⁺与PS组成活化过硫酸盐,对AN具有较好的降解和矿化效果.当NB浓度为100mg/L、S-NZVI和PS的投加量分别为0.5,2.5g/L时,NB去除率达91%,AN出水浓度为1.96mg/L,TOC去除率达64.09%.反应后S-NZVI的主要铁氧化产物为Fe₃O₄和FeO（OH）.反应带实验结果表明,S-NZVI/PS组合反应带可有效去除地下水的NB并高效消减NB还原产生的AN,当进水中NB浓度为100mg/L,流量为0.4mL/min,注入S-NZVI含量为1200mg/L的浆液200mL,二氧化硅含量为30%、PS含量为12.5%的PS凝胶4.8g时,S-NZVI/PS组合反应带7d内对AN的去除率最高达97.6%,NB当量累计去除率为83.7%.     

S-NZVI/PS凝胶反应带修复硝基苯污染地下水

采用前置硫化法合成制备硫化纳米铁,研究其与过硫酸盐对硝基苯的联合降解效果,检测反应前后溶液中铁离子和TOC浓度变化,对反应前后的S-NZVI进行表征,分析S-NZVI和PS对NB的联合降解机制.以纳米硅胶溶液为胶结剂,以PS为活性成分,制备缓释PS溶胶,注入砂柱中扩散形成凝胶,与S-NZVI构成S-NZVI/PS组合反应带,研究其对模拟硝基苯污染地下水的原位修复效果.结果表明,S-NZVI能够高效去除NB并生成大量苯胺（AN）,S-NZVI被PS氧化产生的Fe²⁺与PS组成活化过硫酸盐,对AN具有较好的降解和矿化效果.当NB浓度为100mg/L、S-NZVI和PS的投加量分别为0.5,2.5g/L时,NB去除率达91%,AN出水浓度为1.96mg/L,TOC去除率达64.09%.反应后S-NZVI的主要铁氧化产物为Fe₃O₄和FeO（OH）.反应带实验结果表明,S-NZVI/PS组合反应带可有效去除地下水的NB并高效消减NB还原产生的AN,当进水中NB浓度为100mg/L,流量为0.4mL/min,注入S-NZVI含量为1200mg/L的浆液200mL,二氧化硅含量为30%、PS含量为12.5%的PS凝胶4.8g时,S-NZVI/PS组合反应带7d内对AN的去除率最高达97.6%,NB当量累计去除率为83.7%.     

生物海绵铁体系降解硝基苯的特性及机理初探

采用硝基苯（NB）模拟废水对生物海绵铁体系进行驯化,考察了NB初始浓度、海绵铁投加量、初始pH值、温度等因素对生物海绵铁体系降解NB的影响,初步探讨了生物海绵铁体系高效降解NB的机理.结果表明：生物海绵铁体系较普通活性污泥系统对NB适应性及氧化作用更强,驯化至第28d对300mg/L NB废水去除率稳定在98%以上,驯化周期比普通活性污泥体系缩短28d;海绵铁的加入大大促进了微生物对NB的降解,NB初始浓度及pH值对生物海绵铁体系降解速率影响较大,该体系适宜的温度范围较广,10~40℃均能高效降解NB,生物海绵铁体系对NB的降解符合零级反应动力学规律;生物海绵铁体系中活性氧化物（ROS）含量明显高于海绵铁体系及污泥体系,尤其是介入铁泥的生物海绵铁体系ROS含量更高,为体系发生较强类Fenton效应提供了条件.在实验确定的最佳工况下,经NB驯化的铁泥与海绵铁形成的生物海绵铁体系,NB降解速率为31.49min^-1,6hNB降解率及TOC去除率分别高达92.0%和63.1%,较单独海绵铁体系与单独铁泥体系降解率的叠加值分别高出22.3%和11.4%.本研究为经济有效地处理NB废水提供了新思路.