O3、O3/H2O2、O3/H2O2/UV工艺降解炸药工业废水中RDX的试验研究

为了研究高级氧化技术对含黑索今(RDX)的炸药工业废水的处理效果,本文采用O3、O3/H2O2、O3/H2O2/UV 3种氧化工艺分别对废水中的RDX进行了降解试验,并对比分析了3种工艺的处理效果和机制。结果表明:O3/H2O2、O3/H2O2/UV工艺对RDX的去除率明显优于O3工艺;提高体系的pH值将有利于RDX的降解;随着RDX初始浓度的增加,RDX的去除率呈现下降趋势;投加H2O2和UV照射可提高臭氧的利用率,且O3/H2O2/UV工艺催化臭氧分解的能力比O3/H2O2工艺强。     

A high activity of Ti/SnO2-Sb electrode in the electrochemical degradation of 2,4-dichlorophenol in aqueous solution

Electrochemical degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution was investigated over Ti/SnO₂-Sb anode. The factors influencing the degradation rate, such as applied current density (2-40 mA/cm²), pH (3-11) and initial concentration (5-200 mg/L) were evaluated. The degradation of 2,4-DCP followed apparent pseudo first-order kinetics. The degradation ratio on Ti/SnO₂-Sb anode attained > 99.9% after 20 min of electrolysis at initial 5-200 mg/L concentrations at a constant current density of 30 mA/cm² with a 10 mmol/L sodium sulphate (Na2SO4) supporting electrolyte solution. The results showed that 2,4-DCP (100 mg/L) degradation and total organic carbon (TOC) removal ratio achieved 99.9% and 92.8%, respectively, at the optimal conditions after 30 min electrolysis. Under this condition, the degradation rate constant (k) and the degradation half-life (t_1/2) were 0.21 min^-1 and (2.8±0.2) min, respectively. Mainly carboxylic acids (propanoic acid, maleic acid, propanedioic acid, acetic acid and oxalic acid) were detected as intermediates. The energy efficiencies for 2,4-DCP degradation (5-200 mg/L) with Ti/SnO₂-Sb anode ranged from 0.672 to 1.602 g/kWh. The Ti/SnO₂-Sb anode with a high activity to rapid organic oxidation could be employed to degrade chlorophenols, particularly 2,4-DCP in wastewater.     

UV/H-2O-2/草酸铁处理垃圾渗滤液的研究

利用UV（125W）/H2O2/草酸铁处理已经过生化处理的垃圾渗滤液(CODcr为450mg/L)时，反应较佳条件是PH值为4．0及总药剂用量为14mL/L。草酸铁的用量要适当，投加量过少，混凝效果较差，有效光子不能完全转化为化学能，处理效果不理想；投加量过多，溶液形成棕色混浊，使紫外光的吸收降低，造成光散射，降低反应速度。而H2O2的投加量过多，特使铁的络合物更加稳定，H202的分解速率受到限制，投加量过少，效果也会降低。当总药刑用量为14mL/L(其中30％过氧化氢6mL/L，0．1mol/L草酸铁溶液8mL/L时，反应30min后，CODcr去除率可达80％左右，脱色率可达90％以上。     

UV／H2O2／草酸铁络合物氧化工艺对染料废水脱色的研究

采用UV／H2O2／草酸铁络合物氧化工艺处理染料活性艳蓝K-3R模拟废水,考察了不同反应条件对脱色效果的影响。试验结果表明：UV／H2P2／草酸铁络合物氧化工艺对活性艳蓝K-3R具有较好的脱色效果,pH值,H2O2,Fe^3＋,C2O4^2-的浓度对脱色效果有较大影响。对7种不同类型的染料模拟废水的UV／H2O2／草酸铁络合物氧化工艺脱色实验结果表明,染料结构对于脱色效果也有很大影响,偶氮染料比蒽醌染料更易于脱色。     

溶液中阴离子对UV/H2O2降解4-硝基酚的影响

利用间歇式光反应器,研究了溶液中阴离子HCO3-、Cl-、及NO3-对UV/H2O2氧化4-硝基酚的影响.结果表明,UV/H2O2能有效地除去水溶液中4-硝基酚及TOC.随着HCO3-、Cl-及NO3-浓度的增加,4-硝基酚氧化速率减少.溶液中阴离子对UV/H2O2体系中主要氧化剂OH自由基的清除作用是4-硝基酚降解速率下降的原因.利用一级反应动力学对4-硝基酚的降解进行了拟合,得到了满意的结果.     

A simple and sensitive method for the determination of 4-n-octylphenol based on multi-walled carbon nanotubes modified glassy carbon electrode

A simple and sensitive electroanalytical method was presented for the determination of 4-n-octylphenol (OP) based on multi-walled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE). OP was directly oxidized on the MWCNTs/GCE, and the electrochemical oxidation mechanism was demonstrated by a one-electron and one-proton process in the reaction. The oxidation peak current of OP was significantly enhanced by the use of MWCNTs/GCE compared with those of bare glassy carbon electrode, suggesting that the modified electrode can remarkably improve the performance for OP determination. Factors influencing the detection processes were optimized. Under these optimal conditions, a linear relationship between concentration of OP and current response was obtained in the range of 5×10^-8 to 1×10^-5 mol/L with a detection limit of 1.5×10^-8 mol/L and correlation coefficient 0.9986. The modified electrode showed good selectivity, sensitivity, reproducibility and high stability.     

Effects of DOM characteristics from real wastewater on the degradation of pharmaceutically active compounds by the UV/H2O2 process

The characteristics of dissolved organic matter (DOM) can significantly affect the degradation of target compounds by the advanced oxidation processes. In this study, the effects of the different hydrophobicity/hydrophilicity fractions, molecular weight (MW) fractions, fluorescence components and molecular components of DOM extracted from municipal wastewater on the degradation of 4 pharmaceutically active compounds (PhACs), including carbamazepine, clofibric acid, atenolol and erythromycin by the UV/H₂O₂ process were investigated. The results showed that the degradation rate constants of 4 PhACs decreased dramatically in the presence of DOM. The linear regressions of 4 PhACs degradation as a function of specific fluorescence intensity (SFI) are exhibited during the degradation of 4 PhACs and the SFI may be used to evaluate effect of DOM on target compounds in wastewater. The hydrophobic acid (HPO-A) exhibited the strongest inhibitory effect on degradation of 4 PhACs during oxidation process. The small MW fractions of DOM significantly inhibited the degradation of 4 PhACs during oxidation process. Among three fluorescence components, hydrophobic humic-like substances may significantly inhibit the degradation of 4 PhACs during oxidation process. At the molecular level, the formulas may be derived from terrestrial sources. CHO compound may significantly inhibit the degradation of 4 PhACs during oxidation process on formula classes. The unsaturated hydrocarbons, carbohydrates and tannins compounds may significantly inhibit the effectiveness of the UV/H₂O₂ process on compound classes.     

A new photon kinetic-measure based on the kinetics of electron-hole pairs in photodegradation of textile wastewater using the UV-H2O2FS-TiO2 process

Actual textile wastewater and synthesized wastewater containing various textile dyes were photocatalytic degraded by the UVH2O2Fs-TiO2 process in an aimular-flow photocatalytic reactor. In this process, a photon kinetic-measure was adopted to obtain constant rates of dyes decomposition. It was theorized that, by illumination at different UV frequencies, the electrons within the semiconductor were excited from the valence band to the conduction band, yielding the formation of electron-hole pairs which are the pre-requisites for photocatalysis. CPT （critical photonic time） exposure required to cause 90% of vibrations between the double and single bonds along the molecular chain of the dyes to be oxidized, was taken to measure the photocatalytic activities. The CPTs varied with the frequencies of the UV spectral areas. The derivatization of CPT from the first-order kinetic law was presented.     

基于模糊神经网络的A2/O工艺出水氨氮在线预测模型

采用厌氧/缺氧/好氧污水处理系统(A2/O)对人工合成污水进行处理,并利用人工神经网络(ANN)模型和自适应模糊人工神经网络(ANFIS)模型对A2/O处理污水的过程进行仿真模拟.在MATLAB环境下,选取可在线监测的水力停留时间(HRT)、进水pH值(pH)、好氧池溶解氧(DO)和混合液回流比(r)作为输入参量,系统出水氨氮浓度(NH4+eff)为输出量,建立在线预测模型.结合自适应模糊C均值聚类算法,确定ANFIS模型的模糊规则数及最优运行参数,对实验数据进行仿真预测.结果表明,与ANN模型相比,ANFIS模型的仿真输出值与实际值的拟合程度更高,相对误差在6.45%之内,平均绝对百分比误差(MAPE)为2.8%,均方根误差(RMSE)为0.1209,相关系数(R)达0.9956.模型训练过程中所得到的三维曲面图,可直观的反映各因素与出水氨氮浓度之间的非线性函数关系,为A2/O系统的高效稳定运行提供指导.