硝酸氧化和负载铁氧化物改性活性炭催化臭氧化性能

采用硝酸氧化与硝酸铁负载对颗粒活性炭进行改性处理,研究了活性炭样品表面官能团的变化,分析了活性炭样品对酸性大红3R吸附和催化臭氧化能力,探讨了p H值与·OH捕获剂对催化臭氧化效果的影响。结果表明,硝酸改性后活性炭表面羧基、内酯基、酚羟基以及总官能团的含量均明显增加,其中羧基增幅最大;负载铁氧化物后,活性炭表面官能团数量有所降低。活性炭样品化学吸附性能随官能团含量的增加而增强。催化臭氧化对酸性大红3R的氧化降解效果明显优于单独臭氧化。增加表面官能团含量可以加速催化臭氧化反应,但反应速率随着表面官能团消耗而降低;负载金属组分具有更为稳定和有效的催化臭氧化活性。活性炭催化臭氧化性能在碱性条件下明显优于酸性条件,且随着p H值升高而提高。投加·OH捕获剂(Na2CO3)后,其对·OH的消耗使得催化臭氧化效果显著下降。     

氧化铈/活性炭催化臭氧氧化技术去除水中邻苯二甲酸二甲酯

用浸渍法在活性炭(AC)上负载氧化铈(CeO2)制备催化刺CeO2/AC催化臭氧氧化去除邻苯二甲酸二甲酯(DMP),考察了臭氧投加量,DMP初始浓度和溶液初始pH的影响.结果表明,CeO2/AC催化臭氧氧化去除DMP的最佳臭氧投加量为50mg/h,DMP初始浓度和溶液初始pH对CeO2/AC催化臭氧氧化DMP过程都有一定的影响.在DMP初始质量浓度为30 mg/L、溶液初始pH为5、臭氧投加量为50 mg/h、反应60 min时,CeO2/AC的加入(1.5g/L)有利于催化臭氧氧化DMP过程中总有机碳(TOC)的去除,TOC去除率由AC催化臭氧氧化的48%提高到68%.而单独臭氧氧化过程中的TOC去除率仅22%;且单独臭氧氧化与AC、CeO2/AC催化臭氧氧化DMP的矿化过程均符合二级反应动力学方程,CeO2/AC催化臭氧氧化DMP时TOC降解的二级反应动力学常数为0.0015L/(mg·min),分别是AC催化臭氧氧化的2.5倍和单独臭氧氧化的7.5倍.     

活性炭负载Fe~(3+)催化H_2O_2氧化邻苯二甲酸二甲酯

将Fe3+负载在活性炭上制得载铁催化剂Fe/AC,并研究了该催化剂对邻苯二甲酸二甲酯(DMP)的催化降解性能。通过正交实验和单因素实验,探讨了催化剂投加量、H2O2投加量、溶液pH值和反应温度对水中DMP降解率的影响,同时对DMP矿化度进行了分析。实验结果表明,制得的载铁催化剂具有较高的催化活性;降解效果的影响顺序是反应温度催化剂投加量H2O2投加量溶液pH值;在反应温度为80℃、催化剂投加量为4 g/L、H2O2投加量为20 mL/L和溶液pH值为3的条件下反应120 min后,质量浓度为10 mg/L的DMP降解率最高可达97.73%;在优化的实验条件下反应150 min,DMP矿化度可达62.73%;催化剂反复使用5次仍具有较好的催化活性,DMP降解率仍可达到77%以上;反应过程中溶液Fe3+浓度的变化维持在1.07 mg/L左右,且可推测催化降解DMP主要是由非均相和均相催化氧化反应共同作用的。     

活性炭负载Fe^3＋催化H2O2氧化邻苯二甲酸二甲酯

将Fe3＋负载在活性炭上制得载铁催化剂Fe/AC,并研究了该催化剂对邻苯二甲酸二甲酯（DMP）的催化降解性能。通过正交实验和单因素实验,探讨了催化剂投加量、H2O2投加量、溶液pH值和反应温度对水中DMP降解率的影响,同时对DMP矿化度进行了分析。实验结果表明,制得的载铁催化剂具有较高的催化活性;降解效果的影响顺序是反应温度〉催化剂投加量〉H2O2投加量〉溶液pH值;在反应温度为80℃、催化剂投加量为4 g/L、H2O2投加量为20 mL/L和溶液pH值为3的条件下反应120 min后,质量浓度为10 mg/L的DMP降解率最高可达97.73%;在优化的实验条件下反应150 min,DMP矿化度可达62.73%;催化剂反复使用5次仍具有较好的催化活性,DMP降解率仍可达到77%以上;反应过程中溶液Fe3＋浓度的变化维持在1.07 mg/L左右,且可推测催化降解DMP主要是由非均相和均相催化氧化反应共同作用的。     

臭氧/Mn2+催化降解水溶液中的2,4-二氯苯氧乙酸

以Mn2 为催化剂与臭氧联合降解除草剂2,4-二氯苯氧乙酸(2,4-D).考察了反应温度、pH、2,4-D初始浓度和臭氧气体流量等因素对2,4-D降解效果的影响.pH对2,4-D降解效果影响很大,当pH=2.0、反应5 min时,2,4-D的去除率达99.8%;当pH=10.1、反应20min时,2,4-D的去除率仅为50.0%.反应温度升高、臭氧气体流量增加、2,4-D初始浓度降低均有助于2,4-D降解速率的提高.单独臭氧氧化2,4-D的表观反应速率常数为0.170 min-1;催化臭氧氧化2,4-D的表观反应速率常数为0.295min-1,是单独臭氧氧化的1.74倍.2,4-D的Mn2 催化臭氧反应遵循拟一级反应动力学方程.     

水溶液中活性艳红KE-3B的臭氧超声联合脱除

采用臭氧/超声联合技术去除模拟废水中的活性艳红KE-3B。臭氧/超声处理前后KE-3B的紫外可见吸收谱没有明显的变化。臭氧/超声联合作用、单独臭氧化和单独超声处理脱除活性艳红KE-3B模拟废水5 min后的去除率分别为97%、73%和5%，表明臭氧/超声联合降解活性染料具有更高的氧化速率。实验研究了pH值、臭氧投加量、超声能量密度、反应温度对超声/臭氧降解活性艳红KE-3B反应速率的影响，在实验研究范围内，随着溶液初始pH的增大，KE-3B的去除率先增大后减小，超声能量密度的改变对KE-3B的去除影响不大，温度升高有利于氧化反应的进行。在溶液初始pH值为9.0，臭氧投加量3.2 g/h，超声能量密度176 W/L，反应温度20℃时，浓度为100 mg/L的活性艳红KE-3B溶液的去除率最高。     

UV/Fenton法处理酸性红B研究

采用UV/Fenton高级氧化技术对酸性红B模拟废水进行处理,当进水浓度为400mg/L时,确定了各影响因素的最佳投加量:H2O2投加量为2 mL/L,Fe2 投加量为0.08g/L,最佳pH值为4;并采用一级动力学公式对酸性红B降解速率进行拟合,研究了反应条件对速率常数的影响.最后通过对单独UV法、单独Fenton法和UV/Fenton法3种处理方法效果的比较,发现UV与Fenton试剂具有协同作用.     

UV／Fenton法处理酸性红B研究

采用UV／Fenton高级氧化技术对酸性红B模拟废水进行处理，当进水浓度为400mg／L时，确定了各影响因素的最佳投加量：H2O2投加量为2mL／L，Fe^2＋投加量为0．08g／L，最佳pH值为4；并采用一级动力学公式对酸性红B降解速率进行拟合，研究了反应条件对速率常数的影响。最后通过对单独UV法、单独Fenton法和UV／Fenton法3种处理方法效果的比较，发现UV与Fenton试剂具有协同作用。     

非均相催化臭氧氧化深度处理炼油废水

采用非均相催化剂催化臭氧氧化处理炼油废水,考察了催化剂负载率、p H、催化剂投加量和臭氧投加量及反应时间对处理效果的影响。结果表明,组合工艺最佳工艺条件为:催化剂负载率2.1%、p H 9、催化剂投量80 g/L、臭氧投量8.1 mg/L、反应时间60 min,COD、石油类、NH3-N、硫化物和SS去除率分别为91.3%、92.7%、80.5%、34.5%和59%。处理炼油废水过程中组合工艺存在明显协同效应,协同因子为1.47。中间臭氧氧化和催化臭氧氧化在最优工艺条件下对炼油废水COD的降解均符合准一级动力学规律。基于叔丁醇的实验结果,结合降解动力学可以推测,降解炼油废水过程中非均相催化剂催化臭氧产生高活性羟基自由基是降解效率提高的主导因素。     

响应面法优化催化臭氧氧化处理邻苯二甲酸二甲酯废水的研究

采用浸渍法制备负载铁锰氧化物的活性炭催化剂,并用其催化臭氧氧化处理邻苯二甲酸二甲酯(DMP)废水。利用响应面法(RSM)对催化臭氧氧化处理的工艺参数进行优化,以DMP废水的COD去除率为响应值,初始pH、催化剂投加量和臭氧通量的水平编码为自变量,建立了COD去除率与3个自变量的二次多项式回归方程。结果表明,二次多项式回归方程的F为15.660,P0.000 1,相关系数R2为0.933 7,说明该模型可以较好地模拟催化臭氧氧化处理DMP废水的效果。优化得到最佳的工艺参数为臭氧通量5.0L/min、催化剂投加量25.0g、初始pH=4.8,在此条件下处理60min后,DMP废水的COD去除率平均值为82.1%,与预测值84.3%接近。     

Catalytic oxidation of gaseous PCDD/Fs with ozone over iron oxide catalysts

Catalytic oxidation of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone (catalytic ozonation) over nano-sized iron oxides (denoted as FexOy) was carried out at temperature of 120-180 degrees C. The effects of operating temperature, ozone concentration, space velocity (SV) and water vapor contents on PCDD/F removal and destruction efficiencies via catalytic ozonation were investigated. High activity of the iron oxide catalyst towards PCDD/F decomposition was observed even at low temperatures with the aid of ozone. The PCDD/F removal and destruction efficiencies achieved with FexOy/O3 at 180 degrees C reach 94% and 91%, respectively. In the absence of ozone, the destruction efficiencies of all PCDD/F congeners are below 20% and decrease with increasing chlorination level of PCDD/F congener at lower temperature (120 degrees C). However, in the presence of ozone, the destruction efficiencies of all PCDD/F congeners are over 80% on FexOy/O3 at 180 degrees C. Higher temperature and ozone addition increase the activity of iron oxide for the decomposition of PCDD/Fs. Additionally, in the presence of 5% water vapor, the destruction efficiency of the PCDD/Fs is above 90% even at lower operating temperature (150 degrees C). It indicates that the presence of appropriate amount of water vapor enhances the catalytic activity for the decomposition of gas-phase PCDD/Fs.     

Effect of manganese ion on the mineralization of 2,4-dichlorophenol by ozone

Mineralization of 2,4-dichlorophenol (DCP) was studied by ozone with Mn(2+) as an ozonation catalyst. Laboratory scale semi-batch ozonation experiments were conducted at room temperature. The results showed that trace amount of Mn(2+) accelerated the mineralization of DCP. Total organic carbon removal rate was independent on Mn(2+) dosage at its range of 0.1-0.5 mgL(-1). Dissolved ozone concentration in the solution remained low level in the catalytic ozonation process, which indicated that Mn(2+) catalyzed decomposition of ozone. DCP mineralization was inhibited in catalytic ozonation by the addition of carbonate. Electron spin resonance/spin-trapping technique was used to determine hydroxyl radicals, and the results showed that larger amounts of hydroxyl radicals were produced in catalytic ozonation system than those of single ozonation. Intermediates mainly including aliphatic carboxylic acids were determined qualitatively and semi-quantitatively by GC-MS. And, a general pathway for mineralization of DCP was proposed.     

Chemical oxidation of wastewater from molasses fermentation with ozone

Color removal from biologically pre-treated molasses wastewater by means of chemical oxidation with ozone has been investigated. Batch experiments have been performed in order to analyze the influence of ozone dosage and reaction time on color removal, molecular weight distribution and decolorization kinetics. Depending on the applied ozone dosage, color removal from 71% to 93% and COD reduction from 15% to 25% were reached after 30 min reaction time. TOC values remained constant throughout ozonation. Gel permeation chromatography corroborated that high molecular weight compounds, responsible for the brown color, were present in raw wastewater. UV spectral studies confirmed that these colored compounds were melanoidins. As a result of ozonation the concentration of chromophore groups decreased. Ozonation of synthetic melanoidin under the same experimental conditions provided similar color removal efficiencies. Pseudo-first order kinetics with respect to colored compounds were found.     

Enhancement of chemical-oxygen demand and color removal of distillery spent-wash by ozonation.

Distillery spent-wash has very high organic content (75,000 to 125,000 mg/L chemical-oxygen demand [COD]), color, and contains difficult-to-biodegrade organic compounds. For example, anaerobic treatment of the distillery spent-wash used in this study resulted in 60% COD reduction and low color removal. Subsequent aerobic treatment of the anaerobic effluent resulted in enhancement of COD removal to 66%. In this paper, the effect of ozonation on various properties of the anaerobically treated distillery effluent, including the effect on its subsequent aerobic biodegradation, was investigated. Ozonation of the anaerobically treated distillery effluent at various ozone doses resulted in the reduction of total-organic carbon (TOC), COD, COD/TOC ratio, absorbance, color, and increase in the biochemical-oxygen demand (BOD)/COD ratio of the effluent. Further, ozonation of the anaerobically treated distillery effluent at an ozone dose of 2.08 mg/mg initial TOC and subsequent aerobic biodegradation resulted in 87.4% COD removal, as compared to 66% removal when ozonation was not used.     

Variables affecting efficiency of molasses fermentation wastewater ozonation

The main operating variables affecting ozonation efficiencies of wastewater from beet molasses alcoholic fermentation have been studied. Semibatch experiments have been performed in order to analyze the influence of pH, bicarbonate ion, temperature and stirring rate on color and organic matter removals. The efficiencies were similar regardless of the pH, which indicates that direct reactions of ozone with wastewater organics were predominant to radical reactions. Gel permeation chromatography confirmed the reduction in the concentration of organics absorbing light at 475 nm after ozonation. The elimination of bicarbonate ion, strong inhibitor of hydroxyl radical reactions, yielded an improvement in both color and COD reduction efficiencies. Acidification for removing bicarbonate ions produced a shift of colored compounds to smaller molecular weights. The highest efficiencies were achieved at 40 degrees C. Color and COD reductions at 40 degrees C were about 90% and 37%, respectively. In no case, the percentage of TOC removed was higher than 10-15%. Stirring rate had a slightly positive effect during the first stage of the ozonation showing that mass transfer played a role only during the initial reaction phase when direct attack of ozone molecules to aromatic/olefinic structures of colored substances was the predominant pathway.     

臭氧氧化法深度处理生活垃圾焚烧厂沥滤液

采用臭氧氧化法对生活垃圾焚烧厂沥滤液经生化处理后的废水(称沥滤液生化处理水)进行深度处理。实验结果表明,COD降解速率随废水pH的提高明显增加,其中pH=10.5时的COD降解速率常数约为pH=4时的5.8倍。在臭氧投量为52.92 mg/min、pH=10.5的条件下反应70 min后,UV254和COD去除率分别达到84.7%和59.3%。向反应体系投加叔丁醇后COD去除率下降了约15%,由羟自由基氧化去除的COD占总COD去除量的26.7%。毒性实验结果表明,沥滤液生化处理水的96 h-EC50为38%,经臭氧氧化进一步处理后出水的96 h-EC50为77%,表明经臭氧深度处理后沥滤液生化处理水的毒性明显降低。     

Characteristics of electrolysis, ozonation, and their combination process on treatment of municipal wastewater.

The characteristics of municipal wastewater treatment by electrolysis, ozonation, and combination processes of electrolysis and aeration using three gaseous species (nitrogen [N2], oxygen [O2], and ozone [O3]) were discussed in this research using ruthenium oxide (RuO2)-coated titanium anodes and stainless-steel (SUS304) cathodes. Electrolysis and electrolysis with nitrogen aeration were characterized by a rapid decrease in 5-day biochemical oxygen demand (BODs) and total nitrogen and a slow decrease in chemical oxygen demand (COD). In contrast, ozonation, electrolysis with oxygen aeration, and electrolysis with ozone aeration were characterized by transformation of persistent organic matter to biodegradable matter and preservation of total nitrogen. The best energy efficiency in removing BOD5 and total nitrogen was demonstrated by electrolysis, as a result of direct anodic oxidation and indirect oxidation with free chlorine produced from the chloride ion (Cl-) at the anodes. However, electrolysis with ozone aeration was found to be superior to the other processes, in terms of its energy efficiency in removing COD and its ability to remove COD completely, as a result of hydroxyl radical (*OH) production via cathodic reduction of ozone.     

活性炭-臭氧体系处理含氰废水的作用机理

针对活性炭催化臭氧化降解低质量浓度含氰废水体系,研究了活性炭吸附、催化作用在催化臭氧化体系中的作用,提出了吸附-催化臭氧化协同作用机理。在活性炭-臭氧体系中,活性炭吸附CN-的能力很弱,活性炭在反应体系中主要起了吸附、催化臭氧的作用。活性炭-臭氧体系降解CN-的过程是臭氧直接氧化、活性炭吸附臭氧与活性炭催化臭氧产生.OH自由基间接氧化三者共同作用的结果。     

Ce-PbO_2/C电极的制备及其去除水中酸性红B

采用电沉积法制备铈修饰的PbO2/C电极,通过SEM、XRD、XPS及循环伏安对PbO2/C、Ce-PbO2/C电极进行表征,结果表明,Ce-PbO2/C电极比PbO2/C颗粒细小,表面均匀致密,电化学氧化能力较强,修饰电极中Ce以CeO2的形态存在。以Ce-PbO2/C为工作电极,电解浓度为1 000 mg/L的高盐酸性红B模拟活性染料废水,考察了电压、pH、电解质浓度、极间距对脱色率、氨氮去除率及COD去除率的影响。确定适宜工艺条件为：初始酸性红B溶液浓度为1 000 mg/L,pH值为6,电压10 V,电解时间1 h,电极间距1.5 cm,该条件下脱色率、氨氮去除率和COD去除率分别为99.98%、97.23%和90.17%。通过UV-Vis及GC-MS初步分析了降解过程可能存在的中间产物及降解途径。     

铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制

以市售活性炭、硅藻土和氧化铝小球为载体，考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况，其中，铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性，证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制，以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明，与单独臭氧化相比，该催化剂既能有效去除水中的溶解性有机物，又能明显抑制溴酸盐的生成，反应50h，其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降，可以通过负载铁氧化物来实现催化剂的再生。