O_3/H_2O_2工艺降解1,2,4-三氯苯的优化设计

考察用不同的氧化剂降解1,2,4-三氯苯(TCB),3种不同方法对TCB的去除效果存在较大差别,其处理效果依次为:H2O2O3O3/H2O2。采用响应面法优化O3/H2O2工艺降解TCB的条件。结果表明,TCB初始浓度和H2O2投加量对TCB去除效果影响较大。TCB的降解符合准一级反应动力学规律,最佳降解条件为TCB初始浓度0.3 mg/L,pH=8.13,H2O2投加量0.40 mmol/L,O3转化率75%。在此条件下,TCB的平均去除率为91.5%,与预测值93.1%吻合度较高。     

O3、H2O2/O3及UV/O3在焦化废水深度处理中的应用

采用O₃、H₂O₂/O₃和UV/O₃等高级氧化技术(AOPs)对某焦化公司的生化出水进行深度处理，考察了O₃与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响，确定出O₃氧化反应的最佳工艺参数为：接触时间40 min，溶液pH 8.5，反应温度25℃，此条件下废水COD及UV₂₅₄的去除率最高可达47.14%和73.47%；H₂O₂/O₃及UV/O₃两种组合工艺对焦化废水COD及UV₂₅₄的去除率均有一定程度的提高，但H₂O₂/O₃系统的运行效果取决于H₂O₂的投加量。研究结论表明，单纯采用COD作为评价指标，并不能准确反映出O₃系列AOPs对焦化废水中有机污染物的降解作用。     

六氯苯的O3及UV/O3高级氧化降解试验研究

采用O₃、UV/O₃高级氧化法对水中六氯苯（HCB）的降解效果及机理进行了研究，并对结果进行了比较，结果表明，UV本身对HCB的去除率贡献不大，HCB可被O₃、UV/O₃快速降解，即UV＜O₃＜UV/O₃；O₃、UV/O₃作用时，提高体系的初始pH值不利于HCB的降解，在pH＝3，HCB=0.2 mg/L，反应40 min时，HCB的去除可达50%左右，酸性条件下有利于降解反应的进行；无论是O₃单独作用还是UV/O₃联合作用，HCB的降解基本上满足准一级反应动力学规律，如果体系的pH值基本保持恒定，这种规律就更为明显。根据离子色谱(IC)、GC对六氯苯降解中间产物进行了测定，探讨了O₃、UV/O₃降解六氯苯的途径和机理。     

镍网负载纳米TiO_2光催化反应器对酸性品红脱色效果实验研究

采用负载纳米TiO2的三维镍网装配了光催化反应器,就其对酸性品红溶液进行脱色效果进行了实验研究。考察了反应器的3种装配条件、品红初始浓度、pH值、H2O2投加量、紫外光剂量等因素对酸性品红脱色效果的影响。结果表明:UV灯+镍网+TiO2模式组合的反应器脱色效果最好;在相同的处理时间内酸性品红溶液的脱色率随起始浓度的增大而减小;将酸性品红溶液pH值调至5时脱色效果最明显,70 min的脱色率可高达94.8%。脱色效果还可以通过溶液中添加H2O2和控制紫外线剂量来调节。当溶液中H2O2投加量为0.5 g/L时,处理70 min后的脱色率可高达98.3%;到达反应界面紫外光剂量越多则能够获得越高的酸性品红脱色率。     

高级氧化法脱除PVA浆料的清洁生产新工艺研究

为了研究高级氧化法脱除聚乙烯醇(PVA)浆料清洁生产新工艺的可行性,研究了3种高级氧化法UV/H2O2、UV/TiO2、Nafion-Fe2 /H2O2对含PVA溶液的氧化降解,其降解效果依次为:UV/H2O2＞Nafion-Fe2 /H2O2＞UV/TiO2.对于UV/H2O2法,PVA降解速率与H2O2的初始浓度成正相关,且H2O2浓度为2.95 mmol/L时14 min内就能使PVA的去除率达到98%;pH和温度对PVA的氧化降解效果影响不明显.在此基础上,对建立在高级氧化法基础上的退浆新工艺进行了探讨,结果表明,在65℃和75℃下,高级氧化法条件下的纯棉织物PVA退浆率分别达到70.16%和95.65%;该法不仅可以促进PVA从纯棉织物上的脱附,而且可以达到对PVA的较高降解效果,使得所排退浆废水的生化处理难度明显降低.     

UV/H2O2工艺降解环丙沙星的研究

采用UV/₂O₂工艺去除水体中的喹诺酮类抗生素环丙沙星（CIP）。考察了溶液pH值、₂O₂投加量以及水体基质对环丙沙星降解效率的影响，分析了降解产物的生成情况。研究表明，环丙沙星的降解符合拟一级反应动力学模型。降解速率受溶液pH值的影响，酸性及中性条件，有利于环丙沙星的降解。₂O₂投加量的增大，使得降解速率逐渐增大，但速率增幅逐渐变缓；最佳₂O₂/环丙沙星摩尔比为2 000。实际水体中存在的NOM、NO^-₃，促进了单独UV作用下，环丙沙星的降解。水体中的?OH焠灭剂，抑制了UV/₂O₂联合作用下，环丙沙星的降解；实际水体中的光解速率常数低于超纯水中的光解速率常数。GC-MS分析表明，UV/₂O₂工艺，使环丙沙星氧化降解生成氨基乙酸、丙二酸、丙三醇和对苯二甲酸等小分子有机物。     

微气泡曝气 O3/ H2O2处理 RO 浓水的效能及影响因素简

采用O₃/H₂O₂高级氧化工艺处理炼油厂反渗透（RO）浓水，用溶气泵加压溶气并产生微气泡强化传质，确定装置运行条件，考察气体中臭氧浓度、H₂O₂/O₃初始摩尔比、pH和温度对O₃/H₂O₂处理RO浓水效果的影响，并对RO浓水处理效能进行研究。结果表明，随着气体中臭氧浓度的增加，COD的去除率基本呈线性增加；加入适当量H₂O₂能提高臭氧氧化RO浓水的效果，H₂O₂/O₃初始摩尔比在0~0.8范围内，COD的去除率先增加后下降，H₂O₂/O₃初始摩尔比为0.5时COD去除率最大；pH从6.84增加到9.01，COD去除率逐渐增大，pH为10.03时COD去除率反而降低；在14~28℃范围内，温度低时，升高温度COD去除率增加较大，温度较高时，升高温度对COD去除率的影响较小。为考察该工艺的稳定性，在H₂O₂/O₃初始摩尔比为0.5、溶液pH为8~9、臭氧浓度为80~100 mg/L、温度为10~28℃条件下，对COD为90~140 mg/L的RO浓水氧化处理4~10 h，出水COD维持在39.9~49.9 mg/L，达到《城镇污水处理厂污染物排放标准（GB 18918-2002）》中的一级A标准；去除1 g COD消耗O₃ 1.4~3.3 g，消耗O₃与H₂O₂的总氧量为2.2~4.4 g。     

O3氧化工艺处理黄连素制药废水研究

采用臭氧(O₃)氧化法处理含高浓度黄连素和COD的制药废水，探讨了废水初始pH、O₃投加量及初始黄连素浓度等因素对O₃氧化过程的影响，确定了O₃氧化技术处理黄连素制药废水的最佳操作条件。结果表明，O₃能够有效分解废水中的黄连素，降低其COD浓度；黄连素浓度为700 mg/L、COD为3 500 mg/L、pH为0.88的废水，进气O₃浓度为14.05 mg/（L?min），处理时间为180 min（即投加量为2 529 mg/L）时，黄连素和COD的降解率分别可达77.46%和41.28%，BOD₅/COD比（B/C比）从0.06提高到0.34，增加了4.7倍；随着废水中初始黄连素浓度的升高，废水COD降解率逐渐降低。O₃氧化法是一种有效的黄连素制药废水预处理技术，可以大大提高废水的可生化性。     

O3、H2O2／O3及UV／O3在焦化废水深度处理中的应用

采用O3、H2O2／O3及UV／O3等高级氧化技术（AOPs）对某焦化公司的生化出水进行深度处理，考察了O3与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响，确定出O3氧化反应的最佳工艺参数为：接触时间40min，溶液pH8．5，反应温度25℃，此条件下废水COD及UV254的去除率最高可达47．14％和73．47％；H2O2／O3及UV／O3两种组合工艺对焦化废水COD及UV254的去除率均有一定程度的提高，但H2O2／O3系统的运行效果取决于H2O2的投加量。研究结论表明，单纯采用COD作为评价指标，并不能准确反映出O3系列AOPs对焦化废水中有机污染物的降解作用。     

膜分离-光电催化深度处理高盐含聚污水

海上油田含聚采油污水黏度大、乳化程度高、有机物种类繁多且盐含量高,处理难度极大。尝试采用膜分离-光电催化组合工艺深度处理高盐含聚采油污水,效果较好。考察了停留时间、电流密度、废水p H对光电催化体系运行效果的影响。结果表明:光电催化氧化技术可有效处理该类废水;p H对体系处理效率影响不大;停留时间越长,处理效果越好;随电流密度的增大,油类去除率逐渐提高,COD去除率先提高后趋于稳定。在p H 6~8.5、光电催化单元停留时间50 min、电流密度10 m A·cm-2条件下,出水COD浓度≤50 mg·L~(-1)、石油类浓度≤3 mg·L~(-1),完全满足《辽宁省污水综合排放标准》(DB 21/1627-2008)要求。     

Fenton试剂法降解餐厨垃圾异味

自行设计Fenton试剂法降解还原性气体异味的反应器,研究了Fenton试剂法处理餐厨垃圾异味主要成分(苯、乙酸乙酯、苯乙烯)的降解效果。以苯为典型代表物,优化得出该实验的最佳反应条件为:pH=3,FeSO4.7H2O投加量为1 g/L液相,30%H2O2投加量为10 mL/L液相,紫外光源辅助。结果证明,Fenton试剂法处理单一异味气体的效果较理想,在前180 min内能达到90%以上,该法在处理气态异味污染物方面具有广阔的应用前景。     

微波辐射Bi2O3/沸石-H2O2体系降解废水中的硝基苯

研究了微波辐射下，以负载于沸石上的三氧化二铋为催化剂，以双氧水为氧化剂的催化氧化体系处理硝基苯工艺。通过单因素实验法，从反应催化剂负载量、pH、双氧水用量、微波功率、反应时间、催化剂用量等方面初步考察了硝基苯在该体系中的催化氧化效果。在氧化铋负载量3%（质量比），pH=2，2 mL 30%双氧水，火力为中火，催化剂投加量为0.7 g，反应2 min，对降解过程所得的中间产物和终产物进行了分析。结果表明，该体系对硝基苯的去除率能够达到99.2%，COD去除率为73.91%。     

Photooxidative removal of the herbicide Acid Blue 9 in the presence of hydrogen peroxide: modeling of the reaction for evaluation of electrical energy per order (EEO)

The present work deals with photooxidative removal of the herbicide, Acid Blue 9 (AB9), in water in the presence of hydrogen peroxide (H₂O₂) under UV light illumination (30 W). The influence of the basic operational parameters such as amount of H₂O₂, irradiation time and initial concentration of AB9 on the photodegradation efficiency of the herbicide was investigated. The degradation rate of AB9 was not appreciably high when the photolysis was carried out in the absence of H₂O₂ and it was negligible in the absence of UV light. The photooxidative removal of the herbicide was found to follow pseudo-first-order kinetic, and hence the figure-of-merit electrical energy per order (E_Eo) was considered appropriate for estimating the electrical energy efficiency. A mathematical relation between the apparent reaction rate constant and H₂O₂ used was applied for prediction of the electricity consumption in the photooxidative removal of AB9. The results indicated that this kinetic model, based on the initial rates of degradation, provided good prediction of the E_Eo values for a variety of conditions. The results also indicated that the UV/H₂O₂ process was appropriate as the effective treatment method for removal of AB9 from the contaminated wastewater.     

Effectiveness evaluation of glyphosate oxidation employing the H2O2/UVC process: Toxicity assays with Vibrio fischeri and Rhinella arenarum tadpoles

The H₂O₂/UVC process was applied to the photodegradation of a commercial formulation of glyphosate in water. Two organisms (Vibrio fischeri bacteria and Rhinella arenarum tadpoles) were used to investigate the toxicity of glyphosate in samples M_1, M₂, and M₃ following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H₂O₂. Subsamples of M₁, M₂, and M₃ were then used to create samples M_1,E, M_2,E and M_3,E in which the H₂O₂ had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M_1,E, which was collected early in the photodegradation process, caused 52% inhibition, while M_3,E, which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M₂, M₃, and in M_1,E, M_2,E and M_3,E. The lowest percentages of enzymatic inhibition were observed in samples without removal of H₂O₂: 13.96% (AChE) and 16% (BChE) for M₂, and 24.12% (AChE) and 13.83% (BChE) for M₃. These results show the efficiency of the H₂O₂/UVC process in reducing the toxicity of water or wastewater polluted by commercial formulations of glyphosate. According to the ecotoxicity assays, the conditions corresponding to M₂ (11 ± 1 mg a.e. L^?1 glyphosate and 11 ± 1 mg L^?1 H₂O₂) could be used as a final point for glyphosate treatment with the H₂O₂/UV process.     

Experimental and numerical study of methylparaben decomposition in aqueous solution using the UV/H2O2 process

The present paper aims at presenting a kinetic model that is supposed to result in the decomposition of methylparaben in completely mixed batch reactor (CMBR) using the UV/H₂O₂ process. The proposed model incorporates photochemical, chemical reactions and their constant rates to formulate the overall kinetic rate expressions which are integrated into MATLAB. Thus, the changes in pH values during the process of oxidation are taken into consideration. In addition, the effects of hydrogen peroxide (HP) dosage, as well as the concentration of hydroxyl radicals, are examined. Accordingly, the pseudo-first-order rate constant, its variation as functions of HP concentration, incident UV-light intensity and the limitations of the adopted approach are discussed. In line with that, the authors provided evidence of the validity of the kinetic model through the exposure of previous experimental studies as reported in the literature review then through the evidence of the present experimental data.     

Removal of AOX, total nitrogen and chlorinated lignin from bleached Kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO2 as photocatalyst

Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m³/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H₂O₂ and TiO₂ concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O₂ is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H₂O₂ and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H₂O₂ was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H₂O₂ concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H₂O₂ concentration, the concentration of 20.0 mL/L H₂O₂ appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min⁻¹) for the UV/TiO₂/H₂O₂ system were higher than that of the corresponding values for the UV/H₂O₂ system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. It was found that the UV/TiO₂/H₂O₂ system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO₂/H₂O₂ photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

天然沸石负载La2O3-ZnO-TiO2光催化降解活性艳红K-2BP

利用80目天然斜发沸石作载体制备La₂O₃(0.5%)-ZnO(20%)-TiO₂/沸石复合光催化剂，以20 W紫外灯为光源，在自制的光催化反应器中降解活性艳红K-2BP，考察了光照时间、空气通入量、催化剂用量、溶液初始浓度、H₂O₂与Fe³⁺投加量等对活性艳红K-2BP光催化降解率的影响。结果表明，当溶液初始浓度为60 mg/L，催化剂投加量为12 g/L，通气量为1 200 mL/min，光照2.5 h，活性艳红K-2BP的降解率可达99.2%；H₂O₂和Fe³⁺投加量为4 mL/L和3 g/L时，光照1 h活性艳红K-2BP降解率分别为100%和97.2%。紫外可见吸收光谱显示，LZTZ光催化剂可有效降解印染废水。     

超声波协同H_2O_2处理养殖场污水

为了有效地改善养猪场污水的质量,以H2O2为药剂,对污水进行了水浴加热和超声波辅助的对比实验,考察了超声波发生器输出端电流强度、处理时间、H2O2用量对污水的COD、氨气及颜色的影响,并进行正交实验优化。结果表明,超声波协同H2O2处理养殖污水是一种切实可行的方法,超声波协同H2O2处理污水的最佳工艺条件:电流0.7 A、处理时间2 min、H2O2用量3%,在此条件下降低COD量可达95%以上,氨氮的含量可降至14~15 mg/L,氨臭味大大得到了改善,并将原污水由黑色变为浅黄色。     

Performance evaluation of the UV/H2O2 process on selected nitrogenous organic compounds: reductions of organic contents vs. corresponding C-, N-DBPs formations

The presence of various organic contaminants in water sources is of concern due to their direct threats to human health and potential to react with disinfectants to form carcinogenic byproducts including trihalomethanes, haloacetic acids and nitrosamines in finished water. This study applied both medium-pressure and low-pressure ultraviolet light coupled with hydrogen peroxide (UV/H₂O₂) to evaluate its efficacy for degradation of selected nitrogenous organic compounds and corresponding disinfection byproduct (DBP) formation. Six organic compounds were chosen as target precursors based on their nitrogen contents and molecular structures. The results showed that higher oxidation capacity resulted in better reduction of organic matters and DBP formation potentials (DBPFPs). However, insufficient contact time and oxidant doses could lead to a rise of DBPFPs in the early stages of UV/H₂O₂ reactions. A greater percentage removal was achieved for organic carbon than organic nitrogen after UV/H₂O₂ treatment, especially for compounds with complicated structure such as diltiazem. During the UV/H₂O₂ treatment, the intermediate products include tertiary amine, dimethyl amine (DMA) or DMA-like structures, which are N-nitrosodimethylamine (NDMA) precursors after chlorination or chloramination. Furthermore, it was observed that using dissolved organic nitrogen and DMA to predict NDMAFP could lead to biased conclusions because of the complex nature of nitrogenous matters in aqueous environments.     

臭氧辅助UV/Fenton法处理电镀添加剂生产废水

采用臭氧辅助光芬顿法处理电镀添加剂生产废水，考察双氧水、FeSO₄·7H₂O、pH和反应时间等因素对废水COD和UV₂₅₄去除的影响。实验结果表明，pH=4，臭氧通入量为0.25 g，双氧水的投加量93.3 mL/L，FeSO₄·7H₂O投加量为5.3 g/L，最佳反应时间为30 min，COD和UV₂₅₄去除率分别达到92.64%和87.95%。这表明，臭氧辅助光芬顿法对电镀添加剂生产废水处理效果显著，处理时间大大减少。