O3/H2O2氧化法处理油田采油废水的试验研究

为降低出水COD,提高采油废水的可生化性,采用O_3、O_3/H_2O_2组合工艺对某油田采油废水进行处理,考察氧化反应时间、O_3质量浓度、pH、H_2O_2投加量、n(H_2O_2)∶n(O_3)对废水处理效果的影响。结果表明,单独使用O_3处理油田采油废水时,在O_3为20 mg/L、反应时间为60 min、废水pH为8.50条件下,COD去除率为28.5%,B/C由0.08提至0.248;O_3/H_2O_2组合工艺的处理效果更显著,在O_3为30 mg/L、反应时间为60 min、H_2O_2投加量为0.24 g/L、废水pH为8.50的最佳条件下,COD去除率达到55.4%,B/C提升至0.440。氧化处理不仅降低了废水COD,还可提高废水的可生化性,是一种较为有效的预处理技术。     

O_3/H_2O_2氧化工艺深度处理胞苷酸生产废水

采用O_3/H_2O_2高级氧化工艺深度处理胞苷酸企业二级生化出水,考察了pH、H_2O_2用量、O_3浓度、反应时间等因素对深度处理效果的影响,探讨了有机磷矿化反应的动力学。结果表明,当废水有机磷质量浓度约为56 mg/L,COD约为640 mg/L时,适宜的反应条件为:pH 8.5,H_2O_2投加量20 mmol/L,O_3质量浓度12 mg/L,反应时间90 min;有机磷矿化反应遵循表观一级动力学,动力学常数为0.024 7 min-1。优化条件下,有机磷矿化率和COD去除率分别为91.6%和56.8%。O_3/H_2O_2氧化出水经混凝沉淀处理后,TP和COD符合纳管排放要求。     

Fe_2O_3/γ-Al_2O_3/H_2O_2/O_3对制药二级生化出水的深度处理研究

采用浸渍法将Fe_2O_3负载在γ-Al_2O_3表面,制备高活性催化剂。采用Fe_2O_3/γ-Al_2O_3/H_2O_2/O_3催化氧化深度处理制药二级生化出水,考察催化剂投加量、pH值、双氧水投加量、臭氧流量等对废水中COD去除率的影响。结果显示,在催化剂投加量3 g/L,废水pH为9,双氧水投加量1 mg/L,臭氧流量1.0 L/min条件下,COD去除率达到85.96%。催化剂循环使用10次后,COD去除率仍然可达到83%以上,证明催化剂稳定性良好。     

Fe_2O_3/γ-Al_2O_3/H_2O_2/O_3对制药二级生化出水的深度处理研究

采用浸渍法将Fe_2O_3负载在γ-Al_2O_3表面,制备高活性催化剂。采用Fe_2O_3/γ-Al_2O_3/H_2O_2/O_3催化氧化深度处理制药二级生化出水,考察催化剂投加量、pH值、双氧水投加量、臭氧流量等对废水中COD去除率的影响。结果显示,在催化剂投加量3 g/L,废水pH为9,双氧水投加量1 mg/L,臭氧流量1.0 L/min条件下,COD去除率达到85.96%。催化剂循环使用10次后,COD去除率仍然可达到83%以上,证明催化剂稳定性良好。     

采用UV/H_2O_2和UV/S_2O_8~(2-)对垃圾渗沥液的预处理实验研究

垃圾渗沥液属于较难处理的废水之一。对玻璃光反应器中紫外光UV分别与双氧水(H_2O_2)和过硫酸盐(S_2O_8~(2-))组合对垃圾渗沥液进行预处理,以提高其可生化性。分别在UV/H_2O_2和UV/S_2O_8~(2-)体系下,研究了H_2O_2和S_2O_8~(2-)的试剂用量、辐照时间等因素对COD、TOC及色度等去除率的影响。实验结果表明,UV/H_2O_2对COD、TOC和色度的最高去除率分别为15.8%、6.9%和39.1%。而采用UV/S_2O_8~(2-)法对COD、TOC和色度的最高去除率分别为23.9%、18.7%及63.7%。     

UV/H_2O_2高级氧化+MBR工艺处理垃圾渗滤液的研究

采取UV/H_2O_2+膜生物反应器组合工艺深度处理垃圾渗滤液,研究工艺对有机物及氨氮处理效果。结果表明,当工艺条件为双氧水投加量为2.1 g(H_2O_2)/g(COD),pH呈弱酸性,反应时间2 h、温度30℃左右时,UV/H_2O_2工艺处理效果好。MBR反应器对UV/H_2O_2工艺段出水中有机物的生化降解效果显著,出水有机物去除率稳定在80%以上。     

CuO-Fe_2O_3/γ-Al_2O_3/H_2O_2/O_3催化氧化深度处理制药二级生化出水

采用浸渍法将Cu O、Fe_2O_3负载在γ-Al_2O_3表面,制备高活性臭氧催化氧化催化剂,通过N_2吸附脱附曲线,X射线衍射、扫描电镜、X射线荧光光谱等方法对催化剂性能进行表征。与Cu O-Fe_2O_3/γ-Al_2O_3/O_3、H_2O_2/O_3、γ-Al_2O_3/O_3等工艺相比,采用Cu O-Fe_2O_(3/)γ-Al_2O_3/H_2O_2/O_3工艺降解制药二级生化出水效果最为明显,较高的催化氧化效率主要归功于H_2O_2的诱导作用和催化剂的催化作用的双重作用加速臭氧生成更多·OH。考察废水中COD去除率及影响降解的因素,包括催化剂投加量、p H、双氧水投加量、臭氧流量等,实验结果显示在催化剂投加量2g/L、废水p H为9、双氧水投加量3.6mg/L、臭氧流量1.0L/min条件下,COD去除率达到62.96%。催化剂循环使用10次后,COD去除率仍然可达到58%以上,并且金属离子浸出较少,其结构稳定。通过自由基捕获剂测试,探讨该催化氧化过程遵循自由基反应机理。     

O_3、O_3/H_2O_2、O_3/S_2O_8~(2-)处理畜禽养殖废水生化出水

采用O_3、O_3/H_2O_2、O_3/S_2O_8~(2-)体系来深度处理畜禽养殖废水。在实验条件下,臭氧/过硫酸盐联合氧化体系表现出更好的处理性能:COD去除率高达35.9%～40.6%,处理后出水的pH在6.5～8.8,可生化性提升到0.39～0.41,虽然硫酸根略有上升,但是不妨碍后续的生化处理。此外,臭氧/过硫酸盐联合氧化体系表现出良好的经济性能:在实验条件下,臭氧消耗系数在0.18～0.21 kg O_3/kg COD,处理成本仅为0.99元/吨水和6.60元/kg COD。     

不同高级氧化工艺处理焦化废水二级生化工艺出水研究

针对焦化废水二级生化处理工艺出水化学需氧量(COD)难以达标的问题,采用实际焦化废水,通过开展半连续实验室小试试验,对比研究了单独臭氧氧化、O_3/H_2O_2氧化和UV-Fenton氧化3种工艺深度处理焦化废水的效果,并对不同工艺出水的UV_(254)、BOD_5/COD、发光细菌毒性、三维荧光光谱进行分析,研究不同高级氧化工艺对出水水质的影响规律。结果表明:增加臭氧投加量和添加H_2O_2能显著提高焦化废水二级生化工艺出水中有机物的去除效果。进水COD为(200±10)mg/L、O_3投加量为30 mg/L时,反应120 min后单独臭氧氧化对COD的去除率仅为36%;而对于UV-Fenton氧化,进水COD为(200±10)mg/L、H_2O_2(30%)投加浓度为2 g/L、Fe~(2+)与H_2O_2摩尔比为1∶10时,COD的去除率为50%;单独臭氧氧化和UV-Fenton均不能满足排放标准。进水COD为(200±10)mg/L、O_3投加量为30 mg/L、H_2O_2(30%)投加浓度为2 g/L,反应120 min后COD去除率达到63%,O_3/H_2O_2氧化工艺出水COD达到74 mg/L,满足GB 16171—2012《炼焦化学工业污染物排放标准》的要求。3种工艺中,O_3/H_2O_2氧化的COD去除效果最好,这主要归因于O_3和H_2O_2协同产生强氧化性自由基,但当H_2O_2浓度过高时,体系中产生的·OH反而与H_2O_2反应,从而导致O_3/H_2O_2体系的氧化能力下降。3种工艺都能有效降低出水毒性,出水发光细菌急性毒性试验显示,单独O_3氧化、O_3/H_2O_2氧化处理15 min后,相对发光度分别上升到90%和87%,UV-Fenton氧化处理30 min后,出水的相对发光度上升到71.57%。与单独臭氧氧化和O_3/H_2O_2氧化工艺相比,UV-Fenton工艺处理出水急性毒性相对较高,可能与臭氧的消毒作用有关。3种工艺对废水可生化性的提高程度不明显,BOD_5/COD从0.02最大提升到0.1左右。UV_(254)和三维荧光光谱的对比分析表明,3种工艺对出水中芳香族化合物和荧光物质具有明显的分解作用。单独O_3氧化可优先降解废水中腐植酸类物质中的共轭双键结构,而O_3/H_2O_2氧化工艺对环状共轭污染物的氧化效果更显著。随着UV-Fenton氧化处理,焦化废水中大分子的类腐植酸以及紫外区类富里酸优先被氧化降解,最终转化为可见区类富里酸和类蛋白质,而类蛋白质和可见区类富里酸物质在出水中仍存在较高浓度,UV-Fenton氧化工艺对荧光物质去除能力最差。     

O_3-H_2O_2预处理提高农药废水处理效果生产性试验研究

某农药厂利用O_3-H_2O_2取代Fe/C-H_2O_2氧化工艺对农药废水进行预处理,研究了O_3和H_2O_2投加量分别对O_3-H_2O_2和Fe/C-H_2O_2去除COD效果的影响,分析并探讨O_3-H_2O_2预处理对抑制好氧池由丝状菌导致的污泥膨胀的途径。结果表明,O_3-H_2O_2和Fe/C-H_2O_2工艺处理后出水COD浓度从33000 mg/L分别下降为11000 mg/L和5700 mg/L,Fe/C-H_2O_2预处理对COD去除效果更好;可生化性试验结果表明O_3-H_2O_2和Fe/C-H_2O_2预处理后废水B/C比分别为0.64和0.48;污泥镜检结果表明O_3-H_2O_2工艺提高废水可生化性能够有效抑制好氧池丝状菌生长,防止污泥膨胀产生。     

Self-organized nano-crystallisation of BaF2 from Na2O/K2O/BaF2/Al2O3/SiO2 glasses

In glasses with the compositions (100 ? x)(2Na₂O·16K₂O·8Al₂O₃·74SiO₂)xBaF₂ (with x = 0 to 6), the glass transition temperature decreases with increasing BaF₂-concentration. Samples with x = 6 were thermally treated at temperatures in the range from 500 to 600 °C for 5–160 h. This leads to the crystallisation of BaF₂. The quantity of crystalline BaF₂ increases with increasing time of thermal treatment, while the mean crystallite size remains constant within the limits of error. The glass transformation temperature of partially crystallised samples increases with increasing crystallisation time and approaches a value equal to the temperature, at which the samples were treated. This is explained by the formation of a highly viscous layer enriched in SiO₂ which is formed during crystallisation. This layer acts as a diffusion barrier and hinders further crystal growth.     

H2O2 / O3, H2O2 / UV And H2O2 / Fe2+ Processes For The Oxidation Of Hazardous Wastes

Activated hydrogen peroxide produces very reactive OH-radicals which destroy hazardous contaminants in water. The principles and different methods of activation are described. Results from laboratory studies show the numerous applications of this new technology. A successful scaleup of laboratory tests to an industrial level is discussed. Finally, a cost estimate for treating different types of water with hydrogen peroxide is presented.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.     

Pd/Na2O/K2O/γ-Al2O3三元催化活性分析与评价

本文以浸渍法制备了活性γ-Al₂O₃涂层及Pd/Na₂O/K₂O/γ-Al₂O₃三元催化剂。考察了γ-Al₂O₃涂层比表面积随高温老化时间变化的规律。在实验室模拟尾气配气系统上，对Pd/Na₂O/K₂O/γ-Al₂O₃三元催化剂的起燃温度、抗高温老化及抗SO₂中毒能力进行了分析与评价。本文的γ-Al2O3涂层能经受1050℃的高温老化。Pd/Na₂O/K₂O/γ-Al₂O₃三元催化剂经900℃高温老化两次共13h后，其最大催化活性几乎不变，其老化样经600℃硫中毒1h后对CO和HC的催化转化率仍在75％以上。Pd/Na₂O/K₂O/γ-Al₂O₃新鲜样的起燃温度为280℃，二次老化样的起燃温度为320～350℃，具有很高三元催化活性。     

O3/UV,O3/TiO2/UV,O3/VO2/TiO2降解磺基水杨酸

实验利用O3/UV,O3/TiO2/UV,O3/VO2/TiO2降解了磺基水杨酸.结果表明,在这三种高级氧化技术中,O3/VO2/TiO2的氧化效果最好,如在相同的条件下,30 min后取样表明三者COD的去除率分别为47%,55%和70%.在不同pH条件下研究表明O3/TiO2/UV对水体pH的影响较为敏感.通过加入自由基猝灭剂研究表明三者产生羟基自由基的活性顺序是O3/VO2/TiO2＞O3/TiO2/UV＞O3/UV.     

O1/A1/O2/A2工艺处理焦化废水试验研究

通过对短程硝化反硝化工艺的研究,开发了好氧/厌氧/好氧/缺氧(O1/A1/O2/A2)生物脱氮新工艺并用于焦化废水的处理。考察了NH4+-N、COD、TN对反应器运行效果影响。结果表明,当进水COD平均为3 012.9 mg/L,NH4+-N、TN、挥发酚、总氰平均质量浓度分别为590.5、608.4、361.8、34.5 mg/L;出水COD平均为81.7 mg/L,出水NH4+-N、TN、挥发酚、总氰的平均质量浓度分别为0.1、9.9、0.1、0.1 mg/L,出水指标达到国家污水综合排放一级标准,A/O工艺处理这种焦化废水TN偏高,而用O1/A1/O2/A2工艺可以解决这一问题,实现了TN脱除。考察了温度、DO、pH对短程硝化影响。结果表明,在DO质量浓度为1.0～1.5 mg/L、温度在30～35℃、pH 7.5～8.0,系统能够进行稳定短程硝化反硝化。     

TNT的O3/H2O2降解规律

利用自制装置,采用连续投加O3、H2O2的方式,研究了O。／H：O：对废水中TNT的降解规律。结果表明,与Oa作用相比,O3／H2O2工艺可显著提高TNT的降解率,还可避免中间产物的形成与积累;在试验研究条件下,H2O2：O3的最优摩尔比为1,最佳初始pH值在11左右,利用缓冲溶液可维持反应体系pH值的稳定,但不利于O3／H2O2功效的发挥,反应适合在常温下进行,尽量避开40℃左右;动力学特征分析表明,O／H2O2降解TNT偏离伪一级反应动力学规律。     

Polycrystalline In2O3 and In2O3/Y2O3 photoanodes

Single crystal In₂O₃ shows promise as a photoanode for the decomposition of water. Because of various difficulties in the preparation of the single crystal material, two simple techniques were developed for the preparation of polycrystalline In₂O₃ anodes. One method involves the thermal decomposition of the nitrate while the other utilizes the chemical vapour deposition technique. Voltammograms and photoresponse spectra of these anodes are compared to the single crystal material. Among other observations, it is noted that the quantum efficiencies of the thermally decomposed films are comparable to the single crystal material. It is also shown that the on-set potential can be shifted to more negative values by forming the mixed oxide In₂O₃/Y₂O₃.     

Ethylene Hydrogenation over Pt/Ga2O3/Al2O3 Catalysts

The effects of gallia addition on the Pt dispersion and the activity for ethylene hydrogenation at 0 °C were studied for Pt-supported catalysts as a function of the reduction temperature (350, 450, and 550 °C). The catalysts contained 0.5 wt.% Pt and were prepared by successive incipient wetness impregnations with Ga(NO₃)₃ and H₂PtCl₆ aqueous solutions. CO and H₂ chemisorption data indicated that, the addition of small amount of Ga₂O₃ caused an increase of the Pt dispersion and a decrease of ethylene conversion. Both of them decreased appreciably when Ga₂O₃ addition was increased, particularly, for the case where β-Ga₂O₃ was used as a support. The increase in reduction temperature magnified the negative effects of the gallia addition on dispersion and activity, although the addition of small amount of gallia improved the resistance to metal sintering. Results were interpreted in terms of the presence of reduced Ga species, which can encapsulate Pt particles.     

Propylene metathesis over Re2O7/Al2O3-B2O3 catalysts

A series of alumina aluminum borate (AAB) with various Al/B molar ratios were prepared by the coprecipitation method. The supported rhenium oxide catalysts with various contents of Re₂O₇ were also prepared by the impregnation method with perrhenic acid. The catalytic activity and stability of Re₂O₇/AAB catalysts for the reaction of propylene metathesis were tested in a fixed-bed microreactor. It was found that Re₂O₇/AAB is more active, stable and regenerable than Re₂O₇/Al₂O₃ for propylene metathesis. The optimum Al/B molar ratio was found to be in the range of 4–10.