催化臭氧氧化去除垃圾渗滤液中难降解有机物的研究

研究了Fe(Ⅱ),Mn(Ⅱ),Cu(Ⅱ)作用下,均相催化臭氧氧化去除垃圾渗滤液中高浓度的腐殖质.分析催化剂用量、溶液pH值对腐殖质催化臭氧氧化降解的影响.结果表明,与单纯臭氧氧化比较,催化臭氧氧化对UV254和色度去除率无明显改善,但可明显提高以TOC和CODCr表征的有机物去除率;当投加催化剂过量时,以TOC和CODCr表征的有机物去除率虽降低,但仍有促进作用.但Fe2 的过量投加将明显抑制UV254和色度的去除效果.在碱性条件下,催化臭氧氧化法具有更好的去除效果.三种催化剂催化效果为Cu(Ⅱ)＞Mn(Ⅱ)＞Fe(Ⅱ).采用Cu(Ⅱ)催化臭氧氧化处理实际渗滤液生化处理出水,对CODCr,色度和UV254都显示出较好的去除效果.     

颗粒活性炭催化臭氧氧化降解活性黑5

本文以深度处理后印染废水为配水模拟实际废水,对颗粒活性炭催化臭氧氧化降解活性黑5进行了研究.用低温N_2吸附-脱附等温线、SEM-EDS等对颗粒活性炭进行了表征,发现颗粒活性炭比表面积高达931 m~2·g~(-1).考察了颗粒活性炭吸附性能和催化臭氧活性,结果表明单独臭氧与颗粒活性炭催化臭氧脱色率在反应30 min内均高达100%.反应1h时,5 g·L~(-1)、10 g·L~(-1)颗粒活性炭催化臭氧TOC去除率分别为57%、74%,比单独臭氧高出33%和50%,颗粒活性炭具有良好的催化效果,能提高对污染物的矿化效果.颗粒活性炭促进了溶解性臭氧分解,重复使用6次后10 g·L~(-1)活性炭在反应时间为2 h时染料废水TOC去除率均能稳定在85%左右,多次利用后活性炭的催化活性没有明显降低.EPR检测表明,其主要机制为颗粒活性炭能够稳定地催化臭氧分子分解产生羟基自由基,实现污水中有机物的矿化.     

铈负载SBA-15分子筛催化臭氧氧化水中环丙沙星

通过水热法合成纯硅介孔分子筛SBA-15,并采用等体积浸渍法制备Ce负载SBA-15分子筛催化剂(Ce/SBA-15),将其应用于催化臭氧氧化环丙沙星(CIP).小角X射线衍射(XRD)、透射电镜(TEM)表征结果表明,Ce/SBA-15保持了纯硅SBA-15有序的介孔结构.Ce/SBA-15催化臭氧氧化环丙沙星(CIP)结果显示,催化剂有良好的活性,对环丙沙星的矿化率为63.3%,比单独臭氧氧化高出22.9%;随着铈负载量增加,催化剂活性呈现先增大后减小趋势,负载量为2%时催化效果最佳;TOC去除率随着反应温度增加而提高;溶液初始pH对反应有显著的影响,pH=5.01时TOC去除率最大.以水杨酸作为羟基自由基(·OH)捕获剂,用比色法测定·OH产量为0.0072 mmol·L~(-1).溶液中投加1 mmol·L~(-1)磷酸根时,催化臭氧氧化中TOC去除率降低了25.8%,催化效果受到明显抑制,表明·OH的生成发生在Ce/SBA-15表面.     

垃圾渗滤液湿式氧化催化剂Fe-Co-Pt-Ce/FSC的组分配比优化及表征

采用等量浸渍法制备不同金属组分配比的Fe-Co-Pt-Ce/FSC负载型催化剂,并用于催化湿式氧化垃圾渗滤液,以COD去除率、浊度去除率和垃圾渗滤液处理中p H值的变化评价催化剂的活性,以金属溶出浓度评价催化剂的稳定性,考察金属组分配比对催化剂活性和稳定性的影响.通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、热重-差热(TG-DTA)、孔结构、X射线衍射(XRD)和X射线光电子能谱法(XPS)表征优选催化剂的组构性能,结果表明,Fe_1Co_1Pt_1Ce_3/FSC催化剂表现出最佳的催化性能,其作用下垃圾渗滤液的COD去除率、浊度去除率和最低pH值分别为86.2%、99.9%和6.34,金属溶出浓度为2.88 mg·L~(-1);焙烧温度的提高使催化剂活性降低但是稳定性提高,适宜的焙烧温度是500℃;催化剂的比表面为240.6 m~2·g~(-1),活性组分在载体表面分布均匀,组分粒子尺寸约为8.02 nm;催化剂组分主要以FeO、CoO、Pt和CeO_2的形式存在,且催化剂的金属元素之间存在协同作用.     

催化臭氧氧化降解罗丹明B的初步研究

研究了过渡金属硝酸盐及Al2O3为载体担载催化剂在罗丹明B臭氧氧化过程中的催化作用,考察了温度、pH值以及催化剂浓度等因素对反应的影响.结果表明,过渡金属离子可显著地提高罗丹明B的脱色速率,而担载型过渡金属氧化物催化剂活性较低.较低的pH值和反应温度有利于罗丹明B的催化臭氧化.罗丹明B溶液经过催化臭氧氧化后COD去除率可提高24%.     

Ca(OH)_2絮凝沉淀-臭氧氧化垃圾渗滤液生化出水提高反渗透性能

为了提高生化出水的反渗透性能,本文提出采用Ca(OH)_2絮凝沉淀预处理生化出水,再经O_3氧化后,用于反渗透膜的深度处理工艺.研究表明,Ca(OH)_2絮凝沉淀可以有效地去除垃圾渗滤液生化出水中的大分子有机物及Ca~(2+)、Mg~(2+)离子.当废水絮凝沉淀出水的电导率最低时,废水中的Ca~(2+)和Mg~(2+)离子浓度降到最低,同时也去除了较大比例的COD.对电导率最低条件下的Ca(OH)_2絮凝沉淀出水再经O_3处理后,废水中的Ca~(2+)和Mg~(2+)离子浓度和COD进一步降低,其反渗透膜通量比MBR出水的通量增高25%—35%,膜污染明显减轻,可延长膜清洗周期.臭氧氧化Ca(OH)_2絮凝沉淀出水涉及到臭氧分子直接氧化和氢氧根催化臭氧氧化两种机理,但前者起主导作用.臭氧氧化处理进一步降低了废水中的COD和Ca~(2+)、Mg~(2+)离子浓度,是提高反渗透膜通量的主要原因.     

二氧化氯催化氧化处理直接大红染料

研究了ClO2化学氧化体系和ClO2催化氧化体系。实验结果表明:单用ClO2化学氧化处理COD为3 400mg/L的直接大红染料配制废水时,最佳反应pH值为1,氧化剂ClO2经济用量为400 mg/L废水,反应时间为10 min,COD去除率可达85.9%,氧化指数(COD削减量∶ClO2投加量)=7。当ClO2与自制催化剂所组成的催化氧化体系用于对直接大红染料配制废水的处理时,最佳反应pH值为2左右,氧化剂ClO2经济用量为600 mg/L废水,反应时间为6 min,COD去除率可达96.6%,氧化指数=6。结果表明,ClO2催化氧化法是一种新型高效的处理难降解废水的技术,有着广阔的应用前景。     

水热电催化氧化法降解高浓度苯胺废水

以CuO-MnO2-CeO2/C为催化剂,对COD=9000mg·l-1,NH3-N=700mg·l-1的模拟苯胺废水进行实验,讨论了催化剂用量对实验的影响,以及pH值和温度对COD及NH3-N去除率的影响.结果表明,在T=225℃,pH=10.03时,用湿式催化氧化法(CWO)处理1h后,苯胺废水中COD的去除率高达90%左右,NH3-N的去除率可达94%以上.利用水热电催化氧化法,以RuO2/Ti为电极,NaCl为电解质,在相同条件下,135℃时COD和NH3-N的去除率都可达到96%以上.     

多通道网状电极电化学预处理垃圾渗滤液反渗透浓缩液

反渗透(Reverse Osmosis,RO)因出水水质好、运行成本低等优势常用于垃圾渗滤液的处理,但产生的RO浓缩液具有COD高、色度高、盐分高、难降解等特点,其处理存在效果差、能耗和成本均较高等问题.本工作采用氧化钌/氧化铱涂层电极(RuO2/IrO2-Ti)的钛网为阳极,以304不锈钢电极为阴极,设计制作了6通道的电化学反应器,通过电化学氧化处理RO浓缩液,研究考查了电流密度、循环流速、比电极面积等参数对COD去除效果的影响,分析了电化学氧化去除难降解有机物并同时脱盐的过程机理与能耗.结果表明,在电流密度32.89 mA·cm^-2,循环流速0.46 cm·s^-1,比电极面积65.10 m²·m^-3的条件下,电化学氧化处理RO浓缩液3 h,COD去除率可达68.0%,TOC去除率可达40.6%,脱盐率可达72.1%,去除单位质量COD能耗仅为常规的板状电极电化学反应器的25.5%.本工作可为垃圾渗滤液RO浓缩液的预处理提供新思路.     

催化湿式过氧化氢氧化农药废水Cu-Ni-Ce/SiO2催化剂的研究

研究了Cu-Ni-Ce/SiO2催化剂的载体粒度、负载量、焙烧温度和Ce添加量等因素对催化剂活性及稳定性的影响,其最佳制备条件为:80-100目SiO2载体、4%负载量,700℃焙烧温度,0.16?添加量.利用BET比表面积、XRD和金属溶出量对催化剂进行了表征.结果表明:Cu-Ni-Ce/SiO2催化剂催化湿式过氧化氢氧化降解处理吡虫啉农药废水,在催化剂用量10g·l-1,反应温度110℃,双氧水用量为理论需用量,进水pH值为9.0,反应60min的条件下,COD去除率为88.7%,活性组分溶出量较小.     

Catalytic ozonation of organic compounds in water over the catalyst of RuO2/ZrO2-CeO2

This research investigates the performances of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment. The results show that RuO₂/ZrO₂-CeO₂ was active for the catalytic ozonation of oxalic acid and possessed higher stability than RuO₂/Al₂O₃ and Ru/AC. In the catalytic ozonation of dimethyl phthalate (DMP), RuO₂/ZrO₂-CeO₂ did not enhance the DMP degradation rate but significantly improved the total organic carbon (TOC) removal rate. The TOC removal in catalytic ozonation was 56% more than that in noncatalytic ozonation. However this does not mean the catalyst was very active because the contribution of catalysis to the overall TOC removal was only 30%. The adsorption of the intermediates on RuO₂/ZrO₂-CeO₂ played an important role on the overall TOC removal while the adsorption of DMP on it was negligible. This adsorption difference was due to their different ozonation rates. In the catalytic ozonation of disinfection byproduct precursors with RuO₂/ZrO₂-CeO₂, the reductions of the haloacetic acid and trihalomethane formation potentials (HAAFPs and THMFPs) for the natural water samples were 38%–57% and 50%–64%, respectively. The catalyst significantly promoted the reduction of HAAFPs but insignificantly improved the reduction of THMFPs as ozone reacts fast with the THMs precursors. These results illustrate the good promise of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment.     

Catalytic activity of cerium-doped Ru/AlO during ozonation of dimethyl phthalate

In this paper, factors influencing the mineralization of dimethyl phthalate (DMP) during catalytic ozonation with a cerium-doped Ru/Al₂O₃ catalyst were studied. The catalytic contribution was calculated through the results of a comparison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 min reached 75.1%, 61.3% using Ru/Al₂O₃ catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al₂O₃ support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru–Ce/Al₂O₃ on catalytic activity.     

Catalytic activity of cerium-doped Ru/Al2O3 during ozonation of dimethyl phthalate

In this paper, factors influencing the mineralization of dimethyl phthalate (DMP) during catalytic ozonation with a cerium-doped Ru/Al₂O₃ catalyst were studied. The catalytic contribution was calculated through the results of a comparison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 min reached 75.1%, 61.3% using Ru/Al₂O₃ catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al₂O₃ support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru-Ce/Al₂O₃ on catalytic activity.     

膜生物反应器（MBR）处理垃圾渗滤液的脱氮研究

采用一体式MBR处理垃圾渗滤液,系统考察MBR对COD、NH4＋-N和TN的去除效果。结果表明：可将垃圾渗滤液的COD降至650-1 500 mg·L-1范围;在HRT为1.5 d、DO为0.75-1.20 mg·L-1、不排泥条件下运行时,对TN质量浓度低于2 300 mg·L-1、容积负荷低于0.25 kg.m-3.d-1（以N计）的渗滤液进行处理,MBR对NH4＋-N与TN的去除率可分别达到87%和72%以上。在MBR处理垃圾渗滤液的运行中发现,膜的污染速度较快,并且呈现＂两段性＂的规律,采用碱＋氧化剂的清洗方式可有效去除膜污染,降低过膜压力。     

光照法处理垃圾渗滤液试验研究

采用直接光照处理青山垃圾填埋场和流芳垃圾填埋场的渗滤液,结果表明,直接光照处理4h,COD去除率分别为31%和18%,其主要原因在于青山垃圾填埋场中含有较多Fe和Cu等光催化物质及自身的光降解.直接光照对NH3-N和总-N的处理效果不佳.     

Ce-MCM-41分子筛用于臭氧氧化对氯苯甲酸的活性评价

通过水热法合成了铈掺杂MCM-41(Ce-MCM-41)介孔分子筛,并将其用于臭氧氧化水中对氯苯甲酸(p-CBA).小角X射线衍射(XRD)、氮气吸附-脱附(BET)、紫外可见漫反射光谱(UV-Vis DRS)、透射电镜(TEM)表征结果表明,铈成功进入MCM-41分子筛骨架,以正四面体形式存在,且Ce-MCM-41保持了纯硅MCM-41有序的介孔结构,具有较高的比表面积;铈的掺杂显著提高MCM-41催化臭氧氧化对氯苯甲酸的活性,反应60 min后,TOC去除率由MCM-41的63%提高到86%(Si/Ce=60),而单独臭氧氧化仅为52%;铈的溶出仅为0.085 mg.L-1,较同样负载量的铈负载Ce/MCM-41的溶出(0.44 mg.L-1)有较大减少.催化剂重复使用3次后仍保持较高的活性,这表明Ce-MCM-41具有较好的活性和稳定性,是一种有前景的臭氧氧化催化剂.     

厌氧-膜生物反应器处理垃圾渗滤液中多环芳烃的研究

采用固相萃取前处理和气相色谱／质谱联用的方法，分析厌氧．膜生物反应器处理垃圾渗滤液中多环芳烃的去除效果．结果表明，对多环芳烃的总去除效率超过80％；大部分三环、四环和五环的芳烃可在处理过程中被厌氧降解．多环芳烃的主要降解反应发生在厌氧滤池工艺段，然而SCOD(溶解性化学耗氧量)，BOD和TOC的主要去除工艺段则是膜生物反应器．     

Effect of preparation parameters on catalytic properties of Pt/graphite

Catalytic ozonation of aqueous solutions of oxalic acid was examined in the presence of graphite-supported platinum catalysts. The catalytic activity of graphite was significantly enhanced by loading platinum. The removal efficiency of oxalic acid was 3.0%, 47.6% and 99.3% for ozonation alone, graphite catalytic ozonation and Pt/graphite catalytic ozonation in 30 min under the experimental condition, respectively. The influence of support pretreatment, solvent, impregnation time, platinum loading amount and reduction temperature on the activity of Pt/graphite catalyst was investigated. The pretreatment of graphite support had no effect on activity improvement of Pt/graphite catalyst. Solvent and impregnation time also no great effect on the activity. Platinum loading amount and reduction temperature influenced the catalyst activity significantly. The optimal catalytic performance of Pt/graphite was obtained when 1.0% platinum loading and 623 K of reduction temperature was adopted. The Pt/graphite catalyst was used for five times with no significant decrease in its activity and more than 90% oxalic acid removal was obtained.     

利用矿化垃圾层预防和控制渗滤液导排系统堵塞

在卫生填埋场中,垃圾渗滤液导排系统堵塞普遍存在,悬浮固体形成的物理堵塞、有机物降解和金属离子沉淀导致的生物-化学堵塞是引起导排系统堵塞的关键因素.本文构建了"矿化垃圾+砾石层导排"的渗滤液下渗装置,通过矿化垃圾预处理渗滤液中悬浮固体和有机物以控制导排系统发生的物理和生物-化学堵塞.结果表明,在矿化垃圾层,渗滤液中化学需氧量(COD)和悬浮固体(SS)去除较多,去除率分别达到了85%和87%,并且Ca²⁺浓度也出现了波动较大的现象;然而,渗滤液在砾石层下渗过程中,其COD、SS和Ca²⁺浓度保持稳定.并且,砾石层可排水孔隙率在长期运行的过程中没有明显变化,表明渗滤液在砾石导排层没有形成明显的沉淀.与此同时,在没有添加矿化垃圾的对照组发现,砾石层可排水孔隙率减少最多的区段是渗滤液的进水点位(可排水孔隙率减少达到了53%),即渗滤液有机负荷最大处的饱和砾石层堵塞最为严重,其无机堵塞物主要是碳酸钙等.因此,在渗滤液流入砾石层前,采用矿化垃圾层部分饱和的方式对渗滤液中有机物和悬浮固体进行预处理,可以预防和控制渗滤液在砾石层形成沉淀堵塞.研究为填埋场的运行管理渗滤液导排系统堵塞提供了新的思路和方法.     

金属负载活性炭催化氧化法处理ZPT生产废水

研究了金属负载活性炭催化剂在常温常压下催化氧化处理吡啶硫酮锌(ZPT)废水的技术，在探讨影响催化氧化效果诸因素的基础上，确定出中和预处理、后接两级催化氧化处理该废水的工艺流程，该流程的COD的去除率最高可达92％，处理出水达到国家污水综合排放标准二级指标。