原子力显微观测新生态水合二氧化锰与天然有机物的微观吸附形貌

采用云母片吸附的方式,较好地捕捉到了新生态水合二氧化锰的微观结构,并采用轻敲模式下的原子力显微成像技术,对其吸附天然有机物(NOM)前后的微观形貌进行了观测.与陈化2 h后的水合二氧化锰相比,新生态水合二氧化锰呈现出不定形的穿孔层状结构(厚度仅为0～1.75 nm)和球形颗粒结构,具有大的比表面积和附着能力.当向NOM中加入1 mmol/L新生态水合二氧化锰后,NOM分子的吸附形貌由松散分布的扁平粒状结构(吸附高度为5～8.5 nm)转变为密集分布、水平尺寸均匀的球形结构,表明了NOM分子容易以水合二氧化锰为吸附中心包裹在其表面.从直观上进一步证实了新生态水合二氧化锰的除污染效能,为高锰酸盐的预氧化助凝机理提供了有力的依据.     

高锰酸钾净水的氧化副产物研究

在高锰酸钾预氧化条件下 ,对北京京密引水渠水和松花江水进行混凝处理 ,并将原水与出水水样经色谱 质谱联用仪分析 ,以 1997年美国国家环保局 (USEPA)提出的饮用水规程和健康建议为标准 ,初步探讨了高锰酸钾净水过程中产生的副产物是否对人体有毒害作用 .试验结果表明 :在试验条件下 ,尚未发现高锰酸钾氧化生成USEPA规定的有毒有害副产物 ,并认为其原因可能与高锰酸钾氧化作用方式以及氧化过程中生成的新生态水合二氧化锰的吸附作用有关 .     

氧化剂与新型絮凝剂协同去除酸性大红的研究

选取浓度为25mg/L的酸性大红-GR溶液为模拟染料废水,采用氧化-絮凝耦合工艺,探索了氧化剂种类、絮凝剂种类、废水pH值、氧化剂和絮凝剂投加量对氧化-絮凝耦合处理酸性大红染料的影响,确定最佳处理条件为:酸性大红溶液初始pH值不变,高锰酸钾和PTSS的投加量分别为为20mg/L和10mg/L(以钛离子计),脱色率和COD去除率均最大,分别为96.3%、56.5%。通过FTIR光谱扫描、絮体的显微形貌观察、酸性大红和新型絮凝剂聚硅硫酸钛(PTSS)的表面电动电位随pH值的变化的测定,分析了氧化-絮凝耦合法的反应历程:高锰酸钾破坏酸性大红的发色基团后,自身被还原成新生态二氧化锰胶体;二氧化锰胶体吸附酸性大红及其氧化产物,并被无机高分子絮凝剂PTSS通过电中和及架桥网捕等作用卷裹成絮体。     

Enhanced removal of organics by permanganate preoxidation using tannic acid as a model compound – Role of in situ formed manganese dioxide

The effect of permanganate preoxidation on organic matter removal during the coagulation with aluminum chloride was investigated using tannic acid as a model compound. Results showed that a small amount of KMnO4 (0.75 mg/L) increased the removal efficiency of tannic acid up to 20%, as compared to the process of coagulation by aluminum chloride alone. The key factor enhancing the removal efficiency of tannic acid in preoxidation process was the in situ formation of a reductant manganese dioxide. The complexation model was used to describe the reaction between MnO2 and tannic acid. Under weak pH condition, tannic acid was difficult to be adsorbed by MnO2 due to the static electrical repulsive forces. The presence of Ca2+ served as a bridge to hold the negative charged MnO2 and tannic acid together, which could be a crucial factor influencing tannic acid adsorption by in-situ manganese dioxide.     

新生态MnO2对活性艳红染料废水的处理研究

该研究以高锰酸钾和硫酸锰溶液作为原料,在pH=10．0条件下,采用两种物质混合反应制备新生态二氧化锰。以新生态MnO2作为吸附剂,以活性艳红X-3B为目标物,采用静态吸附实验研究,考察改变pH值、吸附剂投加量、反应时间、反应温度、离子强度等因素对新生态MnO2吸附活性艳红X-3B染料废水性能的影响。该吸附剂作为一种高效、经济的吸附材料对染料废水的脱色处理具有较好的作用。     

二氧化锰改性沸石对废水中Pb2+的吸附性能及其影响因素研究

改性后的沸石材料,可大幅度提高其对金属离子的吸附量,在治理环境污染方面具有巨大的潜力。高锰酸钾和硫酸锰反应生成的二氧化锰包裹在沸石表面,可大大提高其吸附性能,最终达到吸附废水中重金属的目的。研究了二氧化锰改性沸石对废水中Pb²⁺吸附性能的影响因素,如沸石与二氧化锰投料比、反应时间、溶液pH值、反应温度、Pb²⁺初始浓度等,并探讨了其吸附机理。试验结果表明:二氧化锰改性沸石对废水中Pb²⁺的吸附效果随着沸石与二氧化锰投料比的增加而提高,平衡吸附时间为12 h,吸附反应的最佳溶液pH值为5~6;二氧化锰改性沸石对废水中Pb²⁺的吸附为自发的吸热反应,吸附过程符合Langmuir等温吸附模型,说明为单配体吸附模式;红外光谱分析发现,-OH是影响二氧化锰改性沸石吸附废水中Pb²⁺的主要官能团;低浓度腐殖酸对二氧化锰改性沸石吸附废水中Pb²⁺的影响较小,不产生竞争吸附。     

高锰酸盐复合剂强化混凝对水中天然有机物的去除机制研究

利用流动电流、絮凝脉动颗粒检测技术、分子量分布及XAD树脂分类技术对高锰酸盐复合剂强化混凝去除水中天然有机物的机制进行了研究.结果表明,高锰酸盐复合剂提高了硫酸铝的混凝效果,投加0.75 mg/L高锰酸盐复合剂后,较单独投加硫酸铝对天然有机物的去除率可提高13个百分点.流动电流(SC)检测结果表明,高锰酸盐复合剂使有机物表面所带的负电性减弱,稳定性降低.如单独投加60 mg/L硫酸铝时SC值为55.2,而投加0.50、 0.75和1.0 mg/L的高锰酸盐复合剂预氧化处理后,SC值分别升高至61.4、 69.6和87.0.投加高锰酸盐复合剂后,絮凝指数增加,表明高锰酸盐复合剂及反应过程中生成的新生态水合二氧化锰对混凝起到了强化作用.分子质量分布及XAD树脂分类结果表明,高锰酸盐复合剂提高了混凝过程对小分子质量和亲水性有机物的去除能力,如硫酸铝混凝后亲水性有机物的含量为1.90 mg/L,而投加高锰酸盐复合剂后,可使其含量降至1.32 mg/L.     

高锰酸钾对水中天然有机物氯化活性的影响

利用树脂分离技术将水中天然有机物分为腐殖酸(HA)、富里酸(FA)、亲水酸(HPIA)和其它亲水物质(HPI-NA)等4部分,研究了高锰酸钾对不同有机组分卤代活性的影响.结果表明,高锰酸钾增加了腐殖酸和其它亲水物质加氯的卤代活性,降低了富里酸和亲水酸的卤代活性,如投加0.75 mg/L高锰酸钾时,腐殖酸和其它亲水物质的卤代活性增加了39.3%和13.8%,而富里酸和亲水酸卤代活性降低了33.6%和46.9%;通过对SUVA的考察可知,高锰酸钾增加了腐殖酸和其它亲水物质的碳碳不饱和双键的含量,使其卤代活性增     

化学预氧化耦合生物锰氧化对水中有机物的去除

在饮用水处理过程中,高锰酸钾与铁锰氧化物预氧化作为化学预氧化的典型工艺,能有效去除饮用水中有机物的污染,并控制消毒副产物(DBPs)的产生.但研究发现,这两种预氧化都会生成具有遗传毒性效应的Mn2+.为解决该问题,研究构想在化学预氧化后耦合生物锰氧化技术,通过生物作用将Mn2+转化为具有较强氧化吸附能力的生物锰氧化物,从而对水质进一步净化.在以天然有机物酪氨酸(Tyr)和人工合成有机物2-羟基-4-甲氧基二苯甲酮-5-磺酸(BP-4)为基质的模拟污染源水中,试验结果验证了上述构想.高锰酸钾或铁锰氧化物预氧化能够去除Tyr,但无法去除BP-4,并会产生Mn2+;在以锰氧化细菌Pseudomonas sp.QJX-1构建的生物体系中,Pseudomonas sp.QJX-1能利用Tyr进行生长并产生锰氧化,生成的生物锰氧化物能有效去除BP-4;在最优试验条件下,特定强度的高锰酸钾预氧化耦合生物锰氧化试验中Tyr、BP-4及Mn2+去除率分别为100%、50%和98.9%.     

Pyrene partition behavior to the NOM: Effect of NOM characteristics and its modification by ozone preoxidation

Hydrophobic organic contaminants (HOCs)—pyrene, and natural organic matters (NOM) from different sources were taken as the test compounds to investigate the impact of physicochemical characteristics of NOM on HOCs’ partition to the NOM in this study. The effects of solution property, NOM characteristics, and modification by ozone preoxidation on pyrene partition to NOM were systematically evaluated. According to the fluorescence quenching method, the partition coefficient K _oc of pyrene to NOM was calculated, which was found to have a great relationship with the aromatic structures and hydrophobic functional groups of the NOM. The NOM characteristic modification corresponding to solution property could influence the interactions between the NOM and pyrene. Preozonation could destroy the aromatic or hydrophobic structures of the NOM and decrease K _oc of pyrene.     

臭氧氧化对天然有机物在氧化铝表面吸附行为的影响

为进一步明确臭氧预氧化对颗粒的脱稳作用,选用氧化铝（α-Al₂O₃）作为悬浮颗粒,考察了臭氧氧化后天然有机物（natural organic matters,NOM）特性及吸附行为的变化.结果表明,臭氧氧化能够破坏NOM的芳香结构,SUVA值降低25%～35%,氧化后酸性官能团含量增多,总酸度增加0.3～1.4 mmol·g^-1,分子量和极性的变化与NOM的性质有关;有机物初始浓度相对于臭氧投量较低时,NOM的溶解性增强,与其酸性官能团增加产生的吸附促进作用相抵消,因而吸附性能出现不变甚至降低的现象;有机物初始浓度较高时,臭氧能够起到强化NOM吸附的作用.采用2.5　mg·L^-1臭氧进行氧化后,以商用腐殖酸为代表的NOM的吸附形貌,由密集分布的球形对称聚集结构向网状结构过渡,分子之间的交联作用十分明显,吸附高度低于其氧化处理前,云母的表面覆盖率较氧化前略有提高.     

高锰酸钾与接触氧化协同除锰及硬度对除锰效果的影响

针对日益严重的地表水锰污染，本实验采用高锰酸钾与接触氧化的方法协同除锰；通过调配进水中Ca²⁺、Mg²⁺含量模拟我国不同地区硬度差异显著的地表水，探究水体硬度对锰的去除效果的影响.结果表明：Mn²⁺被高锰酸钾氧化并形成"锰质活性滤膜"，可在停药后实现稳定有效除锰.成熟滤池的除锰效果会显著受到硬度的影响，进水硬度在40、200、400 mg·L^-1及700 mg·L^-1（CaCO₃计）时，接触氧化滤池分别在48、56、64 d及72 d实现稳定除锰，而4根滤柱对Mn²⁺去除的极限浓度分别为1.8、1.7、1.2 mg·L^-1及0.7 mg·L^-1.     

Removal of Pb(II) from aqueous solution by hydrous manganese dioxide: Adsorption behavior and mechanism

Hydrous manganese dioxide (HMO) synthesized by redox of potassium permanganate and hydrogen peroxide was used as an adsorbent for Pb(Ⅱ) removal.The specific surface area,pore volume and BJH pore diameter of the HMO were 79.31m2/g,0.07cm3/g and 3.38 nm,respectively.The adsorption equilibrium at 298K could be well described by the Langmuir isotherm equation with q max value of 352.55mg/g.The negative values of G and the positive values of H and S indicated the adsorption process was spontaneous and endothermic.The pseudo second-order equation could best fit the adsorption data.The value of the calculated activation energy for Pb(Ⅱ) adsorption onto the HMO was 38.23 kJ/mol.The uptake of Pb(Ⅱ) by HMO was correlated with increasing surface hydroxyl group content and the main adsorbed speciation was PbOH+.The final chemical state of Pb(Ⅱ) on the surface of HMO was similar to PbO.HMO was a promising candidate for Pb(Ⅱ) removal from aqueous solution.     

高锰酸钾强化三氯化铁共沉降法去除亚砷酸盐的效能与机理

研究了不同水质条件下KMnO₄强化FeCl₃共沉降去除亚砷酸盐[As(Ⅲ)]的效能与机理.考察了pH值、天然有机物(NOM)等因素对As去除效能的影响.结果表明,投加KMnO₄显著提高了FeCl₃共沉降除砷(FCP)工艺对As(Ⅲ)的去除效能.随着Fe(Ⅲ)投量由2.0mg/L增大到8.0mg/L,对于FCP工艺,As去除率由41.3%提高到75.4%;而对于KMnO₄-FeCl₃共沉降除砷(POFCP)工艺,As去除率则由61.2%提高至99.3%.FCP及POFCP工艺对As的去除率均随着pH值的升高而升高;与FCP工艺比较,pH值对POFCP工艺除As效果影响较小;NOM降低了FCP工艺对As的去除率,而对POFCP工艺无明显影响.KMnO₄的氧化作用是强化As(Ⅲ)去除效能的主要因素,而KMnO₄的还原产物水合MnO₂(s)对As(Ⅲ)也具有一定的去除能力.POFCP工艺是强化去除水中As(Ⅲ),以保障安全饮用水供给的有效方法.     

水中单宁酸对强化混凝除污染的影响研究

研究了水中单宁酸在聚合氯化铝做混凝剂时对常规混凝、高锰酸钾预氧化强化混凝以及预氯化强化混凝的影响。结果表明,常规混凝下单宁酸含量的增加对混凝除浊有一定的效果,随着单宁酸投加量从0增加到5mg／L,滤后水的浊度呈现下降趋势,最低可达0．56NTU,但对于有机物的去除影响不大。高锰酸钾预氧化条件下当单宁酸投量小于2mg／L时,增大单宁酸投量有助于浊度的去除,过多则不利于混凝。预氯化下增加单宁酸投加量有助于浊度的去除,但对出水UV25。影响不大;随着单宁酸投加量从0增加到5mg/L,出水的CODMn鼻隆低白谁如,     

高锰酸钾预氧化对大肠杆菌DBPsFP的去除

以大肠杆菌为试验对象,采用高锰酸钾（KMnO₄）预氧化法,研究了不同的高锰酸钾浓度、氯化时间、pH值、预氧化时间及反应温度在氯化消毒过程中对大肠杆菌消毒副产物生成潜能（DBPsFP）的去除影响.研究表明：随着KMnO₄浓度的增加,二氯乙腈（DCAN）、三氯乙腈（TCAN）、1,1,1-三氯丙酮（1,1,1-TCP）及三氯乙醛（CH）浓度先降低,后升高,1,1-二氯丙酮（1,1-DCP）浓度先升高,后降低;三氯甲烷（TCM）浓度逐渐降低.在KMnO₄浓度2mg/L时,DCAN、TCAN、1,1,1-TCP浓度降至最低,对大肠杆菌DBPsFP的氧化去除效果最好;延长氯化时间,TCAN,1,1-DCP浓度逐渐升高,而DCAN,CH和1,1,1-TCP浓度先升高后降低.TCM浓度先升高后趋于稳定;pH值由5升高到9时,1,1,1-TCP、TCAN浓度不断地降低;DCAN浓度先降低,再升高;而1,1-DCP、CH浓度先升高,再降低;延长预氧化时间,TCAN、DCAN、TCM的浓度逐渐降低;1,1-DCP、1,1,1-TCP的浓度先升高,再降低;CH的浓度先升高,之后趋于稳定;随着反应温度的升高,1,1-DCP、DCAN的浓度逐渐升高;1,1,1-TCP浓度则逐渐降低;TCAN、TCM的浓度先升高再降低,而CH浓度则先降低再升高.综上,在KMnO₄浓度2mg/L,氯化时间48h,碱性条件（pH > 8）,预氧化时间30min时最有利于大肠杆菌DBPsFP的去除.     

MnFe2O4 nanoparticles as new catalyst for oxidative degradation of phenol by peroxydisulfate

Manganese ferrite nanopowder was prepared by thermal decomposition at 400°C of the gel synthesized from manganese and iron nitrates and polyvinyl alcohol. X-ray diffractometry evidenced that manganese ferrite was formed as single crystalline phase at this temperature. Scanning electron microscope images evidenced the formation of very fine spherical particles(d 11 nm) of manganese ferrite, with specific surface area of 147 m~2/g.The powder obtained at 400°C was used as a catalyst for the oxidative degradation of phenol in aqueous solutions, in the presence of potassium peroxydisulfate as oxidant. High phenol removal efficiencies above 90% were reached at: pH 3–3.5, phenol initial concentration around 50 mg/L, peroxydisulfate:phenol mass ratio 10:1, and catalyst dose 3 g/L. Total organic carbon measurements showed that the degradation of phenol goes, under these conditions, to mineralization in an extent of 60%.     

Review on heterogeneous oxidation and adsorption for arsenic removal from drinking water

The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to negatively-charged arsenate (As(V)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal; however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(III) by solid oxidants such as manganese oxide, and the adsorption of As(V) accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(III). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(V). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants (DWTPs). This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.     

高锰酸盐复合药剂预氧化缓解超滤膜藻类污染的中试研究

通过中试试验考察了高锰酸盐复合药剂(PPC)预氧化强化混凝/沉淀/超滤的组合工艺的除藻效能以及PPC预氧化对藻类引起的膜污染的缓解作用,并对其机理进行了探讨.试验结果表明,投加0.6mg·L-1PPC能使预处理阶段对藻类的平均去除率提高约28%.组合工艺处理高藻水时,PPC预氧化通过强化预处理,降低膜表面的污染负荷,对藻源污染物引起可逆和不可逆污染均具有一定的缓解作用.化学清洗试验结果表明,碱洗对超滤膜TMP恢复效果远远强于酸洗,因而有机物是超滤膜处理高藻水时的主要污染物质.     

Migration of manganese and iron during the adsorption-regeneration cycles for arsenic removal

Fe-Mn binary oxide incorporated into porous diatomite (FMBO-diatomite) was prepared in situ and regenerated in a fixed-bed column for arsenite [As(III)] and arsenate [As(V)] removal. Four consecutive adsorption cycles were operated under the following conditions: Initial arsenic concentration of 0.1 mg·L⁻¹, empty bed contact time of 5 min, and pH 7.0. About 3000, 3300, 3800, and 4500 bed volumes of eligible effluent (arsenic concentration ⩽ 0.01 mg·L⁻¹) were obtained in four As (III) adsorption cycles; while about 2000, 2300, 2500, and 3100 bed volumes of eligible effluent were obtained in four As(V) adsorption cycles. The dissection results of FMBO-diatomite fixed-bed exhibited that small amounts of manganese and iron were transferred from the top of the fixed-bed to the bottom of the fixed-bed during As(III) removal process. Compared to the extremely low concentration of iron (<0.01 mg·L⁻¹), the fluctuation concentration of Mn²⁺ in effluent of the As(III) removal column was in a range of 0.01–0.08 mg·L⁻¹. The release of manganese suggested that manganese oxides played an important role in As(III) oxidation. Determined with the US EPA toxicity characteristic leaching procedure (TCLP), the leaching risk of As(III) on exhausted FMBO-diatomite was lower than that of As(V).