不同Fe(III)对活性污泥异化铁还原及除磷影响研究

以SBBR反应器活性污泥作为铁还原菌菌种来源,采用兼性厌氧/严格厌氧恒温培养试验,投加不同Fe(III)考察各条件下的异化铁还原能力,同时比较对磷的去除效果.结果表明:2种条件下Fe(III)还原能力具有较好的一致性,依次为:Fe(OH)3>氧化铁皮>青矿>红矿,其中严格厌氧条件下较好.同时,除磷效果与其呈正相关,富集培养至7d, Fe(OH)3及氧化铁皮体系出水磷浓度均达到2mg/L以下,之后继续降低,最终达到0.5mg/L以下.结合异化铁还原除磷机理,可以证明,不同Fe(III)表面吸附作用对TP的去除贡献较小,其主要作用为铁还原菌驱动下的化学沉淀去除.     

Fabrication of bimetallic Ag/Fe immobilized on modified biochar for removal of carbon tetrachloride

As an effective conventional absorbent, biochar exhibited limited adsorption ability toward small hydrophobic molecules. To enhance the adsorption capacity, a novel adsorbent was prepared by immobilizing nanoscale zero-valent iron onto modified biochar (MB) and then the elemental silver was attached to the surface of iron (Ag/Fe/MB). It''s noted that spherical Ag/Fe nanoparticles with diameter of 51 nm were highly dispersed on the surface of MB. As the typical hydrophobic contaminant, carbon tetrachloride was selected for examining the removal efficiency of the adsorbent. The removal efficiencies of carbon tetrachloride by original biochar (OB), Ag/Fe, Ag/Fe/OB and Ag/Fe/MB were fully investigated. It''s found that Ag/Fe/MB showed higher carbon tetrachloride removal efficiency, which is about 5.5 times higher than that of the OB sample due to utilizing the merits of high adsorption and reduction. Thermodynamic parameters revealed that the removal of carbon tetrachloride by Ag/Fe/MB was a spontaneous and exothermic process, which was affected by solution pH, initial carbon tetrachloride concentration and temperature. The novel Ag/Fe/MB composites provided a promising material for carbon tetrachloride removal from effluent.     

H2O2预氧化对负载铁制备污泥炭基催化剂效能的影响

以城市污水厂二沉池污泥为原料,考察了不同H_2O_2投加量下污泥预氧化对铁负载污泥形成前驱体及其热解后制得炭基催化剂性能的影响,研究了污泥预氧化对强化铁负载制备均一分散型污泥炭基催化剂的机理.结果表明,污泥预氧化促进了污泥细胞破解,降低了絮体颗粒粒径和表面Zeta电位,使铁负载量增加、铁活性位点在污泥载体上的分散性明显增强,形成炭基催化剂保持着高催化活性,其稳定性显著增加.对模拟含铬黑T染料废水的多相芬顿降解试验说明,当污泥预氧化H_2O_2投加量为2.25%时制备的炭基催化剂,其反应120 min后铬黑T的降解率为91%,略低于未预氧化时污泥炭基催化剂的降解效率(96%);但未预氧化炭基催化剂其反应后溶液中铁离子的溶出量(18.9%)远高于预氧化后形成的催化剂(2.5%),且后者循环3次对铬黑T的降解率仍可达到86%,表现出较强的稳定性.     

负载型纳米铁吸附剂去除饮用水中As(Ⅴ)的研究

以活性炭为载体制备了一种负载型纳米铁吸附剂.纳米铁在活性炭孔内为针状,其直径为30～500 nm,长度为1 000～3 000 nm,载入量[m(Fe)/m(炭)]为82.1 mg/g.用1.5 g/L该吸附剂对pH 6.5、 (25±2)℃、 2 mg/L的As(Ⅴ)进行吸附其去除率为99.5%,在平衡浓度1.0 mg/L时,该吸附剂对As(Ⅴ)的吸附容量为15.4 mg/g;吸附速度较快,12 h可达91.4%,72 h达到吸附平衡.吸附过程可由孔内扩散模型较好地说明.除PO_4~(3-)、SiO_4~(2-)外其它常见阴阳离子均对As(Ⅴ)的去除影响不大.吸附剂可以用0.1 mol/L NaOH溶液再生,再生效率较高.实验室初步实验数据表明,该吸附剂对饮用水砷去除具有较好的应用前景.     

Adsorptive removal of iron and manganese ions from aqueous solutions with microporous chitosan/polyethylene glycol blend membrane

Microporous chitosan (CS) membranes were directly prepared by extraction of poly(ethylene glycol) (PEG) from CS/PEG blend membrane and were examined for iron and manganese ions removal from aqueous solutions. The different variables affecting the adsorption capacity of the membranes such as contact time, pH of the sorption medium, and initial metal ion concentration in the feed solution were investigated on a batch adsorption basis. The affinity of CS/PEG blend membrane to adsorb Fe(II) ions is higher than that of Mn(II) ions, with adsorption equilibrium achieved after 60 min for Fe(II) and Mn(II) ions. By increasing CS/PEG ratio in the blend membrane the adsorption capacity of metal ions increased. Among all parameters, pH has the most significant effect on the adsorption capacity, particularly in the range of 2.9-5.9. The increase in CS/PEG ratio was found to enhance the adsorption capacity of the membranes. The effects of initial concentration of metal ions on the extent of metal ions removal were investigated in detail. The experimental data were better fitted to Freundlich equation than Langmuir. In addition, it was found that the iron and manganese ions adsorbed on the membranes can be effectively desorbed in 0.1 mol/L HCl solution (up to 98% desorption efficiency) and the blend membranes can be reused almost without loss of the adsorption capacity for iron and manganese ions.     

饮用水源突发挥发酚污染应急处理中试研究

通过为期2个月规模为4m3·h-1的中试试验,考察了常规给水工艺(混凝、沉淀和过滤)对突发挥发酚污染原水的处理情况.重点考察了活性炭吸附、臭氧预氧化和高锰酸钾预氧化等3种应急工艺的除酚效能.结果表明,常规混凝沉淀对挥发酚的去除率低于10%,砂滤在12h内可起到拦截挥发酚的作用,3种应急工艺均可提高挥发酚的去除效果,起到应急的作用.其中活性炭吸附对挥发酚的去除率可达44%;在0.5mg·L-1的投量下高锰酸钾预氧化可达到50%的除酚效率;臭氧预氧化可使沉淀出水挥发酚达标(0.002mg·L-1),挥发酚去除率约99%.     

Enhanced remediation of Cr（Ⅵ）-contaminated groundwater by coupling electrokinetics with ZVI/Fe3O4/AC-based permeable reactive barrier

Although widely used in permeation reaction barrier（PRB） for strengthening the removal of various heavy metals, zero-valent iron（ZVI） is limited by various inherent drawbacks, such as easy passivation and poor electron transfer. As a solution, a synergistic system with PRB and electrokinetics（PRB-EK） was established and applied for the efficient removal of Cr（Ⅵ）-contaminated groundwater. As the filling material of PRB, ZVI/Fe₃O₄/activated carbon（ZVI/Fe₃O₄     

TiO_2/AC催化臭氧氧化处理水中的苯酚

研究了单独臭氧氧化及以活性炭(AC)和负载二氧化钛的活性碳(TiO2/AC)为催化剂催化臭氧氧化处理水中苯酚的效果。考察了AC、TiO2/AC对苯酚的吸附特性及三种方法对苯酚的转化率及矿化率效果及其臭氧利用效率,并对氧化过程进行了动力学分析。实验结果表明:AC、TiO2/AC对苯酚的吸附均较好地符合Freundlich方程;催化臭氧氧化转化苯酚的效果高于单独臭氧氧化;TiO2/AC作催化剂有利于苯酚的最终矿化,同时提高了臭氧的利用效率;3种氧化反应均较好的符合二级动力学方程,TiO2/AC催化臭氧氧化苯酚的二级动力学常数为0.0001L/(mg.min),高于单独臭氧氧化0.00004L/(mg.min)和AC催化臭氧氧化0.00006L/(mg.min)。     

木质垃圾与废铁泥制备Fe0-BC材料及其对水中Cr(Ⅵ)的去除行为

含铬废水的直接排放会对自然环境造成严重危害.为探究零价铁-生物炭材料(Fe⁰-BC)与Cr(Ⅵ)的反应效能,以木质垃圾与印染行业废铁泥两种亟需处理的固体废物作为原料,在不同温度下通过碳热还原制备Fe⁰-BC,并将其应用于水中Cr(Ⅵ)的去除.材料表征结果表明,1 200℃下制备的Fe⁰-BC材料(Fe⁰-BC-1200)性能最佳,其比表面积为105.6 m³/g,孔径为6.23 nm,物相主要由Fe⁰、Cu0、C以及少量杂质构成,其中Fe⁰以球状的颗粒形式分散附着在碳的孔结构中,且大小均匀,粒度基本达到纳米级.通过静态试验考察了Fe⁰-BC材料对Cr(Ⅵ)的去除过程,发现Fe⁰-BC-1200对Cr(Ⅵ)的去除效果最好,在初始浓度为20 mg/L、初始pH为3.5、投加量为2.5 g/L的条件下,Cr(Ⅵ)的去除率达到95.2%. Cr(Ⅵ)的去除过程符合准二级反应动力学过程和Langmui...     

铁铜催化剂非均相Fenton降解苯酚及机制研究

通过浸渍法制备了负载于活性炭(AC)上的金属催化剂Fe/AC、Cu/AC和Fe-Cu/AC,并通过X射线衍射(XRD)、物理吸附仪及X射线光电子能谱(XPS)对其进行了表征.研究了非均相Fenton反应催化H2O2降解苯酚废水的工艺参数,并通过中间产物分析和电子自旋共振谱(ESR)探讨了过程反应机制.实验表明,Cu/AC催化剂中铜主要以CuO形式存在,Fe/AC中铁以多价态形式存在,以无定形形态分散于活性炭中.Fe/AC、Cu/AC和Fe-Cu/AC催化过氧化氢降解苯酚60 min内降解率分别达到96.7%、77.5%和99%;Cu/AC和Fe-Cu/AC催化剂中活性组分铜和铁有一定溶出,而Fe/AC中活性组分铁溶出很少,苯酚降解主要是以非均相催化为主,同时在三轮循环实验后的苯酚降解率仍然高达93%以上,显示了良好的催化稳定性.在优化条件pH=3、T=303 K及初始H2O2为4.38 mmol.L-1下,Fe/AC催化过氧化氢对苯酚和TOC去除率分别达到97%和53%,没有催化剂时苯酚几乎不降解.ESR结果表明Fe/AC催化过氧化氢产生了羟基自由基,证明苯酚降解是以羟基自由基氧化为主;通过高效液相色谱(HPLC)检测苯酚降解中间产物主要有邻苯二酚、对苯二酚和对苯醌,推测苯酚降解途径主要为邻位和对位的羟基取代反应.     

表面活性剂改性活性炭对高氯酸盐的吸附和再生

选用阳离子表面活性剂十六烷基三甲基氯化铵(CTAC)改性活性炭以提高活性炭对高氯酸盐的吸附能力.CTAC改性前后活性炭吸附能力通过吸附穿透曲线来比较.结果表明,未改性活性炭对高氯酸盐几乎没有吸附.CTAC改性则能显著提高活性炭对高氯酸盐的吸附能力.进水pH值对高氯酸盐的吸附影响较小,但水中干扰离子如NO3-、SO42-、SiO42-和PO43-会与高氯酸盐离子发生竞争吸附,从而降低活性炭对高氯酸盐的吸附能力.1mol/L HCl溶液的化学再生的效率在95%左右,再生后的活性炭能重复使用.水蒸汽热再生则能有效恢复活性炭的孔径结构.高氯酸盐在高温下降解得到完全去除,但再生后的炭必须重新改性后才能再次使用.     

In situ adsorption-catalysis system for the removal of o-xylene over an activated carbon supported Pd catalyst

An activated carbon (AC) supported Pd catalyst was used to develop a highly efficient in situ adsorption-catalysis system for the removal of low concentrations of o-xylene. In this study, three kinds of Pd/AC catalysts were prepared and tested to investigate the synergistic efficiency between adsorption and catalysis for o-xylene removal. The Pd/AC catalyst was first used as an adsorbent to concentrate dilute o-xylene at low temperature. After saturated adsorption, the adsorbed o-xylene was oxidized to CO2 and H2O by raising the temperature of the catalyst bed. The results showed that more than 99% of the adsorbed o-xylene was completely oxidized to CO2 over a 5% Pd/AC catalyst at 140℃. Brunauer-Emmett-Teller (BET) analysis, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), and temperature-programmed oxidation (TPO) were applied to investigate the physical properties of o-xylene adsorption-desorption and the in situ adsorption-catalysis activity of the AC support and Pd/AC catalyst. A synergistic relationship between the AC support and the active Pd species for the removal of low concentrations of o-xylene was established.     

表面改性非烧结生态砖材料对模拟城市暴雨径流中低浓度磷的吸附特性

为了寻求城市暴雨后地表径流中低浓度磷的去除方法,考察了粉煤灰、活性炭、沸石等材料对低浓度磷的吸附特性,进而利用筛选出的吸附材料对河岸护坡砖表面进行改性,制成非烧结生态砖材料,系统地研究了吸附材料添加量、磷酸盐浓度、反应时间等对生态砖材料吸附磷酸盐效率的影响,并探究了紫花苜蓿对生态砖表面磷酸盐的吸收能力.结果表明:①在3种吸附材料中,粉煤灰对磷酸盐的吸附效果最佳,3 h内其对磷酸盐的去除率分别比沸石、活性炭提高了54%、67%.②当生态砖表面搭载36 mg/cm2粉煤灰时,生态砖材料表现出最佳的磷酸盐吸附性能,比未搭载粉煤灰的生态砖材料对磷酸盐的去除率提高了14%.③生态砖材料对磷酸盐的吸附符合Freundlich吸附等温方程和颗粒内扩散方程,其对磷酸盐的吸附机理是由颗粒内扩散起主导作用的物理吸附.④在缺磷胁迫环境下,紫花苜蓿根系分泌出的柠檬酸将生态砖表面的磷酸钙晶体溶解,进而将其吸收进植物体内,15 d对生态砖表面磷的脱附比例为38.40%±0.37%.研究显示,粉煤灰改性的非烧结生态砖材料对磷酸盐具有较好的吸附效果,并且吸附的磷酸盐能够被植物所吸收可实现生态砖材料的天然再生.      

白腐菌联合纳米零价铁强化去除水中Cd(II)

采用白腐菌和纳米零价铁(nZVI)联合体系强化去除水中Cd (II),并考察pH值、Cd (II)初始浓度、温度、nZVI投加量对Cd (II)去除的影响,分析nZVI对白腐菌胞内外富集镉的影响特性,同时结合扫描电镜、红外光谱、X射线光电子能谱、三维荧光光谱等手段分析联合体系对Cd (II)的强化去除机制.结果表明,在pH=6,Cd (II)初始浓度为50mg/L,温度为30℃,nZVI投加量为0.1g/L的条件下反应180min后,Cd (II)的去除率可达到99.5%以上.联合体系对Cd (II)的去除过程符合准二级动力学,主要去除机制为白腐菌对Cd (II)的胞外络合吸附,添加nZVI能促进白腐菌对Cd (II)的胞外吸附,FTIR和XPS分析表明,羟基、羧基和氨基参与了Cd (II)的吸附,白腐菌胞外聚合物(EPS)能与铁发生内层配位形成P-O-Fe键,加速富含羟基官能团的纤铁矿、磁铁矿等铁矿物形成,从而促进对溶液中Cd (II)的吸附去除.     

Effect of Na+ impregnated activated carbon on the adsorption of NH4+-N from aqueous solution

Two kinds of activated carbons modified by Na+ impregnation after pre-treatments involving oxidation by nitric acid or acidification by hydrochloric acid (denoted as AC/N-Na and AC/HCl-Na, respectively), were used as adsorbents to remove NH4+-N. The surface features of samples were investigated by BET, SEM, XRD and FT-IR. The adsorption experiments were conducted in equilibrium and kinetic conditions. Influencing factors such as initial solution pH and initial concentration were investigated. A possible mechanism was proposed. Results showed that optimal NH4+-N removal efficiency was achieved at a neutral pH condition for the modified ACs. The Langmuir isotherm adsorption equation provided a better fit than other models for the equilibrium study. The adsorption kinetics followed both the pseudo second-order kinetics model and intra-particle kinetic model. Chemical surface analysis indicated that Na+ ions form ionic bonds with available surface functional groups created by pre-treatment, especially oxidation by nitric acid, thus increasing the removal efficiency of the modified ACs for NH4+-N. Na+-impregnated ACs had a higher removal capability in removing NH4+-N than unmodified AC, possibly resulting from higher numbers of surface functional groups and better intra-particle diffusion. The good fit of Langmuir isotherm adsorption to the data indicated the presence of monolayer NH4+-N adsorption on the active homogenous sites within the adsorbents. The applicability of pseudo second-order and intra-particle kinetic models revealed the complex nature of the adsorption mechanism. The intra-particle diffusion model revealed that the adsorption process consisted not only of surface adsorption but also intra-particle diffusion.     

介孔氮化碳对水中全氟辛烷磺酸的吸附去除研究

以SBA-15为模板、四氯化碳和乙二胺为前驱体,通过聚合反应制备了介孔氮化碳(Mesoporous Carbon Nitride,MCN).同时,采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)和元素分析等手段对MCN进行了表征分析,并考察了MCN对水中全氟辛烷磺酸(PFOS)的吸附性能.结果表明,MCN吸附PFOS的过程符合准二级动力学模型,其吸附行为遵循Langmuir等温线模型;MCN吸附去除PFOS的效率受溶液pH值、溶液温度及共存离子等因素的影响,其中,溶液pH值的影响最为显著,当溶液pH值分别为2.2和10.6时,MCN对PFOS的去除率分别为98.15%和5.59%;吸附PFOS饱和后的MCN可以用0.1 mol·L-1NaOH溶液进行解吸,经5次循环/再生后的MCN对PFOS的去除率仍在95%以上.与介孔碳(CMK-3)和活性炭(AC)相比,MCN对PFOS显示出更优越的吸附能力.     

改性活性炭对内分泌干扰物的吸附效能与机制

为提高活性炭对内分泌干扰物的吸附效率,分别采用混合酸溶液,氨水,KMnO₄溶液和表面活性剂溶液对活性炭进行改性.采用比表面积及孔隙度分析仪、扫描电子显微镜（SEM）、傅里叶红外光谱（FT-IR）和Boehm滴定法对改性后活性炭表面化学性质及孔隙特征的变化进行评价.通过静态吸附实验确定活性炭的最佳改性方法,并对改性后活性炭吸附机理进行探讨.实验结果表明,KMnO₄改性活性炭（AC-K）表现出最佳的污染物吸附性能,其对邻苯二甲酸二丁酯（DBP）、阿特拉津（Atrazine）和磺胺甲恶唑（SMZ）的去除率分别可达到94.5%、93.8%和95.5%,且吸附过程符合二级动力学方程和D-R模型.由模型计算结果可知,AC-K对目标污染物的吸附速率明显加快,其中对Atrazine的二级吸附速率常数是AC的1.75倍.AC-K对DBP、Atrazine和SMZ的理论饱和吸附量也分别比改性前分别提高了42.2%、629%和122%.经KMnO₄改性后,活性炭的吸附机制由物理吸附占主导,转化为离子交换吸附.     

活性炭催化过氧化氢去除荧光增白剂

研究了活性炭(activated carbon,AC)吸附、改性活性炭(activated carbon modified,ACM)吸附、过氧化氢(H2O2)氧化、AC催化H2O2等方法对水体中荧光增白剂VBL的处理效果,并通过自由基俘获剂叔丁醇、催化过程气体分析等探讨了AC催化H2O2分解VBL的机制.结果表明,经硝酸铁[Fe(NO3)3]改性过的ACM对VBL的吸附去除率高于未改性的AC.活性炭催化H2O2对VBL的去除效果明显,但未改性AC催化去除率高于ACM.60 min时,AC催化氧化去除率即可达到95%以上,而ACM仅为58%.叔丁醇的加入降低了AC和ACM催化氧化对VBL的去除率,表明AC催化H2O2氧化能促进H2O2形成羟基自由基(·OH)和原子氧参与反应.AC催化H2O2分解及释放气体分析表明,AC能催化H2O2形成氧气并放热,且ACM明显快于AC.结合催化H2O2去除VBL效率的结果分析,ACM催化反应时活性中间物(自由基和原子氧等)产生速率快于AC,活性中间物自身消耗形成氧气,而不是用于分解VBL.催化反应中活性中间产物的形成速率与反应物供给速率的不匹配可能是导致ACM催化效果弱于AC的重要原因.     

Mg-La-Fe/沸石复合材料的制备及其处理低浓度含磷废水的性能

以沸石为载体,选用镁、镧和铁为改性剂,采用水热法制备了一种新型高效且易于磁性分离回用的载镧磁性沸石吸附剂（MLFZ）.等温吸附和动力学研究结果表明,其吸附行为符合Langmuir等温模型和准二级动力学模型,MLFZ饱和吸附量为13.46 mg·g^-1; MLFZ在pH为3～9范围内均表现出良好的吸附性能,共存离子条件下对磷酸根具有特异吸附能力,通过磁性吸附重复使用5次后,MLFZ对磷酸盐去除率维持在90%左右,突显了其易于回收再利用的优点;FTIR、 XPS和Zeta电位表征显示,表面沉积、静电吸附作用和镧与磷酸盐通过配体交换形成内层络合物在吸附过程中为主要作用.将MLFZ用于处理自然池塘污水,结果显示磷酸盐浓度由0.86 mg·L^-1降低到0.013 mg·L^-1,表明该吸附剂具有良好的实际应用前景.     

活性炭催化双氧水氧化处理分散橙结晶废母液

采用Fe2+/H2O2、活性炭(AC)/H2O2和AC/H2O2/Fe2+三种氧化体系对高浓度、高酸度和高盐分的分散橙结晶废母液进行处理,探讨了H2O2投加量、n(H2O2)/n(Fe2+)比值和初始pH对TOC去除率影响,比较三种氧化体系对TOC和色度的去除效果。结果表明:AC/H2O2/Fe2+氧化体系对TOC去除率最高,AC/H2O2氧化体系对色度去除率最高。即使在强酸环境中下,AC对H2O2仍然具有较高的催化活性,并可多次重复利用。AC/H2O2氧化体系为分散橙结晶废母液处理及资源化利用提供了新途径。