亚硫酸盐浆CEH漂白废水的特性及其光催化氧化处理

本文对蔗渣、竹子、芒杆混合亚硫酸盐浆ＣＥＨ 漂白废水的特性进行了较详细的分析研究。研究表明,该废水ＢＯＤ５／ＣＯＤ为０ ．１８３ ,Ｃｌ－ 含量高达１１５２ ．５ｍｇ／ｌ,不适合于传统的生物氧化法处理。废水中的大分子有机污染物是废水色度的主要来源,废水的色度和ｐＨ 值密切相关。采用ＵＶ／ＴｉＯ２ 光催化氧化工艺处理该废水的初步研究结果表明,在充分供氧的条件下,可使废水快速脱色,同时废水的ＣＯＤ指标大大下降。     

UV/Fenton法处理制浆造纸废水相关因子筛选

采用Fenton体系氧化-絮凝工艺深度处理制浆造纸废水,对影响氧化效果的pH值、UV辐射、TiO2催化进行了因子分析与筛选。结果表明,因子效应的显著程度顺序为pH>UV>TiO2,其中,pH、UV对废水污染负荷的降低具有显著的积极效应,而TiO2起消极作用。在筛选后的条件下,废水经UV/Fenton体系氧化-絮凝处理后,色度、COD、BOD污染负荷基本去除,达到制浆造纸工业水污染物排放标准。红外光谱分析表明:废水中木素结构被UV/Fenton氧化降解,苯环结构开裂转化为脂肪族羧酸类物质。     

从好氧污泥中筛选硫酸盐浆漂白废水降解菌株及其降解动力学的研究

将好氧污泥碎解后在LB培养基上活化培养污泥中的微生物群落,根据菌落特征差异,筛选出16种微生物菌株,考察它们对硫酸盐浆漂白废水的降解能力。结果显示,8株菌具有硫酸盐浆漂白废水降解效果,其中菌株BKPE-11效果最佳,在64h内废水COD去除率达到67.46%。研究了BKPE-11在硫酸盐浆漂白废水中的生长曲线及降解该漂白废水的动力学过程,并建立了动力学方程。     

Oxidation mechanism of As(III) in the UV/TiO2 system: evidence for a direct hole oxidation mechanism

Although it is well-known that As(III) is oxidized to As(V) in the UV/TiO2 system, the main oxidant for that reaction is still not clear. Accordingly, the present study aims at reinvestigating the TiO2-photocatalyzed oxidation mechanism of As(III). We performed a series of As(II) oxidation experiments by using UV-C/H2O2 and UV-A/TiO2, focusing on the effects of competing compounds. The experiment with UV-C/H2O2 indicated that HO2*/O2-* is not an effective oxidant of As(III) in the homogeneous phase. The effects of oxalate, formate, and Cu(II) on the photocatalytic oxidation of As(III) contradicted the controversial hypothesis that HO2*/ O2-* is the main oxidant of As(III) in the UV/TiO2 system. The effect of As(III) on the TiO2-photocatalyzed oxidations of benzoate, terephthalate, and formate was also incompatible with the superoxide-based As(II) oxidation mechanism. Instead, the experimental observations implied that OH* and/or the positive hole are largely responsible forthe oxidation of As(III) in the UV/TiO2 system. To determine which species plays a more significant role, the effects of methanol and iodide were tested. Since excess methanol did not retard the oxidation rate of As(III), OH* seems not to be the main oxidant. Therefore, the best rationale regarding the oxidation mechanism of As(III) in the UV/TiO2 system seems to be the direct electron transfer between As(III) and positive holes. Only with this mechanism, it was possible to explain the data of this study. Besides the mechanistic aspect, an application method for this technology was sought. The usage of UV/TiO2 for oxidizing As(II) requires a posttreatment in which both As(V) and TiO2 should be removed from water. For this objective, we applied FeCl3 and AIK(SO4)2 as coagulants, and the result implied that the combined usage of TiO2 and coagulation might be a feasible solution to treat arsenic contamination around the world.     

Fe0-H2O2法深度处理草类制浆造纸中段废水

采用Fe0-H2O2法对制浆造纸中段废水二级处理后的出水进行了深度处理,考察了pH值、Fe/C比、H2O2投加量和载气等不同的操作条件,结果表明:在pH值为3.0、Fe/C(体积比)为2、H2O2投加量为50 mg/L的条件下对污染物去除有利,温度能够加快反应速度;载气不仅能够提高反应效率,且节省H2O2用量。Fe0-H2O2工艺对中段废水的色度去除率超过98%、对CODCr的去除率在77%以上,紫外吸收光谱表明该工艺可有效去除或降解氯化木素。     

光催化对CEH漂白废水的处理研究

以国际通用的商品P25型TiO2为光催化剂,采用自行设计的光催化反应器对传统的CEH三段漂白废水进行光催化降解研究。以CODCr为评价指标,考察了催化剂用量、体系pH、光催化降解时间及通氧方式等对降解CEH废水的影响因素。结果表明：TiO2投加量、光催化降解时间、体系pH以及通氧对CODCr的去除影响显著。当TiO2用量为1．0g/L、初始pH=4．0、连续通气条件下降解效果最佳,光催化降解4h后,CEH漂白废水中CODCr去除率可达84．8％,出水水质达到国家二级排放标准。     

白腐菌处理苇浆氯漂废水的脱色机理研究

利用固定化驯化白腐菌能有效处理氯漂Ｅ段废水。废水色度随ＰＨ值变化而变化,通过紫外光谱图分析,证实２过程中废水中的酚类物质被除去,且主要发生于处理过程的前期。     

制浆造纸中段废水深度处理

采用混凝水解曝气生物滤池工艺对制浆造纸中段废水进行了深度处理。结果表明,该工艺可有效去除中段废水两级生化处理后出水的COD和色度,深度处理出水平均CODCr和色度分别为60.2mg/L和55倍,低于国家排放标准。该系统具有流程简单、处理效率高、运行稳定可靠等优点。     

UV+H2O2和UV+H2O2+Fe2+化学氧化处理CEH漂白废水研究

采用UV+H2O2和UV+H2O2+Fe2+二种高级化学氧化工艺处理硫酸盐苇浆CEH漂白废水,研究了氧化剂用量、Fe2+浓度、初始pH值、处理时间等因素与处理效果(以COD和色度为指标)的关系.研究表明,添加Fe2+可大大加速体系对有机污染物氧化降解,H2O2用量对COD和色度的去除影响显著,硫酸盐苇浆CEH漂白混合废水pH值呈较强的酸性,适合于采用UV+H2O2+Fe2+工艺氧化处理.     

Photocatalytic oxidation of arsenite in TiO2 suspension: kinetics and mechanisms

Arsenite [As(III)] and arsenate [As(V)] are highly toxic aquatic contaminants. Since arsenite is more mobile in natural waters and less efficiently removed in adsorption/coagulation processes than arsenate, the oxidation of arsenite to arsenate is desirable in water treatment. We performed the photocatalytic oxidation of arsenite in aqueous TiO2 suspension and investigated the effects of pH, dissolved oxygen, humic acid (HA), and ferric ions on the kinetics and mechanisms of arsenite oxidation. Arsenite oxidation in UV-illuminated TiO2 suspension was highly efficient in the presence of dissolved oxygen. Homogeneous photooxidation of arsenite in the absence of TiO2 was negligibly slow. Since the addition of excess tert-butyl alcohol (OH radical scavenger) did not reduce the rate of arsenite oxidation, the OH radicals should not be responsible for As(III) oxidation. The addition of HA increased both arsenite oxidation and H2O2 production at pH 3 under illumination, which could be ascribed to the enhanced superoxide generation through sensitization. We propose that the superoxide is the main oxidant of arsenite in the TiO2/UV process. The addition of ferric ions also significantly enhanced the arsenite photooxidation. In this case, the addition of tert-butyl alcohol reduced the arsenite oxidation rate, which implied thatthe OH radical-mediated oxidation path was operative in the presence of ferric ions. Since both Fe3+ and HA that were often found with the arsenic in groundwater were beneficial to the photocatalytic oxidation of arsenite, the TiO2/UV process could be a viable pretreatment method. This can be as simple as exposing the arsenic-polluted water in a TiO2-coated trough to sunlight.     

Arsenic removal and recovery from copper smelting wastewater using TiO2

Removal and recovery of high levels of arsenic (As) in copper smelting wastewater present a great environmental challenge. A novel approach was investigated for the first time using TiO(2) for As adsorptive removal from wastewater and subsequent spent adsorbent regeneration and As recovery using NaOH. EXAFS results demonstrate that As(III), as the only As species present in the raw water, does not form an aqueous complex with other metal ions. An average of 3890 ± 142 mg/L As(III) at pH 1.4 in the wastewater was reduced to 59 ± 79 μg/L in the effluent with final pH at 7 in the 21 successive treatment cycles using regenerated TiO(2). Coexisting heavy metals including Cd, Cu, and Pb with concentrations at 369 mg/L, 24 mg/L, and 5 mg/L, respectively, were reduced to less than 0.02 mg/L. As(III) adsorption followed pseudosecond-order rate kinetics, and the adsorption behavior was described with the charge distribution multisite surface complexation model. Approximately 60% As(III) in the waste solution after the TiO(2) regeneration process was recovered by thermo vaporization and subsequent precipitation of sodium arsenite, as suggested by the EDX and XPS analysis. This "zero" sludge process sheds new light on successful As remediation technology for acidic metallurgical industry wastewater.     

Photocatalytic oxidation of arsenic(III): evidence of hydroxyl radicals

Arsenic contamination has been found in the groundwater of several countries. Photocatalysis can rapidly oxidize arsenite (As(III)) to less labile and less toxic arsenate (As(V)), which then can be removed by adsorption onto photocatalyst surfaces. This study investigates the photocatalytic oxidation of As(III) to As(V) as a function of As(III) concentration, pH, catalyst loading, light intensity, dissolved oxygen concentration, type of TiO2 surfaces, and ferric ions to understand the kinetics and the mechanism of As(III) oxidation in the UV/TiO2 system. Photocatalytic oxidation of As(III) to As(V) takes place in minutes and follows zero-order kinetics. Benzoic acid (BA) was used as a hydroxyl radical (.OH) scavenger to provide evidence for the .OH as the main oxidant for oxidation of As(III). The .OH radical was independently generated by nitrate photolysis, and kinetics of As(III) oxidation by the .OH radical was determined. Formation of salicylic acid (SA) from the oxidation of BA by .OH also demonstrates the involvement of .OH in the mechanism of As(III) oxidation. The effect of Fe(III) on As(III) oxidation at different pH values with and without TiO2 under UV light was examined. The results suggest that .OH is the dominant oxidant for As(III) oxidation. Two commercially available TiO2 suspensions, Degussa P25 and Hombikat UV100, were tested for the removal of arsenic through oxidation of As(III) to As(V) followed by adsorption of As(V) onto TiO2 surfaces. Results showed that complete removal of arsenic below the World Health Organization drinking water limit of 10 microg/L could be achieved.     

絮凝-Fenton氧化处理E段漂白废水的研究

采用絮凝-Fenton氧化处理E段漂白废水。通过正交实验确定了最佳操作参数。Al2（SO4）5-Fen％on氧化配合处理E段漂白废水的最佳操作条件为：Al2（SO4）3用量0．6g／L,氧化反应的pH值为5,H2O2用量1．Og／L,FeSO4用量0．8g／L,在此条件下废水COD的去除率可达90．64％。CPAM-Fenton氧化配合处理E段漂白废水的最佳操作条件为：CPAM用量0．8mg／L,氧化反应pH值6,H202用量1．5g／L,FeSO4用量1．2g／L,在此条件下废水COD的去除率可达82．43％。     

Competitive photocatalytic oxidation of Cu(II)--EDTA and Cd(II)--EDTA with illuminated TiO2

Competitive photocatalytic oxidation (PCO) of mixtures of Cu(II)-EDTA and Cd(II)-EDTA was studied with variation of molar ratio of these two complexes (1 x 10(-4):0, 8 x 10(-5): 2 x 10(-5), 5 x 10-5:5 x 10(-5), 2 x 10-5:8 x 10(-5), 0:1 x 10(-4) M) and in the pH range of 4-8. PCO rates for each compound can be described using a combined aqueous + adsorbed pathway: -dC/dt = k1Caq(1+ k2Caq)+ kadsCads. This expression is valid under both noncompetitive and competitive conditions. Differences in rates under competition result from differences in the partitioning of the two species between the TiO2 surface and the aqueous phase. Total initial complex degradation rates (rTT), obtained by summation of the total destruction rates for Cu(II)-EDTA and Cd(II)-EDTA, were relatively constant at pH 4 and 5 for all ratios. At these pH values, contribution of adsorbed pathways to rTT was important, and rates were similar to those of the aqueous phase pathways. From pH 6 to 8, the degree of adsorption, and thus the adsorbed pathway rate, diminished. Through the adsorbed pathway, no difference in rate constants was found between Cu(II)-EDTA and Cd(II)-EDTA; Cd(II)-EDTA is somewhat more reactive through the aqueous phase pathway.     

棉织物的壳聚糖金属配合物/H2O2室温漂白

通过壳聚糖在极稀的溶液中与金属离子Cu2+、Zn2+进行配位,形成2种壳聚糖金属配合物,研究这2种配合物催化H2O2氧化分解的动力学和对棉织物的室温漂白效果。结果表明：壳聚糖金属配合物在室温下能够较好地催化H2O2分解,分解率符合表观一级反应动力学;pH值、配合物初始浓度是影响壳聚糖金属配合物催化性能的重要因素。CTS′- Zn(II)配合物初始质量浓度为3g/L,pH值为11时催化效果最好;CTS′- Cu (II)配合物初始质量浓度为3g/L,pH值为8时催化效果最好。对棉织物的室温漂白效果与传统工艺相近,且强力保留率能达到90%以上。     

Bactericidal activity of copper-deposited TiO2 thin film under weak UV light illumination

The bactericidal activity of copper-deposited titanium dioxide thin film (Cu/TiO2) was investigated under very weak ultraviolet (UV) light illumination. To elucidate the roles of the film photocatalyst and the deposited copper in the bactericidal activity, cells from a copper-resistant Escherichia coli (E. coli) strain were utilized. A decrease in survival rate was not observed with the copper-resistant cells under dark conditions, but when illuminated with a very weak UV intensity of 1 microW/cm2, the survival rate decreased, suggesting photocatalytic bactericidal activity. The decay curve of survival on the Cu/TiO2 film under very weak UV light illumination consisted of two steps, similar to the survival change of normal E. coli on TiO2 films under rather strong UV illumination. The first step is due to the partial decomposition of the outer membrane in the cell envelope by a photocatalytic process, followed by permeation of the copper ions into the cytoplasmic membrane. The second step is due to a disorder of the cytoplasmic membrane caused by the copper ions, which results in a loss of the cell's integrity. These processes explain why the Cu/TiO2 film system shows an effective bactericidal activity even under very weak UV light illumination.     

碳纳米管-二氧化钛光催化降解普萘洛尔

水环境中普萘洛尔残留会对水产食品安全造成危害,并通过食物链威胁人体健康,因此需采取有效的方法去除普萘洛尔。本实验以碳纳米管- 二氧化钛纳米复合材料(MWCNTs-TiO2)为光催化剂,对普萘洛尔溶液进行光催化降解研究,在最佳实验条件：普萘洛尔质量浓度20mg/L、溶液初始pH 值为7、10% MWCNTs-TiO2 光催化剂加入量2.0g/L 时,紫外光照射180min 普萘洛尔的降解率达到95%。并对普萘洛尔的降解机理进行初步探讨,结果表明MWCNT-TiO2 降解普萘洛尔主要发生·OH 氧化反应,从而达到有效降解普萘洛尔的效果。     

漂白硫酸盐浆厂清洁生产技术(续)

7封闭循环 前面讨论的工艺技术是漂白硫酸盐浆厂封闭循环的基础，通过内部循环，漂白用水和废水排放大大减少。漂白浆厂的全封闭水循环目前还没有实现，部分循环使得水的用量由原来的66m^3／t（风干浆）降为6～8m^3／t（风干浆），减少了90％。     

Visible light Cr(VI) reduction and organic chemical oxidation by TiO2 photocatalysis

Here we report the simultaneous Cr(VI) reduction and 4-chlorophenol (4-CP) oxidation in water under visible light (wavelength > 400 nm) using commercial Degussa P25 TiO2. This remarkable observation was attributed to a synergistic effect among TiO2, Cr(VI), and 4-CP. It is well known that TiO2 alone cannot remove either 4-CP or Cr(VI) efficiently under visible light. Moreover, the interaction between Cr(VI) and 4-CP is minimal if not negligible. However, we found that the combination of TiO2, Cr(VI), and 4-CP together can enable efficient Cr(VI) reduction and 4-CP oxidation under visible light. The specific roles of the three ingredients in the synergistic system were studied parametrically. It was found that optimal concentrations of Cr(VI) and TiO2 exist for the Cr(VI) reduction and 4-CP oxidation. Cr(VI) was compared experimentally with other metals such as Cu(ll), Fe(lll), Mn(IV), Ce(IV), and V(V). Among all these metal ions, only Cr(VI) promotes the photocatalytic oxidation of 4-CP. The amount of 4-CP removed was directly related to the initial concentration of Cr(VI). The system was also tested with four other chemicals (aniline, salicylic acid, formic acid, and diethyl phosphoramidate). We found that the same phenomenon occurred for organics containing acid and/or phenolic groups. Cr(VI) was reduced at the same time as the organic chemicals being oxidized during photoreaction under visible light. The synergistic effect was also found with pure anatase TiO2 and rutile TiO2. This study demonstrates a possible economical way for environmental cleanup under visible light.     

TiO2-photocatalyzed As(III) oxidation in a fixed-bed, flow-through reactor

Compliance with the U.S. drinking water standard for arsenic (As) of 10 microg L(-1) is required in January 2006. This will necessitate implementation of treatment technologies for As removal by thousands of water suppliers. Although a variety of such technologies is available, most require preoxidation of As(III) to As(V) for efficient performance. Previous batch studies with illuminated TiO2 slurries have demonstrated that TiO2-photocatalyzed AS(III) oxidation occurs rapidly. This study examined reaction efficiency in a flow-through, fixed-bed reactor that provides a better model for treatment in practice. Glass beads were coated with mixed P25/sol gel TiO2 and employed in an upflow reactor irradiated from above. The reactor residence time, influent As(III) concentration, number of TiO2 coatings on the beads, solution matrix, and light source were varied to characterize this reaction and determine its feasibility for water treatment. Repeated usage of the same beads in multiple experiments or extended use was found to affect effluent As(V) concentrations but not the steady-state effluent As(III) concentration, which suggests that As(III) oxidation at the TiO2 surface undergoes dynamic sorption equilibration. Catalyst poisoning was not observed either from As(V) or from competitively adsorbing anions, although the higher steady-state effluent As(III) concentrations in synthetic groundwater compared to 5 mM NaNO3 indicated that competitive sorbates in the matrix partially hinder the reaction. A reactive transport model with rate constants proportional to incident light at each bead layer fit the experimental data well despite simplifying assumptions. TiO2-photocatalyzed oxidation of As(III) was also effective under natural sunlight. Limitations to the efficiency of As(III) oxidation in the fixed-bed reactor were attributable to constraints of the reactor geometry, which could be overcome by improved design. The fixed-bed TiO2 reactor offers an environmentally benign method for As(III) oxidation.