Degradation kinetics and mechanism of trace nitrobenzene by granular activated carbon enhanced microwave/hydrogen peroxide system

The kinetics of the degradation of trace nitrobenzene (NB) by a granular activated carbon (GAC) enhanced microwave (MW)/hydrogen peroxide (H₂O₂) system was studied. Effects of pH, NB initial concentration and tert-butyl alcohol on the removal efficiency were examined. It was found that the reaction rate fits well to first-order reaction kinetics in the MW/GAC/H₂O₂ process. Moreover, GAC greatly enhanced the degradation rate of NB in water. Under a given condition (MW power 300 W, H₂O₂ dosage 10 mg/L, pH 6.85 and temperature (60±5)℃), the degradation rate of NB was 0.05214 min^-1 when 4 g/L GAC was added. In general, alkaline pH was better for NB degradation; however, the optimum pH was 8.0 in the tested pH value range of 4.0-12.0. At H₂O₂ dosage of 10 mg/L and GAC dosage of 4 g/L, the removal of NB was decreased with increasing initial concentrations of NB, indicating that a low initial concentration was beneficial for the degradation of NB. These results indicated that the MW/GAC/H₂O₂ process was effective for trace NB degradation in water. Gas chromatography-mass spectrometry analysis indicated that a hydroxyl radical addition reaction and dehydrogenation reaction enhanced NB degradation.     

水溶液中4-氯酚的微波辅助光化学降解

研究了微波辅助无极紫外灯(MW/UV)光化学降解4-氯酚(4CP)模拟废水;为了考察溶液中4CP的降解效果,用紫外可见分光光度法(UV-VIS)和离子色谱法(IC)测定了溶液中4CP的降解率和Cl^-浓度.结果表明,MW/UV体系中30mg/L 4CP反应120min的降解率由紫外(UV)光解体系的21.56%提高到52.40%.提高溶液的pH值、向体系通入氧气、增强光照度以及外加氧化剂H₂O₂均能增加水溶液中4CP的降解率.微波辅助光化学降解4CP服从一级反应动力学方程.     

Photochemical degradation of nonylphenol in aqueous solution：The impact of pH and hydroxyl radical promoters

The degradation of nonylphenol (NP) in aqueous solution with UV, H₂O₂/UV, and Fenton/photo-Fenton processes was studied. The efficacy of direct and hydrogen peroxide photolysis proved to be dependent on the pH value. The addition of H₂O₂ to UV treatment improved NP degradation. The application of UV photolysis and the H₂O₂/UV system at pH 7 resulted in low pseudo first-order rate constants at 10^-4 sec^-1. In the experiments at elevated pH values the pseudo-first order rate constants increased to 10^-3 sec^-1. The efficacy of the Fenton process was lower in comparison with UV and hydrogen peroxide photolysis. The addition of UV irradiation to the H₂O₂/Fe²⁺ system substantially improved NP degradation efficacy. In terms of performance, the photo-Fenton process was similar to the H₂O₂/UV process. The most favourable process for complete nonylphenol degradation considering both operational cost and treatment efficacy was H₂O₂/UV at pH 11 and 250 mol/L H₂O₂.     

纳米Fe3O4/CeO2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解

以浸渍法制备的新型纳米Fe3O4/Ce O2为催化剂,3,4-二氯三氟甲苯(3,4-DCBTE)为目标污染物,在Fe3O4/Ce O2-H2O2非均相类Fenton体系中对目标污染物的降解进行研究,考察催化剂的催化效果和温度、p H、H2O2投加量等因素对催化剂催化效果的影响.结果表明,以纳米Fe3O4/Ce O2作为催化剂的非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;随着温度的升高,纳米Fe3O4/Ce O2的催化效果不断提高;在偏酸性环境中,p H越低催化效果越好,p H=2时反应去除效率可达96.67%;随着H2O2投加量的增加,3,4-二氯三氟甲苯的降解效率先提高后降低,投加量为15 mg·L-1时去除效果最好可达99.47%;随着催化剂投加量的增加,同样出现了处理效果先升高后降低的现象,投加量为0.5 g·L-1时催化效果最好可达99.64%.在以纳米Fe3O4/Ce O2为催化剂的非均相类Fenton体系中,3,4-二氯三氟甲苯的降解符合一级反应动力学,反应所需活化能较低只需30.26 k J·mol-1.     

石墨烯掺杂分子筛负载氧化铁芬顿催化降解苯酚影响因素的研究

通过水热晶化法制备了石墨烯掺杂介孔分子筛MCM-41复合载体,利用该载体浸渍负载氧化铁制备了非均相芬顿催化剂gh-MCM-41-Fe.以苯酚为模拟有机废水,考察了催化剂和H2O2投加量、水质因素(苯酚初始浓度、反应温度和水中腐殖酸和草酸)等对gh-MCM-41-Fe芬顿催化降解苯酚效能的影响.结果表明,当苯酚初始浓度为100 mg·L-1,催化剂在60 min催化降解苯酚去除率高达97.6%,COD去除率为65.9%,反应符合准一级反应动力学模型;苯酚降解速率随着催化剂和H2O2投加量的增加而增加,但投加过多会消耗·OH自由基从而不利苯酚降解过程;苯酚初始浓度从10 mg·L-1增至100 mg·L-1,苯酚降解速率相应降低,但体系中H2O2及·OH自由基的有效利用率反而增加;反应温度对于苯酚废水降解率和COD去除率影响不大,反应表观频率因子为105.68 min-1,表观活化能为18.43 k J·mol-1;腐殖酸和草酸对苯酚废水降解和COD去除均有抑制作用.     

UV/H2O2降解水中硝基酚及影响因素

UV/H₂O₂氧化对硝基酚实验表明,H₂O₂光解产生·OH自由基是对硝基酚降解的直接原因,12min内25mg/L的对硝基酚去除率达到98%以上.溶液中TOC变化与对硝基酚的去除并不同步,说明对硝基酚的降解中生成了一系列的中间产物,然后再达到完全矿化的.体系中H₂O₂浓度变化显示产生的中间产物对H₂O₂光解没有明显影响.研究中还对对硝基酚起始质量浓度、H₂O₂浓度及pH影响进行了考察.研究认为UV/H₂O₂是对硝基酚脱毒的一种有效方法.      

UV和H2 O2联合消毒灭活饮用水中大肠杆菌研究

以大肠杆菌为研究对象,对单独紫外线(UV)、H2O2及两者不同组合方式的灭活效果进行了分析.结果表明,单独H2O2对大肠杆菌基本无灭活效果,加入浓度为20 mg·L-1的H2O2接触时间为30 min时,灭活率仅为0.02个对数级;单独UV工艺可在一定程度上灭活大肠杆菌,紫外线剂量为10 mJ·cm-2时,灭活率可达到4.51个对数级.紫外线和H2O2联合消毒在一定程度上提高了消毒效果,且不同的组合方式对灭活效果有很大的影响.先UV后H2O2消毒效果优于先H2O2后UV,当紫外线剂量为5 mJ·cm-2时,加入H2O2分别反应2.5、5、10、20 min后,两者的灭活率分别较单独UV消毒增加0.09、0.35、0.38、0.68和0.01、0.07、0.14、0.53个对数级.而UV与H2O2同时消毒效果优于UV与H2O2顺序消毒,当紫外线剂量为5 mJ·cm-2时,加入H2O2反应20 min后,灭活率较UV-H2O2和H2O2-UV工艺分别增加了0.43和0.58个对数级.随着紫外线强度的增加,大肠杆菌的灭活效果不断提高.     

水力空化强化H2O2氧化降解水中苯酚的研究

采用水力空化强化H₂O₂降解水中苯酚,考察入口压力,ρ(H₂O₂)和溶解气体等因素对苯酚降解的影响;比较了水力空化方法和超声空化方法降解水中苯酚的能耗效率.研究表明:苯酚降解率随着入口压力的增大而增大,入口压力从1.0×105 Pa增大到3.5×105 Pa时,相应地苯酚降解率从17.6%增加到47.6%;在一定条件下,ρ(H₂O₂)有一个最佳值;不同的溶解气体对苯酚降解效果的影响不同,O₂的效果比N₂好.分析ρ(H₂O₂)和溶解气体对苯酚降解效果的影响及苯酚降解中间产物的分布表明,羟基自由基的产生是苯酚降解的主要原因,水力空化的能量利用率是超声空化的5.4倍.      

Electrolyte effects on aqueous atmospheric oxidation of sulphur dioxide by hydrogen peroxide

The rate of oxidation of sulphur dioxide by hydrogen peroxide in the presence of various supporting electrolytes has been determined by the stopped flow method. In a sodium perchlorate medium (chosen as reference electrolyte) first-order kinetics were observed with respect to HSO₃⁻, H₂O₂ and H⁺. The influence of the ionic strength was investigated and the third-order rate constant was calculated at infinite dilution. The rate constants of the reaction are shown to be far higher when chloride or ammonium ions are added to the solution.The effect of temperature and traces of metals ions (Mn²⁺, Fe²⁺, Fe³, Cu²⁺, Cr³⁺) was studied. The oxidation reaction is virtually insensitive to the effects of Mn²⁺, Fe³⁺, Cu²⁺ and Cr³⁺. Catalytic activity is observed with Fe²⁺.     

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.     

A clean production process of sodium chlorite from sodium chlorate

This paper presents a novel cleaner production process for producing sodium chlorite by reducing sodium chlorate with hydrogen peroxide. In the new process, chlorine dioxide is generated by reducing chlorate ions with hydrogen peroxide in the presence of sulfuric acid: it then reacts with aqueous sodium hydroxide solution and hydrogen peroxide to produce sodium chlorite. The reaction conditions that were experimentally investigated included: reaction temperatures, concentrations of sodium chlorate solution, molar ratio of NaClO₃:H₂SO₄:H₂O₂, and acidity. Waste acid in the chlorine dioxide generator is dramatically reduced with recycling in the new process. The by-produced sodium sulfate in sulfuric acid is minimized and reclaimed.     

Magnetically recoverable Fe3O4@polydopamine nanocomposite as an excellent co-catalyst for Fe3+ reduction in advanced oxidation processes

Advanced oxidation processes are widely applied to removal of persistent toxic substances from wastewater by hydroxyl radicals(·OH),which is generated from hydrogen peroxide(H_2O_2) decomposition.However,their practical applications have been hampered by many strict conditions,such as iron sludge,rigid pH condition,large doses of hydrogen peroxide and Fe~(2+),etc.Herein,a magnetically recyclable Fe_3O_4@polydopamine(Fe_3O_4@PDA) coreshell nanocomposite was fabricated.As an excellent reducing agent,it can convert Fe~(3+)to Fe~(2+).Combined with the coordination of polydopamine and ferric ions,the production of iron sludge is inhibited.The minimum concentration of hydrogen peroxide(0.2 mmol/L and Fe~(2+)(0.18 mmol/L)) is 150-fold and 100-fold lower than that of previous reports,respectively.It also exhibits excellent degradation performance over a wide pH range from 3.0 to 9.0.Even after the tenth recycling,it still achieves over 99% degradation efficiency with the total organic carbon degradation rate of 80%,which is environmentally benign and has a large economic advantage.This discovery paves a way for extensive practical application of advanced oxidation processes,especially in environmental remediation.     

辣根过氧化物酶处理酚和氯酚的催化特性研究

为了研究辣根过氧化物酶处理酚和氯酚的动力学过程,采用人工配不试验,测定了ｐＨ对酶催化反应的影响,Ｈ２Ｏ２抑制酶催化反应的动力学参数和不同度物的酶催化反应动力学参数,结果表明,在试验的ｐＨ范围内,ｐＨ为９时过氧化物酶对苯酚和对氯苯酚的去除效率最高,分别达到９９．５％和９５％。     

过氧化氢-敏化剂强化污泥微波预处理溶胞效果的研究

提高污泥溶胞效率是强化污泥厌氧处理的关键.为加强污泥微波预处理溶胞效果,本研究分别考察了常压、半封闭条件下二氧化钛颗粒、碳质材料作为敏化剂与过氧化氢联合进行微波污泥预处理的效果.结果表明,碳质材料敏化剂对微波、过氧化氢-微波污泥预处理产生了负作用,降低了污泥的溶胞效果,而二氧化钛能有效增加污泥中营养物质的释放.当二氧化钛颗粒投加量为0.12 g·g~(-1)干污泥时,SCOD、PO_4~(3-)-P的浓度比单独微波处理分别增加了11.86%、61%;当二氧化钛颗粒投加量为0.24 g·g~(-1)干污泥时,NH_4~+-N释放比单独微波处理高出27.78%.微波辐射作用下投加二氧化钛颗粒产生了羟基自由基,强化了过氧化氢-微波对污泥细胞的氧化作用.     

Enhanced ozonation degradation of atrazine in the presence of nano-ZnO: Performance, kinetics and effects

Enhanced ozonation degradation of atrazine (ATZ) with nano-ZnO (nZnO) as catalyst and the influences of the operational parameters have been investigated through semi-continuous experiments in this study. The results demonstrated that the combination of ozone (O₃) and nZnO showed an obvious synergetic effect and the ATZ degradation conformed to pseudo-first-order kinetics. An improvement of ATZ degradation efficiency by 41.8% and pseudo-first-order rate constant by more than a factor of four was obtained in the O₃/nZnO process after 5 min of reaction compared to O₃ alone. Meanwhile, the degradation efficiency of ATZ was gradually enhanced with increasing nZnO dosage and initial pH in the range from 3.0 to 8.0, and a higher amount of ATZ was degraded when the initial concentration of ATZ rose from 0.5 to 5 mg/L. Additionally, sulfate ion, chloride ion, nitrate ion and low concentrations of humic acid substances led to enhancement of the ATZ degradation. The notable decrease of ATZ removal efficiency observed in the presence of radical scavengers and the results of free radical tests indicated that OH is the dominant active radical species. The mechanism investigation demonstrated that the enhancement effect could be attributed to the introduction of nZnO, which could promote the utilization of O₃, enhance the formation of superoxide radical, and further accelerate the production of hydrogen peroxide and the generation of OH/O₂-.     

TiO2光催化联合技术降解苯酚机制及动力学

主要研究了TiO2光催化体系结合H2O2或外加电催化(EC)体系对苯酚催化降解效率的影响,评价比较TiO2/UV、H2O2/UV、TiO2/UV/H2O2、TiO2/UV/EC体系下苯酚降解机制及动力学.结果表明,TiO2/UV/H2O2和TiO2/UV/EC体系下苯酚降解效率明显高于TiO2/UV体系,当苯酚溶液pH值为6,TiO2质量浓度0.2 g·L-1,紫外光照2 h,光催化降解效果达到86%,当电流密度为12 mA·cm-2,则苯酚可达到100%去除.比较了不同催化体系下的能量利用率,苯酚降解15 min,TiO2/UV/EC体系能量利用率最大为0.030 6 g·(kW·h)-1,其能量消耗为0.0640 kW·h-1,说明采用TiO2/UV/EC体系能更多地利用能量降解苯酚.通过不同催化体系下中间产物分析,建立苯酚及其中间产物对苯二酚、邻苯二酚和苯醌的拟一级降解动力学模型,通过模型验证各催化体系下苯酚的降解历程,同时也说明了TiO2/UV/EC体系有利于苯酚及其中间产物的降解.     

紫外驱动高级氧化法降解水体中的磷酸三苯酯

有机磷酸酯（OPEs）作为备受关注的一类新污染物,已对偏远的南极地区水环境引发了中等风险.磷酸三苯酯（TPHP）是水体中常见的OPEs,已被证实具有毒性效应、生物富集和放大效应,对环境和人体健康威胁较大.利用傅里叶红外光谱仪（FT-IR）和液相色谱-串联质谱联用仪（LC-MS/MS）探究TPHP在紫外-过氧化氢（UV-H₂ O₂）、紫外-二氧化钛（UV-TiO₂）和紫外-过硫酸盐（UV-PS）这3种高级氧化体系（UV-AOPs）中的降解过程,创新性地利用FT-IR实现了TPHP降解过程中红外特征峰变化的在线观测,并对其降解反应动力学、光降解产物和降解路径进行了分析.结果表明,TPHP在UV-H₂ O₂、UV-TiO₂和UV-PS体系下均能得到有效降解,其光降解半衰期分别为74、150和89 min.其中,UV-H₂ O₂体系对TPHP的降解效果最好.TPHP在3种体系下的降解反应均符合一级动力学.当H₂ O₂浓度为0~0.097 mol ·L^-1时,H₂ O₂浓度升高会促进TPHP降解;当TiO₂浓度为0~0.013 mol ·L^-1时,TiO₂浓度升高会促进TPHP降解.TPHP的光降解路径主要是P—O—C键断裂、苯环结构的C—H键断裂和水解反应.利用UV-H₂ O₂体系对成都市环境水体中OPEs进行降解实验,发现对公园景观水体的水样进行降解反应60 min时,TPHP的去除率为66%.     

A kinetic model of Ti（IV）-catalyzed H2O2/O3 process in aqueous solution

A kinetic model for the Ti(IV)-catalyzed H₂O₂/O₃ process was established, and the experimental results demonstrated that the model could well describe this ozone-based oxidative system mathematically and chemically.     

CuO/AOCF类Fenton催化剂的制备及光催化性能

以偕胺肟纤维(AOCF)为载体,采用配位-沉淀法研制了一种新型的类Fenton催化剂CuO/AOCF.用SEM、EDS和XRD对CuO/AOCF的表面形貌、晶体结构和表面成分进行分析,结果显示:CuO纳米颗粒均匀分布在AOCF表面.以活性红染料为目标降解物及其去除率为评价指标,考察CuO/AOCF与H_2O_2组成类Fenton催化剂的光催化性能.结果表明:在氙灯光照作用下,0.6 g·L~(-1)CuO/AOCF、2 m L·L~(-1)H_2O_2、反应时间为80 min,活性红溶液几乎完全被降解.对比同质量粉体CuO,CuO/AOCF对光催化性能有着更好的促进作用.CuO/AOCF重复使用5次后降解率仍能大于80%.动力学研究表明,该类Fenton催化降解反应遵循一级反应动力学规律.     

纳米四氧化三铁对2,4-D的脱氯降解

采用纳米四氧化三铁(Fe3O4)降解水溶液中的2,4-二氯苯氧乙酸(2,4-D),考察了2,4-D初始浓度、纳米Fe3O4投加量、溶液pH和温度等因素对2,4-D降解率的影响.结果表明,纳米Fe3O4对2,4-D有显著的降解效果,初始浓度为10 mg/L的2,4-D, 48 h内降解率可达48%.纳米Fe3O4对2,4-D的降解是一个还原脱氯过程,反应体系中氯离子浓度随2,4-D浓度降低而升高.LC/MS分析表明,2,4-D降解的主要产物是苯酚,其他中间产物是2,4-二氯苯酚(2,4-DCP)、4-氯苯酚(4-CP)和2-氯苯酚(2-CP).溶液中2,4-D的降解符合准一级反应动力学,产物4-CP、2,4-DCP和苯酚的反应速率常数K分别为0.0043、0.0026和0.0032 h -1.环境条件对降解效率有显著影响,2,4-D初始浓度在0～10 mg/L、纳米Fe3O4投加量0～300 mg/L的范围内,2,4-D降解率随初始浓度和纳米Fe3O4投加量的增加而增大;pH对2,4-D的脱氯降解有显著影响,在pH为3.0时,纳米Fe3O4对2,4-D的还原脱氯效果最好;温度升高,可以提高脱氯反应速率.