TS-1分子筛催化O3/H2O2氧化乙酸

研究了酸性条件下TS-1分子筛催化O3/H2O2体系(O3/H2O2/TS-1)对降解水中乙酸效率的影响,优化了相关工艺参数,并对其作用机理进行了分析。结果表明,在pH为2.8时,TS-1的加入能显著提高臭氧化的降解效率。优化工艺参数表明,当过氧化氢投加量为3 g/L,TS-1投加量为5 g/L时,O3/H2O2/TS-1体系对乙酸具有较高的降解率,60 min后O3/H2 O2/TS-1体系对乙酸(初始浓度为100 mg/L)的去除率达到了58.7%。当pH为0.8时,O3/H2 O2/TS-1体系对乙酸的去除率仅为19.8%,降解效果较差。定量化计算表明,O3/H2O2和O3/H2O2/TS-1的Rct分别为1.62×10-8和8.67×10-7。通过测定乙酸降解过程水样中过氧化氢和液相臭氧的浓度变化,推测了具体反应机理。由于此体系在酸性条件下对乙酸有较好的降解效果,拓宽了现有O3/H2O2体系的应用范围。     

TS-1分子筛催化O_3/H_2O_2氧化乙酸

研究了酸性条件下TS-1分子筛催化O3/H2O2体系（O3/H2O2/TS-1）对降解水中乙酸效率的影响,优化了相关工艺参数,并对其作用机理进行了分析。结果表明,在pH为2.8时,TS-1的加入能显著提高臭氧化的降解效率。优化工艺参数表明,当过氧化氢投加量为3 g/L,TS-1投加量为5 g/L时,O3/H2O2/TS-1体系对乙酸具有较高的降解率,60 min后O3/H2 O2/TS-1体系对乙酸（初始浓度为100 mg/L）的去除率达到了58.7%。当pH为0.8时,O3/H2 O2/TS-1体系对乙酸的去除率仅为19.8%,降解效果较差。定量化计算表明,O3/H2O2和O3/H2O2/TS-1的Rct分别为1.62×10-8和8.67×10-7。通过测定乙酸降解过程水样中过氧化氢和液相臭氧的浓度变化,推测了具体反应机理。由于此体系在酸性条件下对乙酸有较好的降解效果,拓宽了现有O3/H2O2体系的应用范围。     

高级氧化工艺处理煤化工浓盐水

浓盐水处理是一项世界性难题,采用高级氧化工艺能有效去除废水中难降解有机物,从而提高其可处理性。分别采用臭氧氧化、O3/H2O2、GAC/O3和GAC/O3/H2O2等工艺处理煤化工浓盐水,研究了工艺参数对COD去除的影响,探索了有机物去除机理。研究表明,煤化工浓盐水中易被臭氧氧化的有机物大约占55%。增加臭氧投加量和气体流速能提高有机物去除效率。酸性条件下的COD去除率要高于碱性条件下。臭氧氧化、O3/H2O2、GAC/O3和GAC/O3/H2O2工艺中·OH稳定浓度分为4.1、37.7、5.9和41.3×10-14mol/L。O3与H2O2之间存在明显协同作用,GAC与O3协同产生·OH的作用不明显,但GAC对氧化过程中生成的生物抑制物具有较好的吸附去除作用。GAC、O3和H2O2三者之间的协同作用有助于去除煤化工浓盐水中难降解有机物、提高出水可生化性和降低出水水质毒性。     

O3/H2O2降解阿特拉津影响因素研究

采用O3/H2O2氧化去除水中内分泌干扰物阿特拉津,考察了反应条件及水质对去除的影响,并对反应机制进行了初步探讨.阿特拉津初始浓度2 mg/L,投量为7.5 mg/L的O3单独氧化去除率为27.2%;相同O3投量下,控制H2O2/O3摩尔比为0.75,5 min阿特拉津的去除率最高可达96.5%;pH值为7.5～8.5,温度在25～40℃的范围内,都维持了较高的去除率,表明H2O2/O3体系对阿特拉津的去除效果良好,降解速度快,反应条件温和.0.5 mg/L的腐殖酸,对阿特拉津的去除影响不大,腐殖酸浓度为1、2和5 mg/L时,平均去除率分别为63.4%、50.7%和30.2%;碳酸氢钠的浓度为50和200 mg/L时,去除率分别为88.1%和73.8%,说明水质对阿特拉津的去除影响较大.叔丁醇的浓度为5和20 mg/L时,阿特拉津的去除率分别降低到44.7%和27.5%,去除率随自由基抑制剂叔丁醇增加而降低,说明H2O2/O3降解阿特拉津主要为该体系产生的羟基自由基的贡献.     

纳米二氧化钛光催化氧化油田采出水中萘和芴的影响因素分析

利用纳米二氧化钛光催化氧化技术,分析了不同影响因素UV波长(UVA 365 nm、UVB 308 nm和UVC 254nm)、温度、p H、催化剂(Ti O2)、抑制剂(Bu OH)和氧化剂(O2、H2O2和O3)对油田采出水中多环芳烃萘和芴降解效率的影响,并进一步优化出单因子的最佳条件。实验结果表明,各因素对萘和芴降解有不同的影响,但其效果都随波长减小和酸度降低而得到增强。当其他条件为一致最优时(T=90℃,Ti O2=0.5 g/L和Bu OH=0.03 mol),当H2O2=0.01 mol或O2=30 m L/min时,萘的降解率最高,而当H2O2=0.1 mol或O3=30 m L/min对芴的降解效果最好。     

γ-射线辐照降解水中阿莫西林

研究了60Coγ-射线辐照条件下水中阿莫西林(AMX)的辐照降解,考察了AMX初始浓度、辐照剂量、p H、H2O2、自由基消除剂(碳酸氢钠和正丁醇)以及溶解氧等因素对AMX辐照降解的影响。结果表明,γ辐照可有效降解水中AMX,当AMX初始浓度为10.0 mg/L,辐照剂量为15 k Gy时,降解率达100%,随着AMX浓度增大,其降解率降低。碱性条件有利于AMX的降解,当p H为11,且辐照剂量大于10 k Gy时,AMX的降解率在90%以上。同时,加入H2O2可以促进AMX的降解;·OH自由基消除剂的存在和缺氧条件会明显抑制γ-射线对AMX的辐照降解,分析表明,AMX的降解主要是基于·OH自由基的氧化。     

计算机模拟研究UO2+2在人体细胞液的形态分布

建立了由多种金属离子和小分子配体组成的多相细胞液热力学平衡模型.模拟研究了UO2 2在组织液和细胞液的形态分布及CO2-3、氨三乙酸（NTA）和乙二胺四乙酸（EDTA）浓度对细胞液中UO2 2形态分布的影响.在组织液中,正常生理pH下,当各形态UO2 2总摩尔浓度 [U]= 1.0×10-6 mol/L 或[U]=1.0×10-3 mol/L时,UO2 2均主要以[UO2(CO3)3]4-和[UO2(CO3)2]2-形态存在.在细胞液中,当[U]=1.0×10-6 mol/L时,UO2 2主要以[UO2(CO3)3]4-和[UO2(CO3)2]2-存在;当[U]=1.0×10-3 mol/L,pH为6.0～6.8时,细胞液中存在大量的固相(UO2)3(PO4)2·4H2O,当pH为6.8～7.4时,UO2 2主要以[UO2(CO3)3]4-、[UO2(CO3)2]2-和[(UO2)2CO3(OH)3]-存在.细胞液中(UO2)3(PO4)2·4H2O含量随[U]升高而增加.通过调节细胞液pH和增加细胞液CO2-3浓度均能降低其固相UO2 2配合物含量.在细胞液中增加NTA会增加(UO2)3(PO4)2·4H2O含量,当添加EDTA时会显著降低(UO2)3(PO4)2·4H2O含量.     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

涡流空化/Fenton协同降解溶液中活性艳红K-2BP

采用涡流空化(SC)/Fenton协同降解溶液中活性艳红K-2BP,探讨了H2O2、Fe2+、pH、涡流压力以及活性艳红K-2BP初始浓度对SC/Fenton降解效果的影响。结果表明,H2O2和Fe2+的浓度过高或过低都会降低活性艳红K-2BP的降解率,低pH环境有助于活性艳红K-2BP的降解,活性艳红K-2BP的降解率随涡流压力的增大而升高,随其初始浓度的增加而降低。当活性艳红K-2BP初始质量浓度为10mg/L,H2O2质量浓度为165mg/L,Fe2+摩尔浓度为1.5×10-4mol/L,pH为4.0,涡流压力为0.8MPa时,活性艳红K-2BP降解率可达91.81%。     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

The process by which sulphur dioxide is oxidised in atmospheric droplets has been studied in laboratory experiments designed to collect a large amount of chemical data pertinent to the atmospheric situation. Thus the oxidation of sodium sulphite solutions by oxygen, ozone and hydrogen peroxide has been studied at different pH's and temperatures. In all cases the reaction is first order with respect to sulphite ion but the order with respect to oxidant differs. For oxygen the order is zero whereas the order for ozone and hydrogen peroxide is one. Varying the hydrogen ion concentration has little effect on the oxygen reaction rate between pH 6 and 9; the ozone reaction rate is inversely proportional to the square root of the hydrogen ion concentration and the hydrogen peroxide rate is almost directly proportional to the hydrogen ion concentration. These last two observations are very important since in the case of ozone it indicates that the reaction proceeds via a free radical mechanism involving hydroxyl radicals and in the case of hydrogen peroxide it is the only oxidation process of sodium sulphite so far investigated that shows a positive response to the presence of hydrogen ions.The experimental data was used to calculate the rate of sulphate formation in water droplets under atmospheric conditions for each of the three oxidants. If it is assumed that the ozone and hydrogen peroxide gas phase concentrations are initially 50 parts in 10⁹ and 1 part in 10⁹ by volume respectively, then the rates of sulphate formation are equal in cloud water at pH 5.8. Above this pH the ozone reaction is faster and below it the hydrogen peroxide reaction is faster due to the positive catalysis by hydrogen ions; the oxygen rate is unimportant by comparison at all pH's below 7. The rate of hydrogen peroxide reaction is such that substantial amounts of sulphate can still be formed rapidly in water droplets at pH values from 3 to 5, and thus this process will be very important in creating acidity in rainwater.     

光催化降解水体异味物质2-MIB的机理

以水体异味物质2-甲基异莰醇(2-methylisoborneol,2-MIB)为研究对象,在紫外光(λ<380 nm)照射下,探讨TiO2(P25)对2-MIB的光催化降解特性及光化学作用机理。结果表明,UV/TiO2光催化体系可以有效去除水体异味物质2-MIB,紫外光照射60 min,对2-MIB的降解率达95%。同时研究了光催化降解体系介质pH,共存腐殖酸(HA)和过硫酸钾(K2S2O8)对UV/TiO2光催化体系降解2-MIB的影响,发现低浓度HA([HA]≤0.5 mg/L)可以提高2-MIB降解速率,当HA浓度高于0.5 mg/L,2-MIB降解反应受到抑制;同时当加入电子受体K2S2O8后,降解体系中活性物种羟基自由基(.OH)明显增加,提高了TiO2对2-MIB的降解能力。利用苯甲酸荧光光度法和POD-DPD显色法跟踪测定降解过程中羟基自由基(·OH)和过氧化氢(H2O2)的变化,表明光催化反应涉及·OH机理。     

Fresnel lens to concentrate solar energy for the photocatalytic decoloration and mineralization of orange II in aqueous solution

The decoloration and mineralization of the azo dye orange II under conditions of artificial ultraviolet light and solar energy concentrated by a Fresnel lens in the presence of hydrogen peroxide and TiO(2)-P25 was studied. A comparative study to demonstrate the viability of this solar installation was done to establish if the concentration reached in the focus of the Fresnel lens was enough to improve the photocatalytic degradation reaction. The degradation efficiency was higher when the photolysis was carried out under concentrated solar energy irradiation as compared to UV light source in the presence of an electron acceptor such us H(2)O(2) and the catalyst TiO(2). The effect of hydrogen peroxide, pH and catalyst concentration was also determined. The increase of H(2)O(2) concentration until a critical value (14.7 mM) increased both the solar and artificial UV oxidation reaction rate by generating hydroxyl radicals and inhibiting the (e(-)/h(+)) pair recombination, but the excess of hydrogen peroxide decreases the oxidation rate acting as a radical or hole scavenger and reacting with TiO(2) to form peroxo-compounds, contributing to the inhibition of the reaction. The use of the response surface methodology allowed to fit the optimal values of the parameters pH and catalyst concentration leading to the total solar degradation of orange II. The optimal pH range was 4.5-5.5 close to the zero point charge of TiO(2) depending on surface charge of catalyst and dye ionization state. Dosage of catalyst higher than 1.1 gl(-1) decreases the degradation efficiency due to a decrease of light penetration.