超声波-芬顿法协同降解亚甲基蓝的研究

以亚甲基蓝溶液为模型污染物,在超声波芬顿法协同作用下对亚甲基蓝染料废水的降解作用进行了研究,考察了反应时间、H2O2用量、溶液pH值、Fe^2＋的浓度等因素对亚甲基蓝溶液降解的影响。结果表明,超声波单独降解亚甲基蓝溶液脱色效果不明显,超声波协同H2O2降解亚甲基蓝,加入30%H2O26mL,脱色率约45.80%;溶液pH2.80,Fe^2＋浓度为30mmol/L时,超声波芬顿法协同降解甲基蓝180min,脱色率达92.70%。试验证明,超声波芬顿法是一种降解亚甲基蓝的有效方法。     

紫外光及日光下天然金红石光催化降解苯酚的研究

研究了山西代县天然金红石在紫外光和日光照射条件下对苯酚的光催化降解性能,考察了光照时间、pH值、苯酚初始浓度以及H2O2添加量对降解过程的影响。在紫外光照射下,酸性条件(pH=3.5)利于光催化降解,中性和碱性条件下降解效率较低;当初始浓度为60mg/L时,降解速率可达1.922mg/(L.h);H2O2作为电子捕获剂可提高苯酚降解速率,最佳投加量为2mL/L。在日光条件下,天然金红石对苯酚表现出良好的降解性能,照射7h后,降解率达87.68%,仅略低于P25型TiO2(99.72%),可在14h内完全降解。根据电子探针和X射线衍射分析结果,认为天然金红石晶格中的V、Fe等杂质可能是提高其可见光响应效果和光催化活性的主要原因。     

Fenton试剂氧化-微电解-接触氧化法处理丙烯腈废水实验研究

实验采用Fenton试剂氧化-微电解-接触氧化组合工艺处理丙烯腈废水。研究了各单元工艺的最佳控制参数和操作条件。结果表明,在废水pH值为3左右、反应时间2 h的前提下,双氧水投加量40 mL/L,二价铁离子质量浓度为0.4 g/L,再经过微电解处理后的出水进入接触氧化阶段。在溶解氧为4.5 mg/L左右,水力停留时间为10 h、容积负荷1.0 kg COD_Cr/（m³·d）左右的条件下,出水COD_Cr小于100 mg/L,可达到国家对丙烯腈废水处理要求的一级标准。     

鸟粪石结晶法预处理垃圾渗滤液中高浓度氨氮的研究

利用鸟粪石结晶法预处理垃圾渗滤液中的高浓度氨氮,通过单因素实验和正交实验探讨了pH值、添加剂种类、添加剂比例、反应时间4个因素对氨氮去除率的影响,结合反应过程中的经济成本得出鸟粪石结晶法最佳工艺条件为:pH=9,添加剂为MgC12·6H2O和Na2HPO4·12H2O,n(Mg2+):n(NH4+):n(PO43-)=1:1:1,反应时间15min,氨氮去除率达到90.13%,剩余氨氮在300mg/L以下。通过XRD和ESEM分析,沉淀产物为鸟粪石。实验表明鸟粪石结晶法可以有效去除垃圾渗滤液中的高浓度氨氮,为后续使用生物法处理提供条件,也可以弥补矿物吸附法去除氨氮的不足。可将其与生物法、矿物吸附法等方法组合使用,综合处理垃圾渗滤液。     

镍酞菁修饰镍铝水滑石的制备及光催化性能研究

通过共沉淀法将水溶性四羧基镍酞菁(Ni Pc)负载到镍-铝碳酸根水滑石(Ni Al-LDHs)上,制备负载型催化剂(Ni Pc/Ni Al-LDHs)。采用XRD、FT-IR、UV-Vis、TG-DTA和SEM等技术对酞菁衍生物和Ni Pc/Ni Al-LDHs的结构进行表征。结果表明Ni Pc没有改变Ni Al-LDHs的晶型结构和热稳定性能。在10 mg/L、25 m L的甲基橙溶液、p H值为3、H2O2用量50μL的条件下,Ni Pc/Ni Al-LDHs协同H2O2光催化氧化降解甲基橙3 h后,甲基橙剩余率为16.33%。溶液p H值在3~7范围内,Ni Pc/Ni Al-LDHs/H2O2都能有效光催化氧化降解甲基橙,且光催化氧化降解过程涉及到羟基自由基反应。     

Degradation of phenol of high concentration by FeAIOx/MMT catalyzed Fenton reaction

以蒙脱土为载体制备负载型Fe/Al复合氧化物（FeAlOx/MMT）用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。     

蒙脱石基纳米FeOOH/TiO2复合材料的制备与光催化活性研究

以蒙脱石为基底,采用溶胶-凝胶法制备二氧化钛/蒙脱石(TiO2/Mmt)复合光催化材料,通过Fe(NO3)3-HNO3体系水解生长纳米FeOOH,从而制备出负载型羟基氧化铁/二氧化钛/蒙脱石(FeOOH/TiO3/Mmt)复合光催化材料以改善材料在可见光下的光催化性能.高分辨透射电镜的表征结果显示,FeOOH/TiO2复合薄膜厚度约为10～40 nm,TiO2为晶粒粒径约为5～10nm的锐钛矿,FeOOH为长10～30 nm,宽约4 nm的针铁矿.以甲基橙为目标物,对FeOOH/TiO2/Mmt复合材料的光催化性能进行初探,在甲基橙初始浓度为5 mg/L,催化剂用量为1.875 g/L,H2O2初始浓度为2 mmol/L,pH值为6.5,350 W氙灯照射1 h,甲基橙脱色率达到99%,明显优于相同条件下TiO2/Mint对甲基橙的45%脱色率;同时甲基橙残液的红外光谱图显示FeOOH/TiO2/Mmt/H2O2/UV体系比FeOOH/TiO2/Mint/H2O2/Visible light体系具备更好的光催化氧化苯环的能力,降解更为彻底.     

电-Fenton法处理苯酚废水影响因素的研究

采用电-Fenton法对含苯酚废水进行处理,以石墨为阴极、铁为阳极,并向阴极不断通入空气,电解过程产生的H2O2与阳极溶解的Fe^2＋形成Fenton试剂,Fenton试剂在电解过程中产生大量活性羟基自由基,能够很好地氧化降解废水中的苯酚。实验结果表明：影响苯酚去除率的因素主次顺序为pH值、电解质浓度、电解电压、电解时间、进水苯酚浓度。单因素分析得出电-Fenton法处理苯酚模拟废水的最优反应条件：pH值控制在2左右,反应时间为60min,电解电压选10V,Na2SO4的浓度为30g／L,进水苯酚浓度为150mg／L。在最优条件下苯酚的去除率为82％。     

坡缕石粘土固定辣根过氧化酶处理硝基酚废水

以坡缕石粘土、淀粉、水玻璃为原料,研究了固定化酶载体的制备工艺,探究了固定化酶载体在辣根过氧化酶(HRP)降解硝基酚废水中的作用,并探讨了反应时间、酶浓度、H2O2及硝基酚浓度对降解效果的影响。结果表明,固定化酶载体的最佳制备工艺为:水玻璃12%,淀粉20%,煅烧温度550℃,煅烧时间2 h;固定化酶对硝基酚的去除效果明显高于原酶;固定化酶去除水中硝基酚的最佳反应条件为:反应时间1.5 h,加酶量150 U,H2O2浓度0.12%,硝基酚浓度100 mg/L;固定化酶重复使用7次后对硝基酚的去除率仍高于60%。     

臭氧-超声联用处理聚乙烯醇废水

本研究采用臭氧-超声（O₃/US）联用技术处理聚乙烯醇（PVA）废水,分别考察了PVA初始质量浓度、初始pH、臭氧通入速率、超声功率、超声频率及反应时间对PVA和COD去除效率的影响,并在此基础上通过正交实验确定了降解PVA和COD的最佳实验条件。研究结果表明,超声频率对去除率有显著影响,PVA初始质量浓度对去除效率的影响较大,反应时间、超声功率、臭氧通入速率和初始pH的影响相对较小。通过影响实验和正交实验确定的最佳降解条件为:PVA初始质量浓度100 mg/L、初始pH=9、臭氧通入速率4 g/h、超声功率320 W、超声频率40 kHz、反应时间20 min,此时COD和PVA的去除效率分别为86.4%和99.3%。超声对臭氧降解聚乙烯醇废水具有明显的协同作用,在最佳条件下,臭氧-超声联用技术比单独臭氧技术对PVA的去除率增加了5.1%,对COD去除率增加了19.4%。     

Decolorization of simulated spent reactive dye bath using solar / TiO2 / H2O2

Different parameters were investigated to evaluate their effect on the process removal efficiency of reactive dye from simulated spent reactive dye bath, by solar / TiO₂ / H₂O₂, including H₂O₂ concentration, TiO2 loading and pH. As a result 99% of reactive dye can be removed at a TiO₂ loading of 400mg/l, H₂O₂ concentration of 150 mg/l and of pH: 5.2. The effect of photo-catalytic deactivation of TiO₂ on reactive dye removal was studied for ten number of cycles, and found that the extent of deactivation was high for each consecutive repeated use.     

Nitrate removal from water using UV-M/S2O4 2− advanced reduction process

In this work, a new process called advanced reduction process (ARP) was used for nitrate removal from water. This ARP process combines sodium dithionite as reducing agent with ultraviolet irradiation using medium pressure lamps (UV-M) as an activating method. Experimental results showed that UV-M/S₂O₄ ^2? process achieved almost complete removal of nitrate from aqueous solutions containing 25 mg NO₃ ^?/L using stoichiometric dose of dithionite of 68.8 mg/L at neutral pH conditions. Analysis of final products and material balance confirmed that NO₃ ^? ions were reduced to ammonium with formation of nitrite as intermediates in addition to the formation of small amounts of volatile species, mainly ammonia and nitrogen gas. Effects of certain experimental parameters including dithionite dose, initial pH, initial nitrate concentration, and UV light source on the kinetics and efficiency of nitrate reduction were evaluated. Increasing dithionite dose augmented the rate of nitrate reduction and enhanced the efficiency of ARP process. Dithionite doses higher than stoichiometric ratios led to complete removal of nitrate in shorter reaction time. UV-M/S₂O₄ ^2? process was found to be effective only under neutral pH or alkaline conditions, and its removal efficiency is negligible in acidic medium (pH < 4). Irradiation with UV-M was more effective than low pressure or narrow band lamps. These results can be attributed to the contribution of several mechanisms for nitrate reduction to ammonium. These include the following: direct photolysis, chemical reduction of nitrate dithionite, and mediated reduction of nitrate by free reducing radicals.     

Evidence for the production of hydrogen peroxide in rainwater by lightning during thunderstorms

Rain samples were collected sequentially from individual events at a site in Miami, Florida, USA, from April 1995 to October 1996, and analyzed for H₂O₂, major anions, pH, temperature, and rainfall amounts. The measurements showed that in the absence of lightning, the concentration of H₂O₂, like that of sulfate and other conservative constituents, either remained fairly constant or decreased as a function of time during the storms depending on whether rainout or washout process was the dominant pathway for the removal of atmospheric H₂O₂. However, during the course of several thunderstorms, H₂O₂ concentration increased significantly with time, whereas the concentration of sulfate and other conservative constituents remained fairly constant or decreased as a function of time. These observations indicate that substantial amounts of H₂O₂ in rainwater were produced by lightning activities during thunderstorms. Possible mechanisms are proposed here.     

AuPdFe ternary solution model and applications to understanding the fO2 of hydrous, high-pressure experiments

This study provides an experimental calibration of the equilibrium constant for AuPdFe alloys with Fe-bearing silicate melts. The ideal metal capsules for H₂O-bearing experiments are pure Au, because of its slow hydrogen diffusivity. However, above the melting point of Au, other materials must be used. The solution to this problem is to use AuPd alloy capsules. However, under most relevant fO₂ conditions, this alloy absorbs Fe from the coexisting silicate melt, thus changing the bulk composition of the experimental charge. This study combines previous work on the Au–Pd, Pd–Fe, and Au–Fe binary systems to develop a ternary thermodynamic solution model for AuPdFe. This solution model is used with experiments to calculate an equilibrium reaction coefficient for the FeO_melt → Fe_alloy + 1/2O₂ exchange reaction. Using a non-ideal ternary solution model, the fO₂ conditions of hydrous, piston cylinder experiments can be estimated by analyzing the sample capsule alloy and the coexisting liquid composition.     

Reduction of pertechnetate [Tc(VII)] by aqueous Fe(II) and the nature of solid phase redox products

The subsurface behaviour of ⁹⁹Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)_(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10⁻⁹ atm O₂). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)_(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. ⁵⁷Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)_aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O₂·nH₂O_(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O₂·nH₂O_(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit ⁹⁹Tc remobilization upon the return of oxidizing conditions.     

Efficiency removal of phenol, lead and cadmium by means of UV/TiO2/H2O2 processes

A variety of processes can be used in treatment of industrial wastewaters. The relatively newest of which is photo catalysis with titanium dioxide which may also be used plus hydrogen peroxide to improve the treatment rate. In this study, photo catalysis/ hydrogen peroxide processes had been employed for the removal of phenol, lead and cadmium by three different pHs of 3.5, 7 and 11. The treatment tests were also accomplished without UV irradiation. In both experiments, the variables were pH and concentrations of reagent chemicals, but the detention time was kept constant (180 min). Results indicated that the optimum efficiencies of phenol and Cd removal were 76 % and 97.7 % at pH=11, respectively, and for lead, it was 98.8% in all pHs. In other words, no pH dependency was regarded for lead treatment. These results were all obtained by simultaneous use of UV irradiation with 3 mL/L H₂O₂ and 0.8 g/L TiO₂. Finally, the best pH for treatment, when all the three contaminants are presented is considered to be at 11. These results should be regarded by all industrial treatment plants which have experienced the problem of these three special contaminants in their effluents.     

Optimization of aqueous methylparathion biodegradation by Fusarium sp in batch scale process using response surface methodology

Biotreatment of methylparathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate) was studied in aqueous mineral salts medium containing fungal culture to demonstrate the potential of the pure culture (monoculture) of Fusarium sp in degrading high concentration of methylparathion. A statistical Box–Behnken design of experiments was performed to evaluate the effects of individual operating variables and their interactions on the methylparathion removal with initial concentration of 1,000 mg/L as fixed input parameter. A full factorial Box–Behnken design of experiments was used to construct response surfaces with the removal, the extent of methylparathion biodegradation, removal of chemical oxygen demand and total organic carbon, and the specific growth rate as responses. The temperature (X ₁), pH (X ₂), reaction time (X ₃) and agitation (X ₄) were used as design variables. The result was shown that experimental data fitted with the polynomial model. Analysis of variance showed a high coefficient of determination value of 0.99. The maximum biodegradation of methylparathion in terms of the methylparathion removal (Y ₁), chemical oxygen demand removal (Y ₂) and total organic carbon removal (Y ₃) were found to be 92, 79.2 and 57.2 % respectively. The maximum growth in terms of dry biomass (Y ₄) was 150 mg/L. The maximum biodegradation corresponds to the combination of following factors of middle level of temperature (X ₁ = 30 °C), pH (X ₂ = 6.5), agitation (X ₄ = 120 rpm) and the highest level of reaction time (X ₃ = 144 h). The removal efficiency of methylparathion biodegradation was achieved 92 %. It was observed that optimum biotreatment of methylparathion can be successfully predicted by response surface methodology.     

Degradation of dimethyl sulfoxide through fluidized-bed Fenton process: kinetic analysis

In this study, fluidized-bed Fenton process (FBF) was used to degrade dimethyl sulfoxide (DMSO), one of the most widely used solvents. Oxidation by Fenton’s reagent, Fe⁺² and H₂O₂, is one of the cheapest advanced oxidation processes due to the high availability of the reagents. FBF is a modified approach that reduces the large amount of iron oxide sludge formed in conventional Fenton process. The optimal treatment efficiencies by FBF with 2 h of reaction were 95.22 % of DMSO degradation and 34.38 % of COD removal at the conditions of 5 mM DMSO, 68.97 g/L SiO₂ carrier, pH_initial 3.0, 5 mM Fe²⁺, and 32.5 mM H₂O₂. The kinetic study was also done to investigate the two stages involved in the oxidation. The first stage fitted the zero reaction order with overall initial rate’s apparent rate constant, k ₁, of ?0.099. The second stage fitted the first order of DMSO degradation, with rate constant, k ₂, of ?0.0005.     

Treatment of oily sludge by advanced oxidation process

For treating oily sludge, wet peroxide oxidation (WPO) and catalytic wet oxidation (CWO) were investigated. The CWO experiment was carried out in a 0.5?L batch reactor using FeCl₃ as catalyst. By using WPO, the effects of reaction parameters such as residence time, temperature, H₂O₂ excess, and initial COD were investigated. The results demonstrated that >80?% chemical oxygen demand (COD) was removed by CWO and >90?% COD was removed by WPO. Significantly, more of COD could be removed from the oily sludge by adding H₂O₂ in small doses. In conclusion, WPO was much more effective in the removal of organic compounds from oily sludge.     

Reaction mechanism of uranyl in the presence of zero-valent iron nanoparticles

The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O₂ and 0.0017% CO₂) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO₂ was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO₂ occurred in preference to precipitation of UO₃·2H₂O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).