可见光/H2 O2/海藻酸铁非均相催化降解吖啶橙的研究

由海藻酸钠和氯化铁反应制备了海藻酸铁凝胶小球催化剂,考察了该催化剂的吸附和可见光下催化降解吖啶橙的性能.结果表明催化剂的吸附能力随pH升高而提高,且催化剂用量为40个凝胶小球时,可见光下吖啶橙能够在较宽pH值范围内脱色,脱色速率随H2O2的用量增加而增加,该反应符合Arrhenius规律,其表观活化能为49.6 kJ/mol.自由基清除剂的加入不会降低脱色速率,表明催化反应不是羟基自由基的机理,而与高活性的类{ Fe（Ⅳ）=O}高价铁中间产物有关.     

Fe(Ⅱ)EDTA/H2O2电催化降解甲基橙模拟废水的研究

在无隔膜电解槽中,采用SPR(Ru-Ir-Ti0₂)为阳极,石墨为阴极,考察了Fe(Ⅱ)EDTA/H₂O₂电催化降解甲基橙(methyl orange)模拟废水的影响,发现EDTA很大程度上促进了类电Fenton试剂对甲基橙模拟废水的降解。实验研究表明,在外加电压为5.0 V,EDTA∶Fe²⁺=2∶1(摩尔比,Fe²⁺=40 mmol/L),H₂O₂=48 mmol/L,电解质Na₂SO₄=40 mmol/L,废水pH值为(6.5±0.1)的条件下,降解260 mg/L的甲基橙模拟废水90 min, EDTA的加入可以使甲基橙模拟废水的脱色率由29.5%上升到78.4%,COD由571.429 mg/L降至80 mg/L,COD的降解率为86%,EDTA在此过程中既是催化剂又是反应物,可有效避免EDTA带来二次环境污染的可能性。     

Synthesis of highly effective absorbents with waste quenching blast furnace slag to remove Methyl Orange from aqueous solution

Water quenching blast furnace slag(WQBFS) is widely produced in the blast furnace iron making process. It is mainly composed of CaO, MgO, Al_2O_3, and SiO_2 with low contents of other metal elements such as Fe, Mn, Ti, K and Na. In this study, WQBFS was treated with grinding, hydrochloric acid acidification, filtration, filtrate extraction by alkali liquor and a hydration reaction. Then BFS micropowder(BFSMP), BFS acidified solid(BFSAS) and BFS acid-alkali precipitate(BFSAP) were obtained, which were characterized by X-ray diffraction, scanning electron microscopy, X-ray fluorescence and Brunauer-Emmet-Teller(BET)specific surface area. The decoloration efficiency for Methyl Orange(MO) was used to evaluate the adsorptive ability of the three absorbents. The effects of adsorptive reaction conditions(p H and temperature of solution, reaction time, sorbent dosage and initial concentration) on MO removal were also investigated in detail. The results indicated that BFSAP performed better in MO removal than the other two absorbents. When the p H value of MO solutions was in the range 3.0–13.0, the degradation efficiency of a solution with initial MO concentration of 25 mg/L reached 99.97% for a reaction time of 25 min at 25°C.The maximum adsorption capacity of BFSAP for MO was 167 mg/g. Based on optimized experiments, the results conformed with the Langmuir adsorption isotherm and pseudo-second-order kinetics. Among inorganic anions, SO_4~(2-)and PO_4~(3-)had significant inhibitory effects on MO removal in BFSAP treatment due to ion-exchange adsorption.     

甲基橙废水的常温常压催化湿式氧化实验研究

以Fe、Mn、Cu和Zn的金属氧化物为活性组分,以γ-Al2O3为载体,制备了负载型催化剂,并分别以H2O2和NaClO为氧化剂,对比了在常温常压条件下催化湿式氧化工艺中处理甲基橙模拟废水的效果.结果表明,Fe/y-Al2O3催化剂较其他催化剂表现出较好的催化活性和稳定性,H2O2为适宜的氧化剂.在Fe/γ-Al2O3加入量为10g/L,氧化剂H2O2加入量为5 mL/L的条件下,处理甲基橙质量浓度为500 mg/L的模拟废水,其脱色率和COD去除率在3 h内均能达到70%以上.与传统的Fenton试剂法相比,以Fe/γ-Al2O3为催化剂的催化湿式过氧化氢氧化工艺具有矿化程度高,催化剂易回收再用的优点.     

耐高盐撕裂蜡孔菌P2对模拟橙黄G染料废水的脱色及废水脱色前后的毒性测试

为评价撕裂蜡孔菌P2处理橙黄G染料废水的应用潜力,采用批次实验在开敞系统中研究静置与摇动、染料初始浓度、pH、温度、盐度、碳源、氮源、金属离子等因子对该菌降解橙黄G染料废水的影响,同时利用植物萌发与微生物抑菌试验进行染料与脱色溶液的毒性测试.结果表明,与摇动培养相比,静置培养更适合于撕裂蜡孔菌的脱色,最适脱色pH与温度分别为9和25℃.盐度测试结果显示撕裂蜡孔菌能在浓度为128 g L-1的盐溶液中能进行高效脱色,可达70%以上.在上述参数体系的优化基础上,分别进行了碳源、氮源与金属离子的添加优化实验,结果显示碳源、氮源与金属离子的最适浓度分别为4 g L-1葡萄糖、0.15 g L-1硝酸铵和0.1 mmol L-1 Zn2+.菌丝吸附在整个脱色过程中作用较小,撕裂蜡孔菌对橙黄G的脱色过程以酶的降解为主,未发现该菌分泌漆酶,只分泌锰过氧化物酶与木质素过氧化物酶,其最高活性分别为230 U mL-1和158 U mL-1.植物与微生物毒性分析显示撕裂蜡孔菌脱色后的产物对植物与微生物的毒性大大降低.因此,撕裂蜡孔菌对于处理橙黄G染料废水具有良好的应用潜力.     

不同粒径零价铁活化过硫酸钠氧化降解酸性橙7的影响及动力学研究

以偶氮染料酸性橙7(AO7)为目标污染物,研究了不同粒径零价铁(包括1 mm-ZVI、150μm-ZVI、50 nm-ZVI)对活化过硫酸钠(PS)氧化降解AO7的影响,并探讨了这3种不同粒径的零价铁活化体系中AO7的降解动力学及中间产物.结果表明,3种粒径零价铁均可以高效活化PS氧化降解AO7,反应90 min后,1 mm-ZVI、150μm-ZVI和50 nm-ZVI活化体系对AO7的去除率分别为43%、97%和100%.AO7动力学方程拟合结果表明,1 mm-ZVI和150μm-ZVI活化PS降解AO7是一级反应,50 nm-ZVI活化体系中AO7的降解是二级反应,这3种粒径零价铁活化PS降解AO7的速率常数大小顺序为50 nm-ZVI>150μm-ZVI>1 mm-ZVI.反应过程中1 mm-ZVI反应后主要生成α-Fe2O3和少量Fe3O4,150μm-ZVI表面的腐蚀产物主要是Fe3O4,而50 nm-ZVI的主要氧化物为α-Fe2O3和α-FeOOH.GC/MS检测出AO7降解中间产物有2-萘酚、邻甲酚、3-甲基-4-乙基苯酚、邻苯二甲酰亚胺、邻苯二甲酸等,AO7溶液吸收光谱的变化特征及GC/MS检测结果表明3种粒径零价铁活化PS氧化降解AO7的途径可能存在差异.     

Novel Al-doped carbon nanotubes with adsorption and coagulation promotion for organic pollutant removal

Al-doped carbon nanotubes (Al-doped CNTs) were prepared as a multifunctional integrated material of adsorbent and coagulant aid for organic pollutant removal from aqueous solution. It was observed that aluminum species were dispersed homogeneously on the surface of CNTs, and mainly anchored onto defect structures of the CNTs. The introduction of aluminium efficiently improved adsorption ability for methyl orange (MO) onto the CNTs, and maximum adsorption capacity calculated from the Langmuir isotherm model can reach 69.7 mg/g. The MO adsorption kinetics can be better described by the pseudo-second-order and pore diffusion kinetic models, and the diffusion of MO anions into pores of the Al-doped CNT adsorbent should be the rate-determining step. Thermodynamic analyses indicated that the adsorption of MO onto Al-CNTs-2.0 was endothermic and spontaneous. Moreover, adsorption capacity for MO on the Al-doped CNTs was evidently dependent on the CNT dose, solution pH and adsorbent dose. From the perspective of low-cost and multifunctional, suspension obtained during the Al-doped CNT adsorbent preparation, was tested as coagulant to remove humic acid (HA). A significant observation is that the suspension exhibited an excellent coagulation performance for HA, because abundant aluminous polymer and Al-doped CNTs existed in the suspension.     

负载型纳米Fe与负载型纳米Fe-Ni降解甲基橙的对比研究

以阳离子交换树脂为载体,合成了负载型纳米Fe和负载型纳米Fe-Ni双金属材料,并采用扫描电子显微镜和能谱分析对该材料进行表征,考察了m(FeSO4):m(树脂)、负载纳米材料加入量、溶液pH等因素对甲基橙降解率的影响.结果表明,两种负载纳米材料对0.05 g·L-1甲基橙均有较好的降解效果,甲基橙的降解率随负载纳米材料加入量的增加而增加;纳米双金属材料中Ni含量的增加有利于甲基橙的降解.在pH =4酸性条件下降解效果最佳.在优化的降解反应条件下,对比研究了负载型纳米Fe和负载型纳米Fe-Ni对甲基橙的降解效果.结果表明,负载型纳米Fe-Ni对甲基橙的降解效果要优于负载型纳米Fe.制备的材料在多次使用后经活化,仍有良好的催化稳定性.     

壳聚糖季铵盐磁性颗粒的制备及其对甲基橙的吸附效果

首先在甘氨酸盐酸盐离子液体([Gly]Cl)水溶液中制备了不同取代度的壳聚糖季铵盐,采用共沉淀法制备了纳米Fe3O4.进而以Fe3O4为核,戊二醛作交联剂,通过反相悬浮法制备交联壳聚糖季铵盐磁性颗粒,考察了反应条件对吸附效果的影响.并采用静态吸附法研究了磁性颗粒对甲基橙(MO)的吸附效果.结果表明,在25℃,pH=3的条件下,甲基橙初始浓度从20 mg.L-1增加到150 mg.L-1时,平衡吸附量从37.45 mg.g-1增加到277.5 mg.g-1.运用相关数学模型拟合实验数据得出,该吸附符合Freundlich模型,吸附动力学符合拟二级动力学模型.经4次重复使用后磁性颗粒对甲基橙的吸附率仍高于90%.     

Synthesis,crystal structure,photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c = 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^− 1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2 − and NO₃⁻, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography–mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.