Phenol electrooxidation on Fe-Co3O4 thin film electrodes in alkaline medium

Fe-Co₃O₄ thin film with different amounts of Fe have been used for the electro-oxidation of phenol in alkaline medium at room temperature. The electrodes were prepared by coating stainless steel supports with successive layers of the oxides, obtained by thermal decomposition at 673 K. The electrolysis was carried out at constant potential and the phenol disappearance, during the electrolysis, was monitored by UV-Vis absorbance measurements between 250 and 500 nm. After 3 h of electrolysis, the intermediates were identified by comparing the HPLC data and UV-Vis spectra to those from pure standards. The results indicate that the same oxidation products are formed on the different prepared electrodes, namely the decomposition products of phenol such as benzoquinone, hydroquinone and cathecol in basic medium. Simulated results show clearly the decrease of the amount of phenolic species with the electrolysis time. An enhancement of the phenol removal is observed with the presence of iron in the oxide. Under the operating conditions, around 30% of the initial phenol has been removed at ca. 3 h and the complete degradation is obtained after 54 h of electrolysis, when Fe-Co₃O₄ thin film with 10% of Fe is used as anode.     

改性炭化谷壳负载纳米Fe3O4对含As(V)废水的吸附性能

以谷壳为原料,通过600℃缺氧高温热解制备一种炭化谷壳（CRH-I）,并利用CRH-I通过改性负载方法获得另一种新型的负载纳米Fe3O4的碱改性炭化谷壳（CRH-II）。经过对比表面积进行表征分析发现,CRH-II相较CRH-I的BET比表面积增大约30%,达到182 m2·g-1,微比表面积和微孔体积都扩大了6倍左右。FTIR分析结果表明,相比CRH-I,CRH-II分子间的羧基和酚羟基官能团有所增加,产生了芳构化反应和脂肪醚类物质。吸附实验表明,相对CRH-I而言,CRH-II对As（V）的吸附率明显提高。pH=2时,CRH-II对溶液中As（V）的吸附率达到98.3%;但是As的吸附率随着溶液pH值升高而逐渐降低,pH=11时下降最为明显,吸附率只有63.4%。CRH-II吸附反应满足准动力学二级方程,其相关系数为R2=0.999;在不同温度下,将CRH-II对As（V）的吸附验数据进行Langmuir方程和Freundlich等温方程拟合,结果更符合Langmuir方程;在25℃时,相关系数R2=0.985。解吸吸附实验证明,CRH-II依然具备良好的吸附性能,且再生吸附性能稳定。     

N,N-二乙基对苯二胺分光光度法测定饮用水中的游离余氯

文中采用N,N-二乙基对苯二胺分光光度法测定饮用水中的游离余氯,实验结果表明,该方法可以准确测定水中的游离余氯且有好的线性,相关系数大于99%。方法检测限为0.01 mg/L,相对标准偏差为2.47～9.08%,回收率在92.5～105%之间,检测方法符合《生活饮用水卫生标准》(GB 5749-2006)的要求。     

铜掺杂钒酸铋光催化降解橙黄II废水及其机理

针对大多数半导体可见光催化剂光生载流子容易复合、光催化活性受限制的问题,制备了Cu元素掺杂BiVO₄可见光催化剂,对BiVO₄结构进行修饰以提高其光催化活性。通过X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线能谱(XPS)和紫外-可见漫反射光谱(UV-vis)对其进行了表征,对Cu掺杂BiVO₄光催化剂的光催化活性和稳定性进行了检测。结果表明,制备的样品纯度较高,Cu掺杂后并未改变BiVO₄的晶体结构,部分Bi³⁺离子被Cu²⁺取代,从而提高了BiVO₄的可见光催化活性。Cu掺杂BiVO₄催化剂能够在可见LED光照射下,活化过一硫酸盐(PMS)进行光催化降解染料橙黄Ⅱ。当催化剂投加量为0.5 g·L⁻¹、过一硫酸盐投加量为0.6 mmol·L⁻¹,反应60 min后,Cu掺杂BiVO₄催化剂对橙黄Ⅱ的降解率最高。经过Cu掺杂后,光生电子和空穴的分离效率有所提高,增强了BiVO₄的光催化活性。Cu-BiVO₄光催化剂经5次重复使用后,对橙黄Ⅱ的降解效率仍然可以达到78.3%以上,其展现出优异的催化稳定性。     

外源C12-HSL信号分子协同反硝化菌FX-4对活性污泥系统脱氮效果的影响

为探究外源信号分子的群体感应效应对反硝化菌FX-4及活性污泥系统脱氮的影响,将外源AHLs (酰基高丝氨酸内酯类) 的C6-HSL和C12-HSL信号分子投加至反硝化复筛培养基中,探究AHLs对反硝化菌FX-4去除NO₃⁻-N的影响。结果发现,外源投加C6-HSL和C12-HSL均可有效地提高反硝化菌FX-4的NO₃⁻-N去除性能,增加反硝化菌FX-4的生物量,且C12-HSL协同反硝化菌FX-4的NO₃⁻-N去除效果最佳;不同浓度的C12-HSL对反硝化菌FX-4的NO₃⁻-N去除效果均有提升,且50 nmol∙L⁻¹的C12-HSL可较大提升菌株FX-4的NO₃⁻-N去除效果。将浓度为0、5 nmol∙L⁻¹、50 nmol∙L⁻¹、200 nmol∙L⁻¹、500 nmol∙L⁻¹和1 000 nmol∙L⁻¹的C12-HSL和反硝化菌FX-4同时投加至SBR活性污泥系统中,考察两者协同下系统脱氮性能、信号分子浓度和微生物群落结构的变化。结果表明,两者协同作用可对NO₃⁻-N去除性能产生明显影响,投加信号分子的实验组R₁~R₆相对于空白对照组R₀的NO₃⁻-N积累量减少20~50 mg∙L⁻¹,且C12-HSL投加量为100 nmol∙L⁻¹的反应器R₃的NO₃⁻-N消耗量最多,NO₃⁻-N出水质量浓度较R₀降低约45 mg∙L⁻¹;此外C12-HSL信号分子对TN去除产生正影响显著,且C12-HSL投加量为100 nmol∙L⁻¹的反应器能更有效地提升活性污泥系统TN去除效能。信号分子浓度变化检测结果显示,外源投加C12-HSL可以刺激系统其他AHLs分泌,特别是促进系统C4-HSL的分泌。微生物群落结构分析结果显示,外源投加反硝化菌FX-4和信号分子C12-HSL可显著影响活性污泥中微生物群落组成,加快活性污泥中微生物种群演替,使Thauera、Brevundimonas等脱氮相关菌属占比升高。以上结果可为信号分子作为应急手段强化活性污泥系统生物脱氮性能提供参考。     

两相厌氧消化工艺处理鸡粪

以鸡粪为发酵原料,采用序批式两相厌氧消化工艺在中温条件(37℃)下对其进行消化处理。分别将水解酸化相和产甲烷相pH值控制在5.5±0.3和7.0±0.3,通过改变进样含固率(TS)研究有机负荷(OLR)对两相消化系统处理鸡粪过程中污染物转化和去除效果的影响。结果表明,水解酸化相出水总有机碳(TOC)、挥发酸(VFAs)和氨氮(NH4+-N)浓度都随OLR升高而升高。VFAs组成相对稳定,其中乙酸占总VFAs浓度的57%～64%,其次为正丁酸和丙酸。产甲烷相出水TOC和VFAs稳定在较低水平,TOC去除率最大达到90%以上。产甲烷相进水氨氮主要以NH4+形式在反应器内不断积累。实验后期产甲烷相生物气中甲烷体积分数维持在64%上,证明两相消化系统在实验条件下良好运行。     

均相催化强化US/FCME协同体系降解硝基苯

考察了NaCl、AlCl3、Na2SiO3、CuSO44种均相催化剂对超声波(US)/铁炭微电解(FCME)协同体系降解硝基苯的催化效果,结果表明,CuSO4的催化效果最好,在体系反应液初始pH为3.0,混合填料投加量为5.0 g/L(铁炭质量比为1∶1),CuSO4投加量为800 mg/L时,体系对硝基苯的降解率达到99.2%,但溶液COD值仅下降了24.6%,矿化效果一般,红外光谱分析表明降解体系的主要中间产物为苯胺。     

CuO@Fe3O4催化NaClO 对水中丙烯酸及其酯的矿化去除

为实现污水尾端处理中可溶性小分子有机物的完全去除,以克服因它们的大量存在使水体中总有机碳含量增加而引发的严重环境问题,采用氧化剂NaClO和双金属氧化物CuO@Fe₃O₄组成的催化氧化体系,对喷水织机废水中典型的极性小分子有机物丙烯酸和丙烯酸甲酯进行矿化去除研究;通过X射线衍射 (XRD) 、扫描电子显微镜 (SEM) 、X射线能谱 (EDS) 和BET分析等方法对催化剂进行结构表征和形貌观察,确定催化剂最佳合成方法,并通过氧化实验考察催化剂双金属组成、氧化剂NaClO浓度、催化剂加入量、溶液初始pH和循环催化氧化等因素对小分子有机污染物矿化去除的效果。结果表明：初始铁铜摩尔比为5∶1时,合成的5CuO@Fe₃O₄纳米粒子催化活性最高;当5CuO@Fe₃O₄和NaClO投加量分别为0.48 g·L⁻¹、16 mmol·L⁻¹、pH=8.3时,对0.2 g·L⁻¹丙烯酸的COD去除率可达61%;催化剂经过7次循环操作后,对丙烯酸或丙烯酸甲酯仍能保持48%或45%的COD去除率;EPR实验证明·OH是催化氧化体系中降解丙烯酸和丙烯酸甲酯的主要活性物种。上述研究结果为揭示污染水体中难降解极性小分子有机物的矿化去除规律,实现水体中有机碳的总量控制和减排目标提供了技术支撑。     

用煤矸石合成4A沸石分子筛处理氨氮废水

以煤矸石为原料,采用碱熔一水热法合成4A沸石分子筛。由于煤矸石中铝、硅主要以高岭土形式存在,其活化过程是合成4A沸石分子筛关键环节。为提高4A沸石分子筛钙离子的交换能力,增加对模拟废水氨氮的去除率,实验考察了碳酸钠与煤矸石质量比、活化温度、活化时间、晶化温度和晶化时间对4A沸石分子筛钙离子交换能力的影响,同时也考察了模拟废水的pH、4A沸石分子筛加入量及吸附时间对氨氮去除率的影响。结果表明,最佳工艺条件为,碳酸钠与煤矸石质量比为0．9、活化温度为800％、活化时间1．5h、晶化温度90％和晶化时间3h。合成4A沸石分子筛的钙离子交换能力为310mg／g,在pH为6的100mL模拟氨氮废水中加入6g4A沸石分子筛吸附40min后,废水中氨氮的去除率达到86％。通过最佳工艺条件合成4A沸石分子筛,在处理氨氮废水方面具有一定的应用前景。     

Ferrioxalate-mediated photodegradation and mineralization of 4-Chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Advanced oxidation processes are powerful methods which are capable of transforming refractory, nonbiodegradable and/or toxic organic compounds into harmless end products such as carbon dioxide and water. However, one commen problem of all advanced oxidation processes is the high demand of electrical energy for ultraviolet lamps, which causes high operational costs. Minimization of the required irradiation time, and therefore the energy consumption, by optimization of other reaction conditions such as catalyst-oxidant type and concentration, pH, temperature, pollutant/oxidant ratio etc., therefore continues to gain importance. OBJECTIVE: The main objective of this study was the minimization of the required irradiation time through optimization of the use of a newly patented catalyst, ferrioxalate, and also to compare the performance of this catalyst with the performance of other AOPs. METHODS: Oxidation of 4-chlorophenol by photo-Fenton process using potassium ferrioxalate as a mediator was studied in a lab scale photoreactor. The influence of parameters such as hydrogen peroxide and ferrioxalate concentrations, initial pH, power-output, oxalate/iron ratio and different iron sources was evaluated. An upflow photoreactor equipped with a 1000 Watt high-pressure mercury vapour lamp and operating in a recirculation mode was used during photodegradation experiments. The extent of the reduction of 4-chlorophenol, Total Organic Carbon and Chemical Oxygen Demand was used to evaluate the photodegradation reaction. RESULTS AND DISCUSSION: The optimum pH range observed was found to be 2.7-3. The efficiency of 4-chlorophenol oxidation increased with increasing concentrations of hydrogen peroxide and ferrioxalate, reaching a plateau after the addition of 10 and 0.072 mM of those reagents, respectively. Using an Oxalate/iron ratio of 12 was 18% less efficient than using a ratio of 3:1. The efficiency increased with increasing radiation power. However, this increase was not linear. The UV/ferrioxalate/H2O2 process, by which complete mineralization of 100 mg l(-1) 4-chlorophenol was achieved in 20 min of total reaction time, was the most efficient process among the alternatives applied. CONCLUSIONS: The use of ferrioxalate as the catalyst was found to be more efficient than the use of Fe(II) and Fe(III) iron species. It was possible to completely mineralize 4-chlorophenol. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate that the ferrioxalate-mediated degradation of 4-chlorophenol requires less irradiation times than other advanced oxidation processes. There are mainly 19 phenol isomers and other toxic and nonbiodegradable organic compounds. We recommend that similar studies should be performed on many such compounds in order to attain a clear understanding of the performance of this catalyst. Because of its light sensitivity, this catalyst should be used immediately after its preparation. The use of low pressure mercury vapour lamps in this process should also be considered, since low power outputs may be enough for the process.