TiO2/H2O2/超声波协同降解壬基酚聚氧乙烯醚溶液

采用经过处理的锐钛矿型TiO2作为催化剂,在H2O2存在下,以TiO2/H2O2/超声波协同降解壬基酚聚氧乙烯醚反应为模型,探讨了TiO2催化剂用量、H2O2用量、超声波功率、壬基酚聚氧乙烯醚溶液初始浓度、初始pH值对壬基酚聚氧乙烯醚降解率的影响。结果表明,在一定的超声波功率和一定的TiO2用量范围内,壬基酚聚氧乙烯醚降解率随超声波功率和TiO2用量的增大而增大,达到一定值后保持平稳;当H2O2浓度介于一定范围内,增大H2O2用量可提高壬基酚聚氧乙烯醚的降解率,但H2O2用量过多时,反而会使壬基酚聚氧乙烯醚的降解率下降;pH<5时,壬基酚聚氧乙烯醚降解效果较好,且pH值越小,降解率越高;pH>5时,降解率越来越低。TiO2/H2O2/超声波体系降解壬基酚聚氧乙烯醚产生了较强烈的协同效应,在同一时刻三者协同体系的降解率比其3种单独体系的降解率之和高出约60%;在TiO2催化剂用量0.4g/L、H2O2用量0.2g/L、超声波功率600W、降解时间120min的条件下,对初始质量浓度为80mg/L,pH=1的壬基酚聚氧乙烯醚溶液进行降解,其降解率达98%以上。     

H2O2氧化法修复柴油污染土壤

用20 mL H2O2氧化处理柴油重度污染土壤,研究了土壤含水量过饱和状态下pH值对反应的影响。结果表明,24 h之内,5%初始含油量污土,pH值为5~8时,去油率在96%以上,即pH值近中性的土壤介质,在含水量过饱和情况下,处理条件相同时,其氧化去除效果差别不大;反应后溶液pH值由7.34、6.74、5.78降至7.02、6.58、5.49,这主要是由于一些酸性基团如CO2、H 、羧基、β-酮酸等的产生所致;反应溶液中H2O2量下降明显,1 h时由初始浓度0.05 mol/L降至0.000 3 mol/L左右,测出值趋近于0;表层油含量变化不稳定,但总趋势下降,下层油含量变化则呈明显下降趋势,说明整个氧化过程中柴油组分经历了分解、挥发和自下而上的迁移。     

Fenton试剂氧化处理模拟含聚丙烯酰胺污水的研究北大核心CSCD

主要研究了利用Fenton试剂氧化法处理模拟含部分水解聚丙烯酰胺的污水,考察了H2O2浓度、Fe2+浓度、温度、反应时间、pH值等因素对Fenton试剂氧化降解模拟含部分水解聚丙烯酰胺污水的影响。结果表明:H2O2浓度为5.3mmol.L-1、Fe2+浓度为1.44mmol.L-1、温度30℃、反应时间15min、pH值范围3～4时,聚丙烯酰胺的氧化降解效果最好,且在最佳条件下,聚丙烯酰胺和CODCr的去除率分别达到87.61%和82.60%。通过对Fenton氧化降解前后的聚丙烯酰胺样品的红外谱图对比,可以推断出Fenton试剂将侧链的酰胺基氧化成羧基。     

超声强化过氧化氢/三氯乙酸催化氧化柴油深度脱硫研究

选择H₂O₂一三氯乙酸作为催化氧化脱硫反应体系,砜类氧化产物用极性溶剂从柴油中萃取分离,研究了剂油体积比、有机酸用量、氧化反应温度、氧化反应时间等工艺参数对脱硫率的影响。在此基础上,引入功率超声为反应提供能量,并考察了超声频率、超声功率、超声时间等因素对脱硫效果的影响,从而确定最佳操作条件为,反应温度70℃,反应时间60min,三氯乙酸与过氧化氢体积比为1∶1,氧化剂与柴油体积比为1∶10,超声频率40kHz,超声功率200W,超声时间30min。萃取后柴油脱硫率可达97.5%,脱硫油收率94.0%。     

水中菲的类Fenton氧化降解及动力学研究

采用类Fenton氧化法对水溶液中的菲进行深度处理,研究纳米零价铁(n ZVI)投加量、H2O2投加量、溶液p H值和温度四个主要因素对菲去除效果的影响。结果表明在纳米零价铁(n ZVI)投加量为1.0 g/L、H2O2为10 mmol/L、p H为3.0、温度30℃的优化条件下,菲的初始投加量(浓度)为50 mg/L在60 min内菲的去除率达到100%。此外类Fenton氧化降解菲符合伪一级降解动力学模型,且菲的投加量(浓度)越高,降解速率越快,进一步说明类Fenton氧化技术对菲降解有很好的效果。     

UV/H_2O_2体系中SF Blue染料的降解动力学

对UV/H2O2处理SFBlue制衣染料溶液的效果及其影响因素和动力学进行了研究。结果表明,UV/H2O2对SFBlue染料废液具有很好的处理效果,且在发生光助氧化降解的同时还伴随着光分解反应。UV/H2O2体系的光助氧化反应和UV体系的光分解反应均为表观一级反应,前者活化能5.17kJ/mol,指前因子0.168min-1,后者活化能16.9kJ/mol,指前因子1.04min-1。染料溶液初始pH为强碱性(pH=12)时染料降解率最大。     

铁氧化物催化类Fenton反应

高级氧化技术是当今水处理技术领域研究的热点,Fenton试剂因操作简单、反应条件温和及氧化效率高等优势而备受关注。铁氧化物催化类Fenton反应能有效地解决催化剂回收利用难等问题,并且能够在较为广泛的pH范围内使用,从而成为Fenton氧化领域一个新的研究方向,但反应过程和机制往往更为复杂。本文评述了铁氧化物催化类Fenton反应中可能存在的多种机理,主要是羟基自由基理论、氧空位机理和高价态铁络合物机制。类Fenton反应速率的限速步骤是Fe(Ⅲ)/Fe(Ⅱ)循环过程,从提高反应速率的机理出发,本文探讨了类Fenton反应中铁氧化物催化剂的制备和发展,催化剂中多种价态的铁元素,通过相互间发生电子转移以加速Fe(Ⅱ)的再生,提高反应效率。铁氧化物掺杂过渡金属能显著提高催化H2O2有效分解的活性。阐明了多金属掺杂铁氧化物中多金属组分的催化机制和铁氧化物结构形态对反应性能的影响。研究表明催化剂中铁的结构形态、催化剂比表面积、催化剂与H2O2之间电子转移速率等都是决定催化剂性能的重要因素。最后讨论了继续研究方向,为开展非均相类Fenton反应提供参考。     

H2O2氧化降解海藻酸钠

研究了清洁高效的氧化剂H2O2对海藻酸钠的降解,探讨了溶液pH值、反应温度、H2O2用量及金属离子浓度对降解速度的影响. 结果表明,随着溶液pH值的降低、反应温度的升高及H2O2用量的增加,降解速度加快. 当反应pH=5.3、反应温度50 ℃、H2O2用量0.5%时,反应2 h即可降低海藻酸钠的分子量. 4 mg/L的Cu2+或Fe2+可明显加快降解速度,反应30 min的粘度变化相当于不加Cu2+或Fe2+时300 min的变化. GPC结果表明,海藻酸钠被氧化降解后,分子量下降,分布变宽;FTIR显示降解前后海藻酸钠的糖环结构没有改变,主要是糖苷键的断裂.     

UV/H2O2光助氧化降解丽华实军蓝制衣染料（英文）

本文对UV/H2O2光助氧化降解丽华实军蓝制衣染料的效果及其影响因素和动力学进行了研究。结果表明,UV/H2O2对丽华实军蓝染料废液具有很好的处理效果,用量少,处理浓度高,且在发生光助氧化降解的同时还伴随着光分解反应。UV/H2O2体系的光助氧化反应和UV体系的光分解反应均为表观一级反应,前者活化能9.71 kJ.mol-1,指前因子1.61 min-1,后者活化能50.3 kJ.mol-1,指前因子3.88×105min-1。染料溶液初始pH为强碱性(pH=12)时染料降解率最大。     

镀铜铁屑-H_2O_2催化氧化降解含酚废水

采用镀铜铁屑代替传统Fenton体系中的FeSO4作为催化剂,通过改变H2O2与镀铜铁屑的投加量、溶液的pH值、反应温度、反应时间等条件,研究了该体系对处理苯酚废水的影响。结果表明,常温下处理实际含酚印染废水,在pH值为4~6,30%H2O2 12mL/L,镀铜铁屑5g/L,反应时间为45min时,COD去除率可达96%,其CODCr从5827mg/L降至419mg/L,色度从2000降至30,符合国家三级排放标准。     

Desulfurization of model and real fuels by extraction and oxidation processes using an indenylmolybdenum tricarbonyl pre-catalyst

Regulations on the permissible levels of sulfur in transportation fuels are becoming ever more strict, with a global shift towards “zero sulfur” fuels, and the revamp of existing hydrodesulfurization (HDS) facilities to meet these lower caps is cost-prohibitive. Metal-catalyzed sulfoxidation chemistry is viewed as an economically viable desulfurization strategy that could complement conventional HDS technology. In the present work, the complex [η⁵-IndMo(CO)₃Me] ( 1 ) (Ind = indenyl) was employed in the catalytic oxidative desulfurization (CODS) of model and real liquid fuels, using aqueous hydrogen peroxide (H₂O₂) as oxidant. After optimization of the CODS reaction parameters (diesel/H₂O₂ ratio, catalyst amount, temperature), a high-sulfur (2000 ppm) model diesel containing benzothiophene, dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene could be completely desulfurized within 2 hr under solvent-free conditions or in the presence of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF₆) as extraction solvent. The catalyst formed under solvent-free conditions could be recycled without a significant decrease in desulfurization activity. The high performance of the CODS system was verified in the sulfur removal from a commercial untreated diesel fuel with a sulfur content of 2300 ppm, and a jet fuel with a sulfur content of 1100 ppm. Solvent-free CODS in combination with initial/final extraction gave desulfurization efficiencies of 70% for the diesel fuel and 55% for the jet fuel. CODS with [BMIM]PF₆ in combination with initial/final extraction led to a sulfur removal of 95.9% for the diesel fuel, which is one of the best results yet reported for ODS of commercial diesels.     

Ultrasonication-assisted sorption of cadmium from aqueous phase by wheat bran

In the present study, the sorption of cadmium from aqueous phase by wheat bran was investigated with and without the assistance of ultrasound. Kinetic data and sorption equilibrium isotherms were carried out in batch conditions. The influence of different operating parameters such as ultrasonic power, cadmium initial concentration, sorbent mass, temperature, and the combination of ultrasound and mechanical stirring on the kinetics of cadmium removal was studied. The obtained results show that the ultrasonic irradiation significantly enhances and improves the efficiency of the removal of cadmium, especially in the combined method. The sorption kinetic data were found to be well-represented by the pseudo-second-order rate equation, both in the absence and presence of ultrasound as well as in the combined process (stirring and ultrasonication). Ultrasonic power played a key role in the removal of cadmium. Equilibrium isotherm results could be well described by the Langmuir model both with and without the assistance of ultrasound. The effect of temperature on the sorption isotherms of cadmium in the absence and presence of ultrasound has been also studied and the thermodynamic parameters DeltaG degrees, DeltaH degrees, and DeltaS degrees were determined. The monolayer sorption capacities were 51.81, 35.09, and 22.78 mg g(-1) for experiments conducted by the combined process, in the presence of ultrasound, and in passive conditions, respectively. The combination ultrasound-stirring for the sorption process was shown to be of interest for the treatment of wastewaters contaminated with cadmium.     

模拟轻质油品的氧化脱硫

以正庚烷为溶剂，苯并噻吩（BT）、二苯并噻吩（DBT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）作为模型含硫化合物组成模拟轻质油品，在H2O2-HCOOH氧化体系中对模拟轻质油品氧化脱硫进行了研究。考察了氧化剂用量、氧化温度、氧化时间及芳烃、烯烃、含氮化合物的存在等因素对BT、DBT脱除的影响。实验结果表明：在反应温度60 ℃，H2O2∶S＝7∶1（mol/mol）,H2O2∶HCOOH＝1∶1（v/v）,反应时间在40 min的条件下，4,6-DMDBT能全部脱除, DBT、BT的脱除率分别为96% 、58%。向油品中添加芳烃、烯烃、含氮化合物等对BT、DBT的脱除均有不同程度的影响。     

Oxidative desulfurization of model diesel oil over Ti-containing molecular sieves using hydrogen peroxide

Three Ti-containing molecular sieves were studied in the oxidative desulfurization (ODS) of model diesel oil with hydrogen peroxide. Under optimal conditions, dibenzothiophene (DBT) conversion up to 80.6% and 42.6% could be obtained with Ti-HMS and Ti-MSU as catalysts, respectively. However, there is no activity in the sulfoxidation of DBT over TS-1. Effects of the TiO₂/SiO₂ ratio in Ti-HMS and reaction conditions, such as the reaction temperature, reaction time, n(H₂O₂)/n(S) on the sulfur removal were investigated.     

活性炭及甲酸催化过氧化氢氧化噻吩脱硫研究

以噻吩代表汽油中的有机硫化合物,将其溶解于正辛烷配制成反应原料,考察了活性炭对噻吩的吸附脱硫情况,研究了质量分数为30％的过氧化氢水溶液为氧化剂,在活性炭和甲酸的催化作用下,反应原料中噻吩氧化脱硫。考察了活性炭的催化性能及反应条件对其催化性能的影响。实验结果表明,30％H2O2-HCOOH-AC（活性炭）三元体系产生的过氧甲酸和羟基自由基能将模型有机硫化合物氧化,噻吩的氧化脱硫率可达到85％以上;活性炭和甲酸的催化氧化性能明显优于单纯使用甲酸催化性能。甲酸浓度、活性炭加入量、过氧化氢初始浓度及温度对噻吩硫的氧化脱除均有影响。     

高硫煤加氢热解脱硫的研究Ⅱ.反应条件对煤加氢热解脱硫的影响

本文采用红庙褐煤在加压固定床上，详细考察了不同反应条件对加氢热解脱硫的影响。研究结果表明：氢气流速的增加可以显著降低焦中的硫含量，增加脱硫率和硫在气相中的分布。氢气压力增加有利于增加煤中含硫化合物的加氢脱硫反应，提高脱硫率。加氢热解过程中的传质作用对脱硫率和硫分布也有重要影响。在一定的热解温度下，适当增加停留时间有利于氢气与含硫化合物的扩散接触，提高脱硫率。同时红庙煤加氢热解产生的焦油中的硫分布随各种反应条件的变化不大。     

Photo oxidative degradation of azure-B by sono-photo-Fenton and photo-Fenton reagents

A model for the decomposition of azure-B by photo-Fenton reagent in the presence of ultrasound in homogeneous aqueous solution has been described. The photochemical decomposition rate of azure-B is markedly increased in the presence of ultrasound. It is a rather inexpensive reagent for wastewater treatment. The effect of different variables like the concentration of ferric ion, concentration of dye, hydrogen peroxide, pH, light intensity etc. on the reaction rate has been observed. The progress of the sono-photochemical degradation was monitored spectrophotometrically. The optimum sono-photochemical degradation conditions were experimentally determined. The results showed that the dye was completely oxidized and degraded into CO₂ and H₂O. A suitable tentative mechanism for sono-photochemical bleaching of azure-B by sono-photo-Fenton’s reaction has been proposed.     

Desulfurization of tall oil pitch

Method for desulfurization of tall oil pitch is suggested. The method is based on successive treatments with hydrogen peroxide, sulfuric acid, and aqueous solutions of acetonitrile. As a result, the total content of sulfur was reduced from 3800 to 220 ppm. The fuel characteristics of the desulfurized pitch were determined. The purified pitch can be used in the conventional areas of its application, in which restrictions are imposed on the total content of sulfur.     

Intensified removal of 4-Methylpyridine by ultrasonication in presence of advanced oxidants

Water contamination is a big issue in every part of the globe. In response to the rising demand for wastewater with lower pollutant levels, a unique enhanced oxidation technique called ultrasound assisted irradiation has been developed. In the current study, advanced oxidising technology is used to accelerate the breakdown of 4-Methylpyridine (4 MP) utilising ultrasound at a rated frequency of 22 ± 2 KHz. In the presence of ultrasound, the effects of advanced oxidising agents as well as the effects of different operational factors like pH, time, and power were evaluated. The kinetics for degradation of 4 MP were evaluated by second order model. The combined strategy of ultrasound assisted degradation in the presence of various advanced oxidising agents like hydrogen peroxide (H₂O₂), peroxymonosulphate (PMS), potassium per sulphate (KPS) and Fenton reagent was investigated at optimal operating conditions, with the starting concentration of 50 mg/L at pH 9, and temperature 45⁰C. When applying ultrasound at its highest rated power of 120 W while the Fenton reagent was present, the maximum degradation was recorded to be 99 ± 1%. The scavenger effect of ^?OH free radical andions was evaluated on degradation of 4 MP. The synergetic index for all combination approaches was determined, for US/Fenton maximum synergetic index 10.8 established. The tentative degradation pathway was studied for degradation of 4 MP.     

The efficacy of sono-electro-Fenton process for removal of Cefixime antibiotic from aqueous solutions by response surface methodology (RSM) and evaluation of toxicity of effluent by microorganisms

The increasing use of antibiotics by humans and their persistence in the environment leads to the development of drug resistance, which is nowadays considered as an environmental problem. The aim of this study was to determine the efficacy of sono-electro-Fenton process for removal of Cefixime antibiotic from aqueous solutions by Response Surface Methodology (RSM) and to evaluate the toxicity of effluent by microorganisms. In the present study, the degradation of synthetic wastewater containing Cefixime was investigated in a reactor (with a useful volume of 1 L) located in the chamber of the ultrasonic device. The effects of pH, hydrogen peroxide concentration, voltage, initial antibiotic concentration, and electrolysis time were investigated using the Box-Behnken model, and the optimal conditions for elimination were obtained by analyzing the variance. The performance of the electro-Fenton and ultrasonic process was evaluated separately and in combination under optimal conditions. Toxicity of inlet and outlet was tested by Escherichia coli and Staphylococcus aureus, and growth inhibition percentage was calculated. The intermediates were determined by LC-MS with the lowest molecular mass. The results showed that the sono-electro-Fenton process under optimum conditions, including pH of 3.07, hydrogen peroxide concentration of 0.85 mL/L, voltage 15 V, initial antibiotic concentration 10.4 mg/L and electrolysis time of 81.5 min has a percentage of removal of 97.5%. Under optimum conditions, the percentage of removal by electro-Fenton and ultrasonic separately were 81.7% and 9%, respectively, and in the hybrid process of sono-electro-Fenton, the percentage of removal increased to 97.5%. The results also showed that the biological toxicity of the outlet effluent from the sono-electro-Fenton process, compared to the inlet solution, was significantly reduced. So, we conclude that the Sono-electro-Fenton process has a significant effect on the removal of Cefixime from aqueous solutions and can also significantly reduce the biological toxicity of the effluent.