辉光放电等离子体处理有机废水研究进展

辉光放电是一种环境友好的、新兴的电化学高级氧化技术,等离子体是由电极与其周围的电解液产生直流辉光来维持。本文综述了辉光放电等离子体在生物难降解有机废水处理方面的实验装置、特点及机理,介绍了辉光放电等离子体技术的国内外研究现状,探讨了该技术在有机废水处理中存在的问题及其应用前景。     

辉光放电等离子体对农药毒性的消除作用

研究了辉光放电等离子体在不同酸度、不同温度和催化剂存在时对水体中农药克百威、甲基对硫磷毒性的消除作用。结果表明,在直流电压为600V,电流范围为145～155mA的条件下产生辉光放电等离子体处理两种农药水溶液,溶液的毒性降低,弱酸弱碱条件毒性降低更快,Fe2+的催化有利毒性降低,高温对去除毒性不利。     

辉光放电电解等离子体处理次甲基蓝废水

利用辉光放电电解等离子体技术对次甲基蓝废水的降解进行了研究,详细考察了电压、染料浓度、pH值、催化剂对次甲基蓝降解效果的影响。实验发现,次甲基蓝废水的优化降解条件为:工作电压610 V,pH值3.0,Fe2+催化作用下降解效率明显提高。利用紫外-可见吸收光谱监测了次甲基蓝的降解过程,结果表明,次甲基蓝先被降解成小分子,小分子继而被进一步降解。     

辉光放电等离子体处理有机染料直接黑EX废水

辉光放电电解是一种新型的产生等离子体的电化学方法。在惰性电解质水溶液中进行辉光放电电解,可以产生大量的.OH、.H、e-aq、HO2.等活性粒子,且产物的总生成量超过了根据法拉第定律计算的产量,每通过1 mol电子可生成12 mol.OH。.OH氧化能力非常强,可以无选择地降解各种有机物。文章探讨了电压、初始浓度、pH、催化剂Fe2+等因素对辉光放电降解直接黑EX效果的影响。用紫外可见吸收光谱检测了染料的降解过程。实验表明:利用该方法可以使水中染料大部分降解。直接黑EX优化降解条件为:工作电压610 V,pH 3.12,Fe2+催化作用下降解效率明显提高。     

液下辉光放电等离子体重整低碳醇水溶液制氢

探讨了阴极液下辉光放电等离子体重整低碳醇水溶液制氢反应过程.比较了水溶液和低碳醇水混合溶液中阴极等离子体重整制氢实验,发现以低碳醇水溶液为等离子体重整介质时,低碳醇分子在阴极等离子体层中表现出明显高于水分子的反应活性,阴极气体单位体积能耗可以降至2.690×10³ kJ•m^-3,生成气体中氢气含量达95％,并有一氧化碳和二氧化碳.分析了电压对阴极生成气单位体积能耗和气体组成的影响,发现电压越高等离子体密度越大,阴极生成气单位体积能耗降低,被等离子体分解的溶剂溶质分子也越多.比较了不同浓度低碳醇溶液的产气情况,低碳醇浓度对生成气组成和单位体积能耗有重要影响.     

常压辉光放电等离子体研究进展及聚合物表面改性

综述了常压辉光放电等离子体(APGDP)的产生机理及研究进展。介绍了难以产生稳定的APGDP 是由于辉光放电容易向细丝放电和弧光放电过渡,其解决措施是选择合适的介质板材料、电极间距、电源电压及频率、气体成分等。指出APGDP对化纤聚合物表面改性的效果与聚合物的分子结构、等离子体气体、介质板材料等因素有关,且改性效果具有时效性,要根据聚合物的分子结构选择合适的等离子体。     

辉光放电等离子体处理活性艳红X-3B染料废水实验研究

辉光放电电解是一种新型的电化学过程,其中等离子体由电极和电解质液面之间的直流辉光放电来维持。在惰性电解质水溶液中进行辉光放电电解,可以产生大量的·OH、·H、e-aq、HO2·等活性粒子,进而降解各种有机物。文章采用辉光放电等离子体降解活性艳红X-3B,详细考察了多种因素对活性艳红降解效果的影响。实验发现,提高溶液酸度和增加电压均可提高活性艳红的脱色效果,加入一定量Fe2+能明显提高活性艳红的脱色效率。优化后的最佳条件为:电压为570 V,p H为3.04,活性艳红初始浓度为60 mg/L,Fe2+的用量为2 mmol/L,20 min内活性艳红的脱色率达到98.8%。     

辉光放电电解等离子体降解模拟染料废水碱性紫16的研究

用辉光放电电解等离子体(GDEP)技术对模拟染料废水碱性紫16的降解过程进行了研究。通过对电流电压曲线分析,阐述了各阶段变化趋势成因,确定产生辉光放电电压为450 V左右。采用紫外分光光度法对不同降解时间下碱性紫16脱色率进行了分析,结果表明,在600 V电压下,20 mg·L~(-1)碱性紫16可在40 min时脱色率达97.8%,整个降解过程符合一级动力学反应的特征。加入2 g·L~(-1)FeCl2后,促进了HO·的生成速度,使100 mg·L~(-1)碱性紫16在40 min时脱色率达到95.4%。碱性紫16在GDEP降解下,经共轭结构的破坏,助色团最终被矿化为CO2和H2O,其中HO·起到了关键性作用。     

常压辉光放电等离子体对化纤及其它聚合物材料的表面处理研究进展

常压辉光放电等离子体(APGDP)具有不需要在低气压下运行、可实现连续生产、能产生大面积均匀放电且面功率密度合适等优点,其在化纤及其它聚合物的表面改性上有很好的应用前景,是近期等离子体应用研究中的一个热点。主要综述了APGDP对化纤及其它聚合物的表面处理,并扼要地介绍了APGDP对化纤及其它聚合物的等离子体聚合和等离子体引发的聚合或表面接枝,以及有关化纤染色性的研究。     

辉光放电等离子体辅助碱浸铜冶炼烟灰中铜砷分离

采用辉光放电等离子体辅助Na₂S-NaOH浸取体系对铜冶炼烟灰（简称“烟灰”）进行研究,在放电时间10 min、放电功率500 W、放电压强150 Pa、极板间距0.9 cm的条件下,砷的浸出率为92.52%,铜的浸出率为7.76%,实现了砷和铜的有效分离。采用该方法处理后烟灰中的砷从7.11%降到0.45%,铜从2.62%变为2.42%,为烟灰的进一步利用创造了条件。XPS、XRD和重金属形态分析的综合分析结果表明,辉光能将As（Ⅲ）氧化为As（Ⅴ）、Cu（Ⅰ）氧化为Cu（Ⅱ）,且在碱性条件下As（Ⅴ）比As（Ⅲ）更易浸出。因此,辉光放电预氧化有利于砷和铜在碱浸体系中选择性分离。     

Degradation of indole in aqueous solution using contact glow discharge plasma

Exhaustive indole oxidation in aqueous solution was studied using contact glow discharge plasma. The results indicated that the rate of indole degradation increases with the decrease in the solution conductivity. The degradation rate can be enhanced under the following situations. First, the increase in temperature. Second, introduce active carbon and hydrogen peroxide to the solution. Third, the degradation process is performed in alkaline or acidic media rather than the neutral media. Fourth, add Fe²⁺ to solution to undergo Fenton’s reaction. However, n-butanol was found decelerate the degradation of indole. Some major intermediates produced during the degradation were detected by using both HPLC and GC-MS.     

Characterization of diamond fluorinated by glow discharge plasma treatment

The surface fluorination of diamond by treatment in glow discharge plasmas of CF₄ for different times has been investigated. High quality diamond films were deposited onto silicon substrates using hot filament chemical vapor deposition (HFCVD). Subsequently, the films were exposed to a radiofrequency glow discharge plasma of CF₄ for times ranging from 5 min to 1 h. The effects of the plasma treatment on the surface morphology, diamond quality and elemental composition were investigated using atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. Differences in film roughness caused by the plasma treatment were detected by AFM and confirmed by scanning electron microscopy (SEM). Raman spectroscopic analyses showed that the original diamond was of high quality and that the bulk of each film was unchanged by the plasma treatment. Analyses using XPS revealed increased surface fluorination of the films at longer treatment times. In addition, the density of free radicals in the films was probed using electron paramagnetic resonance spectroscopy (EPRS), revealing that untreated diamond possesses an appreciable density of free radicals (6×10¹² g⁻¹) which initially falls with treatment time in the CF₄ plasma but increases for long treatment times.     

Chemical reactions at lipid-gas interfaces: II. Insolubilizing reactions induced by an electrical discharge

Reactions caused by corona discharges (passing through atmospheres of methane, hydrogen or argon) striking the surfaces of aqueous solutions containing long chain fatty acid salts resulted in the formation of solid and insoluble products. These results show that the fatty acid ions were oriented on the aqueous surfaces in such a way that the hydrocarbon chains projected out of the surfaces. Surface layers of long chain alcohols reacted similarly but short and branched chain compounds were not polymerized under the experimental conditions that were used. When methane or hydrogen was used as the discharge gas, reactions occurred along the hydrocarbon chains of the compounds so that the products consisted of networks of many short hydrocarbon chains. These reactions were probably caused by the penetration of hydrogen atoms into the surface layers. Joining of terminal methyl groups of the hydrocarbon chains was the main reaction observed when argon was used as the discharge gas.     

辉光放电电解降解水体中阳离子桃红FG的机理

用辉光放电电解（GDE）技术对模拟染料废水阳离子桃红FG的降解过程进行了研究。通过发射光谱法测定了GDE产生的活性粒子,用紫外光谱和总有机碳（TOC）分析仪研究了不同放电时间下的脱色率和去除率,用电导率仪和酸度计测定了降解过程中溶液的电导率和pH的变化,同时用离子色谱对降解中间产物进行了分析。结合各种分析结果,探讨了GDE降解阳离子桃红FG的机理。结果表明,在最佳电压600 V时,溶液中产生HO·、O·、H·等高活性粒子;放电120 min时,200 ml 20 mg/L阳离子桃红FG的脱色率和TOC去除率分别可达99.0%和72.6%;降解液pH先减小后增大,电导率存在先增大后减小的趋势;离子色谱测试表明,降解过程中产生多种有机小分子酸。羟基自由基（HO·）对阳离子桃红FG的降解起关键作用,GDE降解阳离子桃红FG的机理为：HO·作用下助色基团键断裂,产生酚类等中间产物,然后继续被降解为醌和小分子有机酸,最终矿化为Cl^-、NO₃^-、CO₂和H₂O。     

Degradation of poly(acrylamide) in aqueous solution by glow discharge electrolysis

Summary The glow discharge electrolysis was carried out to an aqueous solution containing poly(acrylamide). The analytical results of the degradation products showed that the degradation takes place stepwise caused by the cleavages of the main and also the side chains of the polymer.     

Polymerisation by glow discharge electrolysis

A glow discharge passed from a metal anode to the surface of aqueous solutions of acrylamide produces radicals which initiate polymerisation. The yield of polymer together with its relative molecular mass has been examined as a function of monomer concentration and pressure in neutral solutions. The form of the variations can be explained in terms of a simplified reaction scheme. On the basis of the proposed mechanism there are two reaction zones. In the primary reaction zone no polymerisation occurs, the radical concentration being too high. About 0·2% of the radicals escape into the secondary reaction zone to initiate polymerisation, the volume of this zone being about 0·4 cm³.In alkaline solutions the yields and relative molecular masses of the polymers are very low and this is attributed to chain termination by oxygen which rises from the destruction of hydrogen peroxide in alkaline solution.     

Synthesis and characterization of superabsorbent composite by using glow discharge electrolysis plasma

A convenient and effective technique for polymerization to produce the poly(acrylic acid-co-acrylamide)/montmorillonite superabsorbent composite in aqueous solution was developed, in which the reaction was initiated by the glow discharge electrolysis (GDE) plasma rather than chemical initiators. The resulted superabsorbent has higher water absorbency, for example, 1024 g g⁻¹ for distilled water and 56 g g⁻¹ for 0.9% NaCl solution. To optimize the synthesis conditions, the following parameters were examined in detail: the discharge voltage, discharge time, ratio of acrylic acid to acrylamide, neutralization of acrylic acid, amount of crosslinking agent and montmorillonite added. The superabsorbent composite was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Results indicated that montmorillonite was effectively bonded with polymer. Moreover, the water absorbency, water retention and thermal stability of the superabsorbent composite prepared by GDE were higher than those of the superabsorbent composite by conventional chemical method under the same polymerization conditions.     

Silicone polymerization by glow discharge application

Polymerization of hexamethyldisiloxane (HMDS) on aluminum by application of capacitively coupled plasma was carried out under different polymerization conditions. The effect of applied frequency, power, and discharge duration on polymerization rate was investigated. Film adhesion was found to be directly related to applied frequency and power. Polymer deposits were examined with SEM and ATR, and the effect of the coat on wattability was sought by measuring the contact angles. The chemical structure of the coat was affected by the energy density applied during coat preparation.     

Graft polymerization of hydrophilic monomers onto textile fibers treated by glow discharge plasma

Graft polymerization of vinyl monomers was made onto some natural and synthetic textile fibers that were pretreated by glow discharge plasmas. Among the monomers investigated, 2-hydroxyethyl methacrylate (HEMA) produced the most improved grafting effects. Effects of plasma gas source, exposing time of glow discharge, grafting time, temperature, etc., on grafting were investigated. Postpolymerization in vacuum allowing oxygen shutoff was desirable for improved grafting yield. Air exposure of the plasma pretreated textile fabrics lead to decrease of grafting yield prominently because of the deactivation of radicals by oxidation. Grafting amount was dependent also on the nature of the substrate textile fibers, and cotton was, in general, more reactive. Breaking strength of yarns increased after graft polymerization of HEMA, while the strength decreased by etching of yarns by plasma treatments using nonpolymerizable gas species. Increase of the strength in the grafted yarn is attributed to binding effect of the grafted polymers as revealed from studies of morphology by scanning electron microscopy. © 1996 John Wiley & Sons, Inc.