光电催化及吸附—电化学联合技术处理难降解废水研究
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摘要
含酚废水和印染废水等难降解有机废水的治理一直是废水处理中的难题,也是当今水处理领域极其活跃的研究课题。电化学技术作为高级氧化技术之一,具有设备简单、易于控制、反应温和、无二次污染等优点,具有良好的前景。虽然电化学技术处理难降解有机废水研究已取得一定进展,但是对于电化学氧化与光催化、吸附等技术耦合处理难降解有机废水的研究较少。
本文采用直接阴极电沉积和阳极氧化法分别制备Fe203、CuO、NiO复合TiO2纳米管(TiO2-NTs)光电催化阳极,并对其表面形貌及光电特性进行了表征。以复合电极为阳极,重点考察了光电催化技术处理含酚废水和甲基橙废水的影响因素和反应机理,并对苯酚废水资源化进行了初步研究。为进一步降低成本,以活性炭纤维为电极,采用吸附-电催化联合技术处理含酚废水,对活性炭纤维吸附特性进行了研究,建立了吸附-电催化技术下苯酚废水CODCr降解的反应动力学模型。研究取得了以下成果：
(1)成功制备了Fe2O3改性TiO2-NTs(Fe2O3/TiO2-NTs)复合电极、CuO改性TiO2-NTs (CuO/TiO2-NTs)复合电极和NiO改性TiO2-NTs(NiO/TiO2-NTs)复合电极,将纯TiO2纳米管的光响应区间拓宽到可见光区域。以复合电极为阳极,采用光电催化技术处理苯酚废水,考察了电极材料、氧化电压、溶液初始pH值、光源、氧气等因素对苯酚去除率和苯醌收率的影响。在以Fe203/Ti02-NTs为阳极,铜片为阴极,碘钨灯为光源,pH=5,氧化电压为10V时,苯酚去除率达到99%。光电催化技术和光催化、电催化技术对苯酚废水的降解结果表明,光电催化技术的苯酚去除率远远高于电催化技术和光催化技术。考察苯酚光电催化降解机理发现,光电催化过程中产生的羟基自由基和空穴首先与苯环发生加成反应,产生苯醌和对苯二酚,然后苯环进一步被氧化开环,产生顺丁烯二酸；顺丁烯二酸被进一步氧化,生成更小分子的有机物或被矿化。研究了苯酚光电催化选择性氧化为苯醌的实验条件,结果表明苯醌收率最大的条件是CuO/TiO2-NTs为阳极,铜片为阴极,紫外光为光源,溶液pH=5,氧化电压为15V；苯酚选择性最大的条件是CuO/TiO2-NTs为阳极,铜片为阴极,无光照,溶液pH=5,氧化电压为15V。
(2)以Fe2O3/TiO2-NTs、CuO/TiO2-NTs和NiO/TiO2-NTs复合电极为阳极,光电催化处理甲基橙废水,考察了电解质浓度、溶液初始pH值、氧化电压、光源、氧气等因素对甲基橙的脱色的影响。增加电解质浓度,可增加甲基橙脱色率。在pH=3时,甲基橙的脱色率最大。15V时,甲基橙脱色率远远高于1OV。可见光条件下光电催化有利于甲基橙的脱色。对比光电催化和电催化技术,光电催化技术下的甲基橙脱色率远远高于电催化技术。对甲基橙溶液进行紫外可见吸收光谱扫描发现,反应时偶氮键与苯环所形成的共轭体系首先受到破坏,使溶液颜色褪去；在紫外区有吸收的一些基团被破坏的速度较慢。分析了甲基橙光电催化脱色机理,酸性条件下,甲基橙以偶氮式和醌式两种形态存在。当以偶氮式结构存在时,苯环首先与羟基自由基发生加成反应,然后与H+发生反应,将甲基橙分子分解成两个小分子,小分子还带有发色基团。小分子再与羟基自由基发生夺氢反应,破坏发色基团；而以醌式结构存在时,与苯环相连的碳氮双键与H+发生加成反应,破坏发色团,使甲基橙脱色。
(3)研究了吸附-电化学联合技术对苯酚废水的处理效果,结果表明吸附-电催化联合作用可以显著提高苯酚的去除率。电流强度、电解质种类对苯酚废水CODcr去除率有一定影响。电流强度为0.6A时,CODcr去除率和电流效率都最高,能量消耗低。以NaCl为电解质时苯酚废水的CODcr去除率明显高于以Na2SO4为电解质时的去除率。在以活性炭纤维为阴极的吸附电催化中,通入氧气有利于苯酚的降解。pH值为3时苯酚CODc,去除率最高。溶液初始浓度越低,CODc,的去除率越高。对活性炭纤维进行微波改性,有利于苯酚去除。活性炭纤维的等温吸附曲线符合Freundlich等温式。建立了吸附-电催化联合作用下苯酚废水CODcr降解的反应动力学模型,较好地解释、关联了实验数据,揭示出吸附是CODcr去除的主要形式。活性炭纤维连续使用时吸附速率有所下降,但苯酚废水仍然能够在2h内取得90%以上的去除效率,显示出较好的应用前景。
Refractory organic wastewater, such as phenol wastewater and dying wastewater, has always been a challenge as well as a hot research topic in wastewater treatment field. Electrochemical technique is one of advanced oxidation processes. Although some research has used the electrochemical techinique to treat the refractory organic wastewater, the united technologies research of electrochemical techniques with photocatalysis or adsorption is still few.
Direct cathodic electrodeposition and anodization were used to prepare TiO2natotubes (TiO2NTs) electrodes modified by metal oxide. The surface features and photoelectrochemical properities were identified. Influencing factors and degradation mechanisms of photoelectrochemical technology on phenol and methyl orange wastewaters were mainly studied. In order to cut down the cost, electrocatalysis combined with adsorption method was further studied to treat the phenol wastewater. Achievements are as follows:
(1) Fe203-modified TiO2-NTs, CuO-modified TiO2-NTs and NiO-modified TiO2NTs were successfully prepared with direct cathodic electrodeposition and anodic oxidation, which can broaden the light response range to visible light region. Photoelectrocatalysis technology has been applied to treat phenol wastewater using the composite anodes. And the influence factors on phenol removal rate and benzoquinone yield, such as electrode materials, oxidation voltage, initial pH value, light source and oxygen were studied. The results indicated that the phenol removal rate of phenol achieved by photoelectrochemical technology is significantly higher compared with that achieved by electrocatalytic technology or photocatalytic technology. When Fe2O3/TiO2-NTs was used as anode, copper as cathode and iodine-tungsten lamp as light source, the phenol removal rate reached99%at a voltage of10V and a pH value of5. When CuO/TiO2NTs was used as anode and copper as cathode, the benzoquinone yield and the selectivity of phenol were all maximum at a voltage of15V and a pH value of5.
(2) Photoelectrocatalycal technology was applied to treat dyeing wastewater using metal oxide modified TiO2-NTs electrodes. And the influence factors, such as electrolyte concentration, initial pH value, oxidation voltage, light source and oxygen have been studied. The results indicated that the decolorization rate of methyl orange achieved was extraordinarily higher by using photoelectricatalytic technology than that using electrocatalysis technology. When Fe2O3/TiO2-NTs was used as anode, the decolorization rate of methyl orange reached91%in10min at a voltage of15V and a pH value of3. Methyl orange had two different morphological structures (azo-type and quinone-type) in acidic solution. For the azo structure, the benzene ring could be oxidized first by reacting with hydroxyl radical. For the quinone-type structure, chromophoric groups were damaged by the reaction between H+and azo double bond.
(3) The degradation of phenol wastewater was investigated by electrocatalysis combined with adsorption method. The result indicated that electrocatalysis combined with adsorption method can significantly improve the removal rate of phenol. Current intensity, electrolyte type, oxygen, pH values and microwave modification have a certain influence on the chemical oxygen demand (CODcr) removal of phenol wastewater. The adsorption equilibrium of phenol on activated carbon fiber was coincident with Freundlich isotherm. A kinetic model for CODCr removal could better explain the experimental data. And it also revealed that adsorption was the main form of CODcr remove. The CODCr removal used activated carbon fiber still could reach90%within2h. It shows a good application prospects.
本文采用直接阴极电沉积和阳极氧化法分别制备Fe203、CuO、NiO复合TiO2纳米管(TiO2-NTs)光电催化阳极,并对其表面形貌及光电特性进行了表征。以复合电极为阳极,重点考察了光电催化技术处理含酚废水和甲基橙废水的影响因素和反应机理,并对苯酚废水资源化进行了初步研究。为进一步降低成本,以活性炭纤维为电极,采用吸附-电催化联合技术处理含酚废水,对活性炭纤维吸附特性进行了研究,建立了吸附-电催化技术下苯酚废水CODCr降解的反应动力学模型。研究取得了以下成果：
(1)成功制备了Fe2O3改性TiO2-NTs(Fe2O3/TiO2-NTs)复合电极、CuO改性TiO2-NTs (CuO/TiO2-NTs)复合电极和NiO改性TiO2-NTs(NiO/TiO2-NTs)复合电极,将纯TiO2纳米管的光响应区间拓宽到可见光区域。以复合电极为阳极,采用光电催化技术处理苯酚废水,考察了电极材料、氧化电压、溶液初始pH值、光源、氧气等因素对苯酚去除率和苯醌收率的影响。在以Fe203/Ti02-NTs为阳极,铜片为阴极,碘钨灯为光源,pH=5,氧化电压为10V时,苯酚去除率达到99%。光电催化技术和光催化、电催化技术对苯酚废水的降解结果表明,光电催化技术的苯酚去除率远远高于电催化技术和光催化技术。考察苯酚光电催化降解机理发现,光电催化过程中产生的羟基自由基和空穴首先与苯环发生加成反应,产生苯醌和对苯二酚,然后苯环进一步被氧化开环,产生顺丁烯二酸；顺丁烯二酸被进一步氧化,生成更小分子的有机物或被矿化。研究了苯酚光电催化选择性氧化为苯醌的实验条件,结果表明苯醌收率最大的条件是CuO/TiO2-NTs为阳极,铜片为阴极,紫外光为光源,溶液pH=5,氧化电压为15V；苯酚选择性最大的条件是CuO/TiO2-NTs为阳极,铜片为阴极,无光照,溶液pH=5,氧化电压为15V。
(2)以Fe2O3/TiO2-NTs、CuO/TiO2-NTs和NiO/TiO2-NTs复合电极为阳极,光电催化处理甲基橙废水,考察了电解质浓度、溶液初始pH值、氧化电压、光源、氧气等因素对甲基橙的脱色的影响。增加电解质浓度,可增加甲基橙脱色率。在pH=3时,甲基橙的脱色率最大。15V时,甲基橙脱色率远远高于1OV。可见光条件下光电催化有利于甲基橙的脱色。对比光电催化和电催化技术,光电催化技术下的甲基橙脱色率远远高于电催化技术。对甲基橙溶液进行紫外可见吸收光谱扫描发现,反应时偶氮键与苯环所形成的共轭体系首先受到破坏,使溶液颜色褪去；在紫外区有吸收的一些基团被破坏的速度较慢。分析了甲基橙光电催化脱色机理,酸性条件下,甲基橙以偶氮式和醌式两种形态存在。当以偶氮式结构存在时,苯环首先与羟基自由基发生加成反应,然后与H+发生反应,将甲基橙分子分解成两个小分子,小分子还带有发色基团。小分子再与羟基自由基发生夺氢反应,破坏发色基团；而以醌式结构存在时,与苯环相连的碳氮双键与H+发生加成反应,破坏发色团,使甲基橙脱色。
(3)研究了吸附-电化学联合技术对苯酚废水的处理效果,结果表明吸附-电催化联合作用可以显著提高苯酚的去除率。电流强度、电解质种类对苯酚废水CODcr去除率有一定影响。电流强度为0.6A时,CODcr去除率和电流效率都最高,能量消耗低。以NaCl为电解质时苯酚废水的CODcr去除率明显高于以Na2SO4为电解质时的去除率。在以活性炭纤维为阴极的吸附电催化中,通入氧气有利于苯酚的降解。pH值为3时苯酚CODc,去除率最高。溶液初始浓度越低,CODc,的去除率越高。对活性炭纤维进行微波改性,有利于苯酚去除。活性炭纤维的等温吸附曲线符合Freundlich等温式。建立了吸附-电催化联合作用下苯酚废水CODcr降解的反应动力学模型,较好地解释、关联了实验数据,揭示出吸附是CODcr去除的主要形式。活性炭纤维连续使用时吸附速率有所下降,但苯酚废水仍然能够在2h内取得90%以上的去除效率,显示出较好的应用前景。
Refractory organic wastewater, such as phenol wastewater and dying wastewater, has always been a challenge as well as a hot research topic in wastewater treatment field. Electrochemical technique is one of advanced oxidation processes. Although some research has used the electrochemical techinique to treat the refractory organic wastewater, the united technologies research of electrochemical techniques with photocatalysis or adsorption is still few.
Direct cathodic electrodeposition and anodization were used to prepare TiO2natotubes (TiO2NTs) electrodes modified by metal oxide. The surface features and photoelectrochemical properities were identified. Influencing factors and degradation mechanisms of photoelectrochemical technology on phenol and methyl orange wastewaters were mainly studied. In order to cut down the cost, electrocatalysis combined with adsorption method was further studied to treat the phenol wastewater. Achievements are as follows:
(1) Fe203-modified TiO2-NTs, CuO-modified TiO2-NTs and NiO-modified TiO2NTs were successfully prepared with direct cathodic electrodeposition and anodic oxidation, which can broaden the light response range to visible light region. Photoelectrocatalysis technology has been applied to treat phenol wastewater using the composite anodes. And the influence factors on phenol removal rate and benzoquinone yield, such as electrode materials, oxidation voltage, initial pH value, light source and oxygen were studied. The results indicated that the phenol removal rate of phenol achieved by photoelectrochemical technology is significantly higher compared with that achieved by electrocatalytic technology or photocatalytic technology. When Fe2O3/TiO2-NTs was used as anode, copper as cathode and iodine-tungsten lamp as light source, the phenol removal rate reached99%at a voltage of10V and a pH value of5. When CuO/TiO2NTs was used as anode and copper as cathode, the benzoquinone yield and the selectivity of phenol were all maximum at a voltage of15V and a pH value of5.
(2) Photoelectrocatalycal technology was applied to treat dyeing wastewater using metal oxide modified TiO2-NTs electrodes. And the influence factors, such as electrolyte concentration, initial pH value, oxidation voltage, light source and oxygen have been studied. The results indicated that the decolorization rate of methyl orange achieved was extraordinarily higher by using photoelectricatalytic technology than that using electrocatalysis technology. When Fe2O3/TiO2-NTs was used as anode, the decolorization rate of methyl orange reached91%in10min at a voltage of15V and a pH value of3. Methyl orange had two different morphological structures (azo-type and quinone-type) in acidic solution. For the azo structure, the benzene ring could be oxidized first by reacting with hydroxyl radical. For the quinone-type structure, chromophoric groups were damaged by the reaction between H+and azo double bond.
(3) The degradation of phenol wastewater was investigated by electrocatalysis combined with adsorption method. The result indicated that electrocatalysis combined with adsorption method can significantly improve the removal rate of phenol. Current intensity, electrolyte type, oxygen, pH values and microwave modification have a certain influence on the chemical oxygen demand (CODcr) removal of phenol wastewater. The adsorption equilibrium of phenol on activated carbon fiber was coincident with Freundlich isotherm. A kinetic model for CODCr removal could better explain the experimental data. And it also revealed that adsorption was the main form of CODcr remove. The CODCr removal used activated carbon fiber still could reach90%within2h. It shows a good application prospects.
引文
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