Fenton试剂降解偶氮染料活性艳红X-3B的实验研究
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摘要
纺织印染行业是我国用水量大，排放废水量也大的工业部门之一。据资料统计，纺织印染行业每年排放废水量达9亿多吨，居我国工业废水排放量的第六位，其中印染废水排放量又占纺织工业废水排放量的80％。而目前我国印染行业废水平均治理率仅为70％，达标率只有30％。大量未经处理或处理未达标的印染废水直接排放，不仅直接危害人们的身体健康，而且严重破坏水体、土壤及生态，将造成不可想象的后果。印染废水具有水量大、色度深、水质变化大、有机毒物含量高、成分复杂以及难生物降解等特点，是国内外公认的难处理的工业废水之一。Fenton试剂因其超强的氧化能力，特别适合于难生物降解废水的处理，成为水污染治理和控制的有效手段之一。
本研究采用Fenton试剂处理活性艳红X-3B染料废水，用单因素优化分析法，对影响Fenton试剂处理效果的主要因素进行了逐一研究，考察其对Fenton试剂催化降解活性艳红X-3B染料废水的影响程度，以确定最优的反应条件。试验结果表明：在25℃室温条件下，当染料浓度为200mg/L，FeSO_4浓度为0．08mmol/L，H_2O_2浓度为1．6mmol/L，溶液pH=3．0时，反应30min，活性艳红X-3B的降解率和COD去除率分别达92．90%和67．8％。此外，还研究了反应温度、光源及其强度等因素对处理效果的影响，结果表明：日常温度情况下，温度变化对反应结果基本没有影响，而紫外光与Fenton试剂具有协同作用，二者联用能明显提高降解率，且随着紫外光强度的增加，降解率也相应提高。
在处理实际废水时，水样中通常会含有一些阴离子和可溶的金属离子，如C1~-，S~(2-)，SO_4~(2-)，NO_3~-，Ca~(2+)，Mn~(2+)，Mg~(2+)，Zn~(2+)等，这些无机离子的存在或许会在一定程度上对Fenton试剂的催化氧化性能产生影响。本文以Fenton试剂降解活性艳红X-3B为研究对象，选择了一些常见的有代表性的无机离子，深入研究了这些无机离子对Fenton试剂反应的影响，并对作用机理进行了探讨。试验研究结果表明，S~(2-)离子对Fenton试剂催化氧化效果的影响非常明显：H_2PO_4~-和Cl~-对Fenton试剂的催化氧化性能有不同程度的抑制作用，其抑制能力的大小为：H_2PO_4~->Cl~-：Cu~(2+)和Mn~(2+)在一定程度上影响Fenton试剂的氧化效果：SO_4~(2-)，NO_3~-，Mg~(2+)和Zn~(2+)对活性艳红X-3B的降解率几乎没有任何影响。
动力学研究是Fenton试剂催化氧化降解有机物研究的重要内容之一，通过对动力学的研究可以计算出Fenton试剂法降解有机物的反应速率，为Fenton试剂法更好地应用于实际工业废水提供有价值的实验数据。本文在Fenton试剂催化氧化降解活性艳红X-3B的作用规律基础之上，用一元回归方程对不同氧化降解时间后活性艳红X-3B残余浓度对反应时间的相关性进行了分析，推导出表观动力学模型。
最后，通过测定活性艳红X-3B反应前后溶液中Cl~-、NO_3~-等离子浓度变化，考察氧化过程中物质结构变化情况；通过对Fenton试剂催化氧化降解活性艳红X-3B后的水样进行紫外可见光光谱分析，初步推测活性艳红X-3B的氧化途径和降解产物。以便更深入地了解羟基自由基HO·氧化活性艳红X-3B的机理，为Fenton试剂更好地应用于染色废水的处理提供一定的理论依据。
The textile dyeing industry is one of largest industry sectors with the water and wastewater emissions in China. According to the material statistics, the wastewater emissions amount to more than 900 million tons at the textile dyeing industry every year, occupies industrial wastewater emissions sixth in China. Dyeing wastewater is 80% of the textile industry wastewater. At present, the average wastewater treatment rate of the textile dyeing industry was only 70%; the pass rate only was 30%. The large quantities dyeing wastewater of untreated or non-standard treated directly discharged, not only has a direct threat to people's health, but also seriously undermining water, soil and ecology, will cause unimaginable consequences. Dyeing wastewater with volume big, color depth, water quality changes big, high content of toxic organic compounds, complex and bio-refractory, is recognized one of the intractable industrial wastewater in the world. Fenton reagent has a super oxidation and appeared to be applicable for the treatment of bio-refractory wastewater, so Fenton reaction has become one of effective means in the treatment and control of wastewater.
Fenton reagent was used to treat reactive red X-3B dyed wastewater. In order to confirm the optimum response condition, the main factors influencing efficiency were investigated one by one. When T=25℃, pH=3.0, the concentrations of H_2O_2 and Fe~(2+) were 1.6mmol/L and 0.08mmol/L, respectively, the experimental results indicated that the removal rate of COD_(Cr) could reach 67.8% and the degradation rate of Reactive red X-3B was 92.9% under the concentration of the raw wastewater reactive red X-3B is 200mg/L. In addition, studies on the effects of treatment by reaction temperature, photosource and its intensity, results showed that: at normal temperature, the reaction temperature change did not affect results; UV-Fenton reagent is synergy, combination can significantly improve the rate of degradation, with the UV intensity and the increase in the degradation rate correspondingly increased.
In the actual wastewater treatment, water samples will usually contain some anions and soluble metal ions, such as Cl~-, S~(2-) SO_4~(2-), NO_3~- Cu~(2+), Mn~(2+), Mg~(2+), Zn~(2+), and so on, these inorganic ions perhaps to a certain extent, Fenton reagent on the catalytic oxidation performance impact. In this paper, the effect of some inorganic ions on Fenton reaction was studied by choosing some representative inorganic ions, and the mechanism was discussed. Experimental results showed that S~(2-) had great influence on catalysis ability of Fenton reagent; H_2PO_4~- and Cl~-suppressed the decomposition of reactive red X-3B in the following sequence H_2PO_4~-> Cl~-; Cu~(2+) and Mn~(2+) also lowered the treatment efficiency to some extent; SO_4~(2-), NO_3~-, Mg~(2+), Zn~(2+) almost had not effect on the degradation rate of reactive red X-3B.
Kinetics is one of the important research contents on the Fenton reagent catalytic oxidation degradation of organic compounds. Through the kinetics study, the reaction rate can be calculated on organic compounds degradation by Fenton reagent, Fenton method better applied to the actual industrial wastewater provide valuable experimental data, In this paper, on the basis of the rules of catalytic decomposition of reactive red X-3B, the relationship between the remained concentration of reactive red X-3B and reaction time was analyzed by the monoacid regression equation, derived the apparent kinetic model.
Finally, through determination Cl~- and NO_3~- concentrations change in the reaction process and UV-Vis spectrum analysis, degradation products of reactive red X-3B were conjectured and degradation pathway of reactive red X-3B was discussed. It provided the theoretical basis for the application of Fenton reagent in the treatment of dyeing wastewater and better understand the oxidation mechanism of reactive red X-3B by hydroxyl radical.
本研究采用Fenton试剂处理活性艳红X-3B染料废水，用单因素优化分析法，对影响Fenton试剂处理效果的主要因素进行了逐一研究，考察其对Fenton试剂催化降解活性艳红X-3B染料废水的影响程度，以确定最优的反应条件。试验结果表明：在25℃室温条件下，当染料浓度为200mg/L，FeSO_4浓度为0．08mmol/L，H_2O_2浓度为1．6mmol/L，溶液pH=3．0时，反应30min，活性艳红X-3B的降解率和COD去除率分别达92．90%和67．8％。此外，还研究了反应温度、光源及其强度等因素对处理效果的影响，结果表明：日常温度情况下，温度变化对反应结果基本没有影响，而紫外光与Fenton试剂具有协同作用，二者联用能明显提高降解率，且随着紫外光强度的增加，降解率也相应提高。
在处理实际废水时，水样中通常会含有一些阴离子和可溶的金属离子，如C1~-，S~(2-)，SO_4~(2-)，NO_3~-，Ca~(2+)，Mn~(2+)，Mg~(2+)，Zn~(2+)等，这些无机离子的存在或许会在一定程度上对Fenton试剂的催化氧化性能产生影响。本文以Fenton试剂降解活性艳红X-3B为研究对象，选择了一些常见的有代表性的无机离子，深入研究了这些无机离子对Fenton试剂反应的影响，并对作用机理进行了探讨。试验研究结果表明，S~(2-)离子对Fenton试剂催化氧化效果的影响非常明显：H_2PO_4~-和Cl~-对Fenton试剂的催化氧化性能有不同程度的抑制作用，其抑制能力的大小为：H_2PO_4~->Cl~-：Cu~(2+)和Mn~(2+)在一定程度上影响Fenton试剂的氧化效果：SO_4~(2-)，NO_3~-，Mg~(2+)和Zn~(2+)对活性艳红X-3B的降解率几乎没有任何影响。
动力学研究是Fenton试剂催化氧化降解有机物研究的重要内容之一，通过对动力学的研究可以计算出Fenton试剂法降解有机物的反应速率，为Fenton试剂法更好地应用于实际工业废水提供有价值的实验数据。本文在Fenton试剂催化氧化降解活性艳红X-3B的作用规律基础之上，用一元回归方程对不同氧化降解时间后活性艳红X-3B残余浓度对反应时间的相关性进行了分析，推导出表观动力学模型。
最后，通过测定活性艳红X-3B反应前后溶液中Cl~-、NO_3~-等离子浓度变化，考察氧化过程中物质结构变化情况；通过对Fenton试剂催化氧化降解活性艳红X-3B后的水样进行紫外可见光光谱分析，初步推测活性艳红X-3B的氧化途径和降解产物。以便更深入地了解羟基自由基HO·氧化活性艳红X-3B的机理，为Fenton试剂更好地应用于染色废水的处理提供一定的理论依据。
The textile dyeing industry is one of largest industry sectors with the water and wastewater emissions in China. According to the material statistics, the wastewater emissions amount to more than 900 million tons at the textile dyeing industry every year, occupies industrial wastewater emissions sixth in China. Dyeing wastewater is 80% of the textile industry wastewater. At present, the average wastewater treatment rate of the textile dyeing industry was only 70%; the pass rate only was 30%. The large quantities dyeing wastewater of untreated or non-standard treated directly discharged, not only has a direct threat to people's health, but also seriously undermining water, soil and ecology, will cause unimaginable consequences. Dyeing wastewater with volume big, color depth, water quality changes big, high content of toxic organic compounds, complex and bio-refractory, is recognized one of the intractable industrial wastewater in the world. Fenton reagent has a super oxidation and appeared to be applicable for the treatment of bio-refractory wastewater, so Fenton reaction has become one of effective means in the treatment and control of wastewater.
Fenton reagent was used to treat reactive red X-3B dyed wastewater. In order to confirm the optimum response condition, the main factors influencing efficiency were investigated one by one. When T=25℃, pH=3.0, the concentrations of H_2O_2 and Fe~(2+) were 1.6mmol/L and 0.08mmol/L, respectively, the experimental results indicated that the removal rate of COD_(Cr) could reach 67.8% and the degradation rate of Reactive red X-3B was 92.9% under the concentration of the raw wastewater reactive red X-3B is 200mg/L. In addition, studies on the effects of treatment by reaction temperature, photosource and its intensity, results showed that: at normal temperature, the reaction temperature change did not affect results; UV-Fenton reagent is synergy, combination can significantly improve the rate of degradation, with the UV intensity and the increase in the degradation rate correspondingly increased.
In the actual wastewater treatment, water samples will usually contain some anions and soluble metal ions, such as Cl~-, S~(2-) SO_4~(2-), NO_3~- Cu~(2+), Mn~(2+), Mg~(2+), Zn~(2+), and so on, these inorganic ions perhaps to a certain extent, Fenton reagent on the catalytic oxidation performance impact. In this paper, the effect of some inorganic ions on Fenton reaction was studied by choosing some representative inorganic ions, and the mechanism was discussed. Experimental results showed that S~(2-) had great influence on catalysis ability of Fenton reagent; H_2PO_4~- and Cl~-suppressed the decomposition of reactive red X-3B in the following sequence H_2PO_4~-> Cl~-; Cu~(2+) and Mn~(2+) also lowered the treatment efficiency to some extent; SO_4~(2-), NO_3~-, Mg~(2+), Zn~(2+) almost had not effect on the degradation rate of reactive red X-3B.
Kinetics is one of the important research contents on the Fenton reagent catalytic oxidation degradation of organic compounds. Through the kinetics study, the reaction rate can be calculated on organic compounds degradation by Fenton reagent, Fenton method better applied to the actual industrial wastewater provide valuable experimental data, In this paper, on the basis of the rules of catalytic decomposition of reactive red X-3B, the relationship between the remained concentration of reactive red X-3B and reaction time was analyzed by the monoacid regression equation, derived the apparent kinetic model.
Finally, through determination Cl~- and NO_3~- concentrations change in the reaction process and UV-Vis spectrum analysis, degradation products of reactive red X-3B were conjectured and degradation pathway of reactive red X-3B was discussed. It provided the theoretical basis for the application of Fenton reagent in the treatment of dyeing wastewater and better understand the oxidation mechanism of reactive red X-3B by hydroxyl radical.
引文
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