负载型氧化铁吸附剂的制备及对五氯苯酚作用研究
摘要
五氯苯酚(Pentachlorophenol，简写PCP)作为杀虫剂、防腐剂而被广泛应用，鉴于其在水环境和土壤中分布的广泛性以及对人类和环境的持久性、高毒性危害，已成为全球性的环境污染物之一。目前对PCP的主要处理方法有：生物方法、芬顿试剂法、光化学、电化学、臭氧处理、超声波及金属催化氧化等处理方法。这些方法各有优缺点，国内外学者研究的也较多，然而对于矿物材料在含PCP废水中的应用研究较少。铁(氢)氧化物矿物在地表土壤和水体沉积物中分布广泛，比表面积巨大，表面氧化还原活性高，以及电子输运能力强，因此铁矿物与PCP的表面作用对PCP的地球化学循环、环境效应起着重要的控制作用。其中尤以赤铁矿(α=Fe_2O_3)对PCP作用最为显著。研究PCP与α-Fe_2O_3的相互作用机理，对深入了解PCP在土壤和水体沉积物中的迁移、转化、降解及残留规律具有理论及实际意义。
本论文选择五氯苯酚为研究对象，采用两种方法制备和负载α-Fe_2O_3，研究了PCP与原位制备的α-Fe_2O_3上的界面作用，并对不同条件下对界面作用的影响以及五氯苯酚与α-Fe_2O_3之间的作用机制进行了研究。主要研究工作内容如下：
1、利用高温氧化法(原位生成)直接制备、负载α-Fe_2O_3，采用陶瓷滤料负载制备α=Fe_2O_3。通过X射线衍射、拉曼光谱、扫描电子显微镜等手段进行分析表征。结果显示：高温氧化法制备的α=Fe_2O_3，不仅制备方法简单可行、α-Fe_2O_3性状稳定，而且在抗酸碱能力、抗机械摩擦能力实验中，损失重量小，有效的解决了吸附剂难以固定的问题。
2、通过静态吸附实验，研究了PCP与α-Fe_2O_3二者之间的吸附动力学、吸附等温线及pH对吸附的影响。实验结果表明：铁板原位生成α-Fe_2O_3矿物对PCP的吸附在2．5h达到吸附和解吸动力学平衡，吸附动力学符合二级动力学；Freundlich吸附等温式可以较好的描述PCP在α-Fe_2O_3上的吸附行为；α=Fe_2O_3对PCP吸附的pH关系等温线是一峰型曲线，α-Fe_2O_3吸附容量峰值出现在pH=6．0处。
3、通过α-Fe_2O_3吸附前后的红外光谱图分析其吸附机理，结果表明：两者的吸附发生在赤铁矿表面；pH值6．0时，两者之间作用以静电吸附为主，氢键作用为辅；pH值8．5时，两者之间主要以氢键作用产生吸附。
4、研究了α-Fe_2O_3的重复利用。采用两种方法处理吸附PCP后的α-Fe_2O_3，结果表明：α-Fe_2O_3的重复利用效果较好，将吸附PCP后的原位生成负载α-Fe_2O_3经过600℃煅烧1 h后能够较好的获得再生，可以完全恢复α-Fe_2O_3原有吸附性能。并且重复利用四次后α-Fe_2O_3对PCP的吸附能力为首次吸附能力的98．9％。
Pentachlorophenol (PCP) because of its broad use as bactericide and antiseptic with high toxicity and hardly degradable by ordinary oxidants and most microorganisms in water and soil, is considered as a substance that should be removed from environment.At present, the main approaches to treatment PCP include: biological methods, Fenton reagent, photochemical, electrochemical, ozone treatment, ultrasonic and metal oxidation and so on. These methods all have advantages and disadvantages.The scholars at home and abroad studied a lot on them, but less studied on the the mineral material applied in the wastewater containing PCP . Hematite is a mineral widely occurred on earth surface with high surface area, large adsorptive capacity and high oxidation - reduction activity and can be used as an important adsorbent as well as catalyst for the removal of pollutant in environment. Therefore, study on the mechanism regarding the interaction between hematite and pentachlorophenol is of theoretical and practical importance for understanding the degradation, transfer and removal of pentachlorophenol in water and soil.
In this thesis, prepared and load hemate by two methods,choosed PCP to be studied. Studied the interaction between PCP and hemate under different condition. Furthermore, the interaction mechanism of PCP and hemate were also investigated. The main research work as follows:
1. Preparated and load the hemate by HTO(situ preparatio) and Ceramic mediums.And characterizated them by XRD, Laman spectrum, SEM and other means of analysis. The results showed that: the hemate preparated by HTO not only has easy preparation and stable character but also has lower lose weight in the anti-acid and alkali ability experiment shockproof test. So it can resolve the difficult problem of absorbent fixed effectively.
2. The Static adsorption experiment used to study the adsorption kinetics、adsorption isotherm and the effect by pH between PCP and hematite adsorption.The results showed that: the adsorption and desorption dynamics reach balance at 2.5h,and the adsorption in line with stair kinetic adsorption dynamics; Freundlich adsorption isotherm can describe the adsorption of PCP on hematite better; The pH adsorption isotherm of pentachlorophenol onto hematite is a peak curve and the largest adsorption quantity occurred at about pH 6.0.
3. The adsorption of pentachlorophenol on hematite was studied in this laboratory through adsorption experiments and FTIR analysis, the results showed that: the adsorption occurred on the surface of hematite; At pH 6.0, The main interaction between PCP and hematite was static electric interaction; At pH 8.5, the interaction was mainly through hydrogen bond.
4. Study on the regeneration of hematite. Used two methods to deal with the hematite after absorbed, the results were that: the ability of hematite regeneration is well, the hematite after adsorption can be Can be fully restored adsorption capacity after burning 600℃for 1 h .The adsorption capacity is 98.9% of first time after rebirth four times.
本论文选择五氯苯酚为研究对象，采用两种方法制备和负载α-Fe_2O_3，研究了PCP与原位制备的α-Fe_2O_3上的界面作用，并对不同条件下对界面作用的影响以及五氯苯酚与α-Fe_2O_3之间的作用机制进行了研究。主要研究工作内容如下：
1、利用高温氧化法(原位生成)直接制备、负载α-Fe_2O_3，采用陶瓷滤料负载制备α=Fe_2O_3。通过X射线衍射、拉曼光谱、扫描电子显微镜等手段进行分析表征。结果显示：高温氧化法制备的α=Fe_2O_3，不仅制备方法简单可行、α-Fe_2O_3性状稳定，而且在抗酸碱能力、抗机械摩擦能力实验中，损失重量小，有效的解决了吸附剂难以固定的问题。
2、通过静态吸附实验，研究了PCP与α-Fe_2O_3二者之间的吸附动力学、吸附等温线及pH对吸附的影响。实验结果表明：铁板原位生成α-Fe_2O_3矿物对PCP的吸附在2．5h达到吸附和解吸动力学平衡，吸附动力学符合二级动力学；Freundlich吸附等温式可以较好的描述PCP在α-Fe_2O_3上的吸附行为；α=Fe_2O_3对PCP吸附的pH关系等温线是一峰型曲线，α-Fe_2O_3吸附容量峰值出现在pH=6．0处。
3、通过α-Fe_2O_3吸附前后的红外光谱图分析其吸附机理，结果表明：两者的吸附发生在赤铁矿表面；pH值6．0时，两者之间作用以静电吸附为主，氢键作用为辅；pH值8．5时，两者之间主要以氢键作用产生吸附。
4、研究了α-Fe_2O_3的重复利用。采用两种方法处理吸附PCP后的α-Fe_2O_3，结果表明：α-Fe_2O_3的重复利用效果较好，将吸附PCP后的原位生成负载α-Fe_2O_3经过600℃煅烧1 h后能够较好的获得再生，可以完全恢复α-Fe_2O_3原有吸附性能。并且重复利用四次后α-Fe_2O_3对PCP的吸附能力为首次吸附能力的98．9％。
Pentachlorophenol (PCP) because of its broad use as bactericide and antiseptic with high toxicity and hardly degradable by ordinary oxidants and most microorganisms in water and soil, is considered as a substance that should be removed from environment.At present, the main approaches to treatment PCP include: biological methods, Fenton reagent, photochemical, electrochemical, ozone treatment, ultrasonic and metal oxidation and so on. These methods all have advantages and disadvantages.The scholars at home and abroad studied a lot on them, but less studied on the the mineral material applied in the wastewater containing PCP . Hematite is a mineral widely occurred on earth surface with high surface area, large adsorptive capacity and high oxidation - reduction activity and can be used as an important adsorbent as well as catalyst for the removal of pollutant in environment. Therefore, study on the mechanism regarding the interaction between hematite and pentachlorophenol is of theoretical and practical importance for understanding the degradation, transfer and removal of pentachlorophenol in water and soil.
In this thesis, prepared and load hemate by two methods,choosed PCP to be studied. Studied the interaction between PCP and hemate under different condition. Furthermore, the interaction mechanism of PCP and hemate were also investigated. The main research work as follows:
1. Preparated and load the hemate by HTO(situ preparatio) and Ceramic mediums.And characterizated them by XRD, Laman spectrum, SEM and other means of analysis. The results showed that: the hemate preparated by HTO not only has easy preparation and stable character but also has lower lose weight in the anti-acid and alkali ability experiment shockproof test. So it can resolve the difficult problem of absorbent fixed effectively.
2. The Static adsorption experiment used to study the adsorption kinetics、adsorption isotherm and the effect by pH between PCP and hematite adsorption.The results showed that: the adsorption and desorption dynamics reach balance at 2.5h,and the adsorption in line with stair kinetic adsorption dynamics; Freundlich adsorption isotherm can describe the adsorption of PCP on hematite better; The pH adsorption isotherm of pentachlorophenol onto hematite is a peak curve and the largest adsorption quantity occurred at about pH 6.0.
3. The adsorption of pentachlorophenol on hematite was studied in this laboratory through adsorption experiments and FTIR analysis, the results showed that: the adsorption occurred on the surface of hematite; At pH 6.0, The main interaction between PCP and hematite was static electric interaction; At pH 8.5, the interaction was mainly through hydrogen bond.
4. Study on the regeneration of hematite. Used two methods to deal with the hematite after absorbed, the results were that: the ability of hematite regeneration is well, the hematite after adsorption can be Can be fully restored adsorption capacity after burning 600℃for 1 h .The adsorption capacity is 98.9% of first time after rebirth four times.
引文
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