水中甲基叔丁基醚和异丙威的光催化降解研究
摘要
本论文通过气相色谱-质谱联用仪、高效液相色谱、红外光谱、离子色谱、紫外-可见光谱等手段研究了甲基叔丁基醚 (MTBE) 和异丙威 （MIPC) 的光催化降解过程，推测了可能的反应历程。并对影响其光催化降解的因素（初始浓度、催化剂量、共存金属离子、pH值、光强等）进行了考察，结果表明：
水中MTBE能被光催化降解并最终矿化，其降解过程产生的主要中间产物有甲酸叔丁酯、叔丁醇和丙酮，尽管降解速率不同，它们也都能被光催化降解。通过对反应中间产物及终产物的追踪分析，表明MTBE的光催化降解首先是通过羟基化过程来进行，进而提出MTBE光催化降解的可能反应历程。MTBE的光催化降解速率受催化剂的焙烧温度和投加量的影响，TiO2的最佳焙烧温度为400 ℃，最佳投加量为0.5g/L；MTBE的初始浓度和溶液的pH值 (5~9) 对其光催化降解速率没有明显影响。
MIPC能被光催化转化成3，4-二羟基苯乙酮、2-异丁基苯酚和乙酸等产物并最终被矿化，MIPC的光催化反应过程符合一级动力学规律，其表观速率常数与MIPC的起始浓度、TiO2量和光强等因素有关，MIPC降解的反应速率与入射光强成正比，与MIPC初始浓度的平方根成反比。催化剂的最佳投加量为0.5g/L，反应速率受共存金属离子的影响，Cu2+离子有明显的抑制作用，提出了MIPC光催化降解反应的动力学经验方程。
The photocatalytic degradations of Methyl tert-Butyl Ether (MTBE) and 2-isopropylphenyl-N-methylcarbamate (MIPC) were studied and the reaction schemes were presumed by using GC-MS, HPLC, FTIR, IC and UV-Vis spectra. The effects of initial concentration(C0) of reactant, the amount of catalyst，coexistence metal ion, pH and light intensity(I) on photodegradation of MTBE and MIPC have been investigated. The results showed:
MTBE was photocatalytically transformed to innocuous products and mineralized ultimately in oxygenated TiO2 slurries. The major intermediates of this reaction had been identified as t-butyl formate，t-butyl alcohol, and acetone, all of which were also readily degraded photocatalytically, albeit at different rates. Based on identification of intermediates and final products, the first step in the destruction of MTBE was thought to be abstraction of a α-hydrogen by ·OH and a reaction scheme was proposed. The degradation rate of MTBE depended on the amount and calcined temperature of catalyst, and the optimum concentration and calcined temperature of catalyst were 0.5g/L and 400 ℃, respectively. However, the degradation rate of MTBE was independent of its initial concentration and solution pH in our experiment.
MIPC was photocatalytically transformed to 3,4-dihydroxyl hypnone, 2-iso-butyl phenol and acetic acid, and mineralized ultimately in oxygenated TiO2 slurries. The photocatalytic degradation processed according to first order kinetics with the apparent rate constant depending on initial concentration, light intensity and the amount of catalyst. The amount of catalyst had an optimum value (0.5g/L). The apparent rate was inversely proportional to square root of the initial concentration approximately. Furthermore, the apparent rate constant was
proportional to light intensity, and affected by coexistence metal ion, especially the existence of Cu2+ inhibited the degradation of MIPC. Based on our experiment, a kinetics empirical equation was proposed.
水中MTBE能被光催化降解并最终矿化，其降解过程产生的主要中间产物有甲酸叔丁酯、叔丁醇和丙酮，尽管降解速率不同，它们也都能被光催化降解。通过对反应中间产物及终产物的追踪分析，表明MTBE的光催化降解首先是通过羟基化过程来进行，进而提出MTBE光催化降解的可能反应历程。MTBE的光催化降解速率受催化剂的焙烧温度和投加量的影响，TiO2的最佳焙烧温度为400 ℃，最佳投加量为0.5g/L；MTBE的初始浓度和溶液的pH值 (5~9) 对其光催化降解速率没有明显影响。
MIPC能被光催化转化成3，4-二羟基苯乙酮、2-异丁基苯酚和乙酸等产物并最终被矿化，MIPC的光催化反应过程符合一级动力学规律，其表观速率常数与MIPC的起始浓度、TiO2量和光强等因素有关，MIPC降解的反应速率与入射光强成正比，与MIPC初始浓度的平方根成反比。催化剂的最佳投加量为0.5g/L，反应速率受共存金属离子的影响，Cu2+离子有明显的抑制作用，提出了MIPC光催化降解反应的动力学经验方程。
The photocatalytic degradations of Methyl tert-Butyl Ether (MTBE) and 2-isopropylphenyl-N-methylcarbamate (MIPC) were studied and the reaction schemes were presumed by using GC-MS, HPLC, FTIR, IC and UV-Vis spectra. The effects of initial concentration(C0) of reactant, the amount of catalyst，coexistence metal ion, pH and light intensity(I) on photodegradation of MTBE and MIPC have been investigated. The results showed:
MTBE was photocatalytically transformed to innocuous products and mineralized ultimately in oxygenated TiO2 slurries. The major intermediates of this reaction had been identified as t-butyl formate，t-butyl alcohol, and acetone, all of which were also readily degraded photocatalytically, albeit at different rates. Based on identification of intermediates and final products, the first step in the destruction of MTBE was thought to be abstraction of a α-hydrogen by ·OH and a reaction scheme was proposed. The degradation rate of MTBE depended on the amount and calcined temperature of catalyst, and the optimum concentration and calcined temperature of catalyst were 0.5g/L and 400 ℃, respectively. However, the degradation rate of MTBE was independent of its initial concentration and solution pH in our experiment.
MIPC was photocatalytically transformed to 3,4-dihydroxyl hypnone, 2-iso-butyl phenol and acetic acid, and mineralized ultimately in oxygenated TiO2 slurries. The photocatalytic degradation processed according to first order kinetics with the apparent rate constant depending on initial concentration, light intensity and the amount of catalyst. The amount of catalyst had an optimum value (0.5g/L). The apparent rate was inversely proportional to square root of the initial concentration approximately. Furthermore, the apparent rate constant was
proportional to light intensity, and affected by coexistence metal ion, especially the existence of Cu2+ inhibited the degradation of MIPC. Based on our experiment, a kinetics empirical equation was proposed.
引文
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