酞菁衍生物/MCM-41的制备及催化苯酚羟基化反应
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摘要
苯二酚(邻苯二酚和对苯二酚)是重要的精细化工原料,用途非常广泛,市场需求量很大。双氧水氧化苯酚羟基化联产邻苯二酚、对苯二酚法是目前最理想的绿色化学生产工艺,该工艺的催化剂成为研究的重点。酞菁衍生物是一类具有良好热稳定性和化学稳定性的大环化合物。近年来,人们发现酞菁具有许多特殊性质和新颖功能,但由于酞菁类化合物的难溶性,使其在应用上受到了很大的限制。为提高其溶解性并获得所需要的理化性质,需要对其分子结构加以修饰,通常有效的做法是在酞菁类化合物的中心、周边以及轴向引入官能团。分子筛MCM-41是一类通过无机前驱体与有机表面活性剂之间的相互作用自组装形成的具有长程有序排列,孔径处于纳米量级(2-10nm)的纳米结构体系。功能材料组装进介孔分子筛的孔道内形成具有纳米结构的新型复合材料,在催化领域有着理论研究价值和实际应用前景。
本文在实验的基础上,建立了苯酚羟基化反应液用高效液相色谱分析的方法。以4-磺酸基邻苯二甲腈和乙酸钴或氯化亚铁为原料,采用固相熔融法合成4,4′,4″,4′″-四磺酸基钴酞菁(CoPcS_4)和4,4′,4″,4′″-四磺酸基铁酞菁(FePcS_4),采用红外光谱、紫外-可见光光谱和质谱对其表征。
以4,4′,4″,4′″-四磺酸基钴酞菁为催化剂作用于苯酚羟基化反应,主要考察了溶剂、pH值、温度、双氧水用量、催化剂用量以及双氧水滴加速度对苯酚羟基化反应的影响,最后得到苯酚羟基化的优化反应条件为:溶剂水,pH值6,反应温度40℃,双氧水/苯酚摩尔比1.2,苯酚/催化剂质量比150,双氧水滴加速度3.90ml/h,在此条件下苯酚的转化率达到28.79%,苯二酚的选择性达到62.07%。以4,4′,4″,4′″-四磺酸基铁酞菁为催化剂苯酚羟基化的优化反应条件为:反应温度50℃,双氧水/苯酚摩尔比1.2,苯酚/催化剂质量比125,双氧水滴加速度2.60ml/h,在此条件下苯酚的转化率达到63.01%,苯二酚的选择性达到49.80%。
通过比较4,4′,4″,4′″-四磺酸基铁酞菁和4,4′,4″,4′″-四磺酸基钴酞菁做催化剂的转化率可知,4,4′,4″,4′″-四磺酸基铁酞菁的催化反应活性相对较好。以MCM-41为载体,FePcS_4为活性中心,采用浸渍法制备催化剂FePcS_4/MCM-41,并应用于苯酚羟基化反应进行研究,发现和FePcS_4相比,虽然苯酚转化率降到了30%,但是苯二酚的选择性最高能达到93.05%。
Catechol and hydroquinone,as the important raw material intermediates in fine chemical industries,are used in many fields.The catalytic hydrogenation of phenol by hydrogen peroxide is the optimal green way to produce pyrocatechtechol and hydroquinone.So the catalysts had become the emphases studied.Phthalocyanine is a kind of microcycle compound with well thermal stabilities and chemical stabilities.In recent years,many special characters and novel functions have been found,the field of applications will increase widely.However, Phthalocyanine compounds can't be resolved easily which limites their application.So the structure of phthalocyanine molecule has to be modified to improve their solubilities and obtain the required physical and chemical properties.The effective method is importing functional groupe to center,circumference and axes of phthalocyanine compounds.Mesoporous molecular sieves(MCM-41) have been obtained by means of the corporative interaction between inorganic presecursors and supramolecular surfactants.Their unique strctures such as large pore size(2-10nm),large area and narrow pore size distribution have attracted considerable attention in porous materials science since 1992.New complex materials with nano-structure which are synthesized by functional materials assembled in mesoporous zeolite have theory and reality value in catalysis fields.
A new method for the separation and determination of phenolic compounds in phenol hydroxylation by reversed-phase high performance chromatogrophy with gradient elution was established.Tetra-substituted sulfonated cobalt(iron) phthalocyanine was synthesized by using 4-sulfonicphthalonitrile as fragment.Theirs structures were identified and characterized byFT-IR,UV-VIS and MS.The influence of various reaction parameters solvent,pH, reaction temperature,the molar ratio H_2O_2/phenol,the mass ratio of phenol/catalyst,and the velocity of H_2O_2,were studied and the optimized reaction condition was acquired.When tetra-substituted sulfonated cobalt phthalocyanine as catalyst,under optimal reaction condition(n_(phenol)=0.05mol,solvent H_2O,pH=6,H_2O_2/phenol molar ratio=1.2,phenol/catalyst quality ratio=150,the velocity of H_2O_2 3.9ml/h),the phenol conversion,the diphenol selectivity and reaches 28.79%and 62.07%,respectively.When tetra-substituted sulfonated iron phthalocyanine as catalyst,under optimal reaction condition(n_(phenol)=0.05mol,H_2O_2/ phenol molar ratio=1.2,phenol/catalyst quality ratio=125,the velocity of H_2O_2 2.6ml/h),the phenol conversion,the diphenol selectivity and reaches 63.01%and 49.8%,respectively.
By comparing,the catalyst activity of tetra-substituted sulfonated iron phthalocyanine was higher than tetra-substituted sulfonated cobalt phthalocyanine,so the catalysts,MCM-41 as carrier and tetra-substituted sulfonated iron phthalocyanine as active components,were prepared by impregnation method.Its structure was identified and characterized by FT-IR、XRD、nitrogen adsorption-desorption method and UV-Vis.When FePcS_4/MCM-41 as a catalyst in phenol hydroxylation,the catalyst activity was higher than FePcS_4,FePcS_4/ MCM-41 showed optimum catalytic properties with phenol conversion of 30.27%and selectivity to diphenols of 93.57%.
本文在实验的基础上,建立了苯酚羟基化反应液用高效液相色谱分析的方法。以4-磺酸基邻苯二甲腈和乙酸钴或氯化亚铁为原料,采用固相熔融法合成4,4′,4″,4′″-四磺酸基钴酞菁(CoPcS_4)和4,4′,4″,4′″-四磺酸基铁酞菁(FePcS_4),采用红外光谱、紫外-可见光光谱和质谱对其表征。
以4,4′,4″,4′″-四磺酸基钴酞菁为催化剂作用于苯酚羟基化反应,主要考察了溶剂、pH值、温度、双氧水用量、催化剂用量以及双氧水滴加速度对苯酚羟基化反应的影响,最后得到苯酚羟基化的优化反应条件为:溶剂水,pH值6,反应温度40℃,双氧水/苯酚摩尔比1.2,苯酚/催化剂质量比150,双氧水滴加速度3.90ml/h,在此条件下苯酚的转化率达到28.79%,苯二酚的选择性达到62.07%。以4,4′,4″,4′″-四磺酸基铁酞菁为催化剂苯酚羟基化的优化反应条件为:反应温度50℃,双氧水/苯酚摩尔比1.2,苯酚/催化剂质量比125,双氧水滴加速度2.60ml/h,在此条件下苯酚的转化率达到63.01%,苯二酚的选择性达到49.80%。
通过比较4,4′,4″,4′″-四磺酸基铁酞菁和4,4′,4″,4′″-四磺酸基钴酞菁做催化剂的转化率可知,4,4′,4″,4′″-四磺酸基铁酞菁的催化反应活性相对较好。以MCM-41为载体,FePcS_4为活性中心,采用浸渍法制备催化剂FePcS_4/MCM-41,并应用于苯酚羟基化反应进行研究,发现和FePcS_4相比,虽然苯酚转化率降到了30%,但是苯二酚的选择性最高能达到93.05%。
Catechol and hydroquinone,as the important raw material intermediates in fine chemical industries,are used in many fields.The catalytic hydrogenation of phenol by hydrogen peroxide is the optimal green way to produce pyrocatechtechol and hydroquinone.So the catalysts had become the emphases studied.Phthalocyanine is a kind of microcycle compound with well thermal stabilities and chemical stabilities.In recent years,many special characters and novel functions have been found,the field of applications will increase widely.However, Phthalocyanine compounds can't be resolved easily which limites their application.So the structure of phthalocyanine molecule has to be modified to improve their solubilities and obtain the required physical and chemical properties.The effective method is importing functional groupe to center,circumference and axes of phthalocyanine compounds.Mesoporous molecular sieves(MCM-41) have been obtained by means of the corporative interaction between inorganic presecursors and supramolecular surfactants.Their unique strctures such as large pore size(2-10nm),large area and narrow pore size distribution have attracted considerable attention in porous materials science since 1992.New complex materials with nano-structure which are synthesized by functional materials assembled in mesoporous zeolite have theory and reality value in catalysis fields.
A new method for the separation and determination of phenolic compounds in phenol hydroxylation by reversed-phase high performance chromatogrophy with gradient elution was established.Tetra-substituted sulfonated cobalt(iron) phthalocyanine was synthesized by using 4-sulfonicphthalonitrile as fragment.Theirs structures were identified and characterized byFT-IR,UV-VIS and MS.The influence of various reaction parameters solvent,pH, reaction temperature,the molar ratio H_2O_2/phenol,the mass ratio of phenol/catalyst,and the velocity of H_2O_2,were studied and the optimized reaction condition was acquired.When tetra-substituted sulfonated cobalt phthalocyanine as catalyst,under optimal reaction condition(n_(phenol)=0.05mol,solvent H_2O,pH=6,H_2O_2/phenol molar ratio=1.2,phenol/catalyst quality ratio=150,the velocity of H_2O_2 3.9ml/h),the phenol conversion,the diphenol selectivity and reaches 28.79%and 62.07%,respectively.When tetra-substituted sulfonated iron phthalocyanine as catalyst,under optimal reaction condition(n_(phenol)=0.05mol,H_2O_2/ phenol molar ratio=1.2,phenol/catalyst quality ratio=125,the velocity of H_2O_2 2.6ml/h),the phenol conversion,the diphenol selectivity and reaches 63.01%and 49.8%,respectively.
By comparing,the catalyst activity of tetra-substituted sulfonated iron phthalocyanine was higher than tetra-substituted sulfonated cobalt phthalocyanine,so the catalysts,MCM-41 as carrier and tetra-substituted sulfonated iron phthalocyanine as active components,were prepared by impregnation method.Its structure was identified and characterized by FT-IR、XRD、nitrogen adsorption-desorption method and UV-Vis.When FePcS_4/MCM-41 as a catalyst in phenol hydroxylation,the catalyst activity was higher than FePcS_4,FePcS_4/ MCM-41 showed optimum catalytic properties with phenol conversion of 30.27%and selectivity to diphenols of 93.57%.
引文
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