M-ZSM-5（M=V，Cr，Mn）分子筛的制备及其在环已烷氧化反应中的催化性能研究
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摘要
本论文采用直接水热合成法制备了不同过渡金属元素(V, Cr, Mn)改性的ZSM-5分子筛催化剂。利用XRD, XRF, SEM, FT-IR, UV-vis和N2吸附-脱附等分析手段对催化剂结构进行表征,结果表明过渡金属能进入分子筛骨架,且合成的M-ZSM-5(M=V, Cr, Mn)分子筛仍保持典型的MFI结构,改性后的分子筛的比表面积、孔容相对全硅分子筛有所增加。在以M-ZSM-5为催化剂,分子氧为氧化剂的无溶剂体系中考察催化剂在环己烷氧化反应中的催化性能,并探索出最佳反应条件和筛选出该反应体系的最佳催化剂。
改性后的催化剂由于过渡金属进入分子筛骨架产生了新的氧化还原活性中心,使催化剂的活性和选择性相对纯硅分子筛有很大的提高。液相无溶剂体系分子氧氧化环己烷的最佳反应条件为：氧气压力1MPa,反应温度120℃下反应3h。不同金属改性的催化剂由于金属的价态、半径等因素的不同导致催化性能不同：V-ZSM-5分子筛用量为0.15g,V的掺杂量为3%时催化活性最高,此时环己烷的转化率可达14.87%,环己醇和环己酮的选择性为92.64%；Cr-ZSM-5分子筛用量为0.12g,Cr的掺杂量为2%时催化活性最高,此时环己烷的转化率为11.43%,环己醇和环己酮的选择性为88.21%；Mn-ZSM-5用量为0.15g,Mn的掺杂量为8%时催化活性最高,此时环己烷的转化率为10.68%,环己醇和环己酮的选择性为90.17%。
In this dissertation, the ZSM-5 molecular sieves catalysts modified by transition metal were prepared by the direct hydrothermal (DHT) method. The structure properties of samples were characterized by XRD, XRF, SEM, FT-IR, UV-vis spectroscopy and N2 adsorption-desorption, which showed that the transitional metal atoms could be incorporated into the framework of the molecular sieves and all the samples held the typical structure of MFI. The ZSM-5 molecular sieves possess a larger surface area and pore volume after modification. The catalytic performance of the M-MFI (M=V, Cr, Mn) samples were investigated in the catalytic oxidation of cyclohexane with molecular oxygen as oxidant agent in a solvent-free system. The reaction conditions were optimized and the best catalyst for the reaction was selected.
The catalyst activity and selectivity of M-MFI is greatly improved after modification due to the creation of new redox active center. The optimum reaction conditions in the liquid solvent-free oxidation of cyclohexane with molecular oxygen as oxidizer was:oxygen pressure at 1.0 MPa, reaction temperature at 120℃and reaction time for 3 hours. Catalysts modified with different metal leaded to different catalytic properties. The conversion of cyclohexane and selectivity of KA oil using 0.15g 3wt%V-ZSM-5 as catalyst was 14.87% and 92.64%, respectively. The conversion of cyclohexane and selectivity of KA oil using 0.12g 2wt%Cr-ZSM-5 as catalyst was 11.43% and 88.21%, respectively. The conversion of cyclohexane and selectivity of KA oil using 0.15g 8wt%Mn-ZSM-5 as catalyst was 10.68% and 90.17%, respectively.
改性后的催化剂由于过渡金属进入分子筛骨架产生了新的氧化还原活性中心,使催化剂的活性和选择性相对纯硅分子筛有很大的提高。液相无溶剂体系分子氧氧化环己烷的最佳反应条件为：氧气压力1MPa,反应温度120℃下反应3h。不同金属改性的催化剂由于金属的价态、半径等因素的不同导致催化性能不同：V-ZSM-5分子筛用量为0.15g,V的掺杂量为3%时催化活性最高,此时环己烷的转化率可达14.87%,环己醇和环己酮的选择性为92.64%；Cr-ZSM-5分子筛用量为0.12g,Cr的掺杂量为2%时催化活性最高,此时环己烷的转化率为11.43%,环己醇和环己酮的选择性为88.21%；Mn-ZSM-5用量为0.15g,Mn的掺杂量为8%时催化活性最高,此时环己烷的转化率为10.68%,环己醇和环己酮的选择性为90.17%。
In this dissertation, the ZSM-5 molecular sieves catalysts modified by transition metal were prepared by the direct hydrothermal (DHT) method. The structure properties of samples were characterized by XRD, XRF, SEM, FT-IR, UV-vis spectroscopy and N2 adsorption-desorption, which showed that the transitional metal atoms could be incorporated into the framework of the molecular sieves and all the samples held the typical structure of MFI. The ZSM-5 molecular sieves possess a larger surface area and pore volume after modification. The catalytic performance of the M-MFI (M=V, Cr, Mn) samples were investigated in the catalytic oxidation of cyclohexane with molecular oxygen as oxidant agent in a solvent-free system. The reaction conditions were optimized and the best catalyst for the reaction was selected.
The catalyst activity and selectivity of M-MFI is greatly improved after modification due to the creation of new redox active center. The optimum reaction conditions in the liquid solvent-free oxidation of cyclohexane with molecular oxygen as oxidizer was:oxygen pressure at 1.0 MPa, reaction temperature at 120℃and reaction time for 3 hours. Catalysts modified with different metal leaded to different catalytic properties. The conversion of cyclohexane and selectivity of KA oil using 0.15g 3wt%V-ZSM-5 as catalyst was 14.87% and 92.64%, respectively. The conversion of cyclohexane and selectivity of KA oil using 0.12g 2wt%Cr-ZSM-5 as catalyst was 11.43% and 88.21%, respectively. The conversion of cyclohexane and selectivity of KA oil using 0.15g 8wt%Mn-ZSM-5 as catalyst was 10.68% and 90.17%, respectively.
引文
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