新型复合分子筛MOR/MCM-41的合成、表征和催化性能研究
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摘要
本文采用“降解法”制备了具有高水热稳定性的丝光沸石MOR/MCM-41介微孔复合分子筛。首先用草酸(H_2C_2O_4)对MOR进行脱铝处理,考察了不同草酸处理时间对MOR的脱铝效果,草酸脱铝可以有效去除沸石孔道中的杂质和无定型非骨架铝,而保持其骨架结构基本不被破坏。其次脱铝后的丝光沸石在偏硅酸纳(Na_2SiO_3)水溶液中进行脱硅降解得到包含沸石结构单元的混合物。我们用正交实验法确定了MOR降解条件:碱度为20.4wt%,温度为60℃,降解时间为120 min。
将丝光沸石降解所得的混合物和偏硅酸纳水解得到的低聚硅物种共同作为硅铝源,以十六烷基三甲基溴化铵(CTAB)为模板剂,进行自组装,得到具有微孔和介孔结构的复合分子筛(MMC)。XRD和TEM表明MOR已经降解完全,MMC具有规整的MCM-41类型介孔结构。IR和N_2等温吸附表明MMC孔壁具有微孔丝光沸石的结构性质以及介微孔双重的孔道分布:吡啶吸附红外谱图表明MMC同时具有B酸和L酸,而与吡啶形成氢键的表面硅羟基物种数量降低。
与采用传统方法合成的Al-MCM-41相比,MMC水热稳定性有明显提高,可能与MMC孔壁内沸石结构单元的引入、孔壁的明显增厚以及表面硅羟基的明显减少等因素有关。将材料应用在苯与长链烯烃烷基化反应中,考察了复合材料的催化反应性能。同丝光沸石和Al-MCM-41以及Si-MCM-41相比,材料表现出良好的催化活性和产物选择性,有可能替代HF成为一种环境友好的新型催化剂。
Hydrothermal stable MOR/MCM-41 composite sieve was prepared by a desilication method:MOR was firstly dealuminized in an oxalic acid,and the Si/AI molar ratio of MOR is effected by the time of dealuminizaion.Oxalic acid could remove the impurities and amorphous aluminum but keep the basic structure of MOR.And then pre-dissolved in sodium metasilicate to yield a mixture containing the MOR zeolitic fragments.We studied the desilication condition of MOR with orthogonal experiment,and the optimal condition:the alkalinity of sodium metasilicate is 20.4 wt%,the temperature is 60℃,the time is 120 min.
The mixture and the oligomeric silicon speicies derived from the hydrolysis of sodium metasilicate were used as silicon and aluminium sources to synthesize the micro-mesoporous composite molecular sieve(MMC) with hexadecyltrimethylammonium bromide(CTAB) as the template.
The XRD patterns and TEM images showed the MOR has been completely dissolved, and MMC possessed MCM-41-like structure.N_2 adsorption/desorption and IR spectra demonstrated that fragments with zeolitic structure were present in the walls of MMC,and MMC exhibited bimodal micro-mesopore distributions.The pyridine adsorption IR indicated both of Bronsted and Lewis acid sites existed on the surface of MMC,whereas the surface silanol groups were significantly decreased.
Compared with A1-MCM-41,hydrothermal stability of MMC was significantly improved,which could be the results of the introduction of the MOR zeolitic fragments to the walls of MMC,the increased wall thickness,and the decrease of surface silanol groups.The catalytic properties of the composite were studied by alkylation of benzene and 1-dodecene, and showed well activity and selectivity,which would substitute HF as a novel friendly-environment catalyst.
将丝光沸石降解所得的混合物和偏硅酸纳水解得到的低聚硅物种共同作为硅铝源,以十六烷基三甲基溴化铵(CTAB)为模板剂,进行自组装,得到具有微孔和介孔结构的复合分子筛(MMC)。XRD和TEM表明MOR已经降解完全,MMC具有规整的MCM-41类型介孔结构。IR和N_2等温吸附表明MMC孔壁具有微孔丝光沸石的结构性质以及介微孔双重的孔道分布:吡啶吸附红外谱图表明MMC同时具有B酸和L酸,而与吡啶形成氢键的表面硅羟基物种数量降低。
与采用传统方法合成的Al-MCM-41相比,MMC水热稳定性有明显提高,可能与MMC孔壁内沸石结构单元的引入、孔壁的明显增厚以及表面硅羟基的明显减少等因素有关。将材料应用在苯与长链烯烃烷基化反应中,考察了复合材料的催化反应性能。同丝光沸石和Al-MCM-41以及Si-MCM-41相比,材料表现出良好的催化活性和产物选择性,有可能替代HF成为一种环境友好的新型催化剂。
Hydrothermal stable MOR/MCM-41 composite sieve was prepared by a desilication method:MOR was firstly dealuminized in an oxalic acid,and the Si/AI molar ratio of MOR is effected by the time of dealuminizaion.Oxalic acid could remove the impurities and amorphous aluminum but keep the basic structure of MOR.And then pre-dissolved in sodium metasilicate to yield a mixture containing the MOR zeolitic fragments.We studied the desilication condition of MOR with orthogonal experiment,and the optimal condition:the alkalinity of sodium metasilicate is 20.4 wt%,the temperature is 60℃,the time is 120 min.
The mixture and the oligomeric silicon speicies derived from the hydrolysis of sodium metasilicate were used as silicon and aluminium sources to synthesize the micro-mesoporous composite molecular sieve(MMC) with hexadecyltrimethylammonium bromide(CTAB) as the template.
The XRD patterns and TEM images showed the MOR has been completely dissolved, and MMC possessed MCM-41-like structure.N_2 adsorption/desorption and IR spectra demonstrated that fragments with zeolitic structure were present in the walls of MMC,and MMC exhibited bimodal micro-mesopore distributions.The pyridine adsorption IR indicated both of Bronsted and Lewis acid sites existed on the surface of MMC,whereas the surface silanol groups were significantly decreased.
Compared with A1-MCM-41,hydrothermal stability of MMC was significantly improved,which could be the results of the introduction of the MOR zeolitic fragments to the walls of MMC,the increased wall thickness,and the decrease of surface silanol groups.The catalytic properties of the composite were studied by alkylation of benzene and 1-dodecene, and showed well activity and selectivity,which would substitute HF as a novel friendly-environment catalyst.
引文
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