微孔—中孔复合分子筛TS-1的研究
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摘要
钛硅分子筛TS-1催化烯烃环氧化反应具有高效性和良好的稳定性。TS-1催化丙烯与H2O2环氧化反应的条件温和、反应速度快、选择性高、过程无污染。但是传统方法合成的TS-1孔径较小,只能催化小分子烯烃的环氧化反应,限制了TS-1的应用范围。本文研究了具有微孔-中孔复合孔结构的分子筛TS-1的合成。
以钛酸丁酯为有机钛源、正硅酸乙酯为硅源,以四丙基氢氧化铵(TPAOH)为模板剂,采用水热合成法合成微孔TS-1。在此基础上以TPAOH和β-环糊精为双模板剂,以纳米碳材料为特殊模板剂合成了微孔-中孔复合孔结构的TS-1;采用NaOH溶液对微孔TS-1进行后处理以形成中孔结构。利用BET、FT-IR、XRD和UV-Vis等技术对合成的分子筛样品进行了表征和分析。实验结果表明,以TPAOH和β-环糊精为双模板剂制备得到的TS-1分子筛具有大量微孔和少量中孔,其中大部分中孔孔径为3.9nm;以纳米碳管和纳米碳棒为特殊模板剂制备得到的TS-1具有更少量中孔结构,中孔的孔径为3.9nm和6.5nm;用不同浓度的NaOH溶液对微孔TS-1进行浸渍等一系列后处理,得到的TS-1分子筛含有较多的中孔结构,大部分孔径为3.9nm左右。但用高浓度的碱处理会造成分子筛中部分骨架钛的流失。
Titanium silicalite (TS-1) is an efficient and stable catalyst for the epoxidation of propene with hydrogen peroxide. The epoxidation of propene catalyzed by TS-1 possesses many merits, such as mild reaction conditions, fast reaction rate, high product selectivity and without pollutants. However, TS-1 prepared with the traditional method can only catalyze the epoxidation of alkenes of small molecules due to its microporous structure and therefore limits its application. In this work, attempt have been made to synthesize TS-1 with both microporous and mesoporous structure which can catalyze the epoxidation of alkenes of large molecules.
TS-1 was first synthesized by a hydrothermal method with tetrabutyl-titanate as organic Ti source, tetraethyl orthosilicate as Si source and tetrapropyl ammonium hydroxide (TPAOH) as template. Then, dual templates, TPAOH andβ-CD, and special template (carbon nano-materials) were used for the synthesis of TS-1 with both micropores and mesopores. The as-made TS-1 was also treated with NaOH solutions to generate mesopores. The samples were characterized by BET, FT-IR, XRD, UV-Vis diffuse reflectance, etc. The results showed that the TS-1 samples synthesized using TPAOH andβ-CD dual templates possessed mainly micropores and some mesopores with pore size of 3.9nm. However, the TS-1 samples synthesized using carbon nanotubes or nanorods as special templates had less mesopores with pore size of 3.9nm and 6.5nm. NaOH solution treatments generated more mesopores in the TS-1 sample with pore size of 3.9nm, but a portion of the titanium in the skeleton was removed as indicated by the appearance of anatase at 340nm in the UV-Vis diffuse reflectance spectra.
以钛酸丁酯为有机钛源、正硅酸乙酯为硅源,以四丙基氢氧化铵(TPAOH)为模板剂,采用水热合成法合成微孔TS-1。在此基础上以TPAOH和β-环糊精为双模板剂,以纳米碳材料为特殊模板剂合成了微孔-中孔复合孔结构的TS-1;采用NaOH溶液对微孔TS-1进行后处理以形成中孔结构。利用BET、FT-IR、XRD和UV-Vis等技术对合成的分子筛样品进行了表征和分析。实验结果表明,以TPAOH和β-环糊精为双模板剂制备得到的TS-1分子筛具有大量微孔和少量中孔,其中大部分中孔孔径为3.9nm;以纳米碳管和纳米碳棒为特殊模板剂制备得到的TS-1具有更少量中孔结构,中孔的孔径为3.9nm和6.5nm;用不同浓度的NaOH溶液对微孔TS-1进行浸渍等一系列后处理,得到的TS-1分子筛含有较多的中孔结构,大部分孔径为3.9nm左右。但用高浓度的碱处理会造成分子筛中部分骨架钛的流失。
Titanium silicalite (TS-1) is an efficient and stable catalyst for the epoxidation of propene with hydrogen peroxide. The epoxidation of propene catalyzed by TS-1 possesses many merits, such as mild reaction conditions, fast reaction rate, high product selectivity and without pollutants. However, TS-1 prepared with the traditional method can only catalyze the epoxidation of alkenes of small molecules due to its microporous structure and therefore limits its application. In this work, attempt have been made to synthesize TS-1 with both microporous and mesoporous structure which can catalyze the epoxidation of alkenes of large molecules.
TS-1 was first synthesized by a hydrothermal method with tetrabutyl-titanate as organic Ti source, tetraethyl orthosilicate as Si source and tetrapropyl ammonium hydroxide (TPAOH) as template. Then, dual templates, TPAOH andβ-CD, and special template (carbon nano-materials) were used for the synthesis of TS-1 with both micropores and mesopores. The as-made TS-1 was also treated with NaOH solutions to generate mesopores. The samples were characterized by BET, FT-IR, XRD, UV-Vis diffuse reflectance, etc. The results showed that the TS-1 samples synthesized using TPAOH andβ-CD dual templates possessed mainly micropores and some mesopores with pore size of 3.9nm. However, the TS-1 samples synthesized using carbon nanotubes or nanorods as special templates had less mesopores with pore size of 3.9nm and 6.5nm. NaOH solution treatments generated more mesopores in the TS-1 sample with pore size of 3.9nm, but a portion of the titanium in the skeleton was removed as indicated by the appearance of anatase at 340nm in the UV-Vis diffuse reflectance spectra.
引文
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