WO2019144253A1 - Preparation method for hollow single crystal beta molecular sieve - Google Patents

Preparation method for hollow single crystal beta molecular sieve Download PDF

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WO2019144253A1
WO2019144253A1 PCT/CN2018/000193 CN2018000193W WO2019144253A1 WO 2019144253 A1 WO2019144253 A1 WO 2019144253A1 CN 2018000193 W CN2018000193 W CN 2018000193W WO 2019144253 A1 WO2019144253 A1 WO 2019144253A1
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molecular sieve
single crystal
beta molecular
sio
hollow single
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徐龙伢
赵东璞
辛文杰
刘盛林
楚卫锋
朱向学
谢素娟
陈福存
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中国科学院大连化学物理研究所
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C01P2006/14—Pore volume

Definitions

  • the invention belongs to the technical field of catalytic chemistry; in particular, to a preparation method of a hollow single crystal Beta molecular sieve.
  • Beta molecular sieve is a medium pore zeolite with a unique cage-free three-dimensional 12-membered ring large pore system, good catalytic stability, thermal stability and hydrothermal stability.
  • the linear channels along the [100] and [010] orientations have a pore size of about 0.77 x 0.67 nm; the [001] direction is a curved channel through the straight channel, and the aperture is about 0.56 x 0.56 nm.
  • Beta molecular sieve has a wide range of industrial applications, mainly for the catalytic conversion process of hydrocarbons, such as: alkylation of benzene with olefins (production of ethylbenzene, cumene), transalkylation of heavy aromatics, hydrocarbon cracking, Hydroisomerization and the like.
  • Beta molecular sieve has many potential catalytic functions, due to its small pore size distribution, the reactant molecules are not easy to access the active site of the molecular sieve and affect its utilization. The larger product molecules are not easy to get rid of the active sites and cause side reactions. It is easy to cause problems such as carbon deposition, low catalytic efficiency, and rapid deactivation of the catalyst.
  • two approaches have been adopted. One is to shorten the pore length of the molecular sieve, that is, synthesize the nano molecular sieve. Nanomolecular sieves have a short diffusion path length and a large specific surface area, which greatly change their catalytic performance and thermal stability.
  • the second is to broaden the pore size of the molecular sieve, that is, to introduce a mesoporous or macroporous into the microporous molecular sieve to form a multistage pore molecular sieve.
  • Multistage pore molecular sieves improve the diffusion properties of macromolecular reactants and products, thereby increasing the reaction rate and selectivity of the target product.
  • a Pt-coated hollow Beta molecular sieve was prepared by a two-step method using a Pt-loaded carbon sphere as a hard template.
  • Fan et al. (Fan Feng, Ling Fengxiang, Wang Shaojun, et al. The 19th National Molecular Sieve Conference) used a solid Beta molecular sieve as a precursor to prepare a Beta molecular sieve with a hollow structure by secondary crystallization in an alkaline aluminum solution.
  • the object of the present invention is to develop a preparation method of a hollow single crystal Beta molecular sieve, which has the advantages of hollow structure, high crystallinity, specific surface area and large pore volume.
  • the present invention mainly solves the above technical problems by adopting a suitable raw material, a molar composition of the finely tuned raw material, and a one-step hydrothermal crystallization method.
  • a method for preparing a hollow single crystal Beta molecular sieve the specific steps are as follows:
  • the high-temperature crystallization is: dynamic crystallization for 10 to 240 hours at 100 to 180 ° C, and hydrothermal synthesis of a hollow single crystal Beta molecular sieve.
  • the dynamic crystallization treatment is carried out in a reactor of a rotary oven having a rotational speed of 10 to 100 rpm.
  • the selected silicon source is one or more of white carbon black, tetraethyl orthosilicate, water glass, silica sol, chromatography silica gel, and coarse pore silica gel, and preferably white carbon black is a silicon source.
  • the selected aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum powder, and pseudoboehmite, and preferably sodium aluminate is an aluminum source;
  • the selected alkali source is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably sodium hydroxide is an alkali source;
  • the selected templating agent is one or more of tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium fluoride, preferably tetraethylammonium hydroxide;
  • the alkalinity of the raw material mixture is adjusted by adding an inorganic base or a templating agent.
  • the selected organic additive lactam R is one of 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, preferably N-methyl- 2-Pyrrolidone is an organic additive.
  • the hollow single crystal Beta molecular sieve synthesized by the method of the invention can synthesize a submicron hollow single crystal Beta molecular sieve which is formed by orderly stacking 10-30 nm primary particles by adjusting the ratio of raw materials and crystallization conditions, and the sample has Hollow, high crystallinity, specific surface area and large pore volume.
  • the aluminum source is combined with a part of the inorganic base and the templating agent to form a solution B 1
  • the silicon source is combined with a part of the inorganic base, the templating agent and the organic additive to form a solution B 2
  • B 1 is added dropwise to the B 2 to form a solution B. Stir well to mix the ingredients evenly.
  • the aluminum source is combined with a part of the inorganic base and the templating agent to form a solution B 1
  • the silicon source is combined with a part of the inorganic base, the templating agent and the organic additive to form a solution B 2
  • the B 2 is added dropwise to the B 1 to form a solution C. Stir well to mix the ingredients evenly.
  • the A, B or C solution after being uniformly stirred is dynamically crystallized at 100 to 180 ° C for 10 to 240 hours, and the hollow single crystal Beta molecular sieve is hydrothermally synthesized.
  • the hollow single crystal Beta molecular sieve synthesized by the invention can be used for alkylation of benzene with olefin (production of ethylbenzene, cumene), transalkylation of heavy aromatic hydrocarbons, hydrocarbon cracking, hydroisomerization and the like.
  • the invention obtains a hollow single by a one-step method using inexpensive N-methyl-2-pyrrolidone or its homologues 2-pyrrolidone, N-ethyl-2-pyrrolidone and N-isopropyl-2-pyrrolidone as organic additives.
  • Crystal Beta molecular sieve is an economical, efficient and simple preparation method, and it is expected to be commercialized on a large scale.
  • the hollow single crystal Beta molecular sieve prepared by the invention has the advantages of hollowness, high crystallinity, large specific surface area and large pore volume, and is expected to have broad application prospects in the fields of nanoreactor, macromolecular catalysis, gas adsorption and separation.
  • Example 1 is an X-ray diffraction (XRD) pattern of a hollow single crystal Beta molecular sieve prepared in Example 1.
  • Example 2 is a field emission scanning electron microscope (FESEM) image of the hollow single crystal Beta molecular sieve prepared in Example 1.
  • FESEM field emission scanning electron microscope
  • FIG. 3 is a transmission electron microscope (TEM) and a selected area electron diffraction (SAED) picture of the hollow single crystal Beta molecular sieve prepared in Example 1, wherein FIG. 3a is a low power TEM photograph, FIG. 3b is a high power TEM photograph, and FIG. 3c is a corresponding FIG. Selected area electron diffraction (SAED) photos.
  • TEM transmission electron microscope
  • SAED selected area electron diffraction
  • Example 4 is a N 2 adsorption-desorption curve of the hollow single crystal Beta molecular sieve prepared in Example 1.
  • Figure 5 is a transmission electron microscope (TEM) image of a solid Beta molecular sieve prepared in Comparative Example 1.
  • Figure 1 is a powder X-ray diffraction pattern of the obtained molecular sieve raw powder. As can be seen from the figure, it is a pure phase Beta molecular sieve and has good crystallinity.
  • Fig. 2 is a field emission scanning electron microscope (FESEM) image. The morphology of the sample is a uniform four-square shape with a particle size of about 300-500 nm, which is formed by sequential stacking of primary particles with a size of about 10-30 nm.
  • Figure 3 is a transmission electron micrograph. The low-power transmission electron microscope (Fig. 3a) shows that the obtained Beta molecular sieve is a four-square crystal with a hollow structure; the high-power transmission electron micrograph (Fig.
  • FIG. 3b shows a uniformly oriented lattice fringe, indicating that the sample is The single crystal structure; in addition, the corresponding selected area electron diffraction (SAED) point of Fig. 3b exhibits a highly discrete state, further indicating that the sample as a whole is a hollow single crystal molecular sieve.
  • Figure 4 is a N 2 adsorption and desorption curve with a BET surface area of 737 m 2 /g (micropore surface area 590 m 2 /g, external surface area 147 m 2 /g), and a total pore volume of 0.52 cm 3 /g (microporous pore volume). It was 0.23 cm 3 /g, and the mesoporous pore volume was 0.29 cm 3 /g).
  • the XRD spectrum of the obtained Beta product is similar to that of Figure 1.
  • the transmission electron microscopy (TEM) image shown in Figure 5 shows that it is a solid Beta molecular sieve with a particle size of about 322 nm and a N 2 adsorption-desorption test with a BET surface area of 527 m 2 /g.
  • the total pore volume is 0.35 cm 3 /g.
  • the XRD spectrum of the obtained Beta product is similar to that of Figure 1.
  • the transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 342 nm.
  • the N 2 adsorption and desorption test has a BET surface area of 711 m 2 /g, and the total pore volume. It is 0.53 cm 3 /g.
  • the XRD spectrum of the obtained Beta product is similar to that of Figure 1.
  • the transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 312 nm.
  • the N 2 adsorption and desorption test has a BET surface area of 682 m 2 /g, and the total pore volume. It is 0.75 cm 3 /g.
  • the XRD spectrum of the obtained Beta product is similar to that of Figure 1.
  • the transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 352 nm.
  • the N 2 adsorption and desorption test has a BET surface area of 725 m 2 /g, and the total pore volume. It is 0.78 cm 3 /g.
  • the XRD spectrum of the obtained Beta product is similar to that of Figure 1.
  • the transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 364 nm.
  • the N 2 adsorption and desorption test has a BET surface area of 730 m 2 /g, and the total pore volume. It is 0.573 cm 3 /g.
  • the XRD spectrum of the obtained Beta product is similar to that of Figure 1.
  • the transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 373 nm.
  • the N 2 adsorption and desorption test has a BET surface area of 736 m 2 /g, and the total pore volume. It is 0.59 cm 3 /g.
  • the molecular sieve raw powder was obtained by drying overnight at 80 °C.
  • the XRD spectrum of the obtained Beta product is similar to that of Figure 1.
  • the transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 305 nm.
  • the N 2 adsorption and desorption test has a BET surface area of 782 m 2 /g, and the total pore volume. It is 0.85 cm 3 /g.

Abstract

Provided is a preparation method for a hollow single crystal Beta molecular sieve. According to the method, the molecular sieve can be directly prepared by means of one-step hydrothermal crystallization of a gel formed by fully mixing a silicon source, an aluminum source, an inorganic base, a microporous template agent and an organic additive of a lactam R, and the synthesized product is formed by orderly stacking and connecting primary nanoparticles having a primary particle size of 10-30 nm. In the method, inexpensive N-methyl-2-pyrrolidone or homologous 2-pyrrolidone, N-ethyl-2-pyrrolidone or N-isopropyl-2-pyrrolidone thereof is used as an organic additive to synthesize a hollow single crystal Beta molecular sieve by means of a one-step method, thus replacing the traditional two-step acid-base treatment for obtaining a hollow structure, and same is an economical, efficient and simple method.

Description

一种中空单晶Beta分子筛的制备方法Preparation method of hollow single crystal Beta molecular sieve 技术领域Technical field
本发明属于催化化学的技术领域；具体涉及一种中空单晶Beta分子筛的制备方法。The invention belongs to the technical field of catalytic chemistry; in particular, to a preparation method of a hollow single crystal Beta molecular sieve.
背景技术Background technique
Beta分子筛是一种中孔沸石，具有独特的无笼三维十二元环大孔道系统、较好的催化稳定性、热稳定性和水热稳定性。沿[100]和[010]取向直线形通道，孔径约为0.77×0.67nm；沿[001]方向为贯穿直通道的弯曲通道，孔径约为0.56×0.56nm。Beta分子筛具有广泛的工业应用价值，主要用于烃类的催化转化过程，例如：苯与烯烃的烷基化(乙苯、异丙苯的生产)，重芳烃的烷基转移、烃类裂解、加氢异构化等。Beta molecular sieve is a medium pore zeolite with a unique cage-free three-dimensional 12-membered ring large pore system, good catalytic stability, thermal stability and hydrothermal stability. The linear channels along the [100] and [010] orientations have a pore size of about 0.77 x 0.67 nm; the [001] direction is a curved channel through the straight channel, and the aperture is about 0.56 x 0.56 nm. Beta molecular sieve has a wide range of industrial applications, mainly for the catalytic conversion process of hydrocarbons, such as: alkylation of benzene with olefins (production of ethylbenzene, cumene), transalkylation of heavy aromatics, hydrocarbon cracking, Hydroisomerization and the like.
虽然Beta分子筛具有很多潜在的催化功能，但是由于其较小的孔径分布，使反应物分子不易接近分子筛的活性位而影响其利用率，较大的产物分子不易脱离活性位而导致副反应发生，容易导致积碳、催化效率低、催化剂快速失活等问题。为了克服微孔分子筛单一微孔结构导致的扩散限制，目前人们采用了两条途径。一是缩短分子筛的孔道长度，即合成纳米分子筛。纳米分子筛具有较短的扩散路径长度和较大的比表面积，使得其催化性能和热稳定性等发生很大变化。二是拓宽分子筛的孔道尺寸，即向微孔分子筛中引入介孔或大孔形成多级孔分子筛。多级孔分子筛可改善大分子反应物和产物的扩散性能，从而提高反应速率和目标产物的选择性。Although Beta molecular sieve has many potential catalytic functions, due to its small pore size distribution, the reactant molecules are not easy to access the active site of the molecular sieve and affect its utilization. The larger product molecules are not easy to get rid of the active sites and cause side reactions. It is easy to cause problems such as carbon deposition, low catalytic efficiency, and rapid deactivation of the catalyst. In order to overcome the diffusion limitation caused by the single micropore structure of microporous molecular sieves, two approaches have been adopted. One is to shorten the pore length of the molecular sieve, that is, synthesize the nano molecular sieve. Nanomolecular sieves have a short diffusion path length and a large specific surface area, which greatly change their catalytic performance and thermal stability. The second is to broaden the pore size of the molecular sieve, that is, to introduce a mesoporous or macroporous into the microporous molecular sieve to form a multistage pore molecular sieve. Multistage pore molecular sieves improve the diffusion properties of macromolecular reactants and products, thereby increasing the reaction rate and selectivity of the target product.
Zhu等人(Zhu Jie，Zhu Yihan，Zhu Liangkui，et al.Journal of the American Chemical Society，2014，136：2503-2510.)在介孔尺度高聚物季铵盐阳离子(聚二烯二甲基丙基氯化铵)的辅助下，借助空间位阻和结构导向效应成功制备出了 介孔Beta分子筛；Zheng等人(Zheng Z，Sun C，Dai R，et al.Catalysis Science&Technology，2016，6：6472-6475)利用担载Pt的炭球为硬模板通过两步法制备出了包覆Pt的中空Beta分子筛。范等人(范峰，凌凤香，王少军，等。第十九届全国分子筛学术大会)以实心Beta分子筛为前驱体通过在碱性铝溶液中二次晶化制备出了具有空心结构的Beta分子筛。Zhu et al. (Zhu Jie, Zhu Yihan, Zhu Liangkui, et al. Journal of the American Chemical Society, 2014, 136: 2503-2510.) in a mesoporous-scale polymer quaternary ammonium salt cation (polydiene dimethyl Mesoporous Beta molecular sieves were successfully prepared with the aid of steric hindrance and structure-directed effects with the aid of propyl ammonium chloride; Zheng et al. (Zheng Z, Sun C, Dai R, et al. Catalysis Science & Technology, 2016, 6: 6472-6475) A Pt-coated hollow Beta molecular sieve was prepared by a two-step method using a Pt-loaded carbon sphere as a hard template. Fan et al. (Fan Feng, Ling Fengxiang, Wang Shaojun, et al. The 19th National Molecular Sieve Conference) used a solid Beta molecular sieve as a precursor to prepare a Beta molecular sieve with a hollow structure by secondary crystallization in an alkaline aluminum solution.
综上所述，目前已报道的多级孔或中空Beta分子筛的制备过程较为繁琐，条件苛刻，在一定程度上限制了其工业化生产。因此，亟待开发出一种环境友好，操作简便的方法用于规模化生产中空Beta分子筛。In summary, the preparation process of multi-stage pores or hollow Beta molecular sieves which have been reported so far is cumbersome and demanding, which limits the industrial production to a certain extent. Therefore, an environmentally friendly and easy-to-use method for the production of hollow Beta molecular sieves has been urgently needed.
发明内容Summary of the invention
本发明的目的在于开发一种中空单晶Beta分子筛的制备方法，该方法合成的Beta分子筛具有中空结构、结晶度高、比表面积和孔体积大等优点。本发明主要通过采用合适的原料、精细调变原料的摩尔组成、采用一步水热晶化法来解决上述技术问题。The object of the present invention is to develop a preparation method of a hollow single crystal Beta molecular sieve, which has the advantages of hollow structure, high crystallinity, specific surface area and large pore volume. The present invention mainly solves the above technical problems by adopting a suitable raw material, a molar composition of the finely tuned raw material, and a one-step hydrothermal crystallization method.
一种中空单晶Beta分子筛的制备方法，具体步骤如下：A method for preparing a hollow single crystal Beta molecular sieve, the specific steps are as follows:
将硅源、铝源、无机碱、微孔模板剂(TEA +水溶液)、去离子水和有机添加剂内酰胺(R)均匀混合，其原始摩尔组成为：SiO 2/Al 2O 3＝20～100，Na 2O/SiO 2＝0.0～0.4，TEA +/SiO 2＝0.10～1.0，H 2O/SiO 2＝5～30，R/SiO 2＝0～6；原料均匀混合后直接进行高温晶化；产物为10-30nm的一次粒子有序堆垛连结而成的中空单晶Beta分子筛。 The silicon source, the aluminum source, the inorganic base, the microporous templating agent (TEA + aqueous solution), the deionized water and the organic additive lactam (R) are uniformly mixed, and the original molar composition thereof is: SiO 2 /Al 2 O 3 =20～ 100, Na 2 O / SiO 2 = 0.0 ~ 0.4, TEA + / SiO 2 = 0.10 ~ 1.0, H 2 O / SiO 2 = 5 ~ 30, R / SiO 2 = 0 ~ 6; the raw materials are uniformly mixed and directly subjected to high temperature Crystallization; the product is a hollow single crystal Beta molecular sieve in which 10-30 nm primary particles are sequentially stacked.
所述高温晶化为：100～180℃进行动态晶化10～240h，水热合成中空单晶Beta分子筛。The high-temperature crystallization is: dynamic crystallization for 10 to 240 hours at 100 to 180 ° C, and hydrothermal synthesis of a hollow single crystal Beta molecular sieve.
所述动态晶化处理是在旋转烘箱的反应器中进行，所述旋转烘箱的转速为10-100转/分钟。The dynamic crystallization treatment is carried out in a reactor of a rotary oven having a rotational speed of 10 to 100 rpm.
所选硅源为白炭黑、正硅酸乙酯、水玻璃、硅溶胶、层析硅胶、粗孔硅胶中的一种或几种，优选白炭黑为硅源。The selected silicon source is one or more of white carbon black, tetraethyl orthosilicate, water glass, silica sol, chromatography silica gel, and coarse pore silica gel, and preferably white carbon black is a silicon source.
所选铝源为铝酸钠、硫酸铝、氯化铝、硝酸铝、乙酸铝、铝粉、拟薄水铝石中的一种或几种，优选铝酸钠为铝源；The selected aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum powder, and pseudoboehmite, and preferably sodium aluminate is an aluminum source;
所选碱源为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或几种，优选氢氧化钠为碱源；The selected alkali source is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably sodium hydroxide is an alkali source;
所选模板剂为四乙基氢氧化铵、四乙基溴化铵、四乙基氯化铵、四乙基氟化铵中的一种或几种，优选四乙基氢氧化铵；The selected templating agent is one or more of tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium fluoride, preferably tetraethylammonium hydroxide;
通过加入无机碱或模板剂来调节原料混合物的碱度。The alkalinity of the raw material mixture is adjusted by adding an inorganic base or a templating agent.
所选有机添加剂内酰胺R为2-吡咯烷酮、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-异丙基-2-吡咯烷酮中的一种，优选N-甲基-2-吡咯烷酮为有机添加剂。The selected organic additive lactam R is one of 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, preferably N-methyl- 2-Pyrrolidone is an organic additive.
本发明方法合成的中空单晶Beta分子筛，通过调节原料配比和晶化条件，可以合成由10-30nm的一次粒子有序堆垛连结而成的亚微米级中空单晶Beta分子筛，该样品具有中空、结晶度高、比表面积和孔体积大等优点。The hollow single crystal Beta molecular sieve synthesized by the method of the invention can synthesize a submicron hollow single crystal Beta molecular sieve which is formed by orderly stacking 10-30 nm primary particles by adjusting the ratio of raw materials and crystallization conditions, and the sample has Hollow, high crystallinity, specific surface area and large pore volume.
本发明的制备方法优选以下技术方案：The preparation method of the present invention preferably has the following technical solutions:
(一)原料的混合采用以下三种方法之一：(1) The mixing of raw materials uses one of the following three methods:
1)将硅源、铝源、无机碱、模板剂、去离子水、有机添加剂在搅拌下，以一定顺序缓慢加入反应釜，形成原料混合物A，充分搅拌，使其混合均匀。1) The silicon source, the aluminum source, the inorganic base, the templating agent, the deionized water, and the organic additive are slowly added to the reaction vessel in a certain order under stirring to form a raw material mixture A, which is thoroughly stirred and uniformly mixed.
2)将铝源与部分无机碱、模板剂配成溶液B 1，将硅源与部分无机碱、模板剂、有机添加剂配成溶液B 2，将B 1逐滴加入B 2中，形成溶液B；充分搅拌，使原料混合均匀。 2) The aluminum source is combined with a part of the inorganic base and the templating agent to form a solution B 1 , the silicon source is combined with a part of the inorganic base, the templating agent and the organic additive to form a solution B 2 , and B 1 is added dropwise to the B 2 to form a solution B. Stir well to mix the ingredients evenly.
3)将铝源与部分无机碱、模板剂配成溶液B 1，将硅源与部分无机碱、模板 剂、有机添加剂配成溶液B 2，将B 2逐滴加入B 1中，形成溶液C；充分搅拌，使原料混合均匀。 3) The aluminum source is combined with a part of the inorganic base and the templating agent to form a solution B 1 , the silicon source is combined with a part of the inorganic base, the templating agent and the organic additive to form a solution B 2 , and the B 2 is added dropwise to the B 1 to form a solution C. Stir well to mix the ingredients evenly.
上述原料混合物的摩尔组成为：SiO 2/Al 2O 3＝20～100，Na 2O/SiO 2＝0.0～0.1，TEA +/SiO 2＝0.10～1.0，H 2O/SiO 2＝5～20，R/SiO 2＝0～6。 The molar composition of the above raw material mixture is: SiO 2 /Al 2 O 3 = 20 to 100, Na 2 O/SiO 2 = 0.0 to 0.1, TEA + /SiO 2 = 0.10 to 1.0, and H 2 O/SiO 2 = 5 to 20, R / SiO 2 = 0 ~ 6.
(二)动态晶化(2) Dynamic crystallization
1)将搅拌均匀后的A、B或C溶液在100～180℃动态晶化10～240h，水热合成中空单晶Beta分子筛。1) The A, B or C solution after being uniformly stirred is dynamically crystallized at 100 to 180 ° C for 10 to 240 hours, and the hollow single crystal Beta molecular sieve is hydrothermally synthesized.
2)用自来水将反应釜骤冷，将产物固液分离，固体产物经过滤、洗涤、干燥得到中空单晶Beta分子筛。2) The reactor is quenched with tap water, the product is solid-liquid separated, and the solid product is filtered, washed, and dried to obtain a hollow single crystal Beta molecular sieve.
通过离子交换技术，可以用其它的阳离子取代本发明合成的中空单晶Beta分子筛中的钠离子，从而得到氢型、铵型、镓型、锌型、镁型Beta分子筛，进而应用于不同的催化反应过程。本发明合成的中空单晶Beta分子筛可以用于苯与烯烃的烷基化(乙苯、异丙苯的生产)，重芳烃的烷基转移、烃类裂解、加氢异构化等反应。By ion exchange technology, sodium ions in the hollow single crystal Beta molecular sieve synthesized by the present invention can be replaced by other cations, thereby obtaining hydrogen type, ammonium type, gallium type, zinc type, magnesium type Beta molecular sieve, and then applied to different catalysis. reaction process. The hollow single crystal Beta molecular sieve synthesized by the invention can be used for alkylation of benzene with olefin (production of ethylbenzene, cumene), transalkylation of heavy aromatic hydrocarbons, hydrocarbon cracking, hydroisomerization and the like.
本发明以廉价的N-甲基-2-吡咯烷酮或其同系物2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-异丙基-2-吡咯烷酮为有机添加剂，通过一步法来获得中空单晶Beta分子筛，是一种经济、高效、简便的制备方法，有望规模化商业化生产。此外，本发明制备的中空单晶Beta分子筛兼具中空、结晶度高、比表面积和孔体积大等优点，有望在纳米反应器、大分子催化、气体吸附和分离等领域有广泛的应用前景。The invention obtains a hollow single by a one-step method using inexpensive N-methyl-2-pyrrolidone or its homologues 2-pyrrolidone, N-ethyl-2-pyrrolidone and N-isopropyl-2-pyrrolidone as organic additives. Crystal Beta molecular sieve is an economical, efficient and simple preparation method, and it is expected to be commercialized on a large scale. In addition, the hollow single crystal Beta molecular sieve prepared by the invention has the advantages of hollowness, high crystallinity, large specific surface area and large pore volume, and is expected to have broad application prospects in the fields of nanoreactor, macromolecular catalysis, gas adsorption and separation.
附图说明DRAWINGS
图1为实施例1制备的中空单晶Beta分子筛的X射线衍射(XRD)图谱。1 is an X-ray diffraction (XRD) pattern of a hollow single crystal Beta molecular sieve prepared in Example 1.
图2为实施例1制备的中空单晶Beta分子筛的场发射扫描电镜(FESEM)图片。2 is a field emission scanning electron microscope (FESEM) image of the hollow single crystal Beta molecular sieve prepared in Example 1.
图3为实施例1制备的中空单晶Beta分子筛的透射电镜(TEM)和选区电子衍射(SAED)图片；其中图3a为低倍TEM照片，图3b为高倍TEM照片，图3c为图3b对应的选区电子衍射(SAED)照片。3 is a transmission electron microscope (TEM) and a selected area electron diffraction (SAED) picture of the hollow single crystal Beta molecular sieve prepared in Example 1, wherein FIG. 3a is a low power TEM photograph, FIG. 3b is a high power TEM photograph, and FIG. 3c is a corresponding FIG. Selected area electron diffraction (SAED) photos.
图4为实施例1制备的中空单晶Beta分子筛的N 2吸脱附曲线。 4 is a N 2 adsorption-desorption curve of the hollow single crystal Beta molecular sieve prepared in Example 1.
图5为对比例1制备的实心Beta分子筛的透射电镜(TEM)图片。Figure 5 is a transmission electron microscope (TEM) image of a solid Beta molecular sieve prepared in Comparative Example 1.
具体实施方式Detailed ways
下面用实施例对本发明予以进一步的说明，但实施例并不限制本发明的内容。The invention is further illustrated by the following examples, but the examples are not intended to limit the invention.
实施例1Example 1
在搅拌条件下，将5.3g白炭黑(95.0wt.％SiO 2，5.0wt.％H 2O)、0.4g铝酸钠(49.0wt.％Al 2O 3，38.0wt.％Na 2O，13.0wt.％H 2O)、0.13g氢氧化钠(96.0wt.％NaOH)、22.3g四乙基氢氧化铵水溶液(TEAOH，纯度≥35wt.％)、25g N-甲基-2吡咯烷酮(NMP，≥99wt.％)、9g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝43.5，Na 2O/SiO 2＝0.048，TEA +/SiO 2＝0.636，NMP/SiO 2＝3.0，H 2O/SiO 2＝16。搅拌30min，使其充分混合均匀，将合成釜密封。直接在140℃动态(30转/分钟)晶化60h。用自来水淬灭反应，离心分离得到固体产物。再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 Under stirring, 5.3 g of white carbon black (95.0 wt.% SiO 2 , 5.0 wt.% H 2 O), 0.4 g of sodium aluminate (49.0 wt.% Al 2 O 3 , 38.0 wt.% Na 2 O) , 13.0 wt.% H 2 O), 0.13 g of sodium hydroxide (96.0 wt.% NaOH), 22.3 g of tetraethylammonium hydroxide aqueous solution (TEAOH, purity ≥ 35 wt.%), 25 g of N-methyl-2 pyrrolidone (NMP, ≥99 wt.%), 9 g of deionized water were added to the reaction kettle in a certain order. The molar composition of the raw material mixture was: SiO 2 /Al 2 O 3 = 43.5, Na 2 O/SiO 2 = 0.048, TEA + /SiO 2 = 0.663, NMP / SiO 2 = 3.0, and H 2 O / SiO 2 = 16. Stir for 30 min, mix well, and seal the synthesis kettle. Crystallization was carried out directly at 140 ° C for 30 h at 30 rpm. The reaction was quenched with tap water and centrifuged to give a solid product. Wash with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
图1为所得分子筛原粉的粉末X射线衍射图。由图可以看出，其为纯相的Beta分子筛，且结晶性良好。图2为其场发射扫描电镜(FESEM)图，样品的形貌为均一的四方块状，粒径约300-500nm，由大小为10-30nm左右的一次粒子有序堆垛连结而成。图3为其透射电镜图，低倍透射电镜(图3a)显示所得Beta分子筛为具有中空结构的四方块状晶体；高倍透射电镜图(图3b)显示出一致取向的晶格条纹，表明样品为单晶结构；此外，图3b相应的选区电子衍射 (SAED)点呈现高度离散状态，进一步说明样品整体为中空单晶分子筛。图4为其N 2吸脱附曲线，其BET表面积为737m 2/g(微孔表面积590m 2/g，外表面积147m 2/g)，总孔容为0.52cm 3/g(微孔孔容为0.23cm 3/g，介孔孔容为0.29cm 3/g)。 Figure 1 is a powder X-ray diffraction pattern of the obtained molecular sieve raw powder. As can be seen from the figure, it is a pure phase Beta molecular sieve and has good crystallinity. Fig. 2 is a field emission scanning electron microscope (FESEM) image. The morphology of the sample is a uniform four-square shape with a particle size of about 300-500 nm, which is formed by sequential stacking of primary particles with a size of about 10-30 nm. Figure 3 is a transmission electron micrograph. The low-power transmission electron microscope (Fig. 3a) shows that the obtained Beta molecular sieve is a four-square crystal with a hollow structure; the high-power transmission electron micrograph (Fig. 3b) shows a uniformly oriented lattice fringe, indicating that the sample is The single crystal structure; in addition, the corresponding selected area electron diffraction (SAED) point of Fig. 3b exhibits a highly discrete state, further indicating that the sample as a whole is a hollow single crystal molecular sieve. Figure 4 is a N 2 adsorption and desorption curve with a BET surface area of 737 m 2 /g (micropore surface area 590 m 2 /g, external surface area 147 m 2 /g), and a total pore volume of 0.52 cm 3 /g (microporous pore volume). It was 0.23 cm 3 /g, and the mesoporous pore volume was 0.29 cm 3 /g).
对比例1Comparative example 1
在搅拌条件下，将19.6g硅溶胶(25.5wt.％SiO 2，74.5wt.％H 2O)、1.45g硝酸铝(≥99wt.％)、0.69g氢氧化钠、32g四乙基溴化铵水溶液(TEABr，纯度≥35wt.％)按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝43.5，Na 2O/SiO 2＝0.1，TEA +/SiO 2＝0.636，H 2O/SiO 2＝16。搅拌30min，使其充分混合均匀，将合成釜密封。直接在140℃动态(10转/分钟)晶化10h。用自来水淬灭反应，离心分离得到固体产物。再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 19.6 g of silica sol (25.5 wt.% SiO 2 , 74.5 wt.% H 2 O), 1.45 g of aluminum nitrate (≥99 wt.%), 0.69 g of sodium hydroxide, and 32 g of tetraethyl bromide were stirred under stirring. An aqueous ammonium solution (TEABr, purity ≥ 35 wt.%) was added to the reactor in a certain order. The molar composition of the raw material mixture was: SiO 2 /Al 2 O 3 = 43.5, Na 2 O/SiO 2 = 0.1, TEA + /SiO 2 = 0.663, H 2 O / SiO 2 = 16. Stir for 30 min, mix well, and seal the synthesis kettle. Crystallization was carried out directly at 140 ° C for 10 h at 10 rpm. The reaction was quenched with tap water and centrifuged to give a solid product. Wash with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
所得Beta产物的XRD谱图与图1类似，图5给出的透射电镜(TEM)图片显示其为实心Beta分子筛，粒径约322nm，N 2吸脱附测试出其BET表面积为527m 2/g，总孔容为0.35cm 3/g。 The XRD spectrum of the obtained Beta product is similar to that of Figure 1. The transmission electron microscopy (TEM) image shown in Figure 5 shows that it is a solid Beta molecular sieve with a particle size of about 322 nm and a N 2 adsorption-desorption test with a BET surface area of 527 m 2 /g. The total pore volume is 0.35 cm 3 /g.
实施例2Example 2
在搅拌条件下，将19.5g水玻璃(26wt.％SiO 2，8.2wt.％Na 2O，65.8wt.％H 2O)、1.29g硫酸铝(≥99wt.％)、1.9g氢氧化钾(≥99wt.％)、25g四乙基氯化铵水溶液(TEACl，纯度≥35wt.％)、25g N-甲基-2吡咯烷酮按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝43.5，K 2O/SiO 2＝0.2，TEA +/SiO 2＝0.636，NMP/SiO 2＝3.0，H 2O/SiO 2＝16。搅拌30min，使其充分混合 均匀，将合成釜密封。直接在100℃动态(100转/分钟)晶化240h。用自来水淬灭反应，离心分离得到固体产物。再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 Under stirring, 19.5 g of water glass (26 wt.% SiO 2 , 8.2 wt.% Na 2 O, 65.8 wt.% H 2 O), 1.29 g of aluminum sulfate (≥99 wt.%), 1.9 g of potassium hydroxide (≥99 wt.%), 25 g of tetraethylammonium chloride aqueous solution (TEACl, purity ≥ 35 wt.%), and 25 g of N-methyl-2 pyrrolidone were added to the reaction kettle in a certain order. The molar composition of the raw material mixture was: SiO 2 /Al 2 O 3 = 43.5, K 2 O/SiO 2 = 0.2, TEA + /SiO 2 = 0.663, NMP/SiO 2 = 3.0, and H 2 O / SiO 2 = 16. Stir for 30 min, mix well, and seal the synthesis kettle. Crystallization was carried out directly at 100 ° C (100 rpm) for 240 h. The reaction was quenched with tap water and centrifuged to give a solid product. Wash with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
所得Beta产物的XRD谱图与图1类似，透射电镜(TEM)图片显示其为中空单晶结构，粒径约342nm，N 2吸脱附测试出其BET表面积为711m 2/g，总孔容为0.53cm 3/g。 The XRD spectrum of the obtained Beta product is similar to that of Figure 1. The transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 342 nm. The N 2 adsorption and desorption test has a BET surface area of 711 m 2 /g, and the total pore volume. It is 0.53 cm 3 /g.
实施例3Example 3
在搅拌条件下，将17.4g正硅酸乙酯(≥99wt.％)、2.0g氯化铝(≥99wt.％)、2.7g氢氧化钠、3.5g四乙基氢氧化铵水溶液、43g N-乙基-2吡咯烷酮、9g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝20，Na 2O/SiO 2＝0.4，TEA +/SiO 2＝0.1，NEP/SiO 2＝6.0，H 2O/SiO 2＝16。搅拌30min，使其充分混合均匀，将合成釜密封。直接在100℃动态(80转/分钟)晶化200h。用自来水淬灭反应，离心分离得到固体产物。再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 Under stirring, 17.4 g of tetraethyl orthosilicate (≥99 wt.%), 2.0 g of aluminum chloride (≥99 wt.%), 2.7 g of sodium hydroxide, 3.5 g of tetraethylammonium hydroxide aqueous solution, 43 g of N Ethyl-2-pyrrolidone and 9 g of deionized water were added to the kettle in a certain order. The molar composition of the raw material mixture was: SiO 2 /Al 2 O 3 =20, Na 2 O/SiO 2 = 0.4, TEA + /SiO 2 = 0.1, NEP/SiO 2 = 6.0, and H 2 O/SiO 2 = 16. Stir for 30 min, mix well, and seal the synthesis kettle. Crystallized directly at 100 ° C (80 rpm) for 200 h. The reaction was quenched with tap water and centrifuged to give a solid product. Wash with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
所得Beta产物的XRD谱图与图1类似，透射电镜(TEM)图片显示其为中空单晶结构，粒径约312nm，N 2吸脱附测试出其BET表面积为682m 2/g，总孔容为0.75cm 3/g。 The XRD spectrum of the obtained Beta product is similar to that of Figure 1. The transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 312 nm. The N 2 adsorption and desorption test has a BET surface area of 682 m 2 /g, and the total pore volume. It is 0.75 cm 3 /g.
实施例4Example 4
在搅拌条件下，将5.3g白炭黑、0.7g乙酸铝(≥90wt.％)、0.33g氢氧化钠、14g四乙基氢氧化铵水溶液、43g N-异丙基-2吡咯烷酮(NPP，纯度≥99wt.％)按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝40， Na 2O/SiO 2＝0.048，TEA +/SiO 2＝0.4，NPP/SiO 2＝4.0，H 2O/SiO 2＝5。搅拌30min，使其充分混合均匀，将合成釜密封。直接在120℃动态(60转/分钟)晶化150h。用自来水淬灭反应，离心分离得到固体产物。再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 Under stirring, 5.3 g of white carbon black, 0.7 g of aluminum acetate (≥90 wt.%), 0.33 g of sodium hydroxide, 14 g of tetraethylammonium hydroxide aqueous solution, and 43 g of N-isopropyl-2-pyrrolidone (NPP, Purity ≥ 99 wt.%) was added to the kettle in a certain order. The molar composition of the raw material mixture was: SiO 2 /Al 2 O 3 =40, Na 2 O/SiO 2 =0.048, TEA + /SiO 2 =0.4, NPP/SiO 2 =4.0, and H 2 O/SiO 2 =5. Stir for 30 min, mix well, and seal the synthesis kettle. Crystallized directly at 120 ° C (60 rpm) for 150 h. The reaction was quenched with tap water and centrifuged to give a solid product. Wash with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
所得Beta产物的XRD谱图与图1类似，透射电镜(TEM)图片显示其为中空单晶结构，粒径约352nm，N 2吸脱附测试出其BET表面积为725m 2/g，总孔容为0.78cm 3/g。 The XRD spectrum of the obtained Beta product is similar to that of Figure 1. The transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 352 nm. The N 2 adsorption and desorption test has a BET surface area of 725 m 2 /g, and the total pore volume. It is 0.78 cm 3 /g.
实施例5Example 5
在搅拌条件下，将5.3g白炭黑、0.075g铝粉(100wt.％)、0.15g氢氧化钠、21g四乙基氢氧化铵水溶液、1.79g 2-吡咯烷酮(R，纯度≥99wt.％)、5g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝60，Na 2O/SiO 2＝0.048，TEA +/SiO 2＝0.6，R/SiO 2＝0.25，H 2O/SiO 2＝10。搅拌30min，使其充分混合均匀，将合成釜密封。直接在140℃动态(40转/分钟)晶化100h。用自来水淬灭反应，离心分离得到固体产物。再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 Under stirring, 5.3 g of white carbon black, 0.075 g of aluminum powder (100 wt.%), 0.15 g of sodium hydroxide, 21 g of tetraethylammonium hydroxide aqueous solution, and 1.79 g of 2-pyrrolidone (R, purity ≥99 wt.%) ), 5 g of deionized water was added to the reaction kettle in a certain order. The molar composition of the raw material mixture was: SiO 2 /Al 2 O 3 =60, Na 2 O/SiO 2 =0.048, TEA + /SiO 2 =0.6, R/SiO 2 =0.25, and H 2 O/SiO 2 =10. Stir for 30 min, mix well, and seal the synthesis kettle. Crystallized directly at 140 ° C (40 rpm) for 100 h. The reaction was quenched with tap water and centrifuged to give a solid product. Wash with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
所得Beta产物的XRD谱图与图1类似，透射电镜(TEM)图片显示其为中空单晶结构，粒径约364nm，N 2吸脱附测试出其BET表面积为730m 2/g，总孔容为0.573cm 3/g。 The XRD spectrum of the obtained Beta product is similar to that of Figure 1. The transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 364 nm. The N 2 adsorption and desorption test has a BET surface area of 730 m 2 /g, and the total pore volume. It is 0.573 cm 3 /g.
实施例6Example 6
在搅拌条件下，将5.1g层析硅胶(98.0wt.％SiO 2，2.0wt.％H 2O)、0.15g拟薄水铝石(69wt.％SiO 2，31wt.％H 2O)、0.56g碳酸钾(≥98wt.％)、40g四 乙基溴化铵水溶液、25g N-甲基-2吡咯烷酮、15g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝80，K 2CO 3/SiO 2＝0.048，TEA +/SiO 2＝0.8，NMP/SiO 2＝3.0，H 2O/SiO 2＝20。搅拌30min，使其充分混合均匀，将合成釜密封。直接在160℃动态(20转/分钟)晶化80h。用自来水淬灭反应，离心分离得到固体产物。再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 5.1g of chromatographic silica gel (98.0 wt.% SiO 2 , 2.0 wt.% H 2 O), 0.15 g of pseudoboehmite (69 wt.% SiO 2 , 31 wt.% H 2 O), under stirring, 0.56 g of potassium carbonate (≥98 wt.%), 40 g of tetraethylammonium bromide aqueous solution, 25 g of N-methyl-2-pyrrolidone, and 15 g of deionized water were added to the reaction kettle in a certain order. The molar composition of the raw material mixture is: SiO 2 /Al 2 O 3 =80, K 2 CO 3 /SiO 2 =0.048, TEA + /SiO 2 =0.8, NMP/SiO 2 =3.0, H 2 O/SiO 2 =20 . Stir for 30 min, mix well, and seal the synthesis kettle. Crystallized directly at 160 ° C (20 rpm) for 80 h. The reaction was quenched with tap water and centrifuged to give a solid product. Wash with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
所得Beta产物的XRD谱图与图1类似，透射电镜(TEM)图片显示其为中空单晶结构，粒径约373nm，N 2吸脱附测试出其BET表面积为736m 2/g，总孔容为0.59cm 3/g。 The XRD spectrum of the obtained Beta product is similar to that of Figure 1. The transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 373 nm. The N 2 adsorption and desorption test has a BET surface area of 736 m 2 /g, and the total pore volume. It is 0.59 cm 3 /g.
实施例7Example 7
在搅拌条件下，将5.15g粗孔硅胶(97.0wt.％SiO 2，3.0wt.％H 2O)、0.56g硫酸铝、0.42g碳酸钠(≥99.5wt.％)、35g四乙基氟化铵水溶液(TEAF，纯度≥35wt.％)、25g N-甲基-2吡咯烷酮、20g去离子水按一定顺序加入反应釜中。原料混合物的摩尔组成为：SiO 2/Al 2O 3＝100，Na 2CO 3/SiO 2＝0.048，TEA +/SiO 2＝1.0，NMP/SiO 2＝3.0，H 2O/SiO 2＝30。搅拌30min，使其充分混合均匀，将合成釜密封。直接在180℃动态(10转/分钟)晶化48h。用自来水淬灭反应，离心分离得到固体产物，再用去离子水洗涤至中性。80℃过夜干燥得到分子筛原粉。 Under stirring, 5.15 g of crude silica gel (97.0 wt.% SiO 2 , 3.0 wt.% H 2 O), 0.56 g of aluminum sulfate, 0.42 g of sodium carbonate (≥99.5 wt.%), 35 g of tetraethyl fluoride An aqueous ammonium solution (TEAF, purity ≥ 35 wt.%), 25 g of N-methyl-2 pyrrolidone, and 20 g of deionized water were added to the kettle in a certain order. The molar composition of the raw material mixture is: SiO 2 /Al 2 O 3 =100, Na 2 CO 3 /SiO 2 =0.048, TEA + /SiO 2 =1.0, NMP/SiO 2 =3.0, H 2 O/SiO 2 =30 . Stir for 30 min, mix well, and seal the synthesis kettle. Crystallized directly at 180 ° C (10 rpm) for 48 h. The reaction was quenched with tap water and the solid product was obtained by centrifugation and washed with deionized water until neutral. The molecular sieve raw powder was obtained by drying overnight at 80 °C.
所得Beta产物的XRD谱图与图1类似，透射电镜(TEM)图片显示其为中空单晶结构，粒径约305nm，N 2吸脱附测试出其BET表面积为782m 2/g，总孔容为0.85cm 3/g。 The XRD spectrum of the obtained Beta product is similar to that of Figure 1. The transmission electron microscopy (TEM) image shows that it is a hollow single crystal structure with a particle size of about 305 nm. The N 2 adsorption and desorption test has a BET surface area of 782 m 2 /g, and the total pore volume. It is 0.85 cm 3 /g.

Claims (7)

  1. 一种中空单晶Beta分子筛的制备方法，其特征在于：将硅源、铝源、无机碱源、微孔模板剂、去离子水和有机添加剂内酰胺R均匀混合，其原始摩尔组成为：SiO 2/Al 2O 3＝20～100，Na 2O/SiO 2＝0.0～0.4，TEA +/SiO 2＝0.10～1.0，H 2O/SiO 2＝5～30，R/SiO 2＝0～6；原料均匀混合后直接进行高温晶化；将产物固液分离，固体产物经过滤、洗涤、干燥得到10-30nm的一次粒子有序堆垛连结而成的中空单晶Beta分子筛。 The invention discloses a preparation method of a hollow single crystal Beta molecular sieve, which is characterized in that: a silicon source, an aluminum source, an inorganic alkali source, a microporous template, a deionized water and an organic additive lactam R are uniformly mixed, and the original molar composition thereof is: SiO 2 /Al 2 O 3 =20 to 100, Na 2 O/SiO 2 =0.0 to 0.4, TEA + /SiO 2 = 0.10 to 1.0, H 2 O/SiO 2 = 5 to 30, R/SiO 2 = 0 to 6; The raw materials are uniformly mixed and directly subjected to high-temperature crystallization; the product is solid-liquid separated, and the solid product is filtered, washed, and dried to obtain a hollow single crystal Beta molecular sieve in which 10-30 nm primary particles are sequentially stacked.
  2. 按照权利要求1所述的中空单晶Beta分子筛制备方法，其特征在于：所述硅源为白炭黑、正硅酸乙酯、水玻璃、硅溶胶、层析硅胶或粗孔硅胶中的一种或几种；The method for preparing a hollow single crystal Beta molecular sieve according to claim 1, wherein the silicon source is one of white carbon black, tetraethyl orthosilicate, water glass, silica sol, chromatography silica gel or coarse pore silica gel. Species or several
    所述铝源为铝酸钠、硫酸铝、氯化铝、硝酸铝、乙酸铝、铝粉或拟薄水铝石中的一种或几种；The aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum powder or pseudoboehmite;
    所述无机碱源为氢氧化钠、氢氧化钾、碳酸钠或碳酸钾中的一种或几种。The inorganic alkali source is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
  3. 按照权利要求1所述的中空单晶Beta分子筛的制备方法，其特征在于：所述微孔模板剂为四乙基氢氧化铵、四乙基溴化铵、四乙基氯化铵或四乙基氟化铵中的一种或几种。The method for preparing a hollow single crystal Beta molecular sieve according to claim 1, wherein the microporous template is tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride or tetraethylidene. One or more of the ammonium fluorides.
  4. 按照权利要求1所述的中空单晶Beta分子筛的制备方法，其特征在于：所述有机添加剂内酰胺R为2-吡咯烷酮、N-甲基-2-吡咯烷酮、N-乙基 -2 -吡咯烷酮或N-异丙基-2-吡咯烷酮中的一种或几种。 The method for preparing a hollow single crystal Beta molecular sieve according to claim 1, wherein the organic additive lactam R is 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl - 2 - pyrrolidone or One or more of N-isopropyl-2-pyrrolidone.
  5. 按照权利要求1所述的中空单晶Beta分子筛的制备方法，其特征在于：所述高温晶化为：100～180℃下动态晶化10～240h，水热合成中空单晶Beta分子筛。The method for preparing a hollow single crystal Beta molecular sieve according to claim 1, wherein the high temperature crystallization is: dynamic crystallization for 10 to 240 hours at 100 to 180 ° C, and hydrothermal synthesis of a hollow single crystal Beta molecular sieve.
  6. 按照权利要求5所述的中空单晶Beta分子筛的制备方法，其特征在于：所述动态晶化是在旋转烘箱的反应器中进行，所述旋转烘箱的转速为10-100转/ 分钟。The method for producing a hollow single crystal Beta molecular sieve according to claim 5, wherein said dynamic crystallization is carried out in a reactor of a rotary oven, and the rotational speed of said rotary oven is from 10 to 100 rpm.
  7. 基于权利要求1-6中任意权利要求所述方法合成的中空单晶Beta分子筛，其特征在于：通过调节原料配比和晶化条件，合成由10-30nm的一次粒子有序堆垛连结而成的亚微米级中空单晶Beta分子筛，该分子筛具有中空结构、结晶度高、比表面积和孔体积大的特点。The hollow single crystal Beta molecular sieve synthesized by the method according to any one of claims 1 to 6, wherein the synthesis is carried out by orderly stacking 10-30 nm primary particles by adjusting the ratio of raw materials and crystallization conditions. The submicron hollow single crystal Beta molecular sieve has the characteristics of hollow structure, high crystallinity, specific surface area and large pore volume.
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