Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Zeolites are microporous crystalline inorganic materials having pore systems of uniform molecular size and are widely used in the fields of gas adsorption and separation, ion exchange and catalysis in connection with environmental protection, chemical conversion and energy conservation. The pore system of the molecular sieve can be divided into small pores, medium pores, large pores and super large pores according to the number of T atoms contained in the pore opening. The macroporous and ultra-macroporous molecular sieves are beneficial to the diffusion of macromolecular reactants, intermediate products and final target products and are beneficial to catalyzing reactions in which macromolecules participate. In addition to pore size, three-dimensional pore connectivity is also critical to diffusion of species. Currently, the most widely used molecular sieves in industry, especially zeolites as catalysts, are still those containing interconnected three-dimensional channel systems with pore sizes in the range of medium (10-Membered Ring (MR)) and large (12MR) pores, such as Y-type molecular sieves, beta molecular sieves, etc. Such a structure can provide both low diffusion limitation and excellent shape selectivity. In addition, zeolites with three-dimensional channels tend to have higher thermal and hydrothermal stability than one-or two-dimensional molecular sieves.
ITQ-7 is a silicon germanium molecular sieve with ISV topology first synthesized by the Corma group in 1999. The ITQ-7 molecular sieve has a three-dimensional intercommunicated twelve-membered ring channel structure, two linear channels are arranged in the directions of a and b, and the pore size is
A crankshaft-like pore canal with the pore diameter of
In addition to ITQ-7 molecular sieves, only 5 zeolitic molecular sieves having a three-dimensional intercommunicating twelve-membered ring channel system have been synthesized, including Y (FAU), Beta (BEA), ITQ-17(BEC), ITQ-21, and ITQ-26 (IWS). Y (FAU) and Beta (BEA) are used in various petroleum processes and fine chemicalsOne of the most important microporous materials produced. It follows that rational design and preparation of novel three-dimensional large pore zeolites remains a difficult problem.
One of the main approaches explored to synthesize macroporous and extra-macroporous porous materials is to use fluoride ions instead of hydroxides as mineralizers or by replacing the framework portion Si with heteroelements such as Ge or Zn to direct and stabilize small secondary building blocks such as bistetracyclics (D4R), tricyclics (3R) and even bistetracyclics (D3R).
Camblor (chem. Mater.2007,19,1601-1612) prepared ITQ-7 molecular sieves using rigid bicyclic amine 1,3, 3-trimethyl-6-azabicyclo [3.2.1] -octane derived organic cations as organic templates in the presence of fluoride ions. At present, 1,3, 3-trimethyl-6-azabicyclo [3.2.1] -octane cannot be obtained technically because the reactants for synthesizing the template agent stop production.
Fernando Rey (C.R. Chimie.200,8, 369-.
ITQ-7 molecular sieves were prepared by using quaternary ammonium salts of Diels-Alder adducts as templates based on Diels-Alder adducts obtained by reacting l-isopropyl-4-methyl-cyclohexane-l, 3-diene (. alpha. -terpinene) with maleimide to form Diels-Alder adducts or analogous unsubstituted cyclohexane-l, 3-dienes (481-488).
The inventors found that the organic templating agent used in the above method is complex in structure and involves multiple reactions and purification steps, which increases the difficulty of ISV molecular sieve synthesis and also limits further research on this material. In addition, fluoride is often used to promote crystallization during ISV molecular sieve synthesis reported in the literature, which raises environmental pollution and safety issues. Due to the charge effect, the existence of fluorine ions also prevents aluminum and other metal elements with catalytic activity from being doped in the zeolite framework, and the subsequent regulation and control of the catalytic performance of the molecular sieve are influenced.
Disclosure of Invention
Aims to solve the problems that the synthesis of an organic template used for synthesizing an ISV molecular sieve in the prior art is too complex and F is required to be used in the synthesis process - The invention provides a simple and easy preparation method of a silicon-germanium ISV zeolite molecular sieve, which solves the problems in the prior art. The preparation process of the present invention uses 6-azaspiro- [5, 6%]Dodecane molecule is used as an organic template agent, the structure is simple, a complex reaction process is not needed, hydroxide radical is used as an alkaline medium for synthesis, and a silicon germanium ISV molecular sieve with perfect crystallization and unique morphology can be obtained without adding fluoride.
In order to achieve the above objects, the present invention provides a method for preparing a silicon germanium ISV zeolite molecular sieve, which comprises using 6-azaspiro- [5, 6] -dodecane molecule as an organic template.
The preparation method specifically comprises the following steps:
(1) adding deionized water into 6-azaspiro- [5, 6] -dodecane molecules to obtain an organic template solution;
(2) adding a germanium source into an organic template solution, and fully dissolving to obtain a clear solution;
(3) adding a silicon source into the clarified solution to obtain a gel mixture;
(4) and transferring the gel mixture into the lining of a high-pressure reaction kettle for rotary crystallization treatment to obtain the silicon-germanium ISV zeolite molecular sieve.
One or more embodiments of the present invention have at least the following advantageous effects:
(1) the invention takes 6-azaspiro- [5, 6] -dodecane molecules as an organic template agent for preparing the silicon-germanium ISV zeolite molecular sieve, the substance has the advantages of easy synthesis and simple structure, compared with the previously reported template agent for synthesizing the ISV molecular sieve, the substance has the advantages of low cost, simple and feasible synthesis process, good selectivity on the ISV molecular sieve, capability of synthesizing a target product in a wider gel system, no fluorine ions added in the crystallization process of the molecular sieve, relatively safe whole synthesis system, small pollution and environmental friendliness. .
(2) The ISV molecular sieve obtained by the preparation method of the silicon-germanium ISV zeolite molecular sieve provided by the invention has an intercommunicated three-dimensional macroporous pore canal system, is a catalytic material with great potential, has good crystallinity of a sample, no impurities, stable structure after high-temperature roasting, good thermal stability and higher germanium content, and creates a powerful condition for subsequent structural recombination.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, the prior art organic templating agents are complex in structure and involve multiple reactions and purification steps. In order to solve the technical problems, the invention provides a preparation method of a silicon-germanium ISV zeolite molecular sieve, which uses 6-azaspiro- [5, 6] -dodecane molecules as an organic template agent to prepare the molecular sieve.
The 6-azaspiro- [5, 6] -dodecane molecule has the advantages of simple structure, no need of multi-step reaction, difficulty in mixing impurities and no need of multiple purification steps; the invention takes the simple and easily synthesized 6-azaspiro- [5, 6] -dodecane molecule as the template agent in the preparation process of the zeolite molecular sieve, is very beneficial to large-scale industrialized preparation of the zeolite molecular sieve, saves the cost to a certain extent and reduces the energy consumption.
In addition, the prior zeolite synthesis process often uses fluoride to promote crystallization, which brings environmental pollution and safety problems, the invention takes 6-azaspiro- [5, 6] -dodecane molecules as an organic template agent, and fluoride is not needed to be added for assistance in the crystallization process, thereby avoiding the environmental pollution problem brought by fluoride. In addition, due to the charge effect, the existence of fluorinion prevents aluminum and other trivalent metal elements from being doped in the zeolite framework, and the invention takes 6-azaspiro- [5, 6] -dodecane molecules as an organic template agent and can be suitable for preparing zeolite molecular sieves doped with trivalent metals.
In one or more embodiments of the present invention, the method for preparing the silicon germanium ISV zeolite molecular sieve specifically comprises the following steps:
(1) adding deionized water into 6-azaspiro- [5, 6] -dodecane molecules to obtain an organic template solution;
(2) adding a germanium source into an organic template solution, and fully dissolving to obtain a clear solution;
(3) adding a silicon source into the clarified solution to obtain a gel mixture;
(4) and transferring the gel mixture into the lining of a high-pressure reaction kettle for rotary crystallization treatment to obtain the silicon-germanium ISV zeolite molecular sieve.
Wherein the 6-azaspiro- [5, 6] -dodecane is synthesized by a single synthesis reaction and simple purification steps, comprising evaporating excess water and recrystallizing the solid in anhydrous ether, and the organic template has the following structural formula:
in order to better play the role of 6-azaspiro- [5, 6] -dodecane molecules as an organic template, deionized water is adopted for dissolving the organic template to form an aqueous solution for application, and as a preferred embodiment, the mass concentration of the formed solution of the 6-azaspiro- [5, 6] -dodecane molecules and the deionized water is 10-50 wt%;
in one or more embodiments of the present invention, in step (2), after the germanium source is added to the organic template solution, stirring is performed at room temperature for 5-10 minutes to fully dissolve the germanium source, so as to obtain a clear solution; 6-azaspiro- [5, 6] in the clear solution]-the molar ratio of dodecane molecules to germanium source is 3: 4; the molar ratio of the deionized water to the germanium source is H 2 O:GeO 2 =37.5:1;
In one or more embodiments of the present invention, in the step (3), the silicon source is added to the clear solution and then stirred at room temperature for 30 minutes to obtain a gel mixture;
the molar ratio of the silicon source to the germanium source in the gel mixture is SiO 2 :GeO 2 =2:1;
In the present invention, the silicon source and the germanium source are not particularly limited as long as they can provide silicon and germanium elements, for example: the silicon source is one or more of tetraethyl silicate, silicic acid, fuming silica gel, water glass and silica sol; the germanium source is one or more of germanium dioxide, tetramethyl germanium, isobutyl germane and germanium nitrate.
In one or more embodiments of the present invention, in the step (4), the crystallization process is a full-course dynamic crystallization at a constant temperature; the conditions of the crystallization treatment are as follows: the gel mixture is subjected to rotary crystallization at 175-180 ℃ for 96-168 hours, the silicon germanium molecular sieve with the ISV topological structure and good crystallinity is obtained after the gel mixture is subjected to dynamic crystallization for 96 hours, but the structure is more complete along with the extension of the crystallization time until the crystallization time reaches 168 hours, and the structure is optimal; therefore, it is preferable to perform spin crystallization at 175 ℃ for 168 hours.
Further, the rotation speed is 15-40rpm, preferably 40rpm, at which the obtained crystal grain size is smaller;
further, in order to avoid mixing unreacted raw materials in the crystallized product, the crystallization treatment further comprises the steps of washing, separating, drying and roasting the crystallized product;
preferably, the washing process is that the deionized water is used for washing while carrying out suction filtration until the obtained product is neutral;
preferably, the drying temperature is 80-90 ℃;
preferably, the roasting temperature is 600-650 ℃, the roasting time is 3-4 hours, and the roasting time is more preferably 3 hours at 600 ℃.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
10.07g of organic template agent 6-azaspiro- [5,6]Dodecane (13.80% in water) and 8.94g of deionized water were mixed homogeneously, then 1.05g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.25g of tetraethyl silicate was added, the mixture was kept in a sealed state, and the mixture was stirred at room temperature for 30 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO 2 :GeO 2 :SDAOH:H 2 O ═ 0.8:0.4:0.3: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into an oven at 175 ℃ for dynamic crystallization for 168 hours (15rpm), taking out a sample, carrying out suction filtration, washing for multiple times, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The obtained solid product is characterized by X-ray diffractometer to obtain XRD data as shown in figure 1, sampleThe crystallinity of the product is intact, and the ISV topological structure can be confirmed by comparing with a standard spectrogram. As shown in a scanning electron micrograph of fig. 2, the molecular sieve is spindle-shaped and is composed of crossed nano sheets with the thickness of about 50nm, the crystal size is relatively uniform, and the length is about 2-3 μm. Thermogravimetric analysis data as shown in figure 3, the ISV-type molecular sieve is stable at a temperature of at least 600 c and has a total weight loss of about 20.0 wt% after calcination.
In this example, the molecular sieve obtained was subjected to nitrogen desorption at 77k to obtain a total specific surface area of 521m
2 Per g, micropore volume of 0.19cm
3 In g, average pore diameter of
And performing an inductively coupled plasma emission spectrometer test to obtain a silicon germanium ratio of 4.
Example 2
10.07g of organic template agent 6-azaspiro- [5,6]Dodecane (13.80% in water) and 8.94g of deionized water were mixed homogeneously, then 1.05g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.25g of tetraethyl silicate was added, and the mixture was stirred at room temperature for 30 minutes while maintaining a sealed state to obtain a gel mixture. The molar ratio of the gel mixture is SiO 2 :GeO 2 :SDAOH:H 2 O ═ 0.8:0.4:0.3: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into an oven at 175 ℃ for dynamic crystallization for 168 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The obtained solid product was characterized by an X-ray diffractometer to obtain XRD data as shown in FIG. 4. As shown in FIG. 5, in the process of crystallization, the rotation speed is increased to 40rpm, and the molecular sieve is observed to be spindle-shaped, but the grain size is reduced to 1-2 μm, which indicates that the size of the rotation speed can affect the particle size of the finally obtained molecular sieve.
Example 3
10.07g of organic template agent 6-azaspiro- [5,6]Dodecane (13.80% in water) and 8.94g of deionized water were mixed homogeneously, then 1.05g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Then 4.25g of silicic acid tetra (IV) are addedEthyl ester, kept in a sealed state, and stirred at room temperature for 30 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO 2 :GeO 2 :SDAOH:H 2 O ═ 0.8:0.4:0.3: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into an oven at 175 ℃ for dynamic crystallization for 96 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The obtained solid product is characterized by an X-ray diffractometer to obtain XRD data as shown in figure 6, and it can be seen that the gel mixture with the same molar ratio has obtained the silicon germanium molecular sieve with ISV topological structure and good crystallinity after dynamic crystallization for 96 hours.
Example 4
10.07g of organic template agent 6-azaspiro- [5,6]Dodecane (13.80% in water) and 8.94g of deionized water were mixed homogeneously, then 1.05g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.25g of tetraethyl silicate was added, the mixture was kept in a sealed state, and the mixture was stirred at room temperature for 30 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO 2 :GeO 2 :SDAOH:H 2 O ═ 0.8:0.4:0.3: 15. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into an oven at 175 ℃ for dynamic crystallization for 168 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The XRD data of the obtained solid product is represented by an X-ray diffractometer and shown in figure 7, the XRD spectrogram is basically the same after water is reduced, but a small new peak appears between 11-12 degrees and 16-17 degrees, and the reduction of water can be seen to synthesize the ISV molecular sieve with fewer structural defects and smaller grains.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.