CN114014335B - Silicon germanium UTL type macroporous molecular sieve and preparation method thereof - Google Patents

Silicon germanium UTL type macroporous molecular sieve and preparation method thereof Download PDF

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CN114014335B
CN114014335B CN202111393150.XA CN202111393150A CN114014335B CN 114014335 B CN114014335 B CN 114014335B CN 202111393150 A CN202111393150 A CN 202111393150A CN 114014335 B CN114014335 B CN 114014335B
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廖礼俊
袁儒婷
杜金浩
崔月芝
陶芙蓉
王楠
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Qilu University of Technology
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Abstract

The invention belongs to the technical field of molecular sieves, and relates to a silicon germanium UTL macroporous molecular sieve and a preparation method thereof. In the preparation method, 7-azaspiro- [6,6]-tenThe trialkyl molecule is prepared as an organic template. Compared with the existing template, the template used in the report of the patent has the advantages of simple structure, simple and feasible operation of the synthesis process, and no need of complex synthesis process and purification steps; the synthesis of UTL molecular sieve adopts hydroxide to replace F ‑ As mineralizer, the silicon germanium UTL molecular sieve with perfect crystallization and unique morphology can be obtained without adding fluoride. The template agent is used for synthesizing the UTL type molecular sieve, the synthesis formula range is wider, no obvious competition phase appears, and pure UTL molecular sieve crystals are easy to obtain.

Description

Silicon germanium UTL type macroporous molecular sieve and preparation method thereof
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to a silicon germanium UTL type macroporous molecular sieve and a preparation method thereof.
Background
The disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
Molecular sieves are microporous crystalline inorganic materials having pore systems of uniform molecular size, and they find wide application in the fields of gas adsorption and separation, ion exchange and catalysis, which are related to environmental protection, chemical conversion, energy saving, and the like. The pore canal 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 super macroporous molecular sieves are beneficial to the diffusion of macromolecular reactants, intermediate products and final target products, and are beneficial to the catalysis of reactions participated by macromolecules.
Germanium-containing molecular sieves are one of the important members of the molecular sieve family, and are synthesized by introducing germanium atoms into the molecular sieve framework. The presence of framework germanium can stabilize smaller secondary building blocks in the molecular sieve structure, including bi-quad, bi-tri-and tri-quad rings. In pure silicon molecular sieves, the presence of these smaller secondary building blocks can lead to structural distortions that affect the stability of the molecular sieve. Thus, the introduction of germanium into the molecular sieve framework may enable the preparation of novel molecular sieve topologies. There are 30 new molecular sieve structures that have been successfully synthesized by the introduction of germanium into the framework.
The ultra-large pore molecular sieve is beneficial to the diffusion of macromolecules and has important advantages in catalytic reactions in the fields related to petroleum refining and fine chemicals. The germanium-containing molecular sieve generally has larger pore size and good application prospect in the field of catalysis. For example, the Ge-TS-1 molecular sieve has higher catalytic activity than TS-1 in the epoxidation reaction of propylene (M.K.Faraj, U.S.Patent 5977009 (1999)). For example, germanium-containing ZSM-5 has improved catalytic activity over conventional ZSM-5 over a series of catalytic reactions (L.G.A.van de Water, J.C.van der Waal, J.C.Jansen, T.Maschmeyer, J.Catal.223 (2004) 170-178). The synthesis of silicon germanium molecular sieves is of great value in the preparation of novel molecular sieve structures and in catalytic applications.
UTL type molecular sieves have a two-dimensional, interconnected 14X12 membered ring channel system, first synthesized by Pailaud and Corma in 2004 and named IM-12 and ITQ-15, respectively (J.L. Pailaud; B.Harbuzaru; J.Patarin; N.bats, science 2004,304,990-992; A.Corma, M.J.Diaz-Cananas, F.Rey, S.Nicolopoulus, K.Boulahya, chem.Commun.,2004, 1356-1357). The synthesis of ITQ-15 and IM-12 both adopts organic quaternary ammonium salt as the template agent, and the process for synthesizing the template agent is complex. The later reported template agent for synthesizing the UTL type molecular sieve needs to carefully regulate reaction conditions to avoid generating other crystalline phases.
The UTL type molecular sieve can be subjected to secondary synthesis to selectively remove part of framework structural units, so that a topological structure is converted, and a novel high-silicon molecular sieve is formed. The high-silicon molecular sieves obtained by the secondary synthesis are similar to the parent molecular sieves UTL in structure and are different from each other in the connection mode between the two layers. After secondary synthesis, the interlayer connection mode can be changed from a double-four-ring mode to a single-four-ring mode, an oxygen bridge mode and a mixed connection mode of the double-four-ring mode and the oxygen bridge mode. Interlaminar can also occurRelative displacement. The secondary synthesis method mainly comprises two kinds of acid treatment and alkali treatment. The concentration, type, use of organic solvents, time and temperature of the acid treatment used will have an effect on the newly formed molecular sieve structure, and the acid treatment process is mainly Inverse Sigma Transformation and two reaction paths of Assembly-Organization-Reassembly (ADOR) (E.Verheyen, L.Joos, K.Van Havenbergh, E.Breynaert, N.Kasian, E.Gobechiya, K.Houthoofd, C.Martineau, M.Hinterstein, F.Taulelle, V.Van Spybrooeck, M.Waroquier, S.Bals, G.Van Tendelloo, C.E.A. Kirschhock and J.A.Martens, nat.Mater.,2012,11,1059-1064; W.J.Roth, P.Nachtigll, R.E. Morris, P.S. Wheatley, V.R.Seymour, S.E. Assbroak, P.Chunbn, L.Grajciar, M.
Figure BDA0003369055320000031
A.Zukal,O.Shvets and J./>
Figure BDA0003369055320000032
Nat.chem.,2013,5,628-633). The acid treatment mainly removes the germanium-containing double-quaternary ring structure unit, and has certain requirements on the chemical composition of the double-quaternary ring structure unit and the distribution of germanium in the double-quaternary ring structure unit, so that the conversion of the topological structure can be successfully realized. The alkali treatment process can cause the dissolution of part of framework silicon, the silicon and germanium in the double-quaternary ring can be removed, and the element composition of the structural unit has little influence on the alkali treatment result.
The inventors found that the structure of the organic template used in the current method for preparing the UTL type molecular sieve is complex, and the multi-step reaction and the multiple purification steps are involved, which increases the difficulty of synthesizing the UTL molecular sieve and limits the further research of the material. Because of the above characteristics of UTL, the molecular sieve is the most interesting member of the family of silicon germanium molecular sieves, and is also one of the most promising silicon germanium molecular sieves. It is therefore necessary to devise a route for synthesizing new synthetic UTL-type molecular sieves.
The 7-azaspiro- [6,6] -tridecane molecule is an azaspiro heterocyclic quaternary ammonium salt, and the literature reports that the quaternary ammonium salt can be used for synthesizing a molecular sieve to prepare an MTW-type silicon-aluminum molecular sieve, but has low structural selectivity to the molecular sieve, and tends to generate MTW crystalline phases under different silicon sources, aluminum sources, synthesis conditions and the like. The subject group adopts the quaternary ammonium salt and combines the guiding function of the double quaternary ring structure of germanium element to prepare various molecular sieves with different topological structures, thereby greatly improving the selectivity of the quaternary ammonium salt molecules to the molecular sieve structure. For example, earlier experiments in the subject group showed that 5-azaspiro- [4,4] -nonane can be used in the synthesis of IWW-type silicon germanium molecular sieves, and 6-azaspiro- [5,6] -dodecane can be used in the synthesis of ISV-type molecular sieves, meaning that such quaternary ammonium salts have a certain selectivity to the structure of the final silicon germanium molecular sieve, showing a certain advantage in the synthesis of silicon germanium molecular sieves. The topology structure of the final molecular sieve can be changed by changing the ring size of the azaspiro, and the method is an innovation in the research field of molecular sieves. There is no information in the prior art that indicates that IWW, ISV and UTL type molecular sieves are competing crystalline phases or are present simultaneously during the synthesis. The synthesis of the molecular sieves requires the participation of different organic templates, the synthesis conditions are not obviously overlapped, and the mutual conversion between the structures is not reported. Therefore, the technical barriers are structures of the molecular sieve, the development of the molecular sieve for synthesizing different structures is a long-standing hot spot and a difficult problem in the field of molecular sieve synthesis, and the aim of synthesizing different molecular sieves is definitely very important if the structure of a template molecule is simply changed. Although the template agents for synthesizing the ISV and UTL type molecular sieves are very similar, the structures of the compounds are different and the synthesis conditions are completely different, and the UTL type molecular sieves reported in the patent can be synthesized under a standing condition, but the synthesis of the ISV type molecular sieves needs to be performed under a rotary crystallization condition. In addition, the minimum time required by crystallization is different, the UTL type molecular sieve can be completely crystallized within three days at the highest speed, the ISV type silicon germanium molecular sieve needs 7 days of crystallization time, otherwise, the crystallization is incomplete and certain amorphous components can be contained. UTL-type molecular sieves can be synthesized at 160 ℃, but ISV synthesis is preferably 175 ℃. In addition, UTL and ISV are two molecular sieves with completely different structures and morphologies, and have different application advantages in the aspect of subsequent catalytic reaction research.
Disclosure of Invention
The invention provides a silicon germanium UTL type macroporous molecular sieve and a preparation method thereof, and aims to solve the problem that the synthesis of an organic template agent used for synthesizing the UTL molecular sieve in the prior art is too complex. In the preparation process, 7-azaspiro- [6,6] -tridecane molecules are used as an organic template agent, the structure is simple, a complex reaction process is not required, hydroxide is used as an alkaline medium in synthesis, fluoride is not required to be added, and the UTL silicon germanium UTL type molecular sieve with perfect crystallization and nano lamellar staggered stacking morphology can be obtained. The prepared UTL molecular sieve sample can realize topological structure conversion after acid treatment and alkali treatment.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a silicon germanium UTL zeolite molecular sieve, which uses 7-azaspiro- [6,6] -tridecane molecules as an organic template agent for preparing the molecular sieve.
The preparation method specifically comprises the following steps:
(1) 7-azaspiro- [6,6] as organic template]Mixing solution of tridecane hydroxide, germanide and deionized water, stirring to clarify to obtain clarified solution, and dropwise adding tetraethoxysilane and SiO into the clarified solution 2 Or water glass, etc., stirring at room temperature for 30min to obtain reactant;
(2) Transferring the gel reactant into a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the high-pressure reaction kettle into a rotary oven, and cooling to room temperature after rotary crystallization to obtain a solid product;
(3) And (3) washing the solid product obtained in the step (2) with deionized water until the pH of the filtrate is less than 8, and putting the filtrate into an oven for drying overnight to obtain the silicon germanium UTL type macroporous molecular sieve.
Further, the invention also comprises (4) putting the UTL type macroporous molecular sieve into a muffle furnace, and roasting to obtain the UTL molecular sieve with high crystallinity and removed the template agent.
Further, in the step (1), the mass concentration of the solution formed by the 7-azaspiro- [6,6] -tridecane molecules and deionized water is 10-50wt%.
Further, in the step (1), 7-nitrogenHeterospiro- [6,6]-the molar ratio of tridecane molecules to germanium sources is 3:4; the molar ratio of deionized water to germanium source is H 2 O:GeO 2 =37.5:1; preferably, the germanium source is at least one of germanium dioxide, tetramethyl germanium, isobutyl germane, germanium tetrachloride and germanium nitrate; more preferably, geO 2 After being added into the organic template solution, the mixture is stirred for 5 to 30 minutes at room temperature, so that the germanium source is fully dissolved, and a precursor structure with guiding function can be formed in the solution.
Further, in the step (1), the molar ratio of the silicon source to the germanium source is SiO 2 :GeO 2 After adding the silicon source to the clear solution, stirring for 30 minutes at room temperature, resulting in a reactant that is a gel mixture or clear solution, depending on the type of silicon source used and the time of stirring; preferably, the silicon source is at least one of tetraethyl silicate, silicic acid, fuming silica gel, water glass and silica sol.
Further, in the step (2), the crystallization conditions are as follows: spin-crystallizing at 150-180deg.C for 24-168 hr, preferably at 175 deg.C for 96 hr to achieve balance of reducing energy consumption and ensuring crystallization degree of sample; preferably, the rotation speed is 15-40rpm, preferably 40rpm if smaller grains are prepared, preferably 15rpm if larger grains are prepared or crystallized under standing conditions; more preferably, the crystallization process is full-course dynamic or static crystallization in a closed autoclave under a constant temperature state; the crystallization treatment also comprises the steps of washing, separating, drying and roasting the obtained crystallized product.
Further, in the step (3), the washing process is that deionized water is used for washing while suction filtration is performed until the pH value of the obtained filtrate is less than 8; the drying temperature is 60-90 ℃.
Further, in the step (4), the firing temperature is 500 to 700℃and the firing time is 3 to 4 hours, and it is more preferable that the firing is performed at 600℃for 3 hours.
Compared with the prior art, the invention has the following advantages:
(1) The invention takes 7-azaspiro- [6,6] -tridecane molecules as the organic template agent for preparing the silicon germanium UTL type zeolite molecular sieve, and the substance has the advantages of easy synthesis and simple structure, compared with the template agent for synthesizing the UTL type zeolite, which is reported before, the invention has low cost, simple and easy synthesis process, good selectivity to the UTL type zeolite, capability of synthesizing target products in a wider gel system, no fluoride ion is added in the crystallization process of the zeolite, relatively safe whole synthesis system, less pollution and environmental protection.
(2) The UTL type molecular sieve obtained by the preparation method of the silicon germanium UTL type zeolite molecular sieve provided by the invention has an intercommunicated two-dimensional 14x12 ultra-large pore canal system, is a catalytic material with great potential, has the advantages of perfect sample crystallinity, no impurities, stable structure after high-temperature roasting, good heat stability, and high germanium content of the sample, and creates a very powerful condition for subsequent structural recombination.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample before and after calcination obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a calcined sample obtained in example 1;
FIG. 3 is a thermogravimetric analysis (TGA) of the unfired sample obtained in example 1;
FIG. 4 is a nitrogen adsorption isotherm plot of the calcined sample obtained in example 1;
FIG. 5 is an X-ray diffraction (XRD) pattern of the calcined sample obtained in example 2;
FIG. 6 is an X-ray diffraction (XRD) pattern of the calcined sample obtained in example 3.
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will become apparent from the description. The embodiments are merely exemplary and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
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 present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As described in the background, the organic templates of the prior art are structurally complex and involve multiple reactions and purification steps. In order to solve the technical problems, the first aspect of the invention provides a preparation method of a silicon germanium UTL type zeolite molecular sieve, which takes 7-azaspiro- [6,6] -tridecane molecules as an organic template agent to prepare the molecular sieve.
The 7-azaspiro- [6,6] -tridecane molecule has the advantages of simple structure, no need of multi-step reaction, no easy mixing of impurities and no need of multiple purification steps; the invention takes the simple and easy-synthesized 7-azaspiro- [6,6] -tridecane molecule as the template agent in the preparation process of the zeolite molecular sieve, is very beneficial to the large-scale industrialized preparation of the zeolite molecular sieve, saves the cost to a certain extent and reduces the energy consumption.
The invention takes the 7-azaspiro- [6,6] -tridecane molecule as the organic template agent, does not need to be added with fluoride for assistance in the crystallization process, and avoids the problem of environmental pollution caused by fluoride. In addition, due to the action of charges, the existence of fluoride ions prevents aluminum and other trivalent metal elements from being doped in a zeolite framework, and the invention takes 7-azaspiro- [6,6] -tridecane molecules as an organic template agent, so that the method can be suitable for preparing the zeolite molecular sieve doped with trivalent metals.
Wherein the 7-azaspiro- [6,6] -tridecane is synthesized by a one-step synthesis reaction and a simple purification step involving evaporation of excess water and recrystallization of the solid from anhydrous diethyl ether.
Example 1
8.21g of the organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 10.32g deionized water were mixed uniformly, then 1.10g germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.48g of tetraethyl silicate was added thereto, and the mixture was stirred at room temperature for 45 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-pressure reaction kettle lining, dynamically crystallizing in an oven at 175 ℃ for 168 hours (40 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and carrying out conventional testing. The obtained solid product is characterized by an X-ray diffractometer to obtain XRD data shown in figure 1, the crystallinity of the sample is good, and the UTL type topological structure can be confirmed by comparing a standard spectrogram. As shown in FIG. 2, the molecular sieve is in a flake shape, the crystal size is relatively uniform, the length and width are about 5x5 μm, and the thickness is about 0.1 μm. The XRD pattern of the UTL-type molecular sieve after calcination at 600℃shows that the structure is still intact, indicating that the molecular sieve is stable at least at 600 ℃. As shown in FIG. 3, TGA analysis revealed that the total weight loss after calcination was about 20.0wt%.
In this example, the molecular sieve obtained was subjected to nitrogen adsorption and desorption at 77k (as shown in FIG. 4) to give a total specific surface area of 577m 2 Per gram, micropore volume of 0.20cm 3 And/g, average pore diameter of 1.7nm. Inductively coupled plasma emission spectrometry (ICP-OES) was performed to obtain a silicon to germanium ratio of about 3.3.
Example 2
8.21g of the organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 10.32g deionized water were mixed uniformly, then 2.3g germanium tetrachloride was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.48g of tetraethyl silicate was added thereto, and the mixture was stirred at room temperature for 45 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, dynamically crystallizing in an oven at 170 ℃ for 168 hours (40 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and carrying out conventional testing. The resulting solid product was characterized by X-ray diffractometry to give XRD data as shown in figure 5. The molecular sieve is well crystallized, and no amorphous product is found. It can be seen that the gel mixture with the same molar ratio has obtained a silicon germanium molecular sieve with good crystallinity and UTL type topological structure after 96 hours of dynamic crystallization.
Example 3
5.59g of the organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 15.37g deionized water were mixed uniformly and then 0.70g germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. After which 0.82g of SiO was added 2 The mixture was stirred at room temperature for 45 minutes while maintaining the sealed state, to obtain a gel mixture. The molar ratio of the gel mixture is SiO 2 :GeO 2 :SDAOH:H 2 O=0.8:0.4:0.3:60. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, dynamically crystallizing in an oven at 170 ℃ for 150 hours (40 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH value of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and carrying out conventional testing. The resulting solid product was characterized by X-ray diffractometry to give XRD data as shown in figure 6.
Example 4
11.97g of the organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 3.97g deionized water were mixed uniformly, then 3.07g germanium tetrachloride was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 6.07g of tetraethyl silicate was added thereto, and the mixture was stirred at room temperature for 45 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=0.8:0.4:0.3:15. Transferring the gel mixture into a high temperature resistant liner of a reaction kettle, dynamically crystallizing in an oven at 165 ℃ for 168 hours (40 rpm), taking out a sample, performing suction filtration, washing with water for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and thenRoutine testing was performed. The XRD data of the obtained solid product is shown in figure 6 by the characterization of an X-ray diffractometer, the XRD spectrum is changed relatively greatly after water is reduced, and small new peaks appear between 11-12 degrees and 16-17 degrees, so that the reduction of the water content of the synthetic gel can lead to the change of the topological structure, and the synthetic water content cannot be too low.
Example 5
10.40g of the organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 8.59g deionized water were mixed uniformly, then 1.35g tetramethyl germanium was added and stirred at room temperature for 10 minutes to give a clear solution. 1.23g of SiO was then added 2 The mixture was stirred at room temperature for 45 minutes while maintaining the sealed state, to obtain a gel mixture. The molar ratio of the gel mixture is SiO 2 :GeO 2 :SDAOH:H 2 O=0.8:0.4:0.4:30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, dynamically crystallizing in an oven at 175 ℃ for 140 hours (15 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH value of the obtained filtrate is less than 8, drying at 80 ℃, and roasting at 600 ℃ for 3 hours to obtain the UTL type molecular sieve with perfect crystallization.
Example 6
13.00g of organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 7.38g deionized water were mixed uniformly, then 1.05g germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. 1.23g of SiO was then added 2 The mixture was stirred at room temperature for 45 minutes while maintaining the sealed state, to obtain a gel mixture. The molar ratio of the gel mixture is SiO 2 :GeO 2 :SDAOH:H 2 O=0.8:0.4:0.5:60. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, dynamically crystallizing in an oven at 180 ℃ for 168 hours (40 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH value of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and obtaining the UTL type molecular sieve with well crystallized property, and carrying out conventional test.
Example 7
7.80g of organic template 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 9.80g deionized water were homogeneously mixed and then2.09g of germanium dioxide was added thereto and stirred at room temperature for 10 minutes to obtain a clear solution. Thereafter, 4.25g of tetraethyl silicate was added thereto, and the mixture was stirred at room temperature for 45 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=0.8:0.8:0.3:30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, dynamically crystallizing in an oven at 160 ℃ for 168 hours (40 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH value of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and carrying out conventional testing.
Example 8
10.40g of the organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 8.59g deionized water were mixed uniformly, then 2.09g 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 thereto, and the mixture was stirred at room temperature for 45 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=0.8:0.8:0.4:30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, dynamically crystallizing in an oven at 150 ℃ for 196 hours (40 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH value of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and carrying out conventional testing.
Example 9
13.00g of organic template 7-azaspiro- [6,6]Tridecane (19.16% in water) and 7.38g deionized water were mixed uniformly, then 2.09g 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 thereto, and the mixture was stirred at room temperature for 45 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=0.8:0.8:0.5:30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, dynamically crystallizing in an oven at 160 ℃ for 96 hours (40 rpm), taking out a sample, carrying out suction filtration, washing for many times until the pH value of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and carrying out conventional testing.

Claims (17)

1. The preparation method of the silicon germanium UTL type macroporous molecular sieve is characterized by comprising the following steps of:
(1) Mixing a solution of an organic template agent 7-azaspiro- [6,6] -tridecane hydroxide, a germanium source and deionized water, stirring until the mixture is clear, then dropwise adding a silicon source, and stirring at room temperature for 30min after the completion of dropwise adding of the silicon source to obtain a reactant;
(2) Transferring the gel reactant into a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the high-pressure reaction kettle into a rotary oven, and cooling to room temperature after rotary crystallization to obtain a solid product;
(3) And (3) washing the solid product obtained in the step (2) with deionized water until the pH of the filtrate is less than 8, and putting the filtrate into an oven for drying overnight to obtain the silicon germanium UTL type macroporous molecular sieve.
2. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 1, further comprising placing the UTL molecular sieve in a muffle furnace, and roasting to obtain the UTL molecular sieve with high crystallinity and removed template.
3. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 1, wherein in the step (1), the mass concentration of the solution formed by the 7-azaspiro- [6,6] -tridecane molecules and deionized water is 10-50wt%.
4. The method for preparing a silicon germanium UTL type macroporous molecular sieve as set forth in claim 3, wherein in said step (1), said 7-azaspiro- [6,6]-the molar ratio of tridecane molecules to germanium sources is 3:4; the molar ratio of deionized water to germanium source is H 2 O:GeO 2 =37.5:1。
5. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 4, wherein the germanium source is at least one of germanium dioxide, tetramethyl germanium, isobutyl germane, germanium tetrachloride and germanium nitrate.
6. The method for preparing a silicon germanium UTL type macroporous molecular sieve according to claim 5, wherein GeO 2 After being added into the organic template agent solution, the mixture is stirred for 5 to 30 minutes at room temperature, so that the germanium source is fully dissolved.
7. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 1, wherein in said step (1), the molar ratio of the silicon source to the germanium source is SiO 2 :GeO 2 After adding the silicon source to the clear solution, stirring for 30 minutes at room temperature, the reaction product was obtained as a gel mixture.
8. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 7, wherein the silicon source is at least one of tetraethyl silicate, silicic acid, fuming silica gel, water glass and silica sol.
9. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 1, wherein in the step (2), the crystallization treatment conditions are as follows: spin crystallizing at 150-180deg.C for 96-168 hr.
10. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 9, wherein the crystallization is rotated at 175 ℃ for 96 hours to achieve a balance between reducing energy consumption and ensuring the crystallization degree of the sample.
11. The method for preparing a silicon germanium UTL type macroporous molecular sieve according to claim 9, wherein the rotation speed is 15-40 rpm.
12. The method for preparing a silicon germanium UTL-type large pore molecular sieve according to claim 11, wherein the rotation speed of the prepared smaller crystal grains is 40 rpm.
13. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 11, wherein the rotation speed of the larger crystal grains is 15 rpm.
14. The method for preparing the silicon germanium UTL type macroporous molecular sieve according to claim 9, wherein the crystallization process is a full-course dynamic crystallization in a closed autoclave at a constant temperature; the crystallization treatment also comprises the steps of washing, separating, drying and roasting the obtained crystallized product.
15. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 1, wherein in the step (3), the washing process is that deionized water is used for washing while suction filtration is performed until the pH of the obtained filtrate is less than 8; the drying temperature is 60-90 ℃.
16. The method for preparing a silicon germanium UTL type macroporous molecular sieve according to claim 2, wherein the calcination temperature is 500-700 ℃ and the calcination time is 3-4 hours.
17. The method for preparing a silicon germanium UTL-type macroporous molecular sieve according to claim 16, wherein the calcination is performed at 600 ℃ for 3 hours.
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