CN117945421A - Synthesis method of large-granularity beta molecular sieve - Google Patents

Synthesis method of large-granularity beta molecular sieve Download PDF

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CN117945421A
CN117945421A CN202211275980.7A CN202211275980A CN117945421A CN 117945421 A CN117945421 A CN 117945421A CN 202211275980 A CN202211275980 A CN 202211275980A CN 117945421 A CN117945421 A CN 117945421A
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molecular sieve
beta molecular
additive
silicon source
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谷成
王永睿
罗一斌
邢恩会
陈腾巍
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Sinopec Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B39/04—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The present disclosure relates to a method of synthesizing a large particle size beta molecular sieve, the method comprising: mixing an organic template agent, a silicon source, an aluminum source, water and an optional alkali source with an additive, and crystallizing to obtain a beta molecular sieve; wherein the additive is an organic compound containing ether bond and hydroxyl, and the molar ratio of the additive to the silicon source is (0.05-0.5): 1, the silicon source is calculated by SiO 2. According to the scheme, on the basis of not changing the original beta molecular sieve synthesis raw materials and the proportion, the additive is added into a synthesis system, so that the granularity of the synthesized beta molecular sieve is increased. The synthesis method disclosed by the scheme has the advantages of simple synthesis steps, easiness in industrialization, good crystallinity of the synthesized sample, capability of meeting the requirements of different reactions on different particle sizes, and expansion of the application range of the beta molecular sieve.

Description

Synthesis method of large-granularity beta molecular sieve
Technical Field
The present disclosure relates to a method of synthesizing large particle size beta molecular sieves.
Background
Beta molecular sieves were first synthesized by Mobil in 1967 (US 3,308,069) and had a three-dimensional twelve-membered ring pore structure. Because the molecular sieve has unique topological structure and good thermal and hydrothermal stability, the molecular sieve has excellent catalytic performance in the reactions of hydrocracking, hydroisomerization, hydrocarbon cracking, alkylation and the like, and industrial production is realized at present.
The Beta molecular sieve can increase the yields of the C 4 component and the gasoline component in the product in the catalytic cracking reaction, but the Beta molecular sieve is easy to deactivate quickly in the reaction because the thermal/hydrothermal stability of the Beta molecular sieve is poorer than that of the ZSM-5 molecular sieve, and the application of the Beta molecular sieve is restricted. It is believed that larger grain molecular sieves are beneficial to enhance the thermal/hydrothermal stability of the molecular sieves and that increasing the particle size of the beta molecular sieves is one of the methods for improving the hydrothermal stability of the beta molecular sieves. Beta molecular sieve with silicon-aluminum ratio of about 50 is synthesized by using tetraethylammonium bromide as template agent in a system by Y J Lee et al (Journal of crystal growth,2006,297 (1): 138-145), the grain size can reach 1 mu m, but the template agent dosage is higher (TEABr/SiO 2 =0.72), and bromine-containing wastewater brought by synthesis is difficult to treat, has larger environmental pollution and is not suitable for industrial production. CN102923728 proposes a synthesis method of large-grain beta molecular sieve, using precipitated silicon and pseudo-boehmite as silicon source and aluminium source, adding tetraethylammonium hydroxide as template agent, and using tertiary alcohol amine as chelating agent. The grain size of the synthesized beta molecular sieve can reach 0.1 to 3 mu m. However, this method requires a high silicon source, too high a template dosage (TEAOH/SiO 2 =0.30), and the addition of seed crystals during synthesis.
In recent years, research has been attempted to introduce additives into a beta molecular sieve synthesis system to achieve the purpose of regulating the size of the molecular sieve, and CN112939008A proposes to introduce imidazole compounds into the beta molecular sieve synthesis system to achieve the purpose of regulating the size of crystal grains freely, but the method has the defects that a large amount of imidazole compounds are required to be added to achieve the purpose of increasing the size of the crystal grains, the synthesis cost is obviously increased, the subsequent recovery and three wastes are troublesome to treat, and the method has no industrial operability. CN108298552a proposes that one or more of dimethyl carbonate, diethyl carbonate or ethylmethyl carbonate is introduced into a beta molecular sieve synthesis system, so as to increase the granularity of beta molecular sieve, and in the actual operation process, the gel needs to be pre-crystallized under the condition of negative pressure, the method is complex in operation, the condition is harsh, and the industrial production is not facilitated.
Disclosure of Invention
It is an object of the present disclosure to provide a synthesis method of a beta molecular sieve that can increase the particle size of the beta molecular sieve.
In order to achieve the above object, the present disclosure provides a synthesis method of a large-particle-size beta molecular sieve, the method comprising:
Mixing an organic template agent, a silicon source, an aluminum source, water and an optional alkali source with an additive, and crystallizing to obtain a beta molecular sieve; wherein the additive is an organic compound containing ether bond and hydroxyl, and the molar ratio of the additive to the silicon source is (0.03-0.5): 1, the silicon source is calculated by SiO 2.
Alternatively, the additive has a carbon number of 3 to 50, preferably 3 to 20, a number of ether linkages of 1 to 20, preferably 1 to 5, and a number of hydroxyl groups of 1 to 25, preferably 1 to 5.
Optionally, the additive is one or more selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, glycerol methyl ether and 1, 3-dimethoxy-2-propanol.
Optionally, the molar ratio of the additive to the silicon source is (0.05-0.2): 1, the silicon source is calculated by SiO 2.
Optionally, the method further comprises mixing the alkali source, the aluminum source, the organic template agent and the water, adding the additive and the silicon source, and then performing the crystallization.
Optionally, the molar ratio of the silicon source to the aluminum source is (15-100): 1, wherein the molar ratio of the alkali source to the silicon source is (0-0.15): 1, the molar ratio of the organic template agent to the silicon source is (0.08-0.3): 1, the molar ratio of the water to the silicon source is (6-15): 1, wherein the silicon source is calculated as SiO 2, the aluminum source is calculated as Al 2O3, and the base source is calculated as OH -.
Optionally, the organic template is one or more selected from tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetrapropylammonium hydroxide.
Optionally, the silicon source is silica gel and/or silica-alumina gel.
Optionally, the aluminum source is one or more selected from hydrated alumina, sodium metaaluminate, aluminum hydroxide and silica-alumina gel.
Optionally, the alkali source is sodium hydroxide and/or potassium hydroxide.
Optionally, the crystallization conditions include: the process is carried out in a closed container, the temperature is 120-160 ℃, and the time is 36-84 h.
Through the technical scheme, the additive is added into the synthesis system on the basis of not changing the original beta molecular sieve synthesis raw materials and the proportion, so that the granularity of the synthesized beta molecular sieve is increased. The synthesis method disclosed by the scheme has the advantages of simple synthesis steps, easiness in industrialization, good crystallinity of the synthesized sample, capability of meeting the requirements of different reactions on different particle sizes, and expansion of the application range of the beta molecular sieve.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
figure 1 is an XRD spectrum of the beta molecular sieve prepared in example 1.
FIG. 2 is an SEM photograph of a beta molecular sieve prepared according to example 1.
Figure 3 is an XRD spectrum of the beta molecular sieve prepared in example 2.
Fig. 4 is an SEM photograph of the beta molecular sieve prepared in example 2.
Fig. 5 is an SEM photograph of the beta molecular sieve prepared in example 3.
Fig. 6 is an SEM photograph of the beta molecular sieve prepared in example 4.
Fig. 7 is an SEM photograph of the beta molecular sieve prepared in example 5.
Fig. 8 is an XRD spectrum of the beta molecular sieve prepared in comparative example 1.
Fig. 9 is an SEM photograph of the beta molecular sieve prepared in comparative example 1.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The present disclosure provides a method of synthesizing a large particle size beta molecular sieve, the method comprising:
Mixing an organic template agent, a silicon source, an aluminum source, water and an optional alkali source with an additive, and crystallizing to obtain a beta molecular sieve; wherein the additive is an organic compound containing ether bond and hydroxyl, and the molar ratio of the additive to the silicon source is (0.03-0.5): 1, the silicon source is calculated by SiO 2.
The proposal of the present disclosure provides a method for increasing the grain size of the beta molecular sieve based on the existing industrial synthesis beta molecular sieve technology, which meets the requirements of different reactions on different grain sizes and expands the application range of the beta molecular sieve.
The inventor of the present disclosure has found through research that the use of an organic compound containing an ether bond and a hydroxyl group as an additive to a synthesis system of a beta molecular sieve can effectively increase the grain size of the beta molecular sieve. The method has low cost and simple process, and is easy for industrial production.
According to the present disclosure, the additive is a water-soluble organic compound, which may have the following general formula: r 1OR2OHR3, wherein R 1、R2、R3 can be substituted or unsubstituted alkyl or alkoxy respectively, and wherein the substituent can be hydroxyl. Further, the carbon number of the additive may be 3 to 50, preferably 3 to 20, the number of ether bonds contained is 1 to 20, preferably 1 to 5, and the number of hydroxyl groups is 1 to 25, preferably 1 to 5. In a preferred embodiment of the present disclosure, R 2 is a group containing 2 carbon atoms, for example, the additive may be selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, glycerol methyl ether, 1, 3-dimethoxy-2-propanol, etc., and the beta molecular sieve synthesized by using the above additive has larger grain size and better crystallinity.
In a preferred embodiment of the present disclosure, the molar ratio of the additive to the silicon source is (0.05 to 0.2): 1, the silicon source is calculated by SiO 2. The beta molecular sieve synthesized by adopting the additive with the proportion is beneficial to further optimizing the grain size and the crystallinity of the product.
The alkali source, the organic template agent, the silicon source, the aluminum source, the water and the additive in the method can be uniformly mixed according to a conventional method, and then the obtained mixture is subjected to crystallization. In a preferred embodiment of the present disclosure, the method may further include mixing the alkali source, the aluminum source, the organic template agent with the water, adding the additive and the silicon source, and then performing the crystallization. The grain size and crystallinity of the product are further optimized by adjusting the addition sequence of the raw materials.
The dosage of each raw material except the additive in the synthesis system can be the common proportion of the synthesized beta molecular sieve. According to one embodiment of the present disclosure, the molar ratio of the silicon source to the aluminum source may be (15 to 100): 1, preferably (20 to 35): 1, a step of; the molar ratio of the alkali source to the silicon source may be (0 to 0.15): 1, preferably (0.05 to 0.12): 1, a step of; the molar ratio of the organic template to the silicon source may be (0.08-0.3): 1, preferably (0.09 to 0.2): 1, a step of; the molar ratio of the water to the silicon source may be (6-15): 1, preferably (7 to 10): 1, a step of; wherein the silicon source is calculated as SiO 2, the aluminum source is calculated as Al 2O3, and the base source is calculated as OH -.
The organic templating agent may be one commonly used in synthesizing beta molecular sieves, which is well known to those skilled in the art, in light of the present disclosure. Preferably, the organic template is one or more selected from tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide and tetrapropylammonium hydroxide.
The silicon source may be a silicon source commonly used in the synthesis of beta molecular sieves, which is well known to those skilled in the art, and is not particularly limited by the present disclosure. Preferably, the silicon source is silica gel and/or aluminosilicate, and the particle size of the silica gel and/or aluminosilicate is not particularly limited, for example, 150 to 250 μm.
The aluminum source may be a material commonly known in the art capable of providing elemental aluminum, preferably, the aluminum source is one or more selected from the group consisting of hydrated alumina, sodium metaaluminate, aluminum hydroxide, and silica-alumina gel. Wherein the hydrated alumina is alumina with crystal water, such as boehmite, surge alumina, boehmite, pseudo-boehmite, and the like. The particle size of the silica-alumina gel is not particularly limited, and is, for example, 150 to 250. Mu.m.
The alkali source may be an inorganic alkaline substance commonly known in the art, the kind of which is not particularly limited, and preferably, the alkali source is sodium hydroxide and/or potassium hydroxide.
The water may be water commonly used in the synthesis of molecular sieves, and deionized water is preferred in the present disclosure to avoid the introduction of heteroatoms.
According to the present disclosure, the crystallization conditions may be common crystallization conditions for synthesizing beta molecular sieves. In one embodiment of the present disclosure, the crystallization conditions may include: the process is carried out in a closed container, the temperature is 120-160 ℃, and the time is 36-84 h. The preferred crystallization conditions are two-stage crystallization, the first stage crystallization is carried out at 120-130 ℃ for 12-24 h and the second stage crystallization is carried out at 140-155 ℃ for 40-60 h.
After the crystallization is completed, the beta molecular sieve can be recovered by a common mode in the field. For example, the crystallized product is washed with water, filtered and dried to obtain the beta molecular sieve, and the drying conditions may be, for example: the temperature is 70-100 ℃ and the time is 12-24 h.
Compared with the traditional beta molecular sieve synthesis technology, the beta molecular sieve synthesized by the scheme has larger grain size, for example, the average grain size can be 150 nm-2 mu m, and compared with the synthesis method without adding the additive, the grain size of the beta molecular sieve can be increased by more than 25%.
The present disclosure is further disclosed below by way of examples, but is not thereby limited thereto.
In the following examples and comparative examples, the crystalline phase diagram history of X-ray diffraction (XRD) was determined by PHILIPS PANALYTICAL X' pert equipment under the following test conditions: cu target, K alpha radiation, ni filter, super energy detector, tube voltage 30KV and tube current 40mA; the crystallinity of Beta30 is 100% with the industrial sample of Hunan Chang Ling catalyst company, china Petroleum Co., ltd. The specific surface area was obtained by measuring a static N 2 adsorption/desorption curve of a sample at a liquid nitrogen temperature (77.4K) using an ASAP2405J static adsorber from Micromeritics company and performing BET fitting on an adsorption curve in the range of P/P 0 =0.05 to 0.35. The pore volume was measured according to the method described in RIPP-90 of petrochemical analysis method, written by Yang Cuiding et al. Scanning Electron Microscope (SEM) pictures were measured by a scanning electron microscope model quanti 200F from FEI company.
Example 1
Sodium metaaluminate solution (287 g/L of sodium oxide, 159.7g/L of aluminum oxide) and tetraethylammonium hydroxide (TEAOH, 2.417mol/L, guangzhou, inc.) are added into deionized water, mixed and stirred uniformly, ethylene glycol diethyl ether as an additive is added, and coarse pore silica gel (150-250 μm,500m 2/g, 0.9mL/g, shandong Yiming industry and trade company, inc.) is mixed with the above liquid, wherein the molar ratio of each component of the synthesis system is ,SiO2/Al2O3＝28,NaOH/SiO2＝0.10,TEAOH/SiO2＝0.12,H2O/SiO2＝7.0, ethylene glycol diethyl ether/SiO 2 =0.10. After stirring uniformly, transferring the obtained beta molecular sieve precursor into a pressure-resistant stainless steel reaction kettle, heating to 120 ℃ under stirring, crystallizing for 24 hours under autogenous pressure, crystallizing for 48 hours at 145 ℃, cooling the stainless steel pressure-resistant reaction kettle to room temperature, separating out a solid product, washing, and drying at 80 ℃ for 24 hours to obtain the beta molecular sieve.
XRD spectra of the beta molecular sieve prepared in the embodiment are shown in figure 1 (with characteristic diffraction peaks of the beta molecular sieve), SEM (scanning electron microscope) images are shown in figure 2, and physicochemical parameters of the product are shown in table 1.
Example 2
Beta molecular sieve was synthesized according to the method of example 1, except that ethylene glycol methyl ether of example 1 was replaced with additive ethylene glycol methyl ether, and the molar ratio of each component of the synthesis system was ,SiO2/Al2O3＝25,NaOH/SiO2＝0.12,TEAOH/SiO2＝0.12,H2O/SiO2＝6.5, ethylene glycol methyl ether/SiO 2 =0.10.
XRD spectra of the beta molecular sieve prepared by the implementation are shown in figure 3 (with characteristic diffraction peaks of the beta molecular sieve), SEM (scanning electron microscope) images are shown in figure 4, and physicochemical parameters of the product are shown in table 1.
Example 3
Sodium metaaluminate solution (287 g/L of sodium oxide, 159.7g/L of alumina) and tetraethylammonium hydroxide (TEAOH, 2.417mol/L, guangzhou Dai fine chemical Co., ltd.) are added into deionized water, 1, 3-dimethoxy-2-propanol is added after uniform mixing, then coarse pore silica gel (150-250 μm,500m 2/g, 0.9mL/g, shandong Yiming industry and trade Co., ltd.) and pseudo-boehmite are added into the suspension, and the molar ratio of each component of the synthesis system is ：SiO2/Al2O3＝25,NaOH/SiO2＝0.12,TEAOH/SiO2＝0.10,H2O/SiO2＝7.0,1,3- dimethoxy-2-propanol/SiO 2 =0.10. Transferring the obtained beta molecular sieve precursor into a pressure-resistant stainless steel reaction kettle, heating to 125 ℃ under stirring, crystallizing for 24 hours under autogenous pressure, crystallizing for 48 hours at 145 ℃, separating out a solid product after the stainless steel pressure-resistant reaction kettle is cooled to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain the beta molecular sieve.
SEM image of beta molecular sieve prepared in this example is shown in FIG. 5, and physicochemical parameters of the product are shown in Table 1.
Example 4
Sodium metaaluminate solution (287 g/L of sodium oxide, 159.7g/L of alumina) and tetraethylammonium hydroxide (TEAOH, 2.417mol/L of Guangzhou large fine chemical industry Co., ltd.) are added into deionized water, ethylene glycol diethyl ether is added after uniform mixing and stirring, coarse pore silica gel (150-250 μm,500m 2/g, 0.9mL/g, shandong Yiming industry trade Co., ltd.) is added into the solution, pseudo-boehmite is added, stirring and mixing are uniform, and the molar ratio of each component of the synthesis system is ：SiO2/Al2O3＝25,NaOH/SiO2＝0.12,TEAOH/SiO2＝0.10,H2O/SiO2＝7.5, ethylene glycol diethyl ether/SiO 2 =0.15. Transferring the obtained beta molecular sieve precursor into a pressure-resistant stainless steel reaction kettle, heating to 120 ℃ under stirring, crystallizing for 24 hours under autogenous pressure, crystallizing for 48 hours at 145 ℃, separating out a solid product after the stainless steel pressure-resistant reaction kettle is cooled to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain the beta molecular sieve.
SEM image of beta molecular sieve prepared in this example is shown in FIG. 6, and physicochemical parameters of the product are shown in Table 1.
Example 5
Beta molecular sieves were synthesized as in example 4, except that the molar ratio of the components of the synthesis system was ,SiO2/Al2O3＝25,NaOH/SiO2＝0.12,TEAOH/SiO2＝0.10,H2O/SiO2＝7.5, ethylene glycol ethyl ether/SiO 2 =0.03.
SEM image of beta molecular sieve prepared by this embodiment is shown in FIG. 7, and physicochemical parameters of the product are shown in Table 1.
Example 6
Beta molecular sieves were synthesized as in example 4, except that the molar ratio of the components of the synthesis system was ,SiO2/Al2O3＝25,NaOH/SiO2＝0.12,TEAOH/SiO2＝0.10,H2O/SiO2＝7.5, ethylene glycol ethyl ether/SiO 2 =0.5.
The physicochemical parameters of the beta molecular sieve prepared by the implementation are shown in table 1.
Comparative example 1
Adding sodium metaaluminate solution (145.8 g/L of sodium oxide, 102.8g/L of aluminum oxide) and tetraethylammonium hydroxide (TEAOH, 2.417mol/L, guangzhou, large and fine chemical industry Co., ltd.) into deionized water, heating for dissolving, stirring uniformly to prepare working solution, mixing coarse pore silica gel (150-250 μm,500m 2/g, 0.9ml/g, qingdao ocean chemical industry Co.) with the working solution, wetting the surface of the silica gel with the working solution to obtain a reaction mixture, crystallizing the reaction mixture in a high-pressure reaction kettle at 120 ℃ for 24 hours at the molar ratio of each component of the synthesis system at 140 ℃ for 48 hours, cooling to room temperature, separating a solid product, washing, and drying at 80 ℃ for 24 hours to obtain beta molecular sieves.
XRD patterns of the beta molecular sieves prepared in this comparative example are shown in FIG. 8 (having characteristic diffraction peaks of beta molecular sieves), and SEM patterns are shown in FIG. 9. The physical and chemical parameters of the product are shown in Table 1.
Comparative example 2
The comparative example synthesizes beta molecular sieve according to the method provided by CN103073018A, which comprises the following concrete steps:
Silica-alumina gel (300-450 μm,415m 2/g, 0.749 ml/g) and tetraethylammonium hydroxide (TEAOH, 2.417mol/g, guangzhou Co., ltd.) were added to deionized water, heated to dissolve, stirred well, and made into working solution, so that the surface of the solid particles was wetted by the working solution. The molar ratio of the components of the synthesis system is SiO 2/Al2O3＝25,TEAOH/SiO2＝0.12,H2O/SiO2 =6.5. Crystallizing the reaction mixture in a high-pressure reaction kettle at 120 ℃ for 24 hours, crystallizing at 145 ℃ for 48 hours, cooling to room temperature, separating out a solid product, washing, and drying at 110 ℃ to obtain the beta molecular sieve.
The physicochemical parameters of the beta molecular sieve prepared in this comparative example are shown in Table 1.
Comparative example 3
Adding sodium metaaluminate solution (sodium oxide 287g/L, aluminum oxide 159.7 g/L) and tetraethylammonium hydroxide (TEAOH, 2.417mol/L, guangzhou large fine chemical industry Co., ltd.) into deionized water, mixing and stirring uniformly, mixing coarse pore silica gel (150-250 μm,500m 2/g, 0.9mL/g, shandong Yiming Yimao Co., ltd.) with the above liquid, stirring uniformly according to the molar ratio of each component of the synthesis system of SiO2/Al2O3＝25,NaOH/SiO2＝0.12,TEAOH/SiO2＝0.10,H2O/SiO2＝6.5., transferring the obtained beta molecular sieve precursor into a pressure-resistant stainless steel reaction kettle, heating to 120 ℃ under stirring condition, crystallizing for 24 hours under autogenous pressure, crystallizing for 48 hours at 145 ℃, separating out a solid product after the stainless steel pressure-resistant reaction kettle is cooled to room temperature, washing, and drying at 80 ℃ for 24 hours to obtain the beta molecular sieve.
The physicochemical parameters of the beta molecular sieve prepared in this comparative example are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the properties of crystallinity, specific surface area, total pore volume and the like of the beta molecular sieve synthesized according to the technical scheme disclosed by the invention are basically the same as those of the beta molecular sieve synthesized by the conventional method, but the average particle size can reach more than 150nm, and the particle size of the beta molecular sieve synthesized by the method without adding the additive is lower than 120nm.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the embodiments described above, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (10)

1. A synthesis method of a large-granularity beta molecular sieve is characterized by comprising the following steps:
Mixing an organic template agent, a silicon source, an aluminum source, water and an optional alkali source with an additive, and crystallizing to obtain a beta molecular sieve; wherein the additive is an organic compound containing ether bond and hydroxyl, and the molar ratio of the additive to the silicon source is (0.03-0.5): 1, the silicon source is calculated by SiO 2.
2. The method according to claim 1, wherein the additive has 3 to 20 carbon atoms, 1 to 5 ether bonds and 1 to 5 hydroxyl groups.
3. The method of claim 2, wherein the additive is one or more selected from the group consisting of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, glycerol methyl ether, and 1, 3-dimethoxy-2-propanol.
4. The method of claim 1, wherein the molar ratio of the additive to the silicon source is (0.05-0.2): 1, the silicon source is calculated by SiO 2.
5. The method of claim 1, further comprising mixing the alkali source, the aluminum source, the organic templating agent with the water, adding the additive and the silicon source, and then performing the crystallization.
6. The method of claim 1, wherein the molar ratio of the silicon source to the aluminum source is (15-100): 1, wherein the molar ratio of the alkali source to the silicon source is (0-0.15): 1, the molar ratio of the organic template agent to the silicon source is (0.08-0.3): 1, the molar ratio of the water to the silicon source is (6-15): 1, wherein the silicon source is calculated as SiO 2, the aluminum source is calculated as Al 2O3, and the base source is calculated as OH -.
7. The method of claim 1, wherein the organic template is one or more selected from tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetrapropylammonium hydroxide.
8. The method of claim 1, wherein the silicon source is a silica gel and/or a silica-alumina gel.
9. The method of claim 1, wherein the aluminum source is one or more selected from the group consisting of hydrated alumina, sodium metaaluminate, aluminum hydroxide, and silica-alumina gel;
The alkali source is sodium metaaluminate, sodium hydroxide and/or potassium hydroxide.
10. The method of claim 1, wherein the crystallization conditions include: the process is carried out in a closed container, the temperature is 120-160 ℃, and the time is 36-84 h.
CN202211275980.7A 2022-10-18 2022-10-18 Synthesis method of large-granularity beta molecular sieve Pending CN117945421A (en)

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