CN108217672B - Preparation method of β molecular sieve - Google Patents

Preparation method of β molecular sieve Download PDF

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CN108217672B
CN108217672B CN201611155367.6A CN201611155367A CN108217672B CN 108217672 B CN108217672 B CN 108217672B CN 201611155367 A CN201611155367 A CN 201611155367A CN 108217672 B CN108217672 B CN 108217672B
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molecular sieve
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CN108217672A (en
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崔岩
王晓化
沈宜泓
邢昕
李梦晨
王飞
郭成玉
刘其武
庞新梅
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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

Abstract

The invention discloses a preparation method of β molecular sieve, which comprises the steps of (1) synthesizing a directing agent, mixing a silicon source, an aluminum source, a template agent, a sodium source, water and a microwave auxiliary agent, uniformly stirring, heating at 120-180 ℃ for 1-20 h by microwave, (2) synthesizing a molecular sieve main body, mixing the silicon source, the aluminum source, the sodium source and the water, uniformly stirring, and (3) synthesizing the molecular sieve, wherein the directing agent prepared in the step (1) and the molecular sieve main body prepared in the step (2) are mixed according to the mass ratio of 0.05-0.25: 1, crystallizing for 10-60 h at the crystallization temperature of 120-180 ℃, and then flocculating by ammonium salt, washing, filtering and drying to obtain β molecular sieve.

Description

Preparation method of β molecular sieve
Technical Field
The invention relates to a preparation method of a molecular sieve, in particular to a synthesis method of an β molecular sieve.
Background
β Zeolite is a proprietary product USP3308069 developed by Mobil Petroleum company in 1967, earlier reports that β Zeolite has excellent catalytic properties and that Mobil corporation develops β Zeolite, later patents EP0159846, EP0159847, disclose that β Zeolite has excellent activity for hydrocarbon cracking and isomerization since 90 s, with the knowledge of β Zeolite crystal structure, the synthesis and catalytic properties of β Zeolite has rapidly developed, and the gleaned reports that β Zeolite is superior to ZMS-5 Zeolite in pore structure, integrating Y and ZSM-5 advantages into one body, and its silica-alumina ratio can be modulated in a very large range, making it possible to produce zeolite with a controlled hydrothermal stability for a period of time, generally more than β hours, and to provide a catalyst with a controlled hydrothermal stability for a period of time, more than β.
93117593.3 discloses a method for synthesizing β zeolite, which is characterized in that a guiding agent is adopted, and the guiding agent is prepared by dissolving aluminum salt in tetraethylammonium hydroxide and sodium hydroxide aqueous solution and adding active silicon dioxide.
CN100344536C discloses a method for synthesizing β zeolite by a template agent concentration uneven distribution method, which comprises the steps of dividing a synthesis system into two parts, namely a main part and an auxiliary part, respectively feeding the two parts, uniformly mixing the main part and the auxiliary part, carrying out sectional crystallization at the temperature of 140-170 ℃, wherein the crystallization time is 24-48 hours, and washing, filtering and drying a product to obtain a β zeolite product with high crystallinity.
In summary, the synthesis of β molecular sieve by the guiding agent method is a general idea, and the molecular sieve synthesized by the method has high crystallinity, but still has the defects of long synthesis time and high cost.
Disclosure of Invention
The invention mainly aims to provide a preparation method of an β molecular sieve, which overcomes the defects of large template dosage and long preparation time in the preparation process of a β molecular sieve in the prior art.
In order to achieve the above object, the present invention provides a preparation method of β molecular sieve, comprising:
(1) synthesis of a directing agent: mixing a silicon source, an aluminum source, a template agent, a sodium source, water and a microwave auxiliary agent, uniformly stirring, heating by microwave at the temperature of 120-180 ℃ for 1-20 h;
(2) synthesizing a molecular sieve main body: mixing a silicon source, an aluminum source, a sodium source and water, and uniformly stirring; and
(3) and (3) synthesizing the molecular sieve, namely mixing the directing agent prepared in the step (1) with the molecular sieve main body prepared in the step (2) according to the mass ratio of 0.05-0.25: 1, crystallizing for 10-60 hours at the crystallization temperature of 120-180 ℃, and then flocculating with ammonium salt, washing, filtering and drying to obtain the β molecular sieve.
The preparation method of the β molecular sieve comprises the step (1) of using SiO as a silicon source2Calculated by Al as the aluminum source2O3In terms of Na as the sodium source2In terms of O, the mixing molar ratio is preferably: SiO 22/Al2O320-100 parts of template agent/SiO2＝0.1～0.3，Na2O/SiO20.05 to 0.12 of water/SiO23.0 to 10.0 of microwave adjuvant/SiO20.01 to 0.2; the mixing temperature is preferably 40-80 ℃.
The preparation method of the β molecular sieve, disclosed by the invention, is characterized in that in the step (2), the silicon source is SiO2Calculated by Al as the aluminum source2O3In terms of Na as the sodium source2In terms of O, the mixing molar ratio is preferably: SiO 22/Al2O3＝20～100，Na2O/SiO20.05 to 0.12 of water/SiO2The mixing temperature is preferably from 40 to 80 ℃ and is from 3.0 to 10.0.
The β molecular sieve preparation method of the invention, wherein the microwave adjuvant is preferably alcohols.
The β molecular sieve preparation method of the invention, wherein the microwave adjuvant is further preferably methanol, ethylene glycol or glycerol.
The β molecular sieve preparation method of the invention, wherein the template agent is preferably tetraethylammonium hydroxide or tetraethylammonium bromide.
The β molecular sieve preparation method of the invention, wherein, the silicon source is preferably silica sol, white carbon black or coarse silica gel.
The β molecular sieve preparation method of the invention, wherein the aluminum source is preferably sodium metaaluminate or aluminum sulfate.
The β molecular sieve preparation method is characterized in that the sodium source is preferably sodium hydroxide.
The invention has the following beneficial effects:
the catalyst main body part of the invention has no template agent, the template agent is only distributed in the guiding agent part, the molecular sieve microcrystal concentration in the guiding agent obtained by microwave treatment is very high, and the invention has very strong capability of inducing and synthesizing β molecular sieve, after the inducing agent is added into the main body part, the induction of the main body part to generate β molecular sieve crystal can be further accelerated, the crystallization time can be shortened on the whole, the dosage of the organic template agent is reduced, and the production cost is reduced.
The synthesized β molecular sieve has higher crystallinity and richer pore structure under the condition of reducing the dosage of the template agent.
Drawings
FIG. 1 is an XRD spectrum of the synthesized material of example 2;
FIG. 2 is an XRD spectrum of the synthesized material of example 3;
FIG. 3 is an XRD spectrum of the as-synthesized material of example 7;
FIG. 4 is an XRD spectrum of the synthetic material of comparative example 1;
FIG. 5 is an XRD spectrum of the synthetic material of comparative example 4;
figure 6 is an XRD spectrum of the standard.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The β molecular sieve preparing process of the present invention has common silicon source, preferably silica sol, silica white and coarse silica gel.
The invention relates to a preparation method of β molecular sieve, wherein the template agent is the commonly used synthetic β molecular sieve template agent, preferably tetraethyl ammonium hydroxide and tetraethyl ammonium bromide.
The β molecular sieve preparing method of the invention, wherein the aluminum source used is a common aluminum source, preferably sodium metaaluminate and aluminum sulfate.
The β molecular sieve is prepared by using common alcohols or other high dielectric loss substances as microwave assistant, preferably methanol, glycol and glycerol.
The β molecular sieve prepared by the preparation method of the β molecular sieve is preferably applied to a cracking or isomerization reaction catalyst.
The microwave is an electromagnetic wave with extremely short wavelength and extremely high frequency, the wavelength is 1mm-1m, the frequency is 300MHz-300GHz, and the microwave is positioned between infrared light and radio wave. The microwave frequency for heating is typically fixed at 2450MHz or 915 MHz. The basic principle of microwave heating is as follows: under the action of the external alternating electromagnetic field, polar molecules in the material are polarized and frequently turn to friction along with the change of the polarity of the external alternating electromagnetic field, so that electromagnetic energy is converted into heat energy. The microwave heating has the characteristics of high and uniform heating speed, high energy utilization rate, environmental protection and the like. Most notably, microwaves have shown the ability to influence reaction kinetics and selectivity in the synthesis of nanoporous materials. The microwave treatment is utilized to synthesize the guiding agent, so that the material can be depolymerized into gel, the time for forming molecular sieve microcrystal is greatly shortened, a high-concentration microcrystal system can be quickly formed, and the subsequent mixed crystallization effect is huge.
The raw materials used in the invention are:
silicon source: silica sol (solid content 30%), white carbon black, coarse-pore silica gel;
template agent: TEAOH (tetraethylammonium hydroxide) solution, the effective concentration of the solution is 35%; TEABr (tetraethylammonium bromide) solid;
an aluminum source: NaAlO2Sodium metaaluminate, Al2(SO4)2(aluminum sulfate);
microwave auxiliary agent: methanol, ethylene glycol, glycerol;
and others: deionized water, NaOH (sodium hydroxide).
Relative crystallinity was determined by phase analysis of samples using powder X-ray diffraction (XRD) techniques, using β molecular sieve (a commercially available Nankai catalyst works β molecular sieve product) standards of known relative crystallinity as external standards, and determining the relative crystallinity of each sample as a relative ratio of the characteristic diffraction peak areas, the XRD pattern of the standard being shown in FIG. 6.
Relative crystallinity measuring instrument: dutch Pasnake X-Pert Pro type X-ray powder diffractometer.
Relative crystallinity determination conditions: and (3) CuK rays, wherein the tube voltage is 45kV, the tube current is 40mA, the scanning range of the measured crystalline phase is 5-60 degrees, and the scanning speed is 4 degrees/min.
Example 1
In a water bath at 70 ℃, 1.78g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 2.80g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse silica gel, adding 0.21g of ethylene glycol, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and processing for 4h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And then, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 10 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 15 hours, and obtaining the β molecular sieve which is marked as β -1 after the reaction is finished and products are washed, filtered, dried and roasted.
Example 2
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse silica gel, adding 0.21g of ethylene glycol, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and processing for 4h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
Secondly, mixing the directing agent and the main body, stirring uniformly, controlling the reaction temperature to be 140 ℃, the reaction time to be 10 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 15 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein an XRD spectrogram marked as β -2, β -2 is shown in figure 1, the relative crystallinity of β -2 is obviously higher than β -1, and the effect of the directing agent is better mainly because the addition amount of a template agent is increased in the directing agent.
Example 3
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse silica gel, adding 0.21g of ethylene glycol, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and processing for 4h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
Secondly, mixing the guiding agent and the main body, stirring uniformly, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein an XRD spectrogram marked as β -3, β -3 is shown in an attached figure 2, and the relative crystallinity of β -3 is obviously higher than β -2, mainly because the crystallization process time is prolonged, the molecular sieve is more beneficial to the growth of molecular sieve crystals.
Example 4
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.38g of aluminum sulfate was added, and 4.20g of TEAOH solution was added and dissolved by stirring. Adding 2.00g of white carbon black and 0.11g of methanol, stirring uniformly, controlling the temperature to be 170 ℃ under microwave, and treating for 1h to prepare the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 3.42g of aluminum sulfate was added and dissolved by stirring. Adding 18.00g of white carbon black, and uniformly stirring to obtain a main body part.
And secondly, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain the β molecular sieve, wherein the relative crystallinity is lower, which is marked as β -4, β -4, mainly because the microwave treatment time of the directing agent is shorter, and the formed molecular sieve has relatively fewer microcrystals.
Example 5
In a water bath at 70 ℃, 1.31 g of deionized water and 0.27g of sodium hydroxide are added and stirred to dissolve. 0.27g of sodium metaaluminate and 6.30g of TEAOH solution were added and dissolved by stirring. Adding 3g of coarse silica gel and 0.31g of ethylene glycol, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and treating for 4h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And then, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein the relative crystallinity is marked as β -5, β -5 is obviously higher than β -3, mainly because the addition amount of the directing agent is increased, the subsequent crystallization effect is better.
Example 6
In a water bath at 70 ℃, 0.87g of deionized water and 0.21g of sodium hydroxide are added and stirred to dissolve. Sodium metaaluminate (0.11 g) and TEAOH (4.20 g) were added and dissolved by stirring. Adding 2.00g of coarse silica gel, adding 0.21g of ethylene glycol, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and processing for 4h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.92g of sodium hydroxide were added and dissolved by stirring. 0.984g of sodium metaaluminate is added and stirred to dissolve. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And secondly, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein the relative crystallinity is marked as β -6, β -6 is obviously lower than β -3, and the relative crystallinity is mainly increased due to the fact that the feeding silicon-aluminum ratio is increased and the crystallization difficulty is increased.
Example 7
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse silica gel, adding 0.21g of ethylene glycol, stirring uniformly, controlling the temperature at 120 ℃ under microwave, and processing for 4h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And then, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein an XRD spectrogram is recorded as β -7, β -7 and is shown in figure 3, the relative crystallinity of β -7 is slightly lower than β -3, mainly because the microwave treatment temperature of the directing agent is lower, the microcrystalline concentration of the molecular sieve in the directing agent is lower, and the subsequent crystallization process is influenced.
Example 8
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse silica gel, adding 0.21g of ethylene glycol, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and processing for 20h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And secondly, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein the relative crystallinity is β -8, β -8 is obviously lower than β -3, mainly because the microwave treatment time of the directing agent is too long, β molecular sieve crystals with small crystal grains are generated in the directing agent, and the action of the directing agent is weakened.
Example 9
In a water bath at 70 ℃, 3.34g of silica sol and 0.30g of sodium hydroxide are added and stirred to dissolve. 0.30g of sodium metaaluminate and 3.50g of TEABr solid are added and dissolved by stirring. Adding 0.51g of glycerol, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and processing for 4h to obtain the guiding agent.
Next, in a 70 ℃ water bath, 22.00g of deionized water and 1.78g of sodium hydroxide were added and dissolved by stirring. 1.82g of sodium metaaluminate is added and dissolved by stirring. Adding 20.00g of silica sol, and stirring uniformly to obtain a main body part.
And then, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and obtaining β molecular sieve, which is marked as β -9, after the reaction is finished and products are washed, filtered, dried and roasted.
Comparative example 1
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse silica gel, stirring uniformly, controlling the temperature at 170 ℃ under microwave, and processing for 4h to obtain the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And then, mixing the guiding agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting the product to obtain the β molecular sieve, wherein an XRD (X-ray diffraction) spectrogram of β -contrast 1, β -contrast 1 is shown in an attached figure 4, the relative crystallinity of β -contrast 1 is slightly lower than that of β -3, because no microwave auxiliary agent is added, the efficiency of the guiding agent for receiving microwave radiation is reduced, and the microcrystalline concentration of the molecular sieve in the guiding agent is lower.
Comparative example 2
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse-pore silica gel, stirring uniformly, standing and aging for 4h at normal temperature to prepare the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And then, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and obtaining the β molecular sieve after the reaction is finished and the product is washed, filtered, dried and roasted, wherein the relative crystallinity is marked as β -contrast 2, β -contrast 2 is poor.
Comparative example 3
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse-pore silica gel, stirring uniformly, standing and aging for 24h at normal temperature to prepare the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And secondly, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein the relative crystallinity is recorded as β -contrast 3, β -contrast 3 is slightly higher than that of β -contrast 2, but the total crystallinity is not high.
Comparative example 4
In a water bath at 70 ℃, 0.87g of deionized water and 0.18g of sodium hydroxide are added and stirred to dissolve. 0.18g of sodium metaaluminate and 4.20g of TEAOH solution were added and dissolved by stirring. Adding 2.00g of coarse-pore silica gel, stirring uniformly, standing and aging for 48h at normal temperature to prepare the guiding agent.
Next, in a water bath at 70 ℃, 32.40g of deionized water and 1.60g of sodium hydroxide were added and dissolved with stirring. 1.64g of sodium metaaluminate is added and dissolved by stirring. 18.00g of coarse silica gel was added thereto, and stirred uniformly to obtain a main body portion.
And then, mixing the directing agent and the main body, uniformly stirring, controlling the reaction temperature to be 140 ℃, the reaction time to be 24 hours, controlling the reaction temperature to be 180 ℃, the reaction time to be 24 hours, and after the reaction is finished, washing, filtering, drying and roasting a product to obtain an β molecular sieve, wherein an XRD spectrogram marked as β -contrast 4, β -contrast 4 is shown in an attached figure 5, the relative crystallinity of β -contrast 4 is slightly higher than that of β -contrast 3, but the total crystallinity is not high.
The relative crystallinity of the example and comparative example molecular sieves obtained from FIGS. 1 to 6 is shown in Table 1.
Table 1 relative crystallinity data for the products of the examples and comparative examples
Figure BDA0001180576030000101
The difference between the comparative example 1 and the example is that the microwave auxiliary agent is not added, so that the efficiency of the guiding agent for receiving microwave radiation is reduced, and the microcrystalline concentration of the molecular sieve in the guiding agent is lower; comparative examples 2 to 4 are different from the examples in that the preparation of the directing agent is not carried out by microwave heating, but is carried out by aging at normal temperature, and after the aging time is up to 48 hours, the product crystallinity is still found to be poor in the subsequent crystallization reaction, and occasionally, mixed crystals appear; it can also be seen from table 1 that the crystallinity of the comparative example is much lower than that of the examples, so the present invention adds a microwave heating step in the preparation process of the directing agent, which can greatly reduce the amount of the template agent and greatly shorten the preparation time of the catalyst on the premise of ensuring high crystallinity.
The invention has the following beneficial effects:
the catalyst main body part of the invention has no template agent, the template agent is only distributed in the guiding agent part, the molecular sieve microcrystal concentration in the guiding agent obtained by microwave treatment is very high, and the invention has very strong capability of inducing and synthesizing β molecular sieve, after the inducing agent is added into the main body part, the induction of the main body part to generate β molecular sieve crystal can be further accelerated, the crystallization time can be shortened on the whole, the dosage of the organic template agent is reduced, and the production cost is reduced.
Compared with the prior art, the method can greatly shorten the time for synthesizing the directing agent, and the microwave treatment is more favorable for forming a large amount of high-activity molecular sieve microcrystals than conventional heating or normal-temperature aging, so that the method is more powerful for shortening the time of the subsequent crystallization process and improving the crystallinity of the product; and the template agent dosage is smaller, thus being more beneficial to reducing the production cost and reducing the environmental pollution.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. A preparation method of β molecular sieve, which is characterized in that the preparation method comprises the following steps:
(1) synthesis of a directing agent: mixing a silicon source, an aluminum source, a template agent, a sodium source, water and a microwave auxiliary agent, uniformly stirring, heating by microwave at the temperature of 120-180 ℃ for 1-20 h; wherein the microwave adjuvant is alcohol;
(2) synthesizing a molecular sieve main body: mixing a silicon source, an aluminum source, a sodium source and water, and uniformly stirring; and
(3) and (3) synthesizing the molecular sieve, namely mixing the directing agent prepared in the step (1) with the molecular sieve main body prepared in the step (2) according to the mass ratio of 0.05-0.25: 1, crystallizing for 10-60 hours at the crystallization temperature of 120-180 ℃, and then flocculating with ammonium salt, washing, filtering and drying to obtain the β molecular sieve.
2. The method of claim 1, wherein the silicon source in step (1) is SiO2Calculated by Al as the aluminum source2O3In terms of Na as the sodium source2Calculated by O, the mixing molar ratio is as follows: SiO 22/Al2O320-100 parts of template agent/SiO2＝0.1～0.3，Na2O/SiO20.05 to 0.12 of water/SiO23.0 to 10.0 of microwave adjuvant/SiO20.01 to 0.2; the mixing temperature is 40-80 ℃.
3. The method of claim 1, wherein the silicon source in step (2) is SiO2Calculated by Al as the aluminum source2O3In terms of Na as the sodium source2Calculated by O, the mixing molar ratio is as follows: SiO 22/Al2O3＝20～100，Na2O/SiO20.05 to 0.12 of water/SiO23.0-10.0 percent; the mixing temperature is 40-80 ℃.
4. The method of claim 1, wherein the microwave adjuvant is methanol, ethylene glycol, or glycerol.
5. The method of claim 1, wherein the templating agent is tetraethylammonium hydroxide or tetraethylammonium bromide.
6. The method of claim 1, wherein the silicon source is silica sol, silica white or silica coarse.
7. The method for preparing β molecular sieve according to claim 1, wherein the aluminum source is sodium metaaluminate or aluminum sulfate.
8. The method of claim 1, wherein the sodium source is sodium hydroxide.
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