CN112499643A - Method for synthesizing MCM-49 type zeolite molecular sieve under organic template-free condition - Google Patents
Method for synthesizing MCM-49 type zeolite molecular sieve under organic template-free condition Download PDFInfo
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Abstract
The invention provides a method for synthesizing an MCM-49 type zeolite molecular sieve under the condition of no organic template agent. Forming the silicon-aluminum gel by stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO23-15. Firstly, aging the silica-alumina gel, adding an MCM-49 type zeolite molecular sieve into the silica-alumina gel to be used as a seed crystal, and then carrying out hydrothermal treatment to obtain a crystallized product. And cooling the product at room temperature, washing to be neutral, drying and calcining to obtain MCM-49 zeolite molecular sieve powder. The synthesis method provided by the invention does not need to add an organic template agent, reduces the cost and avoids the pollution of the environment caused by the use of hexamethyleneimine. The MCM-49 type zeolite molecular sieve product obtained by the method can be used as seed crystals and continuously used in the process of synthesizing the MCM-49 type molecular sieve in a new round.
Description
Technical Field
The invention belongs to the technical field of molecular sieve synthesis, and particularly relates to a method for synthesizing an MCM-49 type zeolite molecular sieve under the condition of no organic template agent.
Background
In 1993, Bennett et al reported the synthesis of MCM-49 molecular sieves. The MCM-49 molecular sieve is the first direct synthesis type MWW lamellar structure molecular sieve which does not undergo precursor calcination, has the same framework structure as the calcination type MCM-22 without changing the structure before and after calcination, but has difference in microstructure and framework aluminum distribution. Lawton et al concluded that MCM-49 has a longer unit cell c-axis parameter than MCM-22 and hypothesize that this may be related to the different framework aluminum distributions of the two. The content of MCM-22 interlayer template agent is higher than that of MCM-49, and the content of framework aluminum in the MCM-49 is higher than that of MCM-22. The MCM-49 molecular sieve has wide application prospect in alkylation, aromatization, catalytic cracking, isomerization and other reactions due to the unique pore channel structure.
CN 1789126A (2006) reports a synthesis method of MCM-22 family molecular sieve, which is technically characterized in that a diamine liquid mixture of hexamethylene imine (HMI) and any one of cyclohexylamine, butylamine or isopropylamine is used as a template agent to hydrothermally synthesize the MWW structure molecular sieve.
CN 103848433a and CN 103848433B8(2012) report a method for producing MCM-49 molecular sieves. The method is technically characterized in that a hexamethylene imine-cyclohexylamine binary template agent is used, and an organic silicon source and a seed crystal are used. However, the system still can not be separated from the classical hexamethylene imine, and the silica-alumina ratio range of the gel is narrow.
CN 104958664(2015) reports a preparation method of a nano MCM-49 molecular sieve. The method is technically characterized by mixing a silicon source, an aluminum source, a template agent and water in proportion, then adding MCM-49 molecular sieve active seed crystals accounting for 0.01-1% of the dry basis weight of the mixture into the mixture, and crystallizing for 0.1-100 hours at the temperature of 156-185 ℃ to obtain the nanoscale MCM-49 molecular sieve. The method uses piperidine as an organic template.
CN 108675313A (2018) reports a synthesis method of an MCM-49 molecular sieve, which is technically characterized in that cyclohexylamine which is relatively cheap replaces hexamethyleneimine to be used as an organic template agent, and a seed crystal liquid obtained by pretreatment is added to assist in synthesis.
In summary, at present, an organic template is required to be used for synthesizing the MCM-49 molecular sieve, hexamethyleneimine is used as the template in most documents, and a mixture template of hexamethyleneimine and other organic amine or piperidine is used in few documents. The organic template greatly increases the production cost of the zeolite catalyst, and releases harmful gases to pollute the environment in the zeolite calcination process, so the synthesis without the organic template is a challenge to the MCM-49 molecular sieve preparation technology.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing the MCM-49 type zeolite molecular sieve under the condition of no organic template agent.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing MCM-49 zeolite molecular sieve under the condition of no organic template agent comprises the following steps:
s100, dissolving an alkali metal oxide source and an alumina source in water, adding a silicon dioxide source, stirring and mixing at room temperature for 1-6 hours to form silicon-aluminum gel; the adding amount of each reactant is controlled, so that the silicon-aluminum gel has the following mole ratio relationship: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO2＝3～15；
S200, aging at 25-90 ℃ for 0-24 h, and adding SiO into the silicon-aluminum gel2/Al2O3Using 25-35 MCM-49 zeolite molecular sieve as seed crystal, crystallizing at 135-160 deg.C for 0.5-8 d, and synthesizing crystal product of MCM-49 zeolite molecular sieve by static hydrothermal method;
and S300, cooling the crystallization product obtained in the step S200 at room temperature, washing the crystallization product to be neutral by using deionized water, drying and calcining to obtain MCM-49 type zeolite molecular sieve powder.
Further, the adding mass of the seed crystal is 1.0-20.0% of the adding mass of the silicon dioxide source.
Further, the synthesis method of the seed crystal comprises the following steps:
s201a, stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature to form the silicon-aluminum gel, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.15～0.25,SiO2/Al2O3＝25～35,H2O/SiO2＝25～50，HMI/SiO2＝0.5～0.6；
S202a, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
Further, the synthesis method of the seed crystal comprises the following steps:
s201b, stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature to form the silicon-aluminum gel, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO2＝3～15；
S202b, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
Further, the MCM-49 type zeolite molecular sieve powder obtained in step S300 can be continuously used as seed crystals in the process of synthesizing the MCM-49 type zeolite molecular sieve in a new round.
Further, the alkali metal oxide source is sodium hydroxide.
Further, the alumina source is one or more of sodium aluminate, aluminum isopropoxide and pseudo-boehmite.
Further, the silicon dioxide source is one or more of water glass, silicic acid and silica sol.
Further, the washing treatment comprises: and carrying out centrifugal washing treatment or suction filtration washing treatment on the crystallized product, wherein the washing times are 1-3 times, and the centrifugal rotating speed is 8000-12000 r/min.
Further, the calcination treatment of the crystallized product comprises: the calcination temperature is 500-600 ℃, and the calcination time is 12-20 h.
The invention provides a method for synthesizing MCM-49 type zeolite molecular sieve under the condition of no organic template agent, which comprises the steps of providing alkali metal oxide source, alumina source and silica sourceForming the silicon-aluminum gel under stirring and mixing at room temperature, and controlling the addition amount of each reactant so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO23-15 parts of ═ a; aging, adding an MCM-49 type zeolite molecular sieve into the silicon-aluminum gel to be used as a seed crystal, and then performing crystallization to obtain a crystallization product; and cooling the crystallized product at room temperature, washing to neutrality, and drying to obtain MCM-49 type zeolite molecular sieve powder. The synthesis method provided by the invention does not need to add an organic template agent, reduces the cost by optimizing the synthesis conditions, and avoids the environmental pollution caused by the use of hexamethyleneimine. Wherein, the MCM-49 type zeolite molecular sieve product can be used as seed crystal and can be continuously used in the process of synthesizing the MCM-49 type molecular sieve in a new round.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is an XRD pattern of MCM-49 type zeolite nanocrystals obtained in exemplary example 1 of the present invention;
FIG. 2 is an SEM photograph of MCM-49 type zeolite nanocrystals obtained in exemplary example 1 of the present invention;
FIG. 3 is an XRD pattern of MCM-49 type zeolite nanocrystals obtained in exemplary example 2 of the invention;
FIG. 4 is an XRD pattern of MCM-49 type zeolite nanocrystals obtained in exemplary example 3 of the invention;
FIG. 5 is an SEM photograph of MCM-49 type zeolite nanocrystals obtained in exemplary example 3 of the present invention;
FIG. 6 is an XRD pattern of MCM-49+ MOR type zeolite nanocrystals obtained in comparative examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a method for synthesizing an MCM-49 type zeolite molecular sieve under the condition of no organic template agent, which comprises the following steps:
s100, dissolving an alkali metal oxide source and an alumina source in water, adding a silicon dioxide source, stirring and mixing at room temperature for 1-6 hours to form silicon-aluminum gel; the adding amount of each reactant is controlled, so that the silicon-aluminum gel has the following mole ratio relationship: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO2＝3～15；
S200, aging at 25-90 ℃ for 0-24 h, and adding SiO into the silicon-aluminum gel2/Al2O3Using 25-35 MCM-49 zeolite molecular sieve as seed crystal, crystallizing at 135-160 deg.C for 0.5-8 d, and synthesizing crystal product of MCM-49 zeolite molecular sieve by static hydrothermal method;
and S300, cooling the crystallization product obtained in the step S200 at room temperature, washing the crystallization product to be neutral by using deionized water, drying and calcining to obtain MCM-49 type zeolite molecular sieve powder.
In the presence of organic template agent, MCM-49 type zeolite molecular sieve synthesized by static method in the prior art is easy to be transformed into MOR zeolite, because the gel proportion of MCM-49 type zeolite and MOR zeolite is very similar, under the condition, two phases have competition relationship. The synthesis method of the MCM-49 type zeolite molecular sieve provided by the invention is characterized in that the gel ratio in the silicon-aluminum gel (the gel ratio is the mol ratio among the molecules, and the gel ratio of the silicon-aluminum gel in the invention has the following mol ratio relation of Na2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO23-15), and adjusting crystallization conditions to ensure that the reaction conditions are favorable for the crystallization of the MCM-49 type zeolite, so that the MCM-49 type zeolite molecular sieve can be efficiently synthesized under the condition of no organic template agent. Under the conventional condition, the dynamic synthesis method is easier to form the pure-phase MCM-49 type zeolite molecular sieve than the static synthesis method, but in the invention, on the contrary, under the same gel proportion, the product is quickly crystallized into MOR zeolite during the synthesis by the dynamic method. Therefore, the invention synthesizes the crystal product of the MCM-49 zeolite molecular sieve by static hydrothermal method.
In a preferred embodiment, the added mass of the seed crystal is 1.0 to 20.0% of the added mass of the silica source.
As a preferred embodiment, the method for synthesizing the seed crystal includes:
s201a, stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature to form the silicon-aluminum gel, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.15～0.25,SiO2/Al2O3＝25～35,H2O/SiO2＝25～50，HMI/SiO2＝0.5～0.6；
S202a, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
As a preferred embodiment, the method for synthesizing the seed crystal includes:
s201b, stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature to form the silicon-aluminum gel, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO2＝3～15；
S202b, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
The synthesis method of the seed crystal provided by the invention does not need to add an organic template agent, reduces the cost by optimizing the synthesis conditions, and avoids the pollution to the environment caused by the use of hexamethyleneimine.
Further, the MCM-49 type zeolite molecular sieve powder obtained in step S300 can be continuously used as seed crystals in the process of synthesizing the MCM-49 type zeolite molecular sieve in a new round.
Further, the source of alkali metal oxide is sodium hydroxide.
Furthermore, the alumina source is one or more of sodium aluminate, aluminum isopropoxide and pseudo-boehmite.
Further, the silicon dioxide source is one or more of water glass, silicic acid and silica sol.
Further, the washing treatment comprises: and carrying out centrifugal washing treatment or suction filtration washing treatment on the crystallized product, wherein the washing times are 1-3 times, and the centrifugal rotating speed is 8000-12000 r/min.
Further, the calcination treatment of the crystallized product comprises: the calcination temperature is 500-600 ℃, and the calcination time is 12-20 h.
Example 1
A method for synthesizing MCM-49 zeolite molecular sieve under the condition of no organic template agent comprises the following steps:
0.3284g of sodium metaaluminate and 0.1344g of sodium hydroxide are dissolved in 21.6g of water, after the sodium metaaluminate and the sodium hydroxide are dissolved, 6g of silica sol is added into the solution, and the solution is stirred for about 1 hour to form silicon-aluminum gel; and (3) putting the gel into a stainless steel reaction kettle with a polytetrafluoroethylene kettle liner, and aging for 12 hours at the temperature of 50 ℃. 0.15g of SiO was added2/Al2O3And adding 25-35 MCM-49 type molecular sieve seed crystals into the silicon-aluminum gel, and continuously stirring at room temperature for 10-15 minutes. Crystallizing for 3d at the temperature of 150 ℃; after cooling, filtering at room temperature to obtain a crystallized product; naturally cooling the crystallized product to room temperature, and then centrifuging the crystallized product at a centrifugal speed ofWashing for 1-3 times in a centrifugal machine at 8000-12000 r/min, drying, and calcining for 15 hours at 500-600 ℃ in an air atmosphere to obtain the pure MCM-49 zeolite molecular sieve.
The synthesis method of the seed crystal comprises the following steps:
s201a, stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature to form the silicon-aluminum gel, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.15～0.25,SiO2/Al2O3＝25～35,H2O/SiO2＝25～50，HMI/SiO2＝0.5～0.6；
S202a, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
The XRD spectrum of fig. 1 shows that the MCM-49 type zeolite molecular sieve synthesized in example 1 is a pure phase of MCM-49 zeolite, and it can be seen that the MCM-49 zeolite synthesized by example 1 has a crystallinity consistent with that of the MCM-49 zeolite synthesized under organic template conditions.
As can be seen from the SEM image of fig. 2, the MCM-49 type zeolite molecular sieve synthesized in example 1 is a single-layer sheet MCM-49 type zeolite, which is not consistent with the doughnut shape synthesized under the organic template condition in the prior art, and therefore, the MCM-49 type zeolite molecular sieve synthesized in this example has a smaller particle size compared to the method in the prior art.
Example 2
A method for synthesizing MCM-49 zeolite molecular sieve under the condition of no organic template agent comprises the following steps:
0.2463g of sodium metaaluminate and 0.0344g of sodium hydroxide are dissolved in 5.9417g of water, after dissolution, 6.9519g of water glass is added to the solution, and after stirring for about 1 hour, a silica-alumina gel is formed, and the gel is put into a stainless steel reaction kettle with a polytetrafluoroethylene kettle lining and aged for 12 hours at 80 ℃. 0.15g of SiO was added2/Al2O325-35 MCM-49 type moleculesAnd adding the sieve seed crystal into the silicon-aluminum gel, and continuously stirring at room temperature for 10-15 minutes. Crystallizing for 5d at the temperature of 150 ℃; after cooling, filtering at room temperature to obtain a crystallized product; and naturally cooling the crystallized product to room temperature, washing the crystallized product for 1-3 times in a centrifuge with the centrifugal speed of 8000-12000 r/min, drying, and calcining for 24 hours at the temperature of 500-600 ℃ in the air atmosphere to obtain the pure MCM-49 zeolite molecular sieve.
The XRD spectrum of fig. 3 shows that the MCM-49 type zeolite molecular sieve synthesized in example 2 is a pure phase of MCM-49 zeolite, and it can be seen that the MCM-49 zeolite synthesized by example 2 has a crystallinity consistent with that of the MCM-49 zeolite synthesized under organic template conditions.
Example 3
A method for synthesizing MCM-49 zeolite molecular sieve under the condition of no organic template agent comprises the following steps:
0.3284g of sodium metaaluminate and 0.1344g of sodium hydroxide are dissolved in 21.6g of water, 6g of silica sol is added into the solution after the dissolution, the solution is stirred for about 1 hour to form a silica-alumina gel, and the gel is put into a stainless steel reaction kettle with a polytetrafluoroethylene kettle lining and aged for 12 hours at the temperature of 50 ℃. Then 0.3g of SiO2/Al2O3Adding 25-35 MCM-49 molecular sieve seed crystals (which are the crystallization products of the embodiment example 1) into the silica-alumina gel, and continuing stirring at room temperature for 10-15 minutes; crystallizing for 3d at 150 ℃. After cooling, filtration at room temperature gave the crystallized product. And naturally cooling the crystallized product to room temperature, washing the crystallized product for 1-3 times in a centrifuge with the centrifugal speed of 8000-12000 r/min, drying, and calcining for 12 hours at the temperature of 500-600 ℃ in the air atmosphere to obtain the pure MCM-49 zeolite molecular sieve.
The synthesis method of the seed crystal comprises the following steps:
s201b, stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature to form the silicon-aluminum gel, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO2＝3～15；
S202b, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
The XRD spectrum of fig. 4 shows that the zeolite molecular sieve of MCM-49 type synthesized in example 3 is a pure phase of MCM-49 zeolite, and it can be seen that the MCM-49 zeolite synthesized by example 3 has a crystallinity consistent with that of the MCM-49 zeolite synthesized under organic template conditions.
As can be seen from the SEM image of fig. 5, the MCM-49 type zeolite molecular sieve synthesized in example 3 is a single-layer sheet MCM-49 type zeolite, which is not consistent with the doughnut shape synthesized under the organic template condition in the prior art, and therefore, the MCM-49 type zeolite molecular sieve synthesized in this example has a smaller particle size compared to the method in the prior art.
Comparative example 1
A method for synthesizing MCM-49 zeolite molecular sieve under the condition of no organic template agent comprises the following steps:
0.3284g of sodium aluminate and 0.1344g of sodium hydroxide were dissolved in 21.6g of water, 6g of silica sol was added to the solution after dissolution, and after stirring for about 1 hour, the gel was charged into a stainless steel reaction vessel equipped with a polytetrafluoroethylene vessel liner and aged at 50 ℃ for 12 hours. 0.15g of SiO was added2/Al2O3Adding 25-35 MCM-49 molecular sieve seed crystals into the solution, and continuously stirring at room temperature for 10-15 minutes; dynamically crystallizing the mixture in a homogeneous reactor at the temperature of 150 ℃ for 3 d; after cooling, filtering at room temperature to obtain a crystallized product; and naturally cooling the crystallized product to room temperature, washing the crystallized product for 1-3 times in a centrifuge with the centrifugal speed of 8000-12000 r/min, drying, and calcining for 6-24 hours at the temperature of 500-600 ℃ in an air atmosphere to obtain the MCM-49 and MOR symbiotic zeolite molecular sieve.
The invention provides a method for synthesizing MCM-49 type zeolite molecular sieve under the condition of no organic template agent, which is implemented by alkali metalThe oxide source, the alumina source and the silicon dioxide source are stirred and mixed at room temperature to form silicon-aluminum gel, and the adding amount of each reactant is controlled, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO23-15 parts of ═ a; aging the silica-alumina gel, adding an MCM-49 type zeolite molecular sieve into the silica-alumina gel as a seed crystal, and crystallizing to obtain a crystallized product; and cooling the crystallized product at room temperature, washing to neutrality, and drying to obtain MCM-49 type zeolite molecular sieve powder. The synthesis method provided by the invention does not need to add an organic template agent, reduces the cost by optimizing the synthesis conditions, avoids the environmental pollution caused by using hexamethyleneimine, and has the silicon source (made of SiO)2Calculated) is improved to more than 85 percent. Wherein, the MCM-49 type zeolite molecular sieve product can be used as seed crystal and can be continuously used in the process of synthesizing the MCM-49 type molecular sieve in a new round.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for synthesizing MCM-49 zeolite molecular sieve under the condition of no organic template agent is characterized by comprising the following steps:
s100, dissolving an alkali metal oxide source and an alumina source in water, adding a silicon dioxide source, stirring and mixing at room temperature for 1-6 hours to form silicon-aluminum gel; the adding amount of each reactant is controlled, so that the silicon-aluminum gel has the following mole ratio relationship: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO2＝3～15；
S200, aging at 25-90 ℃ for 0-24 h, and adding SiO into the silicon-aluminum gel2/Al2O3Using 25-35 MCM-49 zeolite molecular sieve as seed crystal, crystallizing at 135-160 deg.C for 0.5-8 d, and synthesizing crystal product of MCM-49 zeolite molecular sieve by static hydrothermal method;
and S300, cooling the crystallization product obtained in the step S200 at room temperature, washing the crystallization product to be neutral by using deionized water, drying and calcining to obtain MCM-49 type zeolite molecular sieve powder.
2. The method for synthesizing the MCM-49 zeolite molecular sieve of claim 1, wherein the added mass of the seed crystal is 1.0-20.0% of the added mass of the silica source.
3. The method for synthesizing a zeolite molecular sieve of MCM-49 type without organic template according to claim 1, wherein the method for synthesizing the seeds comprises:
s201a, stirring and mixing the alkali metal oxide source, the alumina source and the silica source at room temperature to form the silicon-aluminum gel, so that the silicon-aluminum gel has the following molar ratio relation: na (Na)2O/SiO2＝0.15～0.25,SiO2/Al2O3＝25～35,H2O/SiO2＝25～50，HMI/SiO2＝0.5～0.6；
S202a, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
4. The method for synthesizing a zeolite molecular sieve of MCM-49 type without organic template according to claim 1, wherein the method for synthesizing the seeds comprises:
s201b, forming a silica-alumina gel by stirring and mixing an alkali metal oxide source, an alumina source and a silica source at room temperature to enableThe obtained silicon-aluminum gel has the following mole ratio relation: na (Na)2O/SiO2＝0.017～0.19,SiO2/Al2O3＝10～50,H2O/SiO2＝3～15；
S202b, aging and crystallizing the silicon-aluminum gel to obtain a crystal seed crystal product, cooling the crystal seed crystal product at room temperature, washing the crystal seed crystal product to be neutral, drying and calcining the crystal seed crystal product to obtain the crystal seed of the MCM-49 type zeolite molecular sieve.
5. The method for synthesizing a zeolite molecular sieve of MCM-49 type under the condition of no organic template according to claim 1, wherein the zeolite molecular sieve powder of MCM-49 type obtained in step S300 can be continuously used as seed crystals in a new round of synthesis of zeolite molecular sieve of MCM-49 type.
6. A process for synthesizing a zeolite molecular sieve of MCM-49 type in the absence of an organic template as recited in claim 1 in which the source of alkali metal oxide is sodium hydroxide.
7. The method for synthesizing the MCM-49 zeolite molecular sieve of claim 1, wherein the alumina source is one or more of sodium aluminate, aluminum isopropoxide and pseudo-boehmite.
8. The method for synthesizing a zeolite molecular sieve of MCM-49 type without organic template according to claim 1, wherein the silica source is one or more of water glass, silicic acid and silica sol.
9. A process for the synthesis of a zeolite molecular sieve of MCM-49 type without organic template according to claim 1, characterized in that the washing treatment comprises: and carrying out centrifugal washing treatment or suction filtration washing treatment on the crystallized product, wherein the washing times are 1-3 times, and the centrifugal rotating speed is 8000-12000 r/min.
10. A process for the preparation of a zeolite molecular sieve of MCM-49 type according to any of claims 1 to 9, characterized in that the calcination treatment of the crystalline product comprises: the calcination temperature is 500-600 ℃, and the calcination time is 12-20 h.
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