CN114655963B - Preparation method of SSZ-13 molecular sieve composite material - Google Patents

Preparation method of SSZ-13 molecular sieve composite material Download PDF

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CN114655963B
CN114655963B CN202210334929.2A CN202210334929A CN114655963B CN 114655963 B CN114655963 B CN 114655963B CN 202210334929 A CN202210334929 A CN 202210334929A CN 114655963 B CN114655963 B CN 114655963B
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molecular sieve
ssz
composite material
halloysite
stirring
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CN114655963A (en
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张冬冬
田涛
马殿民
孙建刚
王磊
张纪涛
王�忠
邱勇
马冉
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Shandong Hongtai Hengrui New Material Co ltd
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    • 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
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract

The invention belongs to the field of molecular sieve synthesis, and particularly relates to a preparation method of an SSZ-13 molecular sieve composite material. The preparation method of the SSZ-13 molecular sieve composite material comprises the following steps: synthesizing SSZ-13 molecular sieve seed crystals; pretreating halloysite; synthesizing the SSZ-13 molecular sieve composite material. The method adds the pretreated halloysite into the SSZ-13 growth solution for crystallization reaction, improves the yield and greatly reduces the production cost; the SSZ-13 molecular sieve composite material obtained by the invention has the characteristic of a multi-stage pore channel structure, can improve the porosity of the molecular sieve and the catalyst, and improves the yield and the catalytic performance.

Description

Preparation method of SSZ-13 molecular sieve composite material
Technical Field
The invention belongs to the field of molecular sieve synthesis, and particularly relates to a preparation method of an SSZ-13 molecular sieve composite material.
Background
The SSZ-13 molecular sieve is a molecular sieve with CHA topology, which is prepared from AlO 4 And SiO 4 The tetrahedron is connected end to end through oxygen atoms to form an ellipsoidal cage with an eight-membered ring structure and a three-dimensional cross channel structure, the size of the channel is 0.38nm multiplied by 0.38nm, and the tetrahedral small pore molecular sieve is a small pore molecular sieve. The SSZ-13 molecular sieve is mainly applied to the fields of removing automobile exhaust NOx, preparing low-carbon olefin (MTO) from methanol, separating and adsorbing gas and the like, and has good performance.
At present, all the templates used for synthesizing the SSZ-13 molecular sieve are N, N, N, -trimethyl-1-adamantyl ammonium hydroxide cation, benzyl trimethyl ammonium cation or-N, N-dimethyl-3, 5-dimethylpiperidine hydroxide as templates, but the three templates are expensive, about 1.2 tons to 2.4 tons of the templates are needed for producing one ton of the SSZ-13 molecular sieve, and few domestic industrial manufacturers exist, so that the cost for synthesizing the SSZ-13 molecular sieve is overhigh, and the industrial production of the SSZ-13 molecular sieve is severely limited.
The prior art discloses that choline chloride or other templates are used for synthesizing the SSZ-13 molecular sieve, but choline chloride is unstable under alkaline conditions, and is easily decomposed into trimethylamine, ethylene glycol and the like at a crystallization temperature, so that the final SSZ-13 molecular sieve has defects, the template consumption is high, the yield is extremely low, the product reject ratio is extremely high, and the prospect is limited.
Therefore, the SSZ-13 molecular sieve has long reaction period and low yield, and the key raw material template has large dosage and high price and is not produced in batches in China, so the production cost for producing the SSZ-13 molecular sieve is high.
Disclosure of Invention
The invention aims to provide a preparation method of an SSZ-13 molecular sieve composite material.
A method for preparing an SSZ-13 molecular sieve composite according to an embodiment of the invention comprises the following steps:
(1) Synthesizing SSZ-13 molecular sieve seed crystals;
(2) Treating the halloysite;
(2-1) adding halloysite into the polycation electrolyte solution, mixing and stirring, washing with water, and drying;
(2-2) preparing zeolite ammonia water sol from the SSZ-13 molecular sieve seed crystal obtained in the step (1), adding cetyl trimethyl ammonium bromide, uniformly stirring, and adding the halloysite treated in the step (2-1) into the zeolite ammonia water sol to obtain the pretreated halloysite.
(3) Synthesizing the SSZ-13 molecular sieve composite material:
(3-1) preparing a secondary growth solution, sequentially adding an aluminum source, sodium hydroxide, an organic amine template agent, a silicon source, water and pretreated halloysite, stirring, and crystallizing;
and (3-2) washing the product obtained in the step (3-1), removing supernatant to obtain a solid, and drying and grinding to obtain the SSZ-13 molecular sieve composite material.
According to the preparation method of the SSZ-13 molecular sieve composite material, in the step (1), an aluminum source, a silicon source, sodium hydroxide, an organic amine template and water are adopted according to a molar ratio (0.025-0.1): 1: (0.15-0.25): (0.25-0.35): (25-30) preparing SSZ-13 molecular sieve seed crystals.
According to the preparation method of the SSZ-13 molecular sieve composite material of the specific embodiment of the invention, in the step (1), an aluminum source and sodium hydroxide are dissolved by water, then added as a template agent, stirred, finally added with a silicon source, stirred, placed into a reaction kettle, and crystallized at 150-170 ℃ for 72-120 hours.
According to the preparation method of the SSZ-13 molecular sieve composite material, after crystallization reaction, solid-liquid separation is carried out, supernatant is discarded, the solid is washed by deionized water until the pH value of the supernatant is 7-8, the obtained solid is dried and ground, and then the SSZ-13 molecular sieve seed crystal is obtained.
According to the preparation method of the SSZ-13 molecular sieve composite material, in the step (2-1), halloysite is added into 1.5-3 wt% of polycation electrolyte solution, the mixture is stirred, kept stand, washed for 3-4 times, and dried after solid-liquid separation.
According to the preparation method of the SSZ-13 molecular sieve composite material, in the step (2-1), the mass-to-volume ratio of the halloysite to the polycation electrolyte solution is (1-4): 12.
according to the preparation method of the SSZ-13 molecular sieve composite material, in the step (2-2), the SSZ-13 molecular sieve seed crystal obtained in the step (1) is added into an ammonia water solution with the pH value of 10-11 to prepare zeolite ammonia water sol, hexadecyl trimethyl ammonium bromide is added, stirring is carried out, the halloysite treated in the step (2-1) is added, stirring, standing and washing are carried out for 3-4 times, and solid-liquid separation is carried out, wherein the mass ratio of the SSZ-13 molecular sieve seed crystal to the hexadecyl trimethyl ammonium bromide is (0.05-0.5): (0.5-1).
SSZ-13 molecules according to embodiments of the inventionA method for preparing a screen composite, step (3-1), al 2 O 3 、SiO 2 、Na 2 O, organic amine and water according to a molar ratio (0.025-0.1): 1: (0.15-0.25): (0.25-0.35): (25-30) preparing a secondary growth liquid.
The kaolin in the invention is a halloysite composed of aluminosilicate, shows a rare and natural nano hollow tubular structure, and has more excellent performance compared with the traditional material.
The polycation electrolyte solution is preferably an aqueous solution of polydimethyldiallylammonium chloride; polyacrylamide cations can also be used, formulated as 1.5% -3% aqueous solutions.
The halloysite is soaked in the polycation electrolyte solution, the surface of the halloysite is positively charged, and the halloysite is more easily combined with a negatively charged zeolite molecular sieve, so that the load rate of the molecular sieve is improved, and the specific surface area and the pore volume of the composite material are improved.
The silicon source is one of tetraethyl orthosilicate, silica sol, coarse-pore silica gel, water glass and the like;
the aluminum source is one of sodium metaaluminate, aluminum sulfate, aluminum hydroxide or pseudo-boehmite;
the template agent is one of N, N, N-trimethyl adamantane ammonium hydroxide, benzyl trimethyl ammonium hydroxide, N, N-dimethyl-3, 5-dimethyl piperidine hydroxide and the like.
Cetyl Trimethyl Ammonium Bromide (CTAB) is added as an organic amine promoter, and the function of the CTAB promoter can improve the solubility of the organic amine template in the gel, so that a uniform SSZ-13 molecular sieve synthesis initial gel mixture is prepared.
The invention has the beneficial effects that:
the invention adds the pretreated halloysite into the SSZ-13 growth liquid for crystallization reaction, thereby improving the yield and greatly reducing the production cost.
After the halloysite is treated and modified by the polycation electrolyte solution, the loading rate of the molecular sieve is improved, and the specific surface area and the pore volume of the composite material are further improved; cetyl Trimethyl Ammonium Bromide (CTAB) is added as an organic amine promoter, so that the solubility of the organic amine template in the gel is improved, and a uniform SSZ-13 molecular sieve synthesis initial gel mixture is prepared.
The SSZ-13 molecular sieve composite material obtained by the invention has the characteristic of a multi-stage pore channel structure, can improve the porosity of the molecular sieve and the catalyst, and improves the yield and the catalytic performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a plot of the X-ray diffraction measurements of an SSZ-13 molecular sieve composite, wherein (1) is the XRD pattern of the SSZ-13 molecular sieve composite obtained in example 1, and (2) is the XRD pattern of the SSZ-13 molecular sieve composite obtained in example 6;
FIG. 2 is a scanning electron microscope measurement of SSZ-13 molecular sieve composite material, wherein (1), (2) are SEM spectra of the SSZ-13 molecular sieve composite material obtained in example 1 with CTAB and CTAB added respectively, (3), (4) are SEM spectra of the SSZ-13 molecular sieve composite material obtained in example 6 with CTAB added and CTAB added respectively;
fig. 3 shows the specific surface area and the test of the prepared SSZ-13 molecular sieve composite material by a nitrogen adsorption-desorption (BET) method, and the BET spectrum thereof. Wherein (1) is the BET spectrum of the SSZ-13 molecular sieve composite material obtained in example 1, and (2) is the BET spectrum of the SSZ-13 molecular sieve composite material obtained in example 6, and (3) is the BET spectrum of the SSZ-13 molecular sieve composite material obtained in example 6;
FIG. 4 shows a process for preparing a copper-based catalyst from a Cu-SSZ-13 molecular sieve catalyst and a Cu-SSZ-13 molecular sieve composite.
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 described in detail below. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
(1) Synthesizing SSZ-13 molecular sieve seed crystals;
(2) Treating the halloysite;
(2-1) adding halloysite into the polycation electrolyte solution, mixing and stirring, washing with water, and drying;
(2-2) preparing zeolite ammonia water sol from the SSZ-13 molecular sieve seed crystal obtained in the step (1), adding cetyl trimethyl ammonium bromide, uniformly stirring, and adding the halloysite treated in the step (2-1) into the zeolite ammonia water sol to obtain pretreated halloysite;
(3) Synthesizing the SSZ-13 molecular sieve composite material:
(3-1) preparing a secondary growth liquid, sequentially adding an aluminum source, sodium hydroxide, an organic amine template, a silicon source, water and pretreated halloysite, stirring, and crystallizing;
and (3-2) washing the product obtained in the step (3-1), removing supernatant to obtain a solid, and drying and grinding to obtain the SSZ-13 molecular sieve composite material.
See examples 1-6 for specific procedures.
Example 1
(1) Synthesis of SSZ-13 molecular sieve seed crystal:
(1-1) weighing materials according to a molar ratio of an aluminum source, a silicon source, sodium hydroxide, an organic amine template (R) and water of 0.025.
(1-2) centrifuging or filtering the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(1-3) repeating the step (2) for 3 times until the pH of the supernatant is between 7 and 8 to obtain the solid SSZ-13 molecular sieve, drying at the temperature of between 80 and 100 ℃, and grinding to obtain the SSZ-13 molecular sieve seed crystal.
(2) Treatment of the halloysite:
(2-1) preparing 120ml of 1.5wt% polycation electrolyte solution, adding 10g of halloysite, stirring for 1h, and standing for 30min; washing with water for 3-4 times, centrifuging after each washing, oven drying at 80 deg.C, and grinding.
(2-2) weighing 0.05g of the molecular sieve seed crystal obtained in the step 1, weighing 120ml of water, adjusting the pH value to 10 by using ammonia water, adding the seed crystal into an ammonia water solution to prepare zeolite ammonia water sol, uniformly stirring, adding 0.5g of hexadecyl trimethyl ammonium bromide (CTAB), stirring for 30min, adding the soil sample, stirring for 1h, standing for 30min, washing for 3-4 times, and performing centrifugal separation after each washing.
(3) Synthesis of SSZ-13 molecular sieve composite material
(3-1) preparation of molar ratio Al 2 O 3 :SiO 2 :Na 2 O organic amine H 2 O is 0.025:
dissolving an aluminum source and sodium hydroxide by using water, stirring for 10min, adding an organic amine template (R), stirring for 1h, adding a silicon source, stirring for 1h, filling the reaction kettle with the filling degree of 60%, finally adding the treated halloysite, stirring for 6h, then putting the mixture into the reaction kettle, crystallizing at 150 ℃ for 72 h, and cooling to normal temperature after crystallization.
(3-2) centrifuging the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(3-3) repeating the step (3-2) for 3-4 times until the pH of supernatant is between 7 to obtain a solid SSZ-13 molecular sieve composite material, drying at 80 ℃, and grinding to obtain the SSZ-13 molecular sieve composite material.
And (3-4) roasting at 550 ℃ for 6h to remove the template agent, thus obtaining the SSZ-13 molecular sieve composite material.
Example 2
(1) Synthesis of SSZ-13 molecular sieve seed crystal:
(1-1) weighing materials according to an aluminum source, a silicon source, sodium hydroxide, an organic amine template (R) and water according to a molar ratio of 0.025 to 0.35.
(1-2) after the reaction, performing suction filtration separation on the product, pouring out the supernatant, continuously adding deionized water into the residual solid, performing ultrasonic treatment for 10min, performing centrifugal separation, and pouring out the supernatant.
(1-3) repeating the step (2) for 4 times until the pH value of the supernatant is between 8 to obtain the solid SSZ-13 molecular sieve, drying at 90 ℃, and grinding to obtain the SSZ-13 molecular sieve seed crystal.
(2) Treatment of halloysite:
(2-1) preparing 120ml of 2wt% polycation electrolyte solution, adding 40g of halloysite, stirring for 1h, and standing for 30min. Washing with water for 3-4 times, centrifuging or filtering, drying at 90 deg.C, and grinding.
(2-2) weighing 0.5g of the molecular sieve seed crystal obtained in the step 1, weighing 120ml of water, adjusting the pH value to 11 by using ammonia water, adding the seed crystal into the ammonia water solution to prepare zeolite ammonia water sol, uniformly stirring, adding 1g of Cetyl Trimethyl Ammonium Bromide (CTAB), stirring for 30min, adding the soil sample, stirring for 1h, standing for 30min, washing for 4 times, and performing centrifugal separation after each washing.
(3) Synthesis of SSZ-13 molecular sieve composite material
(3-1) preparation of molar ratio Al 2 O 3 :SiO 2 :Na 2 O organic amine H 2 0.025 for O:
dissolving an aluminum source and sodium hydroxide by using water, stirring for 10min, adding an organic amine template (R), stirring for 1h, adding a silicon source, stirring for 1h, filling the reaction kettle with the filling degree of 60%, finally adding the treated halloysite, stirring for 6 hours, then putting the mixture into the reaction kettle, crystallizing at 170 ℃ for 120 hours, and cooling to normal temperature after crystallization.
(3-2) centrifuging or filtering the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(3-3) repeating the step (3-2) for 4 times until the pH value of supernatant liquor is between 8 to obtain a solid SSZ-13 molecular sieve composite material, drying at the temperature of 80-100 ℃, and grinding to obtain the SSZ-13 molecular sieve composite material.
(3-4) roasting at 550 ℃ for 6h to remove the template agent, and obtaining the SSZ-13 molecular sieve composite material.
Example 3
(1) Synthesis of SSZ-13 molecular sieve seed crystal:
(1-1) weighing materials according to a molar ratio of an aluminum source, a silicon source, sodium hydroxide, an organic amine template (R) and water of 0.033 to 0.3.
(1-2) centrifuging or filtering the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(1-3) repeating the step (2) for 4 times until the pH value of the supernatant is between 8 to obtain the solid SSZ-13 molecular sieve, drying at 100 ℃, and grinding to obtain the SSZ-13 molecular sieve seed crystal.
(2) Treatment of halloysite:
(2-1) preparing 120ml of 3wt% polycation electrolyte solution, adding 10g of halloysite, stirring for 1h, and standing for 30min. Washing with water for 3-4 times, centrifuging or vacuum filtering after each washing, oven drying at 80-100 deg.C, and grinding.
(2-2) weighing 0.05g of the molecular sieve seed crystal obtained in the step 1, weighing 120ml of water, adjusting the pH value to 10 < -11 > by using ammonia water, adding the seed crystal into an ammonia water solution to prepare zeolite ammonia water sol, uniformly stirring, adding 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB), stirring for 30min, adding the soil sample, stirring for 1h, standing for 30min, washing for 4 times, and performing centrifugal separation after each washing.
(3) Synthesis of SSZ-13 molecular sieve composite material
(3-1) preparation of molar ratio Al 2 O 3 :SiO 2 :Na 2 O organic amine H 2 0.033 for O:
dissolving an aluminum source and sodium hydroxide in water, stirring for 10min, adding N, N, N-trimethyl adamantane ammonium hydroxide serving as a template agent (R), stirring for 1h, adding a silicon source, stirring for 1h, filling the reaction kettle for 60%, finally adding the treated halloysite, stirring for 6h, then filling the mixture into the reaction kettle, crystallizing for 72 h at 150 ℃, and cooling to normal temperature after crystallization.
(3-2) centrifuging or filtering the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(3-3) repeating the step (3-2) for 4 times until the pH of supernatant liquor is between 7 and 8 to obtain a solid SSZ-13 molecular sieve composite material, drying at 100 ℃, and grinding to obtain the SSZ-13 molecular sieve composite material.
(3-4) roasting at 550 ℃ for 6h to remove the template agent, and obtaining the SSZ-13 molecular sieve composite material.
Example 4
(1) Synthesis of SSZ-13 molecular sieve seed crystal:
(1-1) weighing materials according to a molar ratio of 0.033 to water of 0.3.
(1-2) centrifuging or filtering the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(1-3) repeating the step (2) for 3 times until the pH value of the supernatant is between 7 and 8 to obtain the solid SSZ-13 molecular sieve, drying at the temperature of between 80 and 100 ℃, and grinding to obtain the SSZ-13 molecular sieve seed crystal.
(2) Treatment of halloysite:
(2-1) preparing 120ml of polycation electrolyte solution with the concentration of 1.5wt%, adding 40g of halloysite, stirring for 1h, and standing for 30min; washing with water for 3-4 times, centrifuging after each washing, oven drying at 80 deg.C, and grinding.
(2-2) weighing 0.5g of the molecular sieve seed crystal obtained in the step 1, weighing 120ml of water, adjusting the pH value to 10 by using ammonia water, adding the seed crystal into the ammonia water solution to prepare zeolite ammonia water sol, uniformly stirring, adding 1g of Cetyl Trimethyl Ammonium Bromide (CTAB), stirring for 30min, adding the soil sample, stirring for 1h, standing for 30min, washing for 3-4 times, and performing centrifugal separation after each washing.
(3) Synthesis of SSZ-13 molecular sieve composite material
(3-1) preparation of molar ratio Al 2 O 3 :SiO 2 :Na 2 O:C 13 H 25 NO:H 2 0.033 for O:
dissolving an aluminum source and sodium hydroxide by using water, stirring for 10min, stirring for 1h by using organic amine as a template agent (R), adding a silicon source, stirring for 1h, filling the reaction kettle with the filling degree of 60%, finally adding the treated halloysite, stirring for 6h, then putting the mixture into the reaction kettle, crystallizing at 170 ℃ for 120 h, and cooling to normal temperature after crystallization.
(3-2) centrifuging the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(3-3) repeating the step (3-2) for 3-4 times until the pH of supernatant is between 7 to obtain a solid SSZ-13 molecular sieve composite material, drying at 80 ℃, and grinding to obtain the SSZ-13 molecular sieve composite material.
And (3-4) roasting at 550 ℃ for 6h to remove the template agent, thus obtaining the SSZ-13 molecular sieve composite material.
Example 5
(1) Synthesis of SSZ-13 molecular sieve seed crystal:
(1-1) weighing materials according to a molar ratio of an aluminum source, a silicon source, sodium hydroxide and organic amine as a template (R) to water of 0.25.
(1-2) centrifuging or filtering the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(1-3) repeating the step (2) for 3 times until the pH value of the supernatant is between 7 and 8 to obtain the solid SSZ-13 molecular sieve, drying at the temperature of between 80 and 100 ℃, and grinding to obtain the SSZ-13 molecular sieve seed crystal.
(2) Treatment of halloysite:
(2-1) preparing 120ml of polycation electrolyte solution with the concentration of 1.5wt%, adding 10g of halloysite, stirring for 1h, and standing for 30min; washing with water for 3-4 times, centrifuging after each washing, drying at 80 deg.C, and grinding.
(2-2) weighing 0.05g of the molecular sieve seed crystal obtained in the step 1, weighing 120ml of water, adjusting the pH value to 10 by using ammonia water, adding the seed crystal into an ammonia water solution to prepare zeolite ammonia water sol, uniformly stirring, adding 0.5g of hexadecyl trimethyl ammonium bromide (CTAB), stirring for 30min, adding the soil sample, stirring for 1h, standing for 30min, washing for 3-4 times, and performing centrifugal separation after each washing.
(3) Synthesis of SSZ-13 molecular sieve composite material
(3-1) preparation of molar ratio Al 2 O 3 :SiO 2 :Na 2 O organic amine H 2 0.05 for O:
dissolving an aluminum source and sodium hydroxide by using water, stirring for 10min, adding an organic amine template (R), stirring for 1h, adding a silicon source, stirring for 1h, finally adding the treated halloysite, stirring for 6h, then putting into a reaction kettle, filling the reaction kettle with the filling degree of 60%, crystallizing at 150 ℃ for 72 h, and cooling to normal temperature after crystallization.
(3-2) centrifuging the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(3-3) repeating the step (3-2) for 3-4 times until the pH of supernatant is between 7 to obtain a solid SSZ-13 molecular sieve composite material, drying at 80 ℃, and grinding to obtain the SSZ-13 molecular sieve composite material.
And (3-4) roasting at 550 ℃ for 6h to remove the template agent, thus obtaining the SSZ-13 molecular sieve composite material.
Example 6
(1) Synthesis of SSZ-13 molecular sieve seed crystal:
(1-1) weighing materials according to a molar ratio of an aluminum source, a silicon source, sodium hydroxide and organic amine as a template agent (R) to water of 0.25.
(1-2) centrifuging or filtering the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(1-3) repeating the step (2) for 3 times until the pH of the supernatant is between 7 and 8 to obtain the solid SSZ-13 molecular sieve, drying at the temperature of between 80 and 100 ℃, and grinding to obtain the SSZ-13 molecular sieve seed crystal.
(2) Treatment of the halloysite:
(2-1) preparing 120ml of polycation electrolyte solution with the concentration of 1.5wt%, adding 40g of halloysite, stirring for 1h, and standing for 30min; washing with water for 3-4 times, centrifuging after each washing, oven drying at 80 deg.C, and grinding.
(2-2) weighing 0.5g of the molecular sieve seed crystal obtained in the step 1, weighing 120ml of water, adjusting the pH value to 10 by using ammonia water, adding the seed crystal into the ammonia water solution to prepare zeolite ammonia water sol, uniformly stirring, adding 1g of Cetyl Trimethyl Ammonium Bromide (CTAB), stirring for 30min, adding the soil sample, stirring for 1h, standing for 30min, washing for 3-4 times, and performing centrifugal separation after each washing.
(3) Synthesis of SSZ-13 molecular sieve composite material
(3-1) preparation of molar ratio Al 2 O 3 :SiO 2 :Na 2 O:C 13 H 25 NO:H 2 0.05:
dissolving an aluminum source and sodium hydroxide by using water, stirring for 10min, adding an organic amine template (R), stirring for 1h, adding a silicon source, stirring for 1h, filling the reaction kettle with the filling degree of 60%, finally adding the treated halloysite, stirring for 6h, then adding the mixture into the reaction kettle, crystallizing at 170 ℃ for 120 h, and cooling to normal temperature after crystallization.
(3-2) centrifuging the product after the reaction, pouring out the supernatant, continuously adding deionized water into the rest solid, performing ultrasonic treatment for 10min, centrifuging, and pouring out the supernatant.
(3-3) repeating the step (3-2) for 3-4 times until the pH of supernatant is between 7 to obtain a solid SSZ-13 molecular sieve composite material, drying at 80 ℃, and grinding to obtain the SSZ-13 molecular sieve composite material.
And (3-4) roasting at 550 ℃ for 6h to remove the template agent, thus obtaining the SSZ-13 molecular sieve composite material.
TABLE 1 variation of preparation conditions and associated yields in examples 1-6
Figure BDA0003576440130000121
The SSZ-13 molecular sieve composite materials prepared in example 1 and example 6 were selected, and the above samples were subjected to X-ray diffraction tests, respectively.
As a result, as shown in fig. 1, it can be seen that the spectral line is flat, no impurity peak is present, and the crystallinity is good.
The SSZ-13 molecular sieve composite materials prepared in the example 1 and the example 6 are selected, and the samples are respectively subjected to a scanning electron microscope test.
As shown in FIG. 2, the molecular sieve composite material provided by the invention has the advantages of good dispersibility, regular crystal form under an electron microscope, uniform particles, good dispersibility and no agglomeration.
The SSZ-13 molecular sieve composite materials prepared in examples 1 and 6 were subjected to specific surface area measurement and testing by a nitrogen adsorption-desorption (BET) method.
FIG. 3 is a diagram showing a nitrogen adsorption-desorption isotherm diagram and a pore size distribution of an SSZ-13 molecular sieve composite material, wherein when P/P0 of the SSZ-13 molecular sieve composite material is less than or equal to 0.1, the adsorption amount of nitrogen rapidly increases, which indicates that the SSZ-13 molecular sieve composite material contains a certain number of micropores, and the SSZ-13 molecular sieve composite material is in a micropore structure, nitrogen rapidly fills the micropores of the molecular sieve to cause rapid increase of the adsorption amount, after rapid increase, the adsorption of nitrogen tends to be smooth, and when P/P0 approaches 0.9, the adsorption amount increases again, which indicates that a certain number of macropores exist in the SSZ-13 molecular sieve composite material, and when the relative pressure is at a 0.5 position, an obvious hysteresis loop appears on the adsorption-desorption isotherm of the SSZ-13 molecular sieve composite material, which indicates that a mesoporous structure appears in the SSZ-13 molecular sieve composite material. Therefore, the synthesized SSZ-13 molecular sieve composite material is a material with a hierarchical pore channel structure.
Preparation of Cu-SSZ-13 molecular sieve catalyst and Cu-SSZ-13 molecular sieve composite material catalyst
The SSZ-13 molecular sieve seeds and the SSZ-13 molecular sieve composite prepared in examples 1 to 6 were subjected to ion exchange and a Cu-based catalyst was prepared.
Firstly, the SSZ-13 molecular sieve and the SSZ-13 molecular sieve composite material are mixed with NH 4 NO 3 And exchanging twice to obtain a hydrogen type molecular sieve, then exchanging the H-SSZ-13 molecular sieve and the H-SSZ-13 molecular sieve composite material with a copper nitrate solution with the mass concentration of 0.2mol/L substance to prepare the Cu-based catalyst, finally determining the Cu loading amount to be 2.5%, and preparing the flow shown in figure 4.
The catalyst evaluation test is carried out on an SCR denitration catalyst performance evaluation device, the simulated smoke composition is shown in table 2, 500ppm NO and 500ppm NH 3 、5％O 2 、92％N 2 200ppm SO is introduced for the purpose of balancing gas when evaluating the water and sulfur resistance of the catalyst 2 Or 5% of H 2 O; space Velocity (GHSV) is 90000h -1 (ii) a When the catalyst is evaluated, the particles obtained by tabletting and screening the catalyst are 20-40 meshes; the amount of the catalyst filled in the reaction tube is 5mL; the evaluation reaction temperature range is 200-550 ℃, the tail gas is detected every 50 ℃, and a flue gas analyzer is used for recording data.
TABLE 2 simulated Smoke composition
Figure BDA0003576440130000131
Catalyst evaluation test at a space velocity of 90000h -1 Under the conditions ofThe test was conducted with the following NOx conversion results at 400 ℃ reaction temperature:
Figure BDA0003576440130000141
when the molecular sieve supports 2.5 percent of Cu, the denitration effect of the Cu-SSZ-13 molecular sieve catalyst and the Cu-SSZ-13 molecular sieve composite catalyst is optimal, the denitration activity at 200 ℃ can reach 80 percent, and the denitration efficiency can be kept above 90 percent within the temperature range of a window of 250-450 ℃, wherein the NOx conversion rate of the Cu-SSZ-13 molecular sieve composite catalyst is obviously higher than that of the Cu-SSZ-13 molecular sieve catalyst, and the Cu-SSZ-13 molecular sieve composite catalyst of the embodiment 6 can reach 99 percent and has very excellent catalytic activity.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (4)

  1. A preparation method of SSZ-13 molecular sieve composite material, which is characterized by comprising the following steps:
    (1) Synthesizing SSZ-13 molecular sieve seed crystals;
    (2) Treating the halloysite;
    (2-1) adding halloysite into the polycation electrolyte solution, mixing and stirring, washing with water, and drying;
    (2-2) preparing zeolite ammonia water sol from the SSZ-13 molecular sieve seed crystal obtained in the step (1), adding cetyl trimethyl ammonium bromide, uniformly stirring, and adding the halloysite treated in the step (2-1) into the zeolite ammonia water sol to obtain pretreated halloysite;
    (3) Synthesizing the SSZ-13 molecular sieve composite material:
    (3-1) preparing a secondary growth liquid, sequentially adding an aluminum source, sodium hydroxide, an organic amine template, a silicon source, water and pretreated halloysite, stirring, and crystallizing;
    (3-2) washing the product obtained in the step (3-1), removing supernatant to obtain a solid, drying and grinding to obtain the SSZ-13 molecular sieve composite material;
    in the step (2-1), halloysite is added into 1.5 to 3 weight percent of polycation electrolyte solution, stirred, stood, washed for 3 to 4 times, and dried after solid-liquid separation;
    in the step (2-1), the mass volume ratio of the halloysite to the polycation electrolyte solution is (1-4) g:12ml;
    in the step (2-2), adding the SSZ-13 molecular sieve seed crystal obtained in the step (1) into an ammonia water solution with the pH value of 10-11 to prepare zeolite ammonia water sol, adding hexadecyl trimethyl ammonium bromide, stirring, adding the halloysite treated in the step (2-1), stirring, standing, washing for 3-4 times, and performing solid-liquid separation, wherein the mass ratio of the SSZ-13 molecular sieve seed crystal to the hexadecyl trimethyl ammonium bromide is (0.05-0.5): (0.5-1);
    in the step (3-1), al 2 O 3 、SiO 2 、Na 2 O, organic amine template and H2O according to a molar ratio (0.025-0.1): 1: (0.15-0.25): (0.25-0.35): (25-30) preparing a secondary growth liquid.
  2. 2. The method for preparing the SSZ-13 molecular sieve composite material according to claim 1, wherein in the step (1), the aluminum source, the silicon source, the sodium hydroxide, the organic amine template and the water are used in a molar ratio (0.025-0.1) of 1: (0.15-0.25): (0.25-0.35): (25-30) preparing SSZ-13 molecular sieve seed crystals.
  3. 3. The method of claim 2, wherein in step (1), the aluminum source and the sodium hydroxide are dissolved with water, the organic amine template is added, the mixture is stirred, and finally the silicon source is added, the mixture is stirred, the mixture is placed into a reaction kettle, and the crystallization is carried out at 150 ℃ to 170 ℃ for 72 to 120 hours.
  4. 4. The method of claim 3, wherein after the crystallization reaction, performing solid-liquid separation, removing the supernatant, washing the solid with deionized water until the pH of the supernatant is between 7 and 8, drying the obtained solid, and grinding to obtain the SSZ-13 molecular sieve seed crystal.
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