CN111330635B - Preparation method of SSZ-13 molecular sieve catalyst - Google Patents
Preparation method of SSZ-13 molecular sieve catalyst Download PDFInfo
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- CN111330635B CN111330635B CN202010140227.1A CN202010140227A CN111330635B CN 111330635 B CN111330635 B CN 111330635B CN 202010140227 A CN202010140227 A CN 202010140227A CN 111330635 B CN111330635 B CN 111330635B
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- 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
- B01J29/80—Mixtures of different zeolites
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- 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
- B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
Abstract
The invention belongs to the field of molecular sieves, and particularly relates to a preparation method of an SSZ-13 molecular sieve catalyst, wherein a ZSM-5 molecular sieve is used as a raw material, crystal conversion is completed under the guidance of a template agent, and the ZSM-5 molecular sieve is directly converted into the SSZ-13 molecular sieve in a crystal conversion mode; the method is simple to operate, the yield of the SSZ-13 is greatly improved, the dosage of the template agent is small, the preparation time is short, and large-scale industrial production can be realized; meanwhile, the synthesized SSZ-13 molecular sieve has the characteristics of good crystallinity, high yield, small crystal size and the like.
Description
Technical Field
The invention belongs to the field of molecular sieves, and particularly relates to a preparation method of an SSZ-13 molecular sieve catalyst.
Background
The molecular sieve has the characteristics of good pore structure, large specific surface area, surface protonic acid center and cation exchange property and the like; molecular sieves have received much attention from the industry because of their industrial value.
According to the international association of molecular sieves (IZA), SSZ-13 zeolite is reported to be of CHA topology, mainly comprising basic units of 4, 6 and 8 membered rings, which are cross-linked into a three-dimensional network. The network structure has uniform pores, and the largest ring in the CHA structure is an eight-membered ring with a diameter of 0.38 nm. Therefore, only compounds with molecular diameter less than 0.38nm are allowed to enter the cage, macromolecular compounds cannot enter the cage, and excellent shape selectivity is shown. SSZ-13 is an important industrial catalyst and is widely applied to the reaction of preparing olefin from methanol and the selective catalytic reduction of nitrogen oxides.
In 1985, the preparation method of SSZ-13 molecular sieve was disclosed in U.S. Pat. No.4,544,538 for the first time, the template agent was N, N, N-trimethyl-1-amantadine cation; in 2006, Zones, in patent No.60/826,882, disclosed the preparation of SSZ-13 molecular sieves by the combined use of benzyl quaternary ammonium ions and N, N, N-trimethyl-1-adamantanamine cations; in the patent No.60/882,010 of Miller in 2006, the traditional template agent is replaced by benzyl trimethyl quaternary ammonium ions, and SSZ-13 is successfully prepared; in 2013, the patent with the publication number of CN103601211B by Chenbianhua of Beijing chemical university mentions that choline chloride is used as a structure directing agent to successfully prepare the SSZ-13 molecular sieve; the problem of the long preparation time of SSZ-13 in the above method is still not solved.
Therefore, it is important to search for the rapid and efficient synthesis of SSZ-13 molecular sieve with high crystallinity and small crystal size.
Disclosure of Invention
The invention discloses a new preparation method of an SSZ-13 molecular sieve, which directly converts a ZSM-5 molecular sieve into the SSZ-13 molecular sieve in a crystal conversion mode, has simple operation, small dosage of a template agent and short preparation time, and can be prepared on a large scale; meanwhile, the synthesized SSZ-13 molecular sieve has the characteristics of good crystallinity, high yield, small crystal size and the like.
The invention provides a preparation method of an SSZ-13 molecular sieve catalyst, which comprises the following steps:
(1) selecting materials for preparing the molecular sieve, and uniformly mixing an alkali source, deionized water, a template agent and the ZSM-5 molecular sieve; the alkali source is one or more of hydroxide ions, ammonia water, an amine reagent and carbonate; the template agent is any one of N, N, N-trimethyl-1-amantadine cation, choline cation, benzyl trimethyl quaternary ammonium ion, dimethyl ethyl cyclohexane quaternary ammonium ion and tetraethyl phosphonium hydroxide.
(2) Mixing an alkali source and deionized water, adding a template agent, uniformly stirring at room temperature, adding ZSM-5, and fully stirring to obtain an initial gel solution.
(3) And (3) aging the obtained initial gel solution, transferring the initial gel solution into a hydrothermal reaction kettle or other similar sealed containers, and performing hydrothermal crystallization reaction to obtain a crystallized product.
(4) And washing, drying and calcining the obtained crystallized product to remove the template agent, thus obtaining the SSZ-13 molecular sieve.
Further, the alkali source may preferably be sodium hydroxide or potassium hydroxide.
Further, the pH value of the initial gel reaction system can be controlled within the range of 9-13, the mass ratio of the ZSM-5 molecular sieve to the template agent is controlled within the range of 0.5-8, the molar ratio of the template agent to the alkali is controlled within the range of 0.2-2, and the molar ratio of the deionized water to the template agent is controlled within the range of 50-600.
Further, the ZSM-5 molecular sieveSilicon to aluminum ratio Selection (SiO)2/Al2O3) Within the range of 15-300; preferably, the ZSM-5 molecular sieve has a silica-alumina ratio (SiO)2/Al2O3The molar ratio of (A) to (B) is 30 to 200.
Furthermore, the aging (aging) time is controlled to be 1-12 h, the crystallization temperature is 120-210 ℃, and the crystallization time is 4-48 h.
Further, fully washing the crystallized product with deionized water to be neutral, drying, and fully calcining at 450-750 ℃ for 2-10 h to obtain the SSZ-13 molecular sieve.
The invention has the beneficial effects that:
the traditional preparation work of the SSZ-13 molecular sieve needs to add an aluminum source, a silicon source, a template agent, an alkali source and water, the crystallization time is at least 4 days, and the microporous molecular sieve with larger particles is obtained; the method has the advantages that the ZSM-5 molecular sieve is directly subjected to crystal transformation by the template agent only under the alkaline condition to prepare the SSZ-13 molecular sieve, and the method is simple and rapid to operate, high in yield, high in crystallinity and short in preparation period.
Drawings
FIG. 1 is an XRD pattern of an SSZ-13 molecular sieve prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of the SSZ-13 molecular sieve prepared in example 2 of the present invention;
FIG. 3 is an XRD pattern of the SSZ-13 molecular sieve prepared in example 3 of the present invention;
FIG. 4 is an SEM image of an SSZ-13 molecular sieve prepared in example 3 of the present invention;
FIG. 5 is an XRD pattern of SSZ-13 molecular sieve prepared in example 4 of the present invention.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
0.31g of sodium hydroxide and 23.10g of deionized water are weighed and mixed evenlyStirring at room temperature for 30min, adding dropwise N, N, N-trimethyl-1-adamantyl ammonium hydroxide 2.57g, stirring for 30min, and adding ZSM-5 molecular Sieve (SiO) 4.04g2/Al2O338), stirring at 25 ℃ for 30min, and aging for 1 h.
Transferring the obtained solution into a reaction kettle, heating to 160 ℃, crystallizing for 4 hours, washing, filtering and drying the obtained product; and fully calcining the dried sample at 450 ℃ for 5h to obtain the SSZ-13 sample.
The XRD information of the resulting SSZ-13 molecular sieve is given in FIG. 1.
The XRD pattern shows that the molecular sieve is SSZ-13 molecular sieve, has no mixed crystal and has better crystallinity.
Example 2
Weighing 0.28g of sodium hydroxide and 23.10g of deionized water, uniformly mixing, stirring at room temperature for 30min, dropwise adding an appropriate amount of N, N, N-trimethyl-1-adamantyl ammonium hydroxide 2.07g, stirring at room temperature for 30min, and adding 2g of ZSM-5 molecular Sieve (SiO)2/Al2O380), stirring at 25 ℃ for 30min, and aging for 4 h.
Transferring the obtained solution into a reaction kettle, heating to 140 ℃, crystallizing for 16 hours, washing, filtering and drying the obtained product; and fully calcining the dried sample at 500 ℃ for 6h to obtain the SSZ-13 molecular sieve.
The XRD information of the resulting SSZ-13 molecular sieve is given in FIG. 2.
The XRD pattern shows that the molecular sieve is SSZ-13 molecular sieve, has no mixed crystal and has better crystallinity.
Example 3
Weighing 0.31g of potassium hydroxide and 18.96g of deionized water, uniformly mixing, stirring at room temperature for 30min, dropwise adding a proper amount of N, N, N-trimethyl-1-adamantyl ammonium hydroxide 4.57g, stirring at room temperature for 30min, and adding 2.69g of ZSM-5 molecular Sieve (SiO)2/Al2O3200 deg.c), stirring at 25 deg.c for 30min, and aging for 8 h.
Transferring the obtained solution into a reaction kettle, heating to 200 ℃, crystallizing for 48 hours, washing, filtering and drying the obtained product; and fully calcining the dried sample at 550 ℃ for 4h to obtain the SSZ-13 molecular sieve.
XRD information of the resulting SSZ-13 molecular sieve is given in FIG. 3, and SEM image of the sample is given in FIG. 4, showing crystal morphology and size of the SSZ-13 molecular sieve.
The XRD pattern shows SSZ-13 molecular sieve, no mixed crystal appears, high crystallinity, and the scanning electron microscope image shows that the particle size is about 2 μm.
Example 4
Weighing 0.20g of sodium hydroxide and 25.83g of deionized water, uniformly mixing, stirring at room temperature for 30min, dropwise adding an appropriate amount of choline chloride 1.07g, stirring at room temperature for 30min, adding 2.14g of ZSM-5 molecular Sieve (SiO)2/Al2O3100), stirring at 25 ℃ for 30min, and aging for 12 h.
Transferring the obtained solution into a reaction kettle, heating to 180 ℃, crystallizing for 24 hours, washing, filtering and drying the obtained product; and fully calcining the dried sample at 600 ℃ for 8h to obtain the SSZ-13 molecular sieve.
The XRD information of the resulting SSZ-13 molecular sieve is given in FIG. 5.
The XRD pattern shows that the molecular sieve is SSZ-13 molecular sieve, has no mixed crystal and has better crystallinity.
Example 5
Weighing 0.35g of potassium hydroxide and 28.10g of deionized water, uniformly mixing, stirring at room temperature for 30min, dropwise adding 2.57g of choline hydroxide, stirring for 30min, and adding 3.04g of ZSM-5 molecular Sieve (SiO)2/Al2O3130), stirring at 25 ℃ for 30min, and aging for 1 h.
Transferring the obtained solution into a reaction kettle, heating to 210 ℃, crystallizing for 10 hours, washing, filtering and drying the obtained product; and fully calcining the dried sample at 700 ℃ for 10h to obtain the SSZ-13 sample.
Example 6
Weighing 0.38g of potassium hydroxide and 34.18g of deionized water, uniformly mixing, stirring at room temperature for 30min, dropwise adding 2.86g of choline hydroxide, stirring for 30min, and adding 2.54g of ZSM-5 molecular Sieve (SiO)2/Al2O3160), stirring for 30min at 25 ℃ and aging for 10 h.
Transferring the obtained solution into a reaction kettle, heating to 120 ℃, crystallizing for 16 hours, washing, filtering and drying the obtained product; and fully calcining the dried sample at 750 ℃ for 2h to obtain the SSZ-13 sample.
Claims (9)
1. A preparation method of an SSZ-13 molecular sieve catalyst is characterized by comprising the following steps:
(1) uniformly mixing an alkali source, deionized water, a template agent and a ZSM-5 molecular sieve to obtain initial gel;
(2) carrying out aging treatment on the initial gel obtained in the step (1), and carrying out hydrothermal crystallization reaction on an aged gel liquid to obtain a crystallization product;
(3) washing, drying and calcining the crystallized product obtained in the step (2) to remove the template agent, thus obtaining the SSZ-13 molecular sieve;
the template agent is any one of N, N, N-trimethyl-1-amantadine cation, choline cation, benzyl trimethyl quaternary ammonium ion, dimethyl ethyl cyclohexane quaternary ammonium ion and tetraethyl phosphonium hydroxide.
2. The method according to claim 1, wherein the alkali source is one or more selected from the group consisting of hydroxide ions, ammonia, amine reagents and carbonates.
3. The method of claim 1, wherein the ZSM-5 molecular sieve has a silica to alumina ratio (SiO)2/Al2O3The molar ratio of (A) to (B) is 15 to 300.
4. The method of claim 3, wherein the ZSM-5 molecular sieve has a silica to alumina ratio (SiO)2/Al2O3The molar ratio of (A) to (B) is 30 to 200.
5. The method of claim 1, wherein the step (1) comprises adding the alkali source, the deionized water, the template agent and the ZSM-5 molecular sieve while stirring to obtain an initial gel solution.
6. The preparation method of claim 1, wherein the mass ratio of the ZSM-5 molecular sieve to the added amount of the template in the step (1) is 0.5 to 8, the molar ratio of the template to the alkali is 0.2 to 2, and the molar ratio of the deionized water to the template is 50 to 600.
7. The method according to claim 1, wherein the pH of the initial gel system is controlled to be 9 to 13 in the step (1).
8. The preparation method according to claim 1, wherein in the step (2), the aging time is 1-12 h, the crystallization reaction time is 4-48 h, and the crystallization reaction temperature is 120-210 ℃.
9. The preparation method according to claim 1, wherein the calcination temperature in the step (3) is 450 to 750 ℃, and the calcination time is 2 to 10 hours.
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