CN111017954A - Preparation method of open type macroporous Beta molecular sieve - Google Patents
Preparation method of open type macroporous Beta molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 53
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 35
- 230000008025 crystallization Effects 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002149 hierarchical pore Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a preparation method of an open type macroporous Beta molecular sieve, belonging to the field of molecular sieve catalyst preparation; the method comprises the following steps: a) uniformly mixing deionized water, an aluminum source, an alkali source, a template agent, a filling agent, a silicon source and seed crystals, and then transferring the mixture to a crystallization kettle for crystallization; b) the crystallization conditions are as follows: crystallizing at 140-180 ℃ for 6-72 hours; the heating rate is not lower than 2 ℃/min and not higher than 10 ℃/min; c) when the pressure in the kettle rises to 0.2-0.4 MPa, the pressure is released and the amine and the water vapor are recovered; maintaining the pressure in the kettle at 0.2-0.4 MPa in the crystallization process; d) after crystallization is finished, the product slurry is rapidly cooled; and separating, washing, drying and roasting the crystallized product to obtain the open type macroporous Beta molecular sieve. The molecular sieve has excellent hydrothermal stability and higher crystallinity. Compared with the macroporous or hierarchical porous Beta molecular sieve prepared by the post-treatment method, the method has the characteristics of simple process, high utilization rate of raw materials and high product yield.
Description
Technical Field
The invention relates to a preparation method of an open type macroporous Beta molecular sieve, belonging to the field of preparation of molecular sieve catalysts.
Background
The Beta molecular sieve has a twelve-membered ring three-dimensional channel structure. Due to the high hydrothermal stability, good shape selection and acidity, the Beta molecular sieve shows excellent catalytic performance in reactions such as hydroisomerization, hydrocracking, preparation of isopropylbenzene from benzene and propylene, alkylation of aromatic hydrocarbon, toluene disproportionation and the like (CN 106430230A). In addition to acidic factors, diffusion limitations are a major cause of molecular sieve catalyst deactivation during molecular sieve catalysis. In order to solve the diffusion problem, researchers try to miniaturize and nanosize the molecular sieve and reduce the particle size of the molecular sieve as much as possible. However, solid-liquid separation of molecular sieves in the nanometer or submicron range is difficult. Meanwhile, the small size of the molecular sieve crystal grains leads to the reduction of the hydrothermal stability of the molecular sieve crystal grains, and the service life of the molecular sieve is seriously influenced. On the other hand, researchers have begun to address the preparation of hierarchical pore molecular sieves. The surface and the interior of the molecular sieve crystal grains are added with mesopores and macropores, so that the diffusion performance and the hydrothermal stability can be ensured.
The patent (CN 110078089A) discloses a preparation method of a hierarchical pore Beta molecular sieve, which mainly comprises the steps of carrying out alkali treatment on the Beta molecular sieve, and then supplementing an aluminum source and a template agent in a desilication solution for crystallization to obtain the hierarchical pore Beta molecular sieve. The patent (CN 109534358A) discloses a hollow hierarchical pore Beta molecular sieve and a preparation method thereof, and the preparation of the hollow hierarchical pore Beta molecular sieve is realized by adding a double-end quaternary ammonium salt surfactant N2-p-N2 and ethanol. The patent (CN108455629A) discloses a method for synthesizing a hierarchical pore Beta molecular sieve in a one-step guiding manner, wherein quaternary ammonium salts with three branched chain structures and rigid benzene rings are used as template agents, and tetraethoxysilane is used as a silicon source to synthesize the hierarchical pore Beta molecular sieve in a one-step guiding manner. The method is beneficial to the later treatment or the auxiliary preparation of the hierarchical porous Beta molecular sieve by a special template agent, but the preparation method of the open type macroporous Beta molecular sieve is not seen.
Disclosure of Invention
According to the defects of the prior art, the technical problems to be solved by the invention are as follows: the preparation method of the open type macroporous Beta molecular sieve is provided, and the pore expansion of the surface and the interior of a crystal grain is realized by using a filling agent, so that the one-step synthesis of the open type macroporous Beta molecular sieve is realized.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the open macroporous Beta molecular sieve comprises the following steps:
a) uniformly mixing deionized water, an aluminum source, an alkali source, a template agent, a filling agent, a silicon source and seed crystals, and then transferring the mixture to a crystallization kettle for crystallization; the crystallization kettle is provided with a backpressure valve with adjustable pressure and has the function of directly communicating cooling water.
b) The crystallization conditions are as follows: crystallizing at 140-180 ℃ for 6-72 hours; the heating rate is not lower than 2 ℃/min and not higher than 10 ℃/min;
in the preferred scheme, the crystallization conditions are as follows: crystallizing at 150-170 deg.C for 12-48 hr. The heating rate is not lower than 2 ℃/min and not higher than 10 ℃/min.
c) When the pressure in the kettle rises to 0.2-0.4 MPa, the pressure is released and the amine and the water vapor are recovered; maintaining the pressure in the kettle at 0.2-0.4 MPa in the crystallization process; when overpressure occurs, the pressure is maintained by adopting a pressure relief and amine recovery mode and a water vapor mode; in the preferable scheme, the pressure in the kettle is maintained at 0.25-0.35 Mpa;
d) after crystallization is finished, the product slurry is rapidly cooled; and separating, washing, drying and roasting the crystallized product to obtain the open type macroporous Beta molecular sieve.
The amount ratio of the deionized water, the aluminum source, the alkali source, the template agent, the filling agent, the silicon source and the seed crystal in the step a) is as follows: SiO 22:Al2O3:Na2O:R:X:H2O＝1:0.01～0.1:0.05～0.3:0.1～0.3:0.001～0.1:1～30。
The added mass of the seed crystal in the step a) accounts for 3-10%, preferably 5-10% of the mass of the silicon dioxide in the gel.
In the step a), an aluminum source is one or a mixture of pseudo-boehmite, aluminum hydroxide, aluminum oxide, sodium metaaluminate, aluminum isopropoxide or aluminum sulfate, and preferably, the aluminum source is aluminum isopropoxide; the alkali source is sodium hydroxide; the template agent is one or a mixture of tetraethyl ammonium hydroxide and tetraethyl ammonium bromide, and in the preferred scheme, the template agent is tetraethyl ammonium hydroxide; the silicon source is one or a mixture of silica sol, silica gel, white carbon black, tetraethoxysilane and water glass, and tetraethoxysilane is used as the silicon source in the preferred scheme.
The filler in the step a) is alcohol, organic amine or carbonate.
The filler in the step a) is methanol, isopropanol, n-hexadecylamine, hexadecyl trimethyl ammonium bromide, lauryl sodium sulfate, ammonium bicarbonate or sodium bicarbonate. Preferably, the filler is selected from isopropanol, cetyl trimethyl ammonium bromide, and ammonium bicarbonate.
The filler rapidly volatilizes or decomposes during rapid temperature increases and can form a large number of bubbles.
The cooling mode in the step d) is to directly feed low-temperature cooling water into the crystallization liquid, and the cooling rate is-1 to-5 ℃/min.
The invention has the beneficial effects that:
the invention is characterized in that the filler generates a large amount of bubbles in the rapid heating process, the bubbles continuously overflow and are recovered, the formation of dense aggregates is prevented, and a porous precursor is formed. And when bubbles overflow, the crystallization nucleation of the molecular sieve begins, and the porous precursor gradually forms the Beta molecular sieve along with the prolonging of the crystallization time. After crystallization is finished, the reaction system needs to be rapidly cooled, and collapse of the formed porous Beta molecular sieve in the slow cooling process is avoided.
The invention is also characterized in that the Beta molecular sieve obtained by using the technology is rich in open pore channels with the diameter of about 300nm, and the total specific surface area is as high as 647.6m2·g-1Total pore volume 0.74cm 3/g. The molecular sieve has excellent hydrothermal stability and higher crystallinity. Compared with the macroporous or multi-stage pore Beta molecular sieve prepared by the post-treatment method, the method has simple and original processHigh material utilization rate and high product yield.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of a sample of examples 1-3, wherein the sample is a pure phase Beta molecular sieve.
Fig. 2 is a Scanning Electron Microscope (SEM) picture of a sample of example 2.
Fig. 3 is a Scanning Electron Microscope (SEM) picture of a sample of example 2.
Detailed Description
The following further describes embodiments of the present invention:
example 1
A preparation method of an open macroporous Beta molecular sieve comprises the following steps:
deionized water, alumina, sodium hydroxide, tetraethyl ammonium hydroxide (R), hexadecyl trimethyl ammonium bromide (X), tetraethoxysilane and seed crystal are uniformly mixed and then transferred to a crystallization kettle for crystallization. The mass ratio of each component substance in the gel is as follows: SiO 22:Al2O3:Na2O:TEAOH:X:H2O ═ 1:0.03:0.3:0.2:0.001: 15. The added mass of the seed crystal accounts for 8 percent of the mass of the silicon dioxide in the gel. Rapidly heating to 160 ℃, heating at a rate of 5 ℃/min, adjusting a back pressure valve to a pressure of 0.3MPa, and keeping the temperature for 24 hours. After crystallization is finished, low-temperature cooling water is introduced into the crystallization liquid, and the cooling rate is-4 ℃/min. And cooling to room temperature, separating, washing, drying and roasting the crystallized product to obtain the Beta molecular sieve which is marked as B-1.
Example 2
A preparation method of an open macroporous Beta molecular sieve comprises the following steps:
uniformly mixing deionized water, aluminum isopropoxide, sodium hydroxide, tetraethylammonium bromide (R), ammonium bicarbonate (X), water glass and seed crystals, and transferring the mixture to a crystallization kettle for crystallization. The mass ratio of each component substance in the gel is as follows: SiO 22:Al2O3:Na2O:TEAOH:X:H2O ═ 1:0.01:0.05:0.1:0.1: 1. The added mass of the seed crystal accounts for 7 percent of the mass of silicon dioxide in the gel. Rapidly heating to 170 deg.C, heating at a rate of 6 deg.C/min, adjusting back pressure valve to 0.35MPa,keeping the temperature for 12 hours. After crystallization is finished, low-temperature cooling water is introduced into the crystallization liquid, and the cooling rate is-4 ℃/min. And cooling to room temperature, separating, washing, drying and roasting the crystallized product to obtain the Beta molecular sieve which is marked as B-2.
It can be seen in fig. 2 that the sample surface has a rich population of open channels with pore diameters of about 300 nm.
Example 3
A preparation method of an open macroporous Beta molecular sieve comprises the following steps:
deionized water, aluminum hydroxide, sodium hydroxide, tetraethyl ammonium hydroxide (R), isopropanol (X), silica gel and seed crystal are uniformly mixed and then transferred to a crystallization kettle for crystallization. The mass ratio of each component substance in the gel is as follows: SiO 22:Al2O3:Na2O:TEAOH:X:H2O ═ 1:0.1:0.1:0.3:0.05: 30. The added mass of the seed crystal accounts for 9 percent of the mass of the silicon dioxide in the gel. Rapidly heating to 150 ℃, wherein the heating rate is 4 ℃/min, adjusting a back pressure valve to the pressure of 0.25MPa, and keeping the temperature for 36 h. After crystallization is finished, low-temperature cooling water is introduced into the crystallization liquid, and the cooling rate is minus 3 ℃/min. And cooling to room temperature, separating, washing, drying and roasting the crystallized product to obtain the Beta molecular sieve which is marked as B-3.
TABLE 1 physical Properties of the samples of the examples and the comparative samples
Claims (7)
1. A preparation method of an open macroporous Beta molecular sieve is characterized by comprising the following steps:
a) uniformly mixing deionized water, an aluminum source, an alkali source, a template agent, a filling agent, a silicon source and seed crystals, and then transferring the mixture to a crystallization kettle for crystallization;
b) the crystallization conditions are as follows: crystallizing at 140-180 ℃ for 6-72 hours; the heating rate is not lower than 2 ℃/min and not higher than 10 ℃/min;
c) when the pressure in the kettle rises to 0.2-0.4 MPa, the pressure is released and the amine and the water vapor are recovered; maintaining the pressure in the kettle at 0.2-0.4 MPa in the crystallization process;
d) after crystallization is finished, the product slurry is rapidly cooled; and separating, washing, drying and roasting the crystallized product to obtain the open type macroporous Beta molecular sieve.
2. The method for preparing an open macroporous Beta molecular sieve according to claim 1, wherein the amount ratio of the deionized water, the aluminum source, the alkali source, the template agent, the filler, the silicon source and the seed crystal in step a) is: SiO 22:Al2O3:Na2O:R:X:H2O＝1:0.01～0.1:0.05～0.3:0.1～0.3:0.001～0.1:1～30。
3. The method for preparing the open macroporous Beta molecular sieve of claim 1, wherein the added mass of the seed crystal in the step a) accounts for 3-10% of the mass of the silica in the gel.
4. The method for preparing the open macroporous Beta molecular sieve of claim 1, wherein the aluminum source in step a) is one or more of pseudoboehmite, aluminum hydroxide, alumina, sodium metaaluminate, aluminum isopropoxide and aluminum sulfate; the alkali source is sodium hydroxide; the template agent is one or two of tetraethyl ammonium hydroxide or tetraethyl ammonium bromide; the silicon source is one or more of silica sol, silica gel, white carbon black, ethyl orthosilicate and water glass.
5. The method of claim 1, wherein said filler in step a) is selected from the group consisting of alcohols, organic amines and carbonates.
6. The method of claim 5, wherein said filler in step a) is selected from the group consisting of methanol, isopropanol, n-hexadecylamine, cetyltrimethylammonium bromide, sodium dodecyl sulfate, ammonium bicarbonate and sodium bicarbonate.
7. The method for preparing the open macroporous Beta molecular sieve of claim 1, wherein the cooling mode in step d) is to directly feed low-temperature cooling water into the crystallization liquid, and the cooling rate is-1 to-5 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911397182.XA CN111017954A (en) | 2019-12-30 | 2019-12-30 | Preparation method of open type macroporous Beta molecular sieve |
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