CN116553574A - A nanometer BETA molecular sieve and its synthesis method - Google Patents
A nanometer BETA molecular sieve and its synthesis method Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 65
- 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 65
- 238000001308 synthesis method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229960004063 propylene glycol Drugs 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
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 10
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000499 gel Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a nano BETA molecular sieve and a synthesis method thereof, wherein the crystal size of the nano BETA molecular sieve is 10-100 nm, the crystal size range is 10-100 nm, and single crystals are formed; the product has high relative crystallinity. The synthesis method comprises the steps of firstly, uniformly mixing an alkali source, a silicon source, an aluminum source, a template agent and water for crystallization reaction; then adding lignosulfonate to continue crystallization reaction, separating, drying and roasting after the reaction is finished to obtain the nano BETA molecular sieve. Solves the problems that the nanometer BETA molecular sieve synthesized by the prior method is mainly nanometer aggregate and affects the use effect.
Description
Technical Field
The invention relates to a molecular sieve synthesis method, belongs to the field of molecular sieve synthesis, and in particular relates to a BETA molecular sieve and a synthesis method thereof.
Background
The molecular sieve belongs to a porous solid material, has higher specific surface area, good hydrothermal stability, moderate acidity, abundant and uniform micropores and adjustable surface property, and can be widely applied to preparing materials such as catalysts, adsorbents, ion exchangers and the like. With the continuous development of the industry, the requirements on the pore channel properties of the molecular sieve are also higher and higher, and the development of the nano molecular sieve receives a great deal of attention. The granularity of the molecular sieve is reduced from micron level to nanometer level, and the properties of mass transfer, heat transfer and the like related to molecular sieve adsorption and catalysis can be changed. As molecular sieve particles decrease, the ratio of the number of atoms on the outer surface to the number of atoms on the inner surface increases rapidly, so that the nano molecular sieve has a larger outer surface and higher surface activity, and plays an increasingly important role in industry.
CN102092741a discloses a nano mesoporous molecular sieve and a synthesis method thereof, the invention takes a silicon source and an aluminum source which are commonly used for synthesizing the mesoporous molecular sieve and a surfactant cetyl trimethyl ammonium bromide as raw materials, ammonia water is used for adjusting the pH value of a reaction mixture, and the nano mesoporous molecular sieve is synthesized by a hydrothermal synthesis method.
CN102464330a discloses a method for synthesizing nano Beta zeolite, which comprises the following steps: firstly, mixing a silicon source, an aluminum source, alkali, a composite template agent and water; crystallizing the mixture at 110-200 deg.c for 5-100 hr to obtain crystallized liquid; then adding an acidic compound into the crystallization liquid, adjusting the pH value of the crystallization liquid to be less than 11, and obtaining the nano Beta zeolite after separation, washing and drying.
CN110668459a discloses a nano Beta molecular sieve with a wider silica-alumina ratio range and a preparation method thereof, and raw materials comprising a silicon source, an alkali source, an aluminum source, a template agent, amino acid and water are mixed to obtain initial gel; placing the initial gel in a reactor, and sequentially carrying out first-stage crystallization and second-stage crystallization; and then washing, drying and roasting to obtain the nano Beta molecular sieve.
CN106698455a discloses a synthesis method of nano Beta molecular sieve, inorganic alkali, water, template agent, aluminum source and silicon source are mixed to obtain gel, the gel is mixed with macroporous carbon and then treated by ultrasonic wave, stirring is carried out at 50-100 ℃ until the gel is in a viscous state, then the gel is dried until the water is completely evaporated, the gel is filled into a reactor and added into a quantitative water-tight reactor for crystallization reaction, and the obtained solid product is filtered, washed and dried and then baked in oxygen or air atmosphere to obtain the nano Beta molecular sieve.
Disclosure of Invention
Aiming at the defects existing in the prior art, the main purpose of the invention is to provide a nano BETA molecular sieve and a synthesis method thereof, which can synthesize the nano BETA molecular sieve, and molecular sieve crystals exist in an independent crystal form, thereby solving the problems that the nano BETA molecular sieve synthesized by the prior method is mainly nano aggregate and affects the use effect.
In order to achieve the above objective, the present invention provides a method for synthesizing a nano BETA molecular sieve, the method comprising the following steps:
(1) Under the contact condition, mixing an alkali source, a silicon source, an aluminum source, a template agent and water uniformly, and carrying out a first-stage crystallization reaction;
(2) After the crystallization reaction of the first stage is completed and the temperature is reduced to 10-30 ℃, lignin sulfonate is added for the crystallization reaction of the second stage, and the nano BETA molecular sieve is obtained after separation, drying and roasting after the reaction is completed.
Further, as a specific embodiment, the alkali source in the step (1) is an inorganic alkali, and the inorganic alkali may be specifically selected from one or more of sodium hydroxide and potassium hydroxide.
Further, as a specific embodiment, the aluminum source in the step (1) may be selected from one or more of sodium aluminate, aluminum sulfate, aluminum chloride, and aluminum nitrate, preferably aluminum chloride and/or aluminum nitrate.
Further, as a specific embodiment, the silicon source in the step (1) may be one or more selected from white carbon black, silica gel, silica sol and water glass.
Further, as a specific embodiment, the template agent in the step (1) may be selected from one or more of tetraethylammonium hydroxide and tetraethylammonium bromide.
Further, as a specific embodiment, the lignosulfonate may be selected from one or more of sodium lignosulfonate and potassium lignosulfonate, preferably sodium lignosulfonate.
Further, as a specific embodiment, the alkali metal chloride is introduced at the same time when the lignosulfonate is introduced in the step (2), and the alkali metal chloride can be specifically selected from one or more of sodium chloride, potassium chloride and lithium chloride, preferably sodium chloride and/or potassium chloride. The molar ratio of the alkali metal chloride to the aluminum source is 0.8-2.1: 1, preferably 1 to 2:1.
further, as a specific embodiment, the molar ratio of the materials in the step (1) is 4-11 Na 2 O：24～110SiO 2 ：Al 2 O 3 ：550～2500H 2 O:3 to 25. 25M, preferably 5 to 10Na 2 O：25～100SiO 2 ：Al 2 O 3 ：600～2000H 2 O: 5-20M, M represents a template agent.
Further, as a specific embodiment, in the step (1), an alcohol is further added, wherein the alcohol is a low molecular alcohol with 1-4 carbon atoms, and specifically may be one or more selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, 1, 2-propylene glycol, glycerol and butanediol, and the mass ratio of the alcohol to the water is 0.8-1.6: 1, preferably 1 to 1.5:1. further adding alcohol after uniformly mixing the alkali source, the silicon source, the aluminum source, the template agent and the water.
Further, as a specific embodiment, the reaction temperature of the crystallization reaction in the first stage in the step (1) is 100 to 160 ℃, preferably 110 to 150 ℃; the crystallization reaction time in the first stage is 2 to 7 hours, preferably 3 to 6 hours.
Further, as a specific embodiment, the mass ratio of the lignosulfonate to the silicon source in the step (2) is 0.03-0.15: 1, preferably 0.05 to 0.1:1.
further, as a specific embodiment, the reaction temperature of the second stage crystallization reaction in the step (2) is 90 to 150 ℃, preferably 100 to 140 ℃; the reaction time of the second stage is 15 to 55 hours, preferably 20 to 50 hours.
Further, as a specific embodiment, the reaction temperature of the second stage crystallization reaction in the step (2) is lower than the reaction temperature of the first stage crystallization reaction in the step (1) by 5 to 25 ℃, preferably 10 to 15 ℃.
Further, as a specific embodiment, the separation in step (2) may be performed by filtration, which typically includes multiple filtration, typically 1 to 10 times.
Further, as a specific embodiment, the drying in the step (2) is drying at 100 to 150 ℃ for 1 to 10 hours.
Further, as a specific embodiment, the firing in the step (2) is a high temperature firing treatment at 400 to 600 ℃ for 1 to 10 hours, the firing being performed in an air or oxygen atmosphere.
The second aspect of the invention provides a nano BETA molecular sieve obtained by the above synthesis method, wherein the crystal size of the nano BETA molecular sieve is 10-100 nm, the crystal size range is 10-100 nm, and the single crystals are formed; the relative crystallinity of the product is high; the total specific surface area is 300-700 m 2 Per gram, pore volume of 0.2-0.5 cm 3 /g。
The nano BETA molecular sieve provided by the invention has good macromolecule substance transmission capability, and can be used as an acidic component of a catalyst or an adsorption separating agent of gas and liquid; can be widely applied to the petrochemical industry or the production process of other chemical industries.
Compared with the existing method, the nanometer BETA molecular sieve and its synthesis method have the following advantages:
the applicant found during the research that, for the synthesis of BETA molecular sieve, the nucleation stage at the initial stage of the synthesis of the molecular sieve is very critical, which directly determines the final structure of the synthesized product, and the synthesis system of the molecular sieve is generally composed of water, an alkali source, a silicon source, an aluminum source and a template agent, but as the requirements for the properties of the molecular sieve are increased, specific additives are generally required to be introduced into the synthesis process for modulating certain properties of the molecular sieve, but when the additives are added into the synthesis system of the molecular sieve, the additives can easily influence the growth of molecular sieve crystal nuclei, and especially when the introduced additives are not matched with the synthesis system, the molecular sieve is prevented from nucleating, and the target product cannot be synthesized. Lignosulfonate is a disadvantage for the synthesis of Beta molecular sieves, which can be rendered impossible if added directly to the synthesis system. The invention relates to a method for synthesizing a nano BETA molecular sieve, which adopts a two-stage crystallization method to synthesize the nano BETA molecular sieve, wherein the first stage is mainly used for molecular sieve nucleation; and in the second stage, the additive lignosulfonate is added, and the temperature and time of the crystallization reaction in the first stage and the second stage are regulated and controlled, so that on one hand, in the molecular sieve crystal growth stage, the added lignosulfonate can be adsorbed on a high-energy crystal face of the molecular sieve and prevent the molecular sieve crystal from further growing and growing, and can prevent the aggregation of the molecular sieve, thereby being beneficial to obtaining the nano BETA molecular sieve product. On the other hand, the lignosulfonate is added in the second stage, so that the influence of lignosulfonate on the nucleation of the molecular sieve can be avoided, and the synthesis of BETA molecular sieve products can not be avoided.
Drawings
FIG. 1 is a TEM image of a nano BETA molecular sieve obtained in example 1 of the present invention.
Detailed Description
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited to the following examples. In the invention, the weight percent is the mass fraction.
The specific surface area and the isoporous structure parameters of the sample are measured by adopting a low-temperature nitrogen adsorption method, and are tested and characterized by adopting an ASAP2400 type physical adsorption instrument manufactured by America microphone instruments. Before measurement, the sample was vacuum-treated at 300℃for 4 or more h. Wherein the total specific surface area is calculated according to a BET isothermal equation, the micropore specific surface area and the mesopore specific surface area are calculated according to a t-plot method, and the pore size distribution is calculated by adopting a BJH method.
The microscopic morphology of the sample is characterized by adopting a high-resolution electron microscope, the morphology of the sample is observed and electron diffraction analysis is carried out by adopting a JEM-2100 LaB6 high-resolution transmission electron microscope of JEOL company, and an 832 CCD camera of Gatan company in America is used for collecting images and electron diffraction spectra.
The crystal structure of the sample is characterized by adopting an X-ray diffractometer, adopting a Japanese D/max2500 type X-ray diffractometer, a Cu target, a K alpha radiation source, a graphite monochromator, a tube voltage of 40 kV, a tube current of 80 mA, a scanning range of 5-40 degrees, a step length of 0.1 degrees and a scanning speed of 1 degree/min.
Example 1
Uniformly mixing 1.3g of sodium hydroxide, 12g of white carbon black, 1.0g of aluminum chloride, 7.6g of tetraethylammonium bromide and 85g of distilled water, then adding 102g of propanol, and reacting for 8 hours at 140 ℃; after the reaction is finished, the temperature is reduced to 25 ℃, then 0.84g of sodium lignin sulfonate and 0.43g of potassium chloride are added for reaction for 35 hours at 130 ℃; the sample obtained was filtered 5 times, dried in an oven at 130℃for 10 hours, and calcined at 600℃for 3 hours in a high temperature oven, the sample number M1 was obtained, the properties of the sample were shown in Table 1, and the TEM photograph thereof was shown in FIG. 1.
Example 2
Uniformly mixing 0.75g of potassium hydroxide, 22.5g of silica gel, 1.0g of aluminum chloride, 4g of tetraethylammonium bromide and 135g of distilled water, then adding 135g of propanol, and reacting for 5 hours at 110 ℃; after the reaction is finished, the temperature is reduced to 20 ℃, then 1.13g of sodium lignin sulfonate and 0.28g of potassium chloride are added, and the reaction is carried out for 20 hours at 100 ℃; the sample obtained was filtered 6 times, then dried in an oven at 120℃for 10 hours, and calcined at 550℃for 4 hours in a high temperature oven, the sample number obtained was M2, and the properties of the sample were shown in Table 1.
Example 3
Uniformly mixing 1.5g of sodium hydroxide, 5.7g of white carbon black, 1.0g of aluminum chloride, 15.5g of tetraethylammonium bromide and 41g of distilled water, then adding 61.5g of propanol, and reacting for 15 hours at 150 ℃; after the reaction is finished, the temperature is reduced to 25 ℃, then 0.57g of sodium lignin sulfonate and 0.56g of potassium chloride are added for reaction for 50 hours at 140 ℃; the sample obtained was filtered 5 times, then dried in an oven at 125℃for 10 hours, and calcined at 510℃for 5 hours in a high temperature oven, the sample number obtained was M3, and the properties of the sample were shown in Table 1.
Example 4
1g of potassium hydroxide, 8.6g of silica gel, 1.0g of aluminum chloride, 28g of tetraethylammonium hydroxide (25 wt percent) and 70g of distilled water are uniformly mixed, 84g of propanol is then added, and the mixture is reacted for 10 hours at 135 ℃; after the reaction is finished, the temperature is reduced to 22 ℃, then 0.6g of sodium lignin sulfonate and 0.36g of sodium chloride are added for reaction for 40 hours at 120 ℃; the sample obtained was filtered 6 times, then dried in an oven at 110℃for 10 hours, and calcined at 540℃for 5 hours in a high temperature oven, the sample number obtained was M4, and the properties of the sample were shown in Table 1.
Example 5
Uniformly mixing 1.2g of sodium hydroxide, 9g of white carbon black, 1.0g of aluminum chloride, 32g of tetraethylammonium hydroxide (25 wt%) and 75g of distilled water, then adding 90g of propanol, and reacting at 140 ℃ for 7h; after the reaction is finished, the temperature is reduced to 25 ℃, then 0.63g of sodium lignin sulfonate and 0.41g of sodium chloride are added for reaction for 45 hours at 125 ℃; the obtained sample was filtered a plurality of times, then dried in an oven at 110℃for 10 hours, and calcined at 550℃for 5 hours in a high temperature oven, the obtained sample number was M5, and the properties of the sample were shown in Table 1.
Example 6
Uniformly mixing 1.3g of sodium hydroxide, 12g of white carbon black, 1.0g of aluminum chloride, 7.6g of tetraethylammonium bromide and 85g of distilled water, and reacting at 140 ℃ for 8 hours; after the reaction is finished, the temperature is reduced to 25 ℃, then 0.84g of sodium lignin sulfonate and 0.43g of potassium chloride are added for reaction for 35 hours at 130 ℃; the sample obtained was filtered 5 times, dried in an oven at 130℃for 10 hours, and calcined at 600℃for 3 hours in a high temperature oven, the sample number M6 was obtained, and the properties of the sample were shown in Table 1.
Example 7
Uniformly mixing 0.75g g potassium hydroxide, 22.5g white carbon black, 1.0g aluminum chloride, 4g tetraethylammonium bromide and 135g distilled water, then adding 135g propanol, and reacting for 5 hours at 110 ℃; after the reaction is finished, the temperature is reduced to 20 ℃, then 1.13g of sodium lignin sulfonate and 0.28g of potassium chloride are added, and the reaction is carried out for 20 hours at 110 ℃; the sample obtained was filtered 6 times, then dried in an oven at 120℃for 10 hours, and calcined at 550℃for 4 hours in a high temperature oven, the sample number obtained was M7, and the properties of the sample were shown in Table 1.
Example 8
Uniformly mixing 1.5g g sodium hydroxide, 5.7g white carbon black, 1.0g aluminum chloride, 15.5g tetraethylammonium bromide and 41g distilled water, then adding 61.5g propanol, and reacting for 15 hours at 150 ℃; after the reaction is finished, the temperature is reduced to 25 ℃, then 0.57g of sodium lignin sulfonate is added, and the reaction is carried out for 50 hours at 140 ℃; the sample obtained was filtered 5 times, then dried in an oven at 125℃for 10 hours, and calcined at 510℃for 5 hours in a high temperature oven, the sample number obtained was M8, and the properties of the sample were shown in Table 1.
Comparative example 1
1.3g of sodium hydroxide, 12g of white carbon black, 1.0g of aluminum chloride, 7.6g of tetraethylammonium bromide, 0.84g of sodium lignin sulfonate and 85g of distilled water are uniformly mixed according to the raw material proportion of the example 1, 102g of propanol is added, and the mixture is reacted for 43 hours at 130 ℃; filtering the obtained sample for 5 times after the reaction is finished, then drying the sample in an oven at 110 ℃ for 10 hours, roasting the sample in a high-temperature furnace at 550 ℃ for 5 hours, wherein the obtained sample is M9 which is an intangible substance, and the fact that the direct addition of lignin can affect the nucleation of a molecular sieve is indicated, so that the raw material cannot crystallize, and the properties of the sample are shown in a table 1.
Comparative example 2
Uniformly mixing 1.3g of sodium hydroxide, 12g of white carbon black, 1.0g of aluminum chloride, 7.6g of tetraethylammonium bromide and 85g of distilled water, then adding 102g of propanol, and reacting for 8 hours at 140 ℃; after the reaction is finished, the temperature is reduced to 25 ℃, and the temperature is increased to 130 ℃ for reaction for 35 hours; after the reaction, the temperature is reduced to 25 ℃, then 0.84g of sodium lignin sulfonate and 0.43g of potassium chloride are added and stirred uniformly, the obtained sample is filtered for 5 times, then the obtained sample is dried in an oven at 130 ℃ for 10 hours, and is roasted in a high-temperature oven at 600 ℃ for 3 hours, the obtained sample is numbered M10, and the properties of the sample are shown in table 1.
Table 1 properties of examples and comparative examples samples
Note that: in the present invention, the crystallinity of the molecular sieve in example 1 was taken as 100%, and the crystallinity of all samples was obtained by comparing with the crystallinity of the samples.
By comparing the examples with the comparative examples, it can be seen that the method of the invention not only can synthesize the nano molecular sieve, but also the molecular sieve crystal exists in a non-aggregation state, which is beneficial to fully exerting the nano characteristic thereof.
The pore structure of the molecular sieve material adopts N 2 Adsorption-desorption characterization, crystal granularity and state adopting transmission electron microscope tableAnd (3) sign.
Claims (19)
1. A method for synthesizing a nano BETA molecular sieve, comprising the following steps:
(1) Under the contact condition, mixing an alkali source, a silicon source, an aluminum source, a template agent and water uniformly, and carrying out a first-stage crystallization reaction;
(2) After the crystallization reaction of the first stage is completed and the temperature is reduced to 10-30 ℃, lignin sulfonate is added for the crystallization reaction of the second stage, and the nano BETA molecular sieve is obtained after separation, drying and roasting after the reaction is completed.
2. The synthesis method according to claim 1, wherein the alkali source in the step (1) is an inorganic alkali selected from one or more of sodium hydroxide and potassium hydroxide.
3. The synthesis method according to claim 1, wherein the aluminum source in step (1) is selected from one or more of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, preferably aluminum chloride and/or aluminum nitrate.
4. The synthesis method according to claim 1, wherein the silicon source in the step (1) is selected from one or more of white carbon black, silica gel, silica sol, and water glass.
5. The synthesis method according to claim 1, wherein the template agent in the step (1) is selected from one or more of tetraethylammonium hydroxide and tetraethylammonium bromide.
6. The synthesis method according to claim 1, wherein the lignosulfonate is selected from one or more of sodium lignosulfonate and potassium lignosulfonate, preferably sodium lignosulfonate.
7. The synthesis method according to claim 1, wherein the alkali metal chloride is introduced simultaneously with the introduction of the lignosulfonate in step (2), and the alkali metal chloride is selected from one or more of sodium chloride, potassium chloride and lithium chloride, preferably sodium chloride and/or potassium chloride.
8. The synthesis method according to claim 7, wherein the molar ratio of the alkali metal chloride to the aluminum source is 0.8 to 2.1:1, preferably 1 to 2:1.
9. the synthesis method according to claim 1, wherein the molar ratio of the materials in the step (1) is 4 to 11Na 2 O：24～110SiO 2 ：Al 2 O 3 ：550～2500H 2 O:3 to 25M, preferably 5 to 10Na 2 O：25～100SiO 2 ：Al 2 O 3 ：600～2000H 2 O: 5-20M, M is template agent.
10. The synthesis method according to claim 1, wherein in the step (1), alcohol is added, wherein the alcohol is low molecular alcohol with 1-4 carbon atoms, the low molecular alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, 1, 2-propylene glycol, glycerol and butanediol, and the mass ratio of the alcohol to the water is 0.8-1.6: 1, preferably 1 to 1.5:1.
11. the synthesis method according to claim 1, wherein the reaction temperature of the first stage crystallization reaction in step (1) is 100 to 160 ℃, preferably 110 to 150 ℃; the crystallization reaction time in the first stage is 2 to 7 hours, preferably 3 to 6 hours.
12. The synthesis method according to claim 1, wherein the mass ratio of the lignin sulfonate to the silicon source in the step (2) is 0.03 to 0.15:1, preferably 0.05 to 0.1:1.
13. the synthesis method according to claim 1, wherein the reaction temperature of the second stage crystallization reaction in step (2) is 90 to 150 ℃, preferably 100 to 140 ℃; the reaction time of the second stage is 15 to 55 hours, preferably 20 to 50 hours.
14. The synthesis method according to claim 1, wherein the reaction temperature of the second stage crystallization reaction in step (2) is 5 to 25 ℃, preferably 10 to 15 ℃ lower than the reaction temperature of the first stage crystallization reaction in step (1).
15. The synthesis method according to claim 1, wherein the drying in step (2) is performed at 100 to 150 ℃ for 1 to 10 hours.
16. The synthesis method according to claim 1, wherein the firing in step (2) is a high temperature firing treatment at 400 to 600 ℃ for 1 to 10 hours, the firing being performed under an air or oxygen atmosphere.
17. A nano-BETA molecular sieve obtained by the synthesis method of any one of claims 1-16.
18. The nano BETA molecular sieve according to claim 17, wherein the nano BETA molecular sieve has a crystal size of 10-100 nm, a crystal size range of 10-100 nm, and is formed as single crystals.
19. The nano BETA molecular sieve according to claim 17, wherein the total specific surface area of the nano BETA molecular sieve is 300-700 m 2 Per gram, pore volume of 0.2-0.5 cm 3 /g。
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