CN114105166A - Organic template agent, preparation method and application thereof, high-silicon KFI zeolite molecular sieve, and preparation method and application thereof - Google Patents
Organic template agent, preparation method and application thereof, high-silicon KFI zeolite molecular sieve, and preparation method and application thereof Download PDFInfo
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- 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 114
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 113
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 83
- 239000010703 silicon Substances 0.000 title claims abstract description 82
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 78
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000010457 zeolite Substances 0.000 title claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 32
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000013078 crystal Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 29
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 238000010668 complexation reaction Methods 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002360 explosive Substances 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 235000010333 potassium nitrate Nutrition 0.000 abstract description 2
- 239000004323 potassium nitrate Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- KSOCVFUBQIXVDC-FMQUCBEESA-N p-azophenyltrimethylammonium Chemical compound C1=CC([N+](C)(C)C)=CC=C1\N=N\C1=CC=C([N+](C)(C)C)C=C1 KSOCVFUBQIXVDC-FMQUCBEESA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000011426 transformation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001131 transforming 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- 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
- C01B39/04—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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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Abstract
The invention relates to the technical field of molecular sieves, and provides an organic template agent, a preparation method and application thereof, a high-silicon KFI zeolite molecular sieve, a preparation method and application thereof. The invention takes KOH, CsOH and 18 crown ether 6 as raw materials, and K is+、Cs+Complexing with 18 crown ether 6 to prepare a novel organic template agent, and synthesizing the high-silicon KFI zeolite molecular sieve by utilizing the guiding action of the organic template agent. The invention providesThe KFI zeolite molecular sieve synthesized by the method has high silicon-aluminum ratio and short synthesis time, explosive potassium nitrate is not needed, and the synthesis process is safer. The results of the examples show that the silicon-aluminum ratio of the high-silicon KFI zeolite molecular sieve synthesized by the method of the invention is up to 5.4, and when the high-silicon KFI zeolite molecular sieve is applied to the reaction of catalyzing methanol to prepare methylamine, the conversion rate and selectivity of methanol are high, and excellent catalytic performance is shown.
Description
Technical Field
The invention relates to the technical field of molecular sieves, in particular to an organic template agent, a preparation method and application thereof, a high-silicon KFI zeolite molecular sieve, a preparation method and application thereof.
Background
The molecular sieve is composed of TO4 -A 3-dimensional structure crystalline compound having a pore channel and constructed by (T ═ Si, Al, Ge … …) tetrahedron. The high-silicon zeolite molecular sieve refers to zeolite with a framework silicon-aluminum ratio higher than 5, and abundant silicon enables the high-silicon molecular sieve to have hydrophobicity and excellent catalytic activity. Originally, low silica molecular sieves, including CHA, MOR, LTA, FAU, etc., were synthesized with alkali or alkaline earth metals under strongly basic conditions, but one of the major challenges in synthesizing molecular sieves with higher silica to alumina ratios was stabilizing the cavities in the framework, preventing the framework from dissolving and converting to other dense phases, which is difficult to do in metal ion-only systems.
The KFI zeolite molecular sieve is a small-pore zeolite molecular sieve discovered in 1948, and has a three-dimensional 8-membered ring channel structure, wherein the framework comprises a larger alpha cage and a smaller gamma cage, and the two cages are connected by an eight-membered ring. Each alpha cage is connected with six gamma cages, each gamma cage is connected with two alpha cages and four gamma cages, the two gamma cages are connected through a double six-membered ring (D6R), and the framework density of KFI is 15.0T atom-The KFI zeolite molecular sieve has wide application in gas adsorption and catalytic reaction.
The KFI zeolite molecular sieve is synthesized by Barrer through a template-free method, the silica-alumina ratio of the product is only about 2, and the KFI zeolite molecular sieve is an aluminum-rich KFI molecular sieve. The hydrothermal stability of the aluminum-rich KFI molecular sieve is poor, which affects the practical application thereof. In recent years, research and development personnel have conducted a great deal of research to improve the silicon-aluminum ratio of KFI molecular sieves. Shichamo Han (Shichamo Han et al, powdered-directed stable synthesis of new high silicon small-pore zeolite with KFI structure (ZJM-7) as an effective catalyst for NH3-SCR reaction applied Catalysis B: Environmental 281 (2021))119480) provides a method for preparing KFI molecular sieve with high silicon-aluminum ratio, wherein NaAlO is adopted2、NaOH、KNO3And silica sol is used as a raw material, silicon-aluminum gel is prepared firstly, a KFI molecular sieve with a silicon-aluminum ratio of 4 is added as a seed crystal, and the seed crystal is crystallized at the temperature of 140 ℃ for about 15 days, and the silicon-aluminum ratio of the KFI molecular sieve finally obtained can reach more than 5.0. The KFI molecular sieve obtained by the method has high silicon-aluminum ratio, but the KFI molecular sieve uses inflammable and explosive KNO3And the crystallization time is longer.
The KFI molecular sieve prepared by adopting the template method is also a common method, wherein the adopted organic template comprises 18 crown ether 6 and the like, but the KFI molecular sieve prepared by the reported template method has lower silicon-aluminum ratio which is generally not higher than 4.0, and the preparation of the KFI zeolite molecular sieve with high silicon-aluminum ratio cannot be realized.
Disclosure of Invention
The invention aims to provide an organic template agent, a preparation method and application thereof, a high-silicon KFI zeolite molecular sieve, a preparation method and application thereof. The invention provides a novel organic template, a KFI zeolite molecular sieve with a silicon-aluminum ratio of more than 5 can be prepared by using the organic template, the obtained high-silicon KFI zeolite molecular sieve has better hydrothermal stability than a low-silicon KFI zeolite molecular sieve, and shows more excellent performance in a catalytic reaction.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of an organic template agent comprises the following steps:
mixing KOH, CsOH, water and 18 crown ether 6 to carry out a complex reaction to obtain an organic template agent; the mass ratio of the KOH, the CsOH and the 18 crown ether 6 is (1.4-3.2): (0-3): 5.3.
Preferably, the temperature of the complexation reaction is 70-90 ℃ and the time is 1-3 h.
The invention also provides the organic template agent prepared by the preparation method in the scheme.
The invention also provides application of the organic template agent in the scheme in preparation of the high-silicon KFI zeolite molecular sieve.
The invention also provides a preparation method of the high-silicon KFI zeolite molecular sieve, which comprises the following steps:
mixing an organic template agent, a silicon source, an aluminum source, ZK-5 seed crystals and water for hydrothermal crystallization to obtain a high-silicon KFI zeolite molecular sieve; the organic template is the organic template in the scheme; the aluminum source is sodium aluminate.
Preferably, the silicon source is silica sol or white carbon black; the silicon-aluminum ratio of the ZK-5 seed crystal is 4.0 +/-0.3;
the mass ratio of the organic template agent to the silicon source to the aluminum source to the ZK-5 seed crystal is (1-2): 0.8-1.0): 0.05-0.06): 0.015;
the mass ratio of the aluminum source to the water is (0.05-0.06) to (1-5).
Preferably, the mixing for hydrothermal crystallization specifically comprises: and mixing the organic template agent, a silicon source, an aluminum source and water for aging treatment, and then adding ZK-5 seed crystal into the aging treatment liquid for hydrothermal crystallization.
Preferably, the temperature of the hydrothermal crystallization is 140-150 ℃ and the time is 3-9 days.
The invention also provides the high-silicon KFI zeolite molecular sieve prepared by the preparation method in the scheme, wherein the silicon-aluminum ratio of the high-silicon KFI zeolite molecular sieve is more than 5.
The invention also provides application of the high-silicon KFI zeolite molecular sieve in the scheme in preparation of methylamine by catalyzing methanol.
The invention provides a preparation method of an organic template agent, which comprises the following steps: mixing KOH, CsOH, water and 18 crown ether 6 to carry out a complex reaction to obtain an organic template agent; the mass ratio of the KOH, the CsOH and the 18 crown ether 6 is (1.4-3.2): (0-3): 5.3. The invention takes KOH, CsOH and 18 crown ether 6 as raw materials, and K is+、Cs+Complexing with 18 crown ether 6 to prepare a novel organic template agent, and synthesizing a high-silicon KFI zeolite molecular sieve by using the organic template agent; in addition, in the existing technology for directly synthesizing the high-silicon KFI zeolite molecular sieve, explosive potassium nitrate is adopted as a raw material, and KOH is adopted as the raw material used in the invention, so that the safety of the whole synthesis process is better.
The invention also provides a preparation method of the high-silicon KFI zeolite molecular sieve, which comprises the step of mixing the organic template agent, the silicon source, the aluminum source, the ZK-5 seed crystal and water for hydrothermal crystallization to obtain the high-silicon KFI zeolite molecular sieve. The high-silicon KFI zeolite molecular sieve is synthesized by utilizing the guiding action of the novel organic template agent, the silicon-aluminum ratio of the obtained high-silicon KFI zeolite molecular sieve is up to 5.4, the high-silicon KFI zeolite molecular sieve has excellent catalytic performance, and the conversion rate and the selectivity of methanol are high when the high-silicon KFI zeolite molecular sieve is applied to the reaction of catalyzing methanol to prepare methylamine.
Furthermore, the hydrothermal crystallization time is only 3-9 days, the method for directly synthesizing the high-silicon KFI zeolite molecular sieve in the prior art generally needs about 15 days of crystallization, and the KFI zeolite molecular sieve is synthesized by utilizing the guiding action of the novel organic template, so that the silicon-aluminum ratio of the KFI zeolite molecular sieve can be improved, the hydrothermal crystallization time can be greatly shortened, and the synthesis efficiency can be improved.
Drawings
FIG. 1 is an XRD pattern of a high silicon KFI zeolite molecular sieve prepared in example 2;
FIG. 2 is an XRD pattern of the high silicon KFI zeolite molecular sieve prepared in example 3;
FIG. 3 is an XRD pattern of the high silicon KFI zeolite molecular sieve prepared in example 4;
FIG. 4 is a graph of selectivity and conversion for the preparation of methylamine using H-KFI (5.4) in example 1 as a catalyst for methanol;
FIG. 5 is a graph of selectivity and conversion for a comparative application of H-KFI (3.8) catalyzed methanol in example 1 to methylamine;
FIG. 6 is a graph showing selectivity and conversion in the preparation of methylamine by catalyzing methanol with H-K, Cs ZK-5 in comparative application example 2.
Detailed Description
The invention provides a preparation method of an organic template agent, which comprises the following steps:
mixing KOH, CsOH, water and 18 crown ether 6 to carry out a complex reaction to obtain an organic template agent; the mass ratio of the KOH, the CsOH and the 18 crown ether 6 is (1.4-3.2): (0-3): 5.3.
Unless otherwise specified, the starting materials used in the present invention are all commercially available.
In the invention, the mass ratio of KOH, CsOH and 18-crown ether 6 is (1.4-3.2): 0-3): 5.3, preferably (1.5-3.0): 1-2): 5.3. In the invention, the mass ratio of KOH to water is preferably (1.4-3.2): 3-4), more preferably (1.5-3): 3-3.5), and even more preferably 2.3: 3; in the present invention, the KOH is preferably used in a solid form, the CsOH is preferably used in a CsOH aqueous solution, and the mass fraction of the CsOH aqueous solution is preferably 50%.
In the present invention, the structural formula of the 18 crown ether 6 is as follows:
in the invention, the temperature of the complexation reaction is preferably 70-90 ℃, more preferably 75-85 ℃, further preferably 80 ℃, and the time is preferably 1-3 h, more preferably 1.5-3 h, further preferably 2-3 h.
In the specific embodiment of the invention, preferably, four substances of KOH, CsOH, water and 18-crown ether 6 are sequentially added into a reaction device, mixed and stirred until the materials are clear, and then the materials are placed in a water bath at 70-90 ℃ to be stirred for 1-3 hours, the upper layer of the obtained product material liquid is yellow transparent liquid, the lower layer of the obtained product material liquid is colorless transparent liquid, and the upper layer of the obtained product material liquid is the organic template agent.
The invention also provides the organic template agent prepared by the preparation method in the scheme. In the invention, the dosage of CsOH can be 0, and when the dosage of CsOH is 0, the obtained organic template agent is K+And 18 crown ether 6, when CsOH is not used in an amount of 0, the obtained organic template is K+、Cs+And 18 crown ether 6.
The invention also provides application of the organic template agent in the scheme in preparation of the high-silicon KFI zeolite molecular sieve. The invention can prepare the KFI zeolite molecular sieve with high silica-alumina ratio by utilizing the guiding action of the organic template agent.
The invention also provides a preparation method of the high-silicon KFI zeolite molecular sieve, which comprises the following steps:
mixing an organic template agent, a silicon source, an aluminum source, ZK-5 seed crystals and water for hydrothermal crystallization to obtain a high-silicon KFI zeolite molecular sieve; the organic template is the organic template in the scheme.
In the present invention, the method for synthesizing ZK-5 seed crystals preferably comprises the steps of:
KOH, sodium aluminate, water, white carbon black and SAPO-34 crystal seeds are mixed and then subjected to hydrothermal crystallization to obtain ZK-5 crystal seeds.
In the invention, the mass ratio of KOH, sodium aluminate and water is preferably 0.4:0.076:8, the mass ratio of sodium aluminate and white carbon black is preferably 0.076:0.5, and the mass ratio of white carbon black and SAPO-34 crystal seeds is preferably 0.5: 0.05; the temperature of the hydrothermal crystallization is preferably 100-160 ℃, the time is preferably 1-5 days, and in the specific embodiment of the invention, the hydrothermal crystallization is preferably performed for 5 days at 100 ℃, or for 1 day at 160 ℃.
In the present invention, the SAPO-34 seed crystals are preferably synthesized with reference to VERIFIED SYNTHESES OF ZEOLITIC MATERIALS (third edition) OF International Zeolite Association (IZA), and the specific method includes:
(i) mixing water, phosphoric acid and pseudo-boehmite to obtain a mixture A;
(ii) mixing white carbon black, morpholine and water to obtain a mixture B;
(iii) and mixing the mixture A, the mixture B and water, and then sequentially carrying out aging and hydrothermal crystallization to obtain the SAPO-34 seed crystal.
In the present invention, the concentration of phosphoric acid is preferably 85 wt%, and the mass ratio of water, phosphoric acid and pseudoboehmite in the step (i) is preferably 28:15.37: 9.2; the purity of the morpholine is preferably 99 wt%, and the mass ratio of the white carbon black to the morpholine to the water in the step (ii) is preferably 4.09:11.62: 15; the mass ratio of the mixture A to the mixture B to the water in the step (iii) is preferably 52-53: 30-31: 24, and more preferably 52.57:30.71: 24; the aging temperature is preferably 38 ℃, the time is preferably 24 hours, the hydrothermal crystallization temperature is preferably 200 ℃, and the time is preferably 24 hours; and after the hydrothermal crystallization is finished, sequentially performing suction filtration, water washing and drying on the obtained product to obtain the SAPO-34 crystal seed.
In the present invention, the silicon source is preferably silica sol; SiO in the silica sol2Is preferably 40%, in a particular embodiment of the invention, the silica sol is preferably AS-40; the aluminum source is sodium aluminate; the silicon-aluminum ratio of the ZK-5 seed crystal is preferably 4.0 +/-0.3.
In the invention, the mass ratio of the organic template agent, the silicon source, the aluminum source and the ZK-5 seed crystal is preferably (1-2): 0.8-1.0): 0.05-0.06): 0.015, more preferably (1.3-1.5): 0.85-0.9): 0.053-0.055): 0.015; the mass ratio of the sodium aluminate to the water is preferably (0.05-0.06): 1-5), and more preferably (0.053-0.055): 2-4.
The invention preferably mixes the organic template agent, the silicon source, the aluminum source and the water for aging treatment, and then adds ZK-5 seed crystal into the aging treatment liquid for hydrothermal crystallization. In the present invention, the aging treatment is preferably performed at room temperature, and the time of the aging treatment is preferably 24 hours; in the invention, preferably, the aluminum source, the water and the organic template agent are mixed and stirred to be dissolved clearly, then the silicon source is added, after the aging treatment is finished, the ZK-5 seed crystal is added and stirred uniformly, and then the material liquid is transferred to a reaction kettle for hydrothermal crystallization.
In the invention, the temperature of the hydrothermal crystallization is preferably 140-150 ℃, more preferably 145-150 ℃, and the time of the hydrothermal crystallization is preferably 3-9 days, more preferably 4-6 days. In the embodiment of the present invention, it is preferable that in the hydrothermal crystallization process, XRD of the product is measured at each time period, and then the crystallization degree is calculated, and the crystallization degree of the product is substantially constant after a certain time point, and it is determined that the crystallization is completed at the time point. In the hydrothermal crystallization process, an aluminum source and a silicon source form a long-range disordered silicon-aluminum polymer under the guiding action of an organic template agent, then the long-range disordered silicon-aluminum polymer is gradually crystallized into a secondary structural unit with a porous structure, and finally the molecular sieve with a multidimensional porous structure is formed.
After the hydrothermal crystallization is finished, the product liquid is preferably cooled to room temperature and then filtered, and the obtained solid product is sequentially washed and dried to obtain the high-silicon KFI zeolite molecular sieve.
The invention also provides the high-silicon KFI zeolite molecular sieve prepared by the preparation method in the scheme, wherein the silicon-aluminum ratio of the high-silicon KFI zeolite molecular sieve is more than 5, preferably 5-5.4, and more preferably 5.2-5.4.
The invention also provides the application of the high-silicon KFI zeolite molecular sieve in the scheme in preparing methylamine by catalyzing methanol; in the present invention, the high-silicon KFI zeolite molecular sieve is particularly useful as a catalyst. In the laboratory examples of the present invention, the applications are specifically: transforming a high-silicon KFI zeolite molecular sieve into an H-KFI molecular sieve, filling the H-KFI molecular sieve serving as a catalyst in a reactor, allowing nitrogen carrying methanol to pass through the reactor, and reacting the methanol under the catalytic action of the catalyst to generate methylamine; in the present invention, the method for the conversion of the high-silicon KFI zeolite molecular sieve is preferably: carrying out water bath exchange on the high-silicon KFI molecular sieve in an ammonium chloride solution to obtain NH4 +-a KFI molecular sieve; reacting the NH with4 +Calcining the-KFI molecular sieve to obtain an H-KFI molecular sieve; the frequency of the water bath exchange is preferably 3 times, the temperature of the water bath exchange is preferably 80 ℃, the time of single water bath exchange is preferably 6 hours, and a new ammonium chloride solution is replaced after each water bath exchange is finished; the calcination temperature is preferably 550 ℃ and the calcination time is preferably 5 hours. In the laboratory example of the invention, the loading of the catalyst is preferably 0.3g and the mass space velocity of the methanol is preferably 0.813h-1The molar ratio of ammonia to methanol is preferably 2:1, and the temperature of the reaction is preferably 350 ℃.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
18g of water and 15.37g of phosphoric acid (85 wt%) were mixed uniformly, 9.2g of pseudo-boehmite was added thereto, and the mixture was stirred uniformly, and 10g of water was added thereto and mixed uniformly to prepare a mixture A. 4.09g of white carbon black, 11.62g of morpholine (99 wt%) and 15g of water were mixed uniformly to prepare a mixture B. And mixing the mixture A and the mixture B, adding 24g of water, stirring and mixing uniformly, then filling the mixture into a reaction kettle, standing for 24 hours at 38 ℃, and standing for 24 hours in an oven at 200 ℃. And after the reaction is finished, carrying out suction filtration, washing and drying on the product to obtain the SAPO-34 crystal seed.
Firstly, 0.4g of KOH and 0.076g of sodium aluminate are dissolved in 8g of water, then 0.5g of white carbon black is added, after uniform stirring, 0.05g of SAPO-34 seed crystal is added, after uniform mixing, the mixture is transferred into a reaction kettle and placed in an oven at 100 ℃ for 5 days, thus obtaining ZK-5 seed crystal, wherein the silicon-aluminum ratio of the obtained ZK-5 seed crystal is 4.0 +/-0.3.
The ZK-5 seed crystals prepared in example 1 were used in the preparation of the high-silicon KFI zeolite molecular sieves of the subsequent examples.
Example 2
Mixing 1.6g of KOH, 5.3g of 18 crown ether 6 and 3.5g of water, stirring until the mixture is clear, placing the mixture in a water bath at the temperature of 80 ℃ and stirring for 3 hours, wherein the upper layer of the obtained product liquid is yellow transparent liquid, the lower layer of the obtained product liquid is colorless transparent liquid, and separating the upper layer of the yellow liquid to obtain the organic template agent.
Mixing 0.055g of sodium aluminate, 4g of water and 1.2g of organic template agent until the solution is clear and transparent, adding 0.87g of 40% silica sol, stirring for 24h, adding 0.015g of ZK-5 seed crystal, stirring for 5min, transferring the feed liquid into a reaction kettle, crystallizing for 8 days at 140 ℃, taking the obtained product feed liquid out of the reaction kettle, cooling to room temperature, centrifugally washing the product for three times, placing the solid obtained after centrifugal washing in an oven at 80 ℃ for drying to obtain the high-silicon KFI zeolite molecular sieve, wherein the XRD of the obtained high-silicon KFI zeolite molecular sieve is shown in figure 1.
And performing nuclear magnetic detection on the high-silicon KFI zeolite molecular sieve, and calculating the silicon-aluminum ratio, wherein the result shows that the silicon-aluminum ratio of the high-silicon KFI zeolite molecular sieve is 5.2.
Example 3
Mixing 2.3g of KOH, 3.0g of CsOH solution (50 wt%), 5.3g of 18 crown ether 6 and 3.5g of water, stirring until the mixture is clear, placing the mixture in a water bath at the temperature of 80 ℃ for stirring for 3 hours, separating the upper yellow liquid layer of the obtained product feed liquid to obtain the organic template agent.
Mixing 0.055g of sodium aluminate, 1.8g of water and 1.2g of organic template agent until the solution is clear and transparent, adding 0.87g of 40% silica sol, stirring for 24h, adding 0.015g of ZK-5 seed crystal, stirring for 5min, transferring the obtained feed liquid into a reaction kettle, crystallizing for 9 days at 140 ℃, taking the obtained feed liquid out of the reaction kettle, cooling to room temperature, centrifugally washing the product for three times, placing the solid obtained after centrifugal washing in an oven at 80 ℃ for drying to obtain the high-silicon KFI zeolite molecular sieve, wherein the XRD pattern of the obtained high-silicon KFI zeolite molecular sieve is shown in figure 2.
And performing nuclear magnetic detection on the high-silicon KFI zeolite molecular sieve, and calculating the silicon-aluminum ratio, wherein the result shows that the silicon-aluminum ratio of the high-silicon KFI zeolite molecular sieve is 5.4.
Example 4
Mixing 3.0g of KOH, 5.3g of 18 crown ether 6 and 3.5g of water, stirring until the mixture is clear, placing the mixture in a water bath at the temperature of 80 ℃ and stirring for 3 hours, wherein the upper layer of the obtained product liquid is yellow transparent liquid, the lower layer of the obtained product liquid is colorless transparent liquid, and separating the upper layer of the yellow liquid to obtain the organic template agent.
Mixing 0.055g of sodium aluminate, 3g of water and 1.2g of organic template agent until the solution is clear and transparent, adding 0.87g of 40% silica sol, stirring for 24h, adding 0.015g of ZK-5 seed crystal, stirring for 5min, transferring the obtained feed liquid into a reaction kettle, crystallizing for 9 days at 140 ℃, taking the obtained product feed liquid out of the reaction kettle, cooling to room temperature, centrifugally washing the product for three times, placing the solid obtained after centrifugal washing in an oven at 80 ℃ for drying to obtain the high-silicon KFI zeolite molecular sieve, wherein the XRD pattern of the obtained high-silicon KFI zeolite molecular sieve is shown in figure 3.
And performing nuclear magnetic detection on the high-silicon KFI zeolite molecular sieve, and calculating the silicon-aluminum ratio, wherein the result shows that the silicon-aluminum ratio of the high-silicon KFI zeolite molecular sieve is 5.0.
Example 5
The other conditions are consistent with those of the example 2, the hydrothermal crystallization temperature is only changed to 150 ℃, the hydrothermal crystallization time is 3 days, and the silicon-aluminum ratio of the obtained high-silicon KFI zeolite molecular sieve is 5.4.
Comparative example 1
Other conditions were the same as in example 2 except that no seed crystals of ZK-5 were added, and the product was collected by filtration, washing and drying. The results show that the product obtained is amorphous and no crystallization occurs.
Comparative example 2
Other conditions were the same as in example 2 except that the KOH solid was replaced with NaOH solid, and the crystallized product was collected by filtration, washing and drying. The results show that the product obtained is amorphous and no crystallization occurs.
The metal ions have a guiding effect on the synthesis of the molecular sieve, each molecular sieve structure only corresponds to one or a few metal ions, and according to the result of the comparative example 2, in the synthesis process of the KFI molecular sieve, K is proved+Can promote the crystallization to obtain the KFI zeolite molecular sieve with high silica-alumina ratio.
Comparative example 3
Other conditions are consistent with those of example 2, and only the aluminum source is replaced by aluminum hydroxide or aluminum chloride respectively, and the experimental result shows that the structure of the KFI molecular sieve is not obtained.
Application example 1
The high-silicon KFI zeolite molecular sieve prepared in example 3 was transformed into an H-KFI molecular sieve by the following specific steps: stirring in ammonium chloride solution in 80 deg.C water bath for 6 hr, replacing with new ammonium chloride solution, and performing water bath under the same conditions for 3 times to obtain NH4 +-KFI molecular sieve, subjecting said NH to4 +Calcination of the-KFI molecular sieve at 550 deg.C for 5H gave the H-KFI molecular sieve (noted as H-KFI (5.4)).
The resulting H-KFI (5.4) molecular sieve was packed in a reactor as a catalyst, and then methanol was carried by nitrogen gas through the reactor, and the composition of the gas at the outlet of the reactor was tested to evaluate the catalytic performance of the catalyst.
The experimental parameters were as follows: catalyst particle size: 20-60 meshes, and the loading amount of the catalyst is as follows: 0.3g, methanol mass space velocity of 0.813h-1,NH3And CH3The molar ratio of OH was 2:1, the reaction temperature was 350 ℃, the analytical capillary column was CP-Volamine, and the product distribution and conversion were expressed as mole percent carbon.
The results are shown in fig. 4, and fig. 4 is a graph of selectivity and conversion of high silicon KFI zeolite molecular sieve catalyzed methanol to methylamine, where MMA is monomethylamine, DMA is dimethylamine, TMA is trimethylamine, and DME is byproduct dimethyl ether. According to fig. 4, it can be seen that when the high-silicon KFI zeolite molecular sieve of the present invention is used as a catalyst to catalyze methanol to prepare methylamine, the conversion rate of methanol is 79.4%, and the selectivity of byproduct DME is only 5.8%, indicating that the high-silicon KFI zeolite molecular sieve has excellent catalytic performance.
Comparative application example 1
When the ZK-5 seed crystal prepared in example 1 was used as a catalyst to perform a methanol catalysis experiment, the Si/Al ratios of the ZK-5 seed crystals prepared in different experimental batches were slightly different but were all within the range of 4.0. + -. 0.3, the Si/Al ratio of the ZK-5 seed crystal used in this application example was 3.8 (i.e., KFI molecular sieve having a Si/Al ratio of 3.8), the ZK-5 seed crystal was first transformed into an H-KFI molecular sieve (denoted as H-KFI (3.8)), and then the catalytic performance was evaluated, and the transformation method was consistent with that of application example 1.
The experimental parameters were consistent with those of application example 1.
The results are shown in FIG. 5, where MMA is monomethylamine, DMA is dimethylamine, TMA is trimethylamine, and DME is by-product dimethyl ether. As can be seen from fig. 5, the methanol conversion for the preparation of methylamine using H-KFI (3.8) as catalyst was only 61.8%.
Comparative application example 2
The KFI molecular sieve is synthesized by a traditional method, which comprises the following steps: 7.6g of KOH (85 wt%) is dissolved in 16.5g of distilled water, 5.0g of CsOH aqueous solution (50 wt%) is added, the mixture is uniformly mixed and stirred for 1h, 6.37g of pseudo-boehmite (the content of alumina is 75.6 wt%) is added, the mixture is stirred for 1h, Ludox-4018.75g is added dropwise and stirred for 1h, the obtained mixed feed liquid is added into a reaction kettle and crystallized for 6 days at 100 ℃, and the KFI molecular sieve (the ratio of silica to alumina is 4.0 +/-0.3) is obtained.
The prepared KFI molecular sieve is used as a catalyst to carry out a methanol catalysis experiment, the KFI molecular sieve is transformed into an H-KFI molecular sieve (marked as H-K and Cs ZK-5) firstly, then the catalysis performance is evaluated, and the transformation method is consistent with the application example 1.
The experimental parameters were consistent with those of application example 1.
The results are shown in FIG. 6, where MMA is monomethylamine, DMA is dimethylamine, TMA is trimethylamine, and DME is by-product dimethyl ether. As can be seen from FIG. 6, the conversion of methanol to methylamine using H-K, Cs ZK-5 as catalyst was only 69.2%.
The data obtained from the catalytic experiments of application example 1 and comparative application examples 1-2 are listed in table 1:
TABLE 1 application example 1 and comparative application examples 1-2 catalytic Experimental data
According to the data in table 1, compared with the catalysts in comparative application examples 1-2, the high-silicon KFI zeolite molecular sieve provided by the invention is used as the catalyst, the conversion rate of methanol is higher, and the generated byproduct DME is less, which shows that the catalyst has excellent catalytic performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of an organic template agent comprises the following steps:
mixing KOH, CsOH, water and 18 crown ether 6 to carry out a complex reaction to obtain an organic template agent; the mass ratio of the KOH, the CsOH and the 18 crown ether 6 is (1.4-3.2): (0-3): 5.3.
2. The preparation method according to claim 1, wherein the temperature of the complexation reaction is 70-90 ℃ and the time is 1-3 h.
3. The organic template agent prepared by the preparation method of any one of claims 1-2.
4. Use of the organic templating agent of claim 3 in the preparation of a high silicon KFI zeolite molecular sieve.
5. A preparation method of a high-silicon KFI zeolite molecular sieve is characterized by comprising the following steps:
mixing an organic template agent, a silicon source, an aluminum source, ZK-5 seed crystals and water for hydrothermal crystallization to obtain a high-silicon KFI zeolite molecular sieve; the organic template is the organic template in claim 3; the aluminum source is sodium aluminate.
6. The preparation method according to claim 5, wherein the silicon source is silica sol or white carbon black; the silicon-aluminum ratio of the ZK-5 seed crystal is 4.0 +/-0.3;
the mass ratio of the organic template agent to the silicon source to the aluminum source to the ZK-5 seed crystal is (1-2): 0.8-1.0): 0.05-0.06): 0.015;
the mass ratio of the aluminum source to the water is (0.05-0.06) to (1-5).
7. The preparation method according to claim 1, wherein the mixing for hydrothermal crystallization specifically comprises: and mixing the organic template agent, a silicon source, an aluminum source and water for aging treatment, and then adding ZK-5 seed crystal into the aging treatment liquid for hydrothermal crystallization.
8. The method according to claim 1 or 7, wherein the temperature of the hydrothermal crystallization is 140 to 150 ℃ and the time is 3 to 9 days.
9. The high-silicon KFI zeolite molecular sieve prepared by the preparation method of any one of claims 1-8, having a silica-alumina ratio of 5 or more.
10. Use of the high silicon KFI zeolite molecular sieve of claim 9 in catalyzing methanol to produce methylamine.
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