CN110683560A - Method for synthesizing high-silicon Beta zeolite molecular sieve under fluorine-free condition - Google Patents
Method for synthesizing high-silicon Beta zeolite molecular sieve under fluorine-free condition Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 58
- 239000010703 silicon Substances 0.000 title claims abstract description 58
- 239000010457 zeolite Substances 0.000 title claims abstract description 52
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 49
- 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 49
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 30
- 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 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001308 synthesis method Methods 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 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
- 238000000967 suction filtration Methods 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052680 mordenite Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- -1 tetraethylammonium ions Chemical class 0.000 description 3
- 238000011426 transformation method Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002429 nitrogen sorption measurement Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 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 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for synthesizing a high-silicon Beta zeolite molecular sieve under a fluorine-free condition. The method obtains the high-silicon Beta zeolite molecular sieve by the preparation processes of thick sol preparation, Beta molecular sieve seed crystal addition, constant-temperature heating crystallization and the like. The invention avoids the use of highly toxic fluorine species, and the synthesized Beta molecular sieve has high silicon-aluminum ratio and high crystallinity. The invention has the advantages of environmental protection, low price, simple process and the like.
Description
Technical Field
The invention belongs to the field of molecular sieve preparation, and particularly relates to a method for synthesizing a high-silicon Beta zeolite molecular sieve by concentrated sol under a fluorine-free condition.
Background
Zeolite Beta was first synthesized by Mobil corporation of america in 1967 in the strongly basic system of tetraethylammonium hydroxide by hydrothermal crystallization (USP 308069). Because of the unique three-dimensional 12-membered ring cross channel structure and good thermal stability and hydrothermal stability, the Beta zeolite used as a catalyst shows excellent catalytic performance in the petroleum refining and petrochemical processes of hydrocracking, dewaxing, aromatic alkylation, olefin hydration and the like, and is an important industrial zeolite molecular sieve.
The structure of zeolite Beta molecular sieves was not published by J. Newsam et al (1988)Proc. R. Soc. London Ser. A-Math. Phys. Eng. Sci.1988,420375-Zeolites1988,8446-. The framework of zeolite Beta is shown to have 3 isomers, A, B, C. the ratio of polymorph A to polymorph B in conventional zeolite Beta crystals is about 45: 55.
Topologically, zeolite Beta belongs to the same family as Mordenite (Mordenite), ZSM-12 zeolites. When Beta zeolite is synthesized in a conventional strong alkaline hydrothermal system, the silicon-aluminum-to-atomic silicon-aluminum ratio (Si/Al) molecular ratio (SiO) of silicon alumina2/Al2O3) The range is very limited by the Si/a 1. Mordenite (Mordenite) heterocrystals are often produced at Si/A1 atomic ratios below 15, and ZSM-12 zeolite and ZSM-5 zeolite heterocrystals are often produced when high silica to alumina ratio Beta zeolite is synthesized at Si/A1 atomic ratios above 30, particularly 50- ∞. And the Beta zeolite with high silicon-aluminum ratio or full silicon has high stability, hydrothermal stability and hydrophobicity, and has a plurality of potential applications as a carrier or an adsorbent of a metal-loaded catalyst and the like.
European patent application EP0095303A1, EP0094827B1 in 1982 and U.S. patent US4554065 in 1985 propose a method for increasing the silicon-aluminum ratio of Beta zeolite by dealumination with inorganic acid, however, for industrial application, the direct obtainment of high-silicon or all-silicon Beta zeolite by hydrothermal synthesis can reduce the production cost, avoid the pollution of inorganic acid emission to the environment, and has obvious practical value.
In 1990, the united states patent of inventions (US4923690) disclosed a direct hydrothermal synthesis of high silicon zeolite Beta. The method is technically characterized in that white carbon black or silica gel is used as a silicon source, sodium aluminate is used as an aluminum source, tetraethylammonium cation is used as a template agent, sodium chloride is selectively added, and crystallization is carried out at the temperature of 90-200 ℃ to obtain the product with the Si/Al atomic ratio of 10-500 (SiO corresponds to the molecular ratio of silicon to aluminum)2/Al2O3Silica to alumina ratio, 20-1000. For ease of comparison, the molecular ratio is converted uniformly to the atomic ratio hereinafter. ) Beta zeolite with relative crystallinity of 30-90%. When the silicon-aluminum ratio is increased, the crystallinity is reduced and the crystallization is incomplete.
In 1992, the U.S. patent application (US5164169) disclosed a direct hydrothermal synthesis of high silicon zeolite Beta. The method is technically characterized in that white carbon black is used as a silicon source, sodium aluminate is used as an aluminum source, a chelating agent such as triethanolamine and tetraethylammonium ions is used as a template agent, high-purity Beta seed crystal is added to be crystallized at the temperature of 70-175 ℃, and the Beta zeolite with the silicon-aluminum atomic ratio Si/Al of 100-500 and higher purity can be obtained. However, the specific surface area of the Beta molecular sieve is obviously reduced while the silicon-aluminum ratio is improved, and in addition, because triethanolamine and tetraethylammonium fluoride are used in the patent, the practicability of the patent is influenced due to safety reasons.
In 1994, chinese patent invention (CN1086792A, CN1086793A) disclosed a method for direct hydrothermal synthesis of zeolite Beta. The method is technically characterized in that active silicon dioxide/water glass is used as a silicon source, tetraethyl ammonium hydroxide is used as a template agent, sodium carbonate is added, and crystallization is carried out for 30 hours at 140 ℃ in a static kettle to obtain the Beta zeolite with the silicon-aluminum ratio of 19.1. It is worth noting that although the SiO ingredient is formulated2/Al2O3= infinity, but no all-silicon or high-silicon zeolite Beta has been synthesized.
Published literature in 1996Chem, Commun, 1996,2365 reports a direct hydrothermal synthesis of all-silicon Process for zeolite Beta. The method is technically characterized in that tetraethoxysilane is used as a silicon source, tetraethylammonium hydroxide is used as a template agent, and hydrofluoric acid is used as a mineralizer. The greatest contribution here is the direct synthesis of low-defect Beta, but the large-scale application of the method is severely hampered by the introduction of the highly toxic hydrofluoric acid as a mineralizer. In the context of the subsequent reports,Top.Catal.1999,9, 59–76，Micropor. Mesopor. Mater.2006，90，237-245,Catal. Today2002,74, 271-279,Stud. Surf. Sci. Catal.,2004,154,725-730,Chem. Mater.2004,4, 725-730，Chem. Mater.2005,17, 4374-4385，3218-3223Micropor. Mesopor.Mater.2006，93，55-61，Micropor. Mesopor.Mater.2006，89，88-95，Angew. Chem. Int. Ed.2006,45,8013-8015，Micropor. Mesopor. Mater.,2007，100，118-127，Chem. Mater.2008,203218-3223 and the patents of the invention (CN1290654, CN101311116A, CN101462738A, CN105800634A, CN1096417C, CN101311116A) use a series of quaternary ammonium salts as organic structure directing agents to synthesize high silicon or all-silicon zeolites, but due to the same problems, the use of fluorine-containing systems causes serious environmental pollution problems in industrial production, thereby limiting the application of these methods.
Chinese patent (CN1154341A, CN1154342A) discloses a method for synthesizing Beta zeolite, which is technically characterized in that silica gel with any pore diameter and 20 ~ 300 meshes is used as a silicon source, the silica gel is mixed with a working solution consisting of an aluminum source, a sodium source, a tetraethylammonium cation source and water to wet the surfaces of silica gel particles with the working solution, and then crystallization reaction is carried out in two or more stepsActa Phys.- Chim. Sin.2008, crystallizing 24, 1192-1198 at the temperature of 180 ℃ for 12 to 32 hours in a standing still to obtain the Beta zeolite with the silicon-aluminum ratio ranging from 24 to 452. Although the method greatly reduces the dosage of the template agent and synthesizes the Beta zeolite with high silica-alumina ratio, the application of the Beta zeolite is influenced by complicated operation steps.
Thereafter, the literatureMicropor. Mesopor. Mater.1999，28519-530 reports a method for direct hydrothermal synthesis of all-silicon Beta zeolite by using an alkali system. The method is technically characterized in that white carbon black is used as a silicon source, a non-corresponding isomer of 4,4' -trimethylenebis (1-benzyl-1-methylpiperidine) quaternary ammonium salt cation is used as a structure directing agent, and the all-silicon Beta zeolite is synthesized by crystallizing for 2-16 days in a standing kettle at 135-150 ℃. The preparation process of the template agent involved in the method is complex.
Open literatureChem. Commun.,2001, 1486-1487 reports a direct hydrothermal synthesis of the all-silicon zeolite Beta C-type. It is technically characterized by that it uses tetraethyl orthosilicate as silicon source and uses DABMe (OH) as silicon sourceCrystallizing the template agent (namely-N-methyl quaternary ammonium base of triethylene diamine) at 150 ℃ for 12 days, and carrying out hydrothermal synthesis to obtain the BEC zeolite. Also, the templating agents involved in this process are quite expensive.
Open literatureACS Appl. Mater. Interfaces2017,927273-27283, which are respectively suitable for acid treatment dealuminization method, crystal transformation method, fluorine system and alkali system synthesis to synthesize the all-silicon Beta zeolite. The problems of the acid treatment method and the fluorine system method have been mentioned above and will not be described in detail. Similar to the Chinese patent (CN106430230A), the crystal transformation method needs to synthesize pure silicon ITQ-1 first, and two expensive templates, namely N, N, N-trimethy-1-adamaramium hydroxide or hexamethynimine, are used, so that the crystal transformation method has no industrialization prospect. In the case of the base system synthesis used herein, too large a quantity of seed crystals (10% relative to SiO) is used2Dosage), also limiting its scale-up applications.
Open literatureJ.Inorg. Mater.,2018,339,963-968 synthesized zeolite Beta from all-silicon by a single template synthesis method, i.e., a seed-guided vapor assisted crystallization (SAC). The method is technically characterized in that white carbon black is used as a silicon source, tetraethylammonium hydroxide is used as a template agent, Beta crystal seeds with the ratio of sodium hydroxide to silicon to aluminum being 28 are added, the raw materials are stirred into paste, then the paste is placed into a 60 ℃ oven to be dried into dry glue and smashed, the dry glue is placed into a porous sieve made of polytetrafluoroethylene, a proper amount of water is placed into the bottom of a 45 mL stainless steel reaction kettle, and the sieve filled with the dry glue is fixed in the middle of the reaction kettle by a stainless steel wire without contacting with the water. And (4) screwing the kettle button, putting the kettle button into a preheated oven at 150 ℃, and standing and crystallizing at constant temperature for about 48 hours to obtain the all-silicon Beta zeolite sample. Open literatureAngew. Chem. Int. Ed.2018,573607-3611 also uses a steam assisted crystallization method to realize the synthesis of the all-silicon Beta zeolite molecular sieve, but because the reaction kettle of the steam assisted crystallization method is too complex, the operation is not easy, and the industrial value is influenced.
Chinese patent (CN107804856) discloses a direct synthesis method of Beta zeolite molecular sieve with high silica-alumina ratio under a fluorine-free system, which is characterized in that sodium salt or ammonium salt of phosphoric acid is used as a mineralizer, and an organic silicon source silane coupling agent is also used. The silane coupling agent is expensive, and the practical value of the method is influenced.
In the above synthesis of zeolite Beta, although carried out under fluorine-free conditions, there are two significant problems: the silicon-aluminum ratio of the synthesized Beta zeolite product is not high; complex operation, complex device and difficult realization of industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing a high-silicon Beta zeolite molecular sieve under the fluorine-free condition without adding a fluorine-containing mineralizer in an aging stage.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing a high-silicon Beta zeolite molecular sieve under a fluorine-free condition comprises the following steps:
dissolving a template agent and an alkali source together, adding a silicon source, stirring and mixing at room temperature to form concentrated sol, adding Beta molecular sieve seed crystals into the concentrated sol, controlling the water content, transferring the mixture to a reaction kettle, heating the mixture in a drying oven at constant temperature to perform crystallization reaction, cooling at room temperature after the reaction is finished, and performing suction filtration and drying on the obtained product to obtain the high-silicon Beta zeolite molecular sieve (Si/Al =200 ~ ∞).
In the above synthesis method, the raw materials are preferably added in a molar ratio of silicon source, alkali source and template =1:0.1 ~ 5:0.3 ~ 6.
Preferably, in the above synthesis method, the silicon source is white carbon black, silica sol, tetramethyl silicate or tetraethyl silicate, the alkali source is sodium hydroxide, and the template agent is tetraethylammonium hydroxide.
Preferably, in the above synthesis method, the amount of the Beta molecular sieve seed crystal added is 1 ~ 15% of the mass of the silicon source.
Preferably, in the above synthesis method, the crystallization reaction temperature is 120 ~ 200 ℃, and the crystallization reaction time is 1 ~ 6 days.
Compared with the prior art, the invention has the beneficial effects that:
1. the method for synthesizing the high-silicon Beta zeolite molecular sieve by using the concentrated sol under the fluorine-free condition avoids the use of high-toxicity fluorine species and greatly reduces the synthesis risk.
2. The invention can synthesize the Beta molecular sieve with high crystallinity and silicon-aluminum ratio of 200 ~ ∞ within 48 hours, and promotes the wide application of the high-silicon Beta molecular sieve.
3. The inorganic raw materials adopted by the invention are environment-friendly, the price is low, the operation steps are simple and feasible, and the method has important significance in the field of actual chemical production.
Drawings
FIG. 1: XRD spectrum of the product of example 1.
FIG. 2: SEM spectrum of the product of example 1.
FIG. 3: the nitrogen sorption and desorption isotherms of the product of example 1.
Detailed Description
The invention is described in further detail below with reference to the following detailed description and accompanying drawings:
example 1:
putting 1.0 g of carbon black, 0.4g of sodium hydroxide solution (mass fraction of 20%), 3.5 ethyl ammonium hydroxide (mass fraction of 25%) and 4.0% of Beta molecular sieve seed crystal into a beaker, stirring for 1 ~ 2h, weighing the mass of the seed crystal, controlling the water content within the range of mole ratio of silicon source to water =5, heating and crystallizing in a constant temperature box at 150 ℃ for 4d, cooling a reaction kettle to room temperature after the crystallization reaction is finished, opening the kettle, taking out a solid crystallization product, washing, drying in a drying oven at 60 ℃ to obtain molecular sieve powder, wherein the mixture ratio of reaction raw materials is that the silicon source is alkali source to template agent =1:0.5:1.2, and the mass ratio is 1SiO2:0.040Beta seeds。
FIG. 1 is an XRD characterization spectrum of a product, which has a typical Beta characteristic peak.
Fig. 2 is an SEM image of the product, and it can be seen that the synthesized product has a plate-like morphology.
FIG. 3 is a nitrogen sorption and desorption isotherm curve for a product having a microporous and mesoporous structure.
Example 2:
3.2g of silicic acidTetraethyl ester, 1.2 sodium oxide solution (mass fraction is 20%), 8.0g tetraethyl ammonium hydroxide (mass fraction is 25%) and 6.0% Beta molecular sieve seed crystal are placed in a beaker, stirred for 1 ~ 5h, the mass of the crystal is weighed, the water content is controlled within the range of the mole ratio of silicon source to water =12, the reaction kettle is heated and crystallized for 4d in a constant temperature box at 150 ℃, the reaction kettle is cooled to the room temperature after the crystallization reaction is finished, the kettle is opened, the solid crystallization product is taken out and washed, and the solid crystallization product is dried in a drying oven at 60 ℃ to obtain molecular sieve powder, and the mixture ratio of the reaction raw materials is that the silicon source to alkali source to template agent =1:2.2:3.2, and the mass ratio is 1SiO2:0.060Beta seeds。
Example 3:
putting 1.8g of white carbon black, 0.7g of sodium hydroxide solution (mass fraction is 20%), 7.5g of tetraethylammonium hydroxide (mass fraction is 25%) and 3.0% of Beta molecular sieve seed crystal into a beaker, stirring for 1 ~ 4h, weighing the mass of the crystal, controlling the water content within the range of mole ratio of silicon source to water =8, heating and crystallizing in a constant temperature box at 150 ℃ for 4d, cooling a reaction kettle to room temperature after the crystallization reaction is finished, opening the kettle, taking out a solid crystallization product, washing, drying in a drying oven at 60 ℃ to obtain molecular sieve powder, wherein the reaction raw materials comprise the silicon source, an alkali source, a template agent =1:4.5:5.1 and the mass ratio of 1SiO to the template agent =1:4.5:5.12:0.030Beta seeds。
Claims (5)
1. A method for synthesizing a high-silicon Beta zeolite molecular sieve under a fluorine-free condition is characterized by comprising the following steps:
dissolving a template agent and an alkali source together, adding a silicon source, stirring and mixing at room temperature to form concentrated sol, adding Beta zeolite seed crystals into the concentrated sol, controlling the water content within the molar ratio of the silicon source to the water =5 ~ 12, transferring to a reaction kettle, heating in an oven at constant temperature for crystallization reaction, cooling at room temperature after the reaction is finished, and performing suction filtration and drying on the obtained product to obtain the high-silicon Beta zeolite molecular sieve.
2. The synthesis method according to claim 1, wherein the raw materials are added in a molar ratio of silicon source to alkali source to template =1:0.1 ~ 5:0.3 ~ 6.
3. The synthesis method according to claim 1, wherein the silicon source is white carbon black, silica sol, tetramethyl silicate or tetraethyl silicate, the alkali source is sodium hydroxide, and the template agent is tetraethylammonium hydroxide.
4. The synthesis method of claim 1, wherein the Beta molecular sieve seed crystal is added in an amount of 1 ~ 15% of the mass of the silicon source.
5. The synthesis method of claim 1, wherein the crystallization reaction temperature is 120 ~ 200 ℃ and the crystallization reaction time is 1 ~ 6 days.
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| CN113443636A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | BEC structure molecular sieve and synthetic method thereof |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
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| CN113443636A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | BEC structure molecular sieve and synthetic method thereof |
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| CN111732111A (en) * | 2020-07-04 | 2020-10-02 | 复榆(张家港)新材料科技有限公司 | Preparation method of pure silicon BEA zeolite |
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| CN114506855B (en) * | 2020-11-17 | 2023-11-17 | 中国科学院大连化学物理研究所 | Preparation method and application of Beta molecular sieve |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
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