CN113683099B - Method for synthesizing defective zeolite molecular sieve rich in hydroxy nest - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 77
- 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 77
- 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 57
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 56
- 239000010457 zeolite Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000002950 deficient Effects 0.000 title claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 32
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 45
- 239000010703 silicon Substances 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000005376 alkyl siloxane group Chemical group 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 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
- 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 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 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
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 4
- 229910018540 Si C Inorganic materials 0.000 abstract description 3
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 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 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 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 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 101100112997 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MCM22 gene Proteins 0.000 description 1
- 229910010280 TiOH Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- C01B39/36—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
-
- 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
- C01B39/04—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a method for synthesizing a defective zeolite molecular sieve rich in hydroxy nest, which takes an inorganic silicon source and an organic silicon source as mixed silicon sources, and mixes the mixed silicon sources with an aluminum source and an OSDA template agent to obtain sol for crystallization; filtering, drying and roasting the obtained solid to obtain a defective zeolite molecular sieve rich in hydroxy nest; the organosilicon source is an alkylsiloxane. According to the invention, alkyl siloxane is introduced in the process of constructing a framework of the molecular sieve to form partial Si-C bond connection, and then C is burnt out in the process of roasting the molecular sieve to form a framework point defect of a single T position of the molecular sieve to form a hydroxyl nest, and the point defect almost has no influence on the crystallinity of the material, and the integrity of the molecular sieve framework is maintained to a great extent; the defect degree of the molecular sieve can be controlled relatively accurately by controlling the type and the content of the alkyl siloxane in the synthesis process, so that the defective zeolite molecular sieve rich in the hydroxy nest is obtained.
Description
Technical Field
The invention belongs to the field of aluminosilicate zeolite synthesis, and particularly relates to a method for synthesizing a defective zeolite molecular sieve rich in hydroxy nest.
Background
Zeolite molecular sieves are the most widely distributed inorganic microporous material in nature. After first finding natural zeolite from a swedish scientist Cronstedt 1756, the natural zeolite is widely focused by scientific researchers due to the unique molecular sieving capability, good adsorption performance and other characteristics, and is gradually applied to actual production and life of people. Although natural zeolite has the characteristics of various types, wide distribution, large reserves, low cost and the like, the natural zeolite has more impurities and low purity, and limits large-scale industrial application, so the artificial synthesis of the zeolite becomes a new direction of research by people. The last 40 th century of the 20 th century, the outstanding chemist Barrer in the field of molecular sieve synthesis successfully prepared the first batch of low-silicon zeolite molecular sieves with a silicon to aluminum ratio of 1.0-1.5 by using a low-temperature hydrothermal synthesis technology. In 1964, a Y-type molecular sieve with a silicon-aluminum ratio of 1.5 to 3.0 was successfully synthesized and developed by Breck in the industry, and the Y-type molecular sieve shows excellent performance in industrial catalysis, thereby promoting the development of artificially synthesized zeolite. Thereafter, with development of technology and various innovative attempts of researchers, zeolite molecular sieve synthesis methods are increasing, and research on zeolite molecular sieve synthesis by researchers is never interrupted from traditional hydrothermal synthesis methods which simulate natural zeolite formation environment from the beginning to subsequent solvothermal synthesis methods, dry gel methods, seed crystal assisted synthesis, solvent-free methods and the like.
However, whatever the synthetic method, it is a final goal to produce molecular sieves that are nearly perfect or have few defects. With the continuous intensive research, scientists have found that the defect positions of molecular sieve frameworks have certain special properties, such as: the hydroxyl nest has relatively strong acidity due to mutual disturbance of hydrogen bonds, is an important adsorption site in VOC adsorption, and can contain certain metal ions so that metal heteroatoms enter a molecular sieve framework; titanium hydroxyl TiOH at the defect site of the titanium-silicon molecular sieve is a catalytic active center of olefin epoxidation reaction and the like. The method which is relatively commonly used at present is a method by post-treatment, namely: the zeolite molecular sieve containing defective sites is prepared by a post-modification method of removing part of framework aluminum or silicon of a molecular sieve matrix through soaking in acid/alkali liquor, but how to precisely control the positions and the sizes of the defective sites without damaging the topological structure of the molecular sieve framework is a great challenge for synthesizing the molecular sieve rich in the defective sites.
Disclosure of Invention
In order to fully utilize the special properties of defective positions of a molecular sieve, the invention provides a synthesis method of a defective zeolite molecular sieve rich in hydroxy nest, an inorganic silicon source and an organosilicon source of alkyl siloxane are used as mixed silicon sources to be mixed and crystallized with a conventional aluminum source and a template agent, partial Si-C bond is formed due to the introduction of the alkyl siloxane in the process of constructing a framework of the molecular sieve, and then C is burnt out in the roasting process of the molecular sieve to form framework point position defects of a single T position of the molecular sieve to form the hydroxy nest. The defect degree of the molecular sieve can be controlled relatively accurately by controlling the type and the content of the alkyl siloxane in the synthesis process, so that the defective zeolite molecular sieve rich in the hydroxy nest is obtained.
The technical scheme of the invention is as follows:
a method for synthesizing a defective zeolite molecular sieve rich in hydroxy nest, comprising the following steps:
s1, inorganic silicon source (Inorg-Si) and organic silicon source (Org-Si) are used as mixed silicon source, and are mixed with aluminum source and OSDA template agent to obtain sol for crystallization;
s2, filtering, drying and roasting to obtain a defective zeolite molecular sieve rich in hydroxy nest;
the organosilicon source is alkyl siloxane, and SiO in the sol 2 Inorg-Si (SiO in inorganic silicon source) 2 ) With SiO 2- Org-Si (SiO in organosilicon Source) 2 ) The molar ratio of (2) is 1:0.001-0.2.
The zeolite molecular sieve is ZSM-5 zeolite molecular sieve, beta zeolite molecular sieve, MCM22 zeolite molecular sieve or SSZ13 zeolite molecular sieve.
The zeolite molecular sieve is a ZSM-5 zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) Preparing an initial raw material silicon solution: under intense stirring, uniformly mixing an inorganic silicon source, an organic silicon source, sodium hydroxide and water to prepare an initial raw material silicon solution, and fully stirring;
(2) Preparing an initial raw material aluminum solution: uniformly mixing an aluminum source, sulfuric acid and water under intense stirring to prepare an initial raw material aluminum solution, and fully stirring;
(3) Slowly dripping the completely dissolved initial raw material aluminum solution into the initial raw material silicon solution, adding OSDA, and stirring at room temperature for 4-10 hours to obtain sol, wherein the mol composition of the sol is as follows:
18Na 2 O:96.8～99.9SiO 2 Inorg-Si (SiO in inorganic silicon source) 2 ):0.1～3.2SiO 2 Org-Si (SiO in organosilicon Source) 2 ):0.5～4Al 2 O 3 :12SO 4 2- :4000H 2 O:16.5～40.7OSDA；
(4) And filling the obtained sol into an autoclave lined with polytetrafluoroethylene for hydrothermal crystallization reaction, wherein the hydrothermal crystallization temperature is 130-190 ℃, and the hydrothermal crystallization time is 5 minutes-48 hours.
The zeolite molecular sieve is Beta zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) Preparing an initial raw material silicon solution: under intense stirring, uniformly mixing an inorganic silicon source, an organic silicon source, sodium hydroxide and water to prepare an initial raw material silicon solution, and fully stirring;
(2) Slowly adding an aluminum source and OSDA into an initial raw material silicon solution under intense stirring, continuously and vigorously stirring for 5-120 minutes, and then carrying out high-speed shearing and emulsifying treatment for 10 minutes by adopting a shearing and emulsifying machine to obtain sol, wherein the molar composition of the sol is as follows:
8.9～16.4Na 2 O:26.2～59.6SiO 2 Inorg-Si (SiO in inorganic silicon source) 2 ):0.4～3.8SiO 2 Org-Si (SiO in organosilicon Source) 2 ):1Al 2 O 3 :480～960H 2 O:10～40OSDA；
(3) And filling the obtained sol into an autoclave lined with polytetrafluoroethylene for hydrothermal crystallization reaction, wherein the hydrothermal crystallization temperature is 120-160 ℃, and the hydrothermal crystallization time is 5 minutes-28 hours.
The inorganic silicon source is selected from one or more of silica sol, white carbon black, water glass and solid silica gel.
The alkyl siloxane is methyl siloxane, and further, the methyl siloxane is one or more of dimethyl siloxane, dimethyl dimethoxy silane, dimethyl diethoxy silane and methyl triethoxy silane.
The aluminum source is one or more of aluminum oxide, aluminum nitrate, sodium metaaluminate and aluminum isopropoxide.
OSDA is one or more of methylamine, ethylamine, propylamine, n-butylamine, tetrapropylammonium hydroxide and tetrapropylammonium bromide in the synthesis of the ZSM-5 zeolite molecular sieve.
OSDA is at least one of tetraethyl bromide and tetraethyl ammonium hydroxide in the synthesis of the zeolite Beta molecular sieve. A step of
The drying temperature in the step S2 is 110 ℃, and the drying time is 8 hours; the roasting temperature is 500-600 ℃ and the roasting time is 10 hours.
Compared with the prior art, the invention has the following beneficial effects:
the traditional post-treatment method, namely the method for removing part of framework silicon or aluminum by acid-base treatment, has difficulty in controlling the removal degree, and the framework atoms are removed by the post-treatment method generally in a piece form to form larger defect vacancies, so that the crystallinity and the framework integrity of the material are damaged to a certain extent. The method utilizes an inorganic silicon source, siloxane and other organic silicon sources as mixed silicon sources to be mixed and crystallized with a conventional aluminum source and a template agent, and partial Si-C bonding is formed due to the fact that the organic siloxane is used as a partial silicon source in the process of constructing a framework of the molecular sieve, and then C is burnt out in the process of roasting the molecular sieve, so that framework point position defects of a single T position of the molecular sieve are formed, and a hydroxyl nest is formed. The point defect has almost no influence on the crystallinity of the material, and the integrity of the molecular sieve framework is maintained to a great extent. More importantly, the hydroxyl nest formed by the single T-site defect is the most hydrogen bond interference and the most unique chemical property. Therefore, the method can relatively precisely control the defect degree of the molecular sieve by controlling the type and the content of siloxane in the synthesis process, thereby obtaining the defective zeolite molecular sieve rich in hydroxy nest.
Drawings
FIG. 1 shows XRD spectra of comparative example D1# and example samples 1#, 2#.
FIG. 2 shows the IR spectra of the hydroxyl groups of comparative example D1# and example samples 1-3#.
FIG. 3 shows the IR spectra of the hydroxyl groups of comparative example D2# and example samples 6# and 9#.
Detailed Description
Comparative example 1
0.75g of NaOH,50g of sodium silicate (SiO 2 Mass fraction 60%, na 2 Adding 10% of O mass fraction into 22.5g of deionized water, and uniformly stirring by using a magnetic stirrer; 4.28g of aluminum sulfate was then completely dissolved in 5g of water, and 2.25g of concentrated sulfuric acid (98%) was slowly added; slowly dripping the completely dissolved aluminum sulfate solution into the solution containing sodium silicate, adding 25.9g of tetrapropylammonium hydroxide TPAOH, and stirring at room temperature for 6 hours to obtain sol, wherein the mol composition of the sol is as follows: 18Na 2 O:100SiO 2 :2.5Al 2 O 3 :12SO 4 2- :4000H 2 O:25.4TPAOH; putting the obtained sol into an autoclave lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to 170 ℃ and the hydrothermal crystallization time to 26 hours; filtering, drying at 110 deg.C for 8 hr, and calcining at 540 deg.C for 10 hr to obtain ZSM-5 with complete crystallization, denoted as D1#.
Comparative example 2
Uniformly mixing 60g of white carbon black, 21.6g of sodium hydroxide and 32g of water, slowly adding 4.9g of sodium metaaluminate under intense stirring, adding 73.5g of tetraethylammonium hydroxide, continuously and vigorously stirring for 1 hour, and then carrying out high-speed shearing and emulsifying treatment for 10 minutes by adopting a shearing emulsifying machine to obtain sol, wherein the mol composition of the sol is as follows: 8.9Na 2 O:30SiO 2 :1Al 2 O 3 :960H 2 O15 TEAOH; filling the obtained sol into an autoclave lined with polytetrafluoroethylene, wherein the crystallization temperature is 150 ℃, and the hydrothermal crystallization time is 48 hours; filtering, drying at 110 ℃ for 8 hours, and roasting at 540 ℃ for 10 hours to obtain the Beta molecular sieve with complete crystallization, which is named as D2#.
Example 1
0.75g of NaOH and 49.8g of sodium silicate (SiO 2 Mass fraction 60%, na 2 Adding 10% of O mass fraction into 22.5g of deionized water, adding 0.36g of methyltriethoxysilane, and uniformly stirring by using a magnetic stirrer; 4.28g of aluminum sulfate was then completely dissolved in 5g of water, and 2.25g of concentrated sulfuric acid (98%) was slowly added; slowly dripping the completely dissolved aluminum sulfate solution into the solution containing sodium silicate, adding 25.9g of tetrapropylammonium hydroxide TPAOH, and stirring at room temperature for 6 hours to obtain sol, wherein the mol composition of the sol is as follows: 18Na 2 O:99.6SiO 2 -Inorg-Si:0.4SiO 2 -Org-Si:2.5Al 2 O 3 :12SO 4 2- :4000H 2 O is 25.4TPAOH; putting the obtained sol into an autoclave lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to 170 ℃ and the hydrothermal crystallization time to 25 hours; the obtained solid is filtered, dried at 110 ℃ for 8 hours and baked at 540 ℃ for 10 hours, and the defective ZM-5 zeolite molecular sieve rich in hydroxy nest is obtained. The resulting product was designated sample # 1.
Example 2
0.75g of NaOH and 49.25g of sodium silicate (SiO 2 Mass fraction 60%, na 2 Adding 10% of O mass fraction into 22.5g of deionized water, adding 1.34g of methyltriethoxysilane, and uniformly stirring by using a magnetic stirrer; 4.28g of aluminum sulfate was then completely dissolved in 5g of water, and 2.25g of concentrated sulfuric acid (98%) was slowly added; slowly dripping the completely dissolved aluminum sulfate solution into the solution containing sodium silicate, adding 30.7g of tetrapropylammonium hydroxide TPAOH, and stirring at room temperature for 6 hours to obtain sol, wherein the mol composition of the sol is as follows: 18Na 2 O:98.5SiO 2 -Inorg-Si:1.5SiO 2 -Org-Si:2.5Al 2 O 3 :12SO 4 2- :4000H 2 30.2TPAOH; putting the obtained sol into an autoclave lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to 170 ℃ and the hydrothermal crystallization time to 25 hours; the obtained solid is filtered, dried at 110 ℃ for 8 hours and baked at 540 ℃ for 10 hours, and the defective ZM-5 zeolite molecular sieve rich in hydroxy nest is obtained. The resulting product was designated sample # 2.
Example 3
0.75g of NaOH,48.6g of sodium silicate (SiO 2 Mass fraction 60%, na 2 Adding 10% of O mass fraction into 22.5g of deionized water, adding 2.50g of methyltriethoxysilane, and uniformly stirring by using a magnetic stirrer; 4.28g of aluminum sulfate was then completely dissolved in 5g of water, and 2.25g of concentrated sulfuric acid (98%) was slowly added; slowly dripping the completely dissolved aluminum sulfate solution into the solution containing sodium silicate, adding 30.7g of tetrapropylammonium hydroxide TPAOH, and stirring at room temperature for 6 hours to obtain sol, wherein the mol composition of the sol is as follows: 18Na 2 O:97.2SiO 2 -Inorg-Si:2.8SiO 2 -Org-Si:2.5Al 2 O 3 :12SO 4 2- :4000H 2 30.2TPAOH; putting the obtained sol into an autoclave lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to 170 ℃ and the hydrothermal crystallization time to 25 hours; the obtained solid is filtered, dried at 110 ℃ for 8 hours and baked at 540 ℃ for 10 hours, and the defective ZM-5 zeolite molecular sieve rich in hydroxy nest is obtained. The resulting product was designated sample 3#.
Examples 4 to 5
The procedure is as in example 3, except that the silicone source and mass are varied, see Table 1, and the other procedures are the same.
TABLE 1 defective ZM-5 zeolite molecular sieves enriched in hydroxy sockets obtained from different organosilicon sources and masses
| Examples numbering | Sample numbering | Organosilicon Source species | Organosilicon Source Mass |
| Example 4 | 4# | Dimethyldiethoxysilane | 2.22g |
| Example 5 | 5# | Dimethyl siloxane | 1.49g |
Example 6
Uniformly mixing 60g of white carbon black, 3.6g of methyltriethoxysilane, 21.6g of sodium hydroxide and 32g of water, slowly adding 4.9g of sodium metaaluminate under intense stirring, adding 73.5g of tetraethylammonium hydroxide, continuously and vigorously stirring for 1 hour, and then carrying out high-speed shearing and emulsifying treatment for 10 minutes by adopting a shearing emulsifying machine; the sol is obtained, and the mol composition in the sol is as follows: 8.9Na 2 O:30SiO 2 (Inorg-Si):0.6SiO 2 (Org-Si):1Al 2 O 3 :960H 2 O15 TEAOH; filling the obtained sol into an autoclave lined with polytetrafluoroethylene, and crystallizingThe temperature is 150 ℃ and the hydrothermal crystallization time is 48 hours; filtering, drying at 110 ℃ for 8 hours and roasting at 540 ℃ for 10 hours to obtain the defect type Beta zeolite molecular sieve rich in hydroxy nest. The resulting product was designated sample 6#.
Examples 7 to 9
The procedure was as in example 6, except that the organosilicon source and the quality were varied, and the other procedures were the same.
TABLE 2 defective Beta zeolite molecular sieves enriched in hydroxy sockets obtained from different organosilicon sources and masses
| Examples numbering | Sample numbering | Organosilicon Source species | Organosilicon Source Mass |
| Example 7 | 7# | Methyltriethoxysilane | 4.8g |
| Example 8 | 8# | Dimethyldiethoxysilane | 3.2g |
| Example 9 | 9# | Dimethyl dimethoxy silane | 2.4g |
Example 10
XRD characterization is carried out on the samples prepared in the examples, and XRD spectra of the samples are shown in figure 1 by taking comparative example D1# and examples 1# and 2# as examples; comparative example D1# and example samples 1-5# have relative crystallinity data as shown in Table 3. The results show that all samples are in accordance with ZSM-5 structural features through XRD analysis, namely, the obtained solid samples are ZSM-5 molecular sieves, and the relative crystallinity of the samples is not obviously reduced due to the complete framework of the defective molecular sieves prepared by introducing the organosilicon source.
TABLE 3 relative crystallinity of different samples
| Sample numbering | Relative crystallinity |
| D1# | 100％ |
| 1# | 97.3％ |
| 2# | 99.1％ |
| 3# | 98.8％ |
| 4# | 99.4％ |
| 5# | 98.9％ |
Example 11
The samples prepared in the above examples were subjected to infrared hydroxyl characterization, and the hydroxyl infrared spectra of comparative example D1# and example samples 1-3# are shown in FIG. 2. The results show that comparative example D1# is 3500cm -1 The absence of vibration indicates that the sample has no hydroxy nest, while the sample with the organosilicon source introduced can be at 3500cm -1 Clear peaks were seen indicating that these samples had rich sites for hydroxyl pit defects and that the extent of material defects increased significantly as the amount of organosilicon source increased.
Example 12
The Beta series of samples were subjected to infrared hydroxyl characterization, and the hydroxyl infrared spectra of comparative example d2# and example samples 6# and 9# are shown in fig. 3. In addition, XRD tests showed that the framework of the 6# and 9# defective molecular sieves was complete. It has the same effect as the ZSM-5 series.
Claims (10)
1. A method for synthesizing a defective zeolite molecular sieve rich in hydroxy nest is characterized in that: the method comprises the following steps:
s1, inorganic silicon source Inorg-Si and organic silicon source Org-Si are used as mixed silicon sources, and are mixed with an aluminum source and an OSDA template agent to obtain sol for crystallization;
s2, filtering, drying and roasting the obtained solid to obtain a defective zeolite molecular sieve rich in hydroxy nest;
the organosilicon source is alkyl siloxane, and SiO in the sol 2 -Inorg-Si and SiO 2- The molar ratio of the Org-Si is 1:0.001-0.2.
2. The method for synthesizing a defective zeolite molecular sieve rich in hydroxy-acid cells according to claim 1, wherein: the zeolite molecular sieve is a ZSM-5 zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) Preparing an initial raw material silicon solution: under intense stirring, uniformly mixing an inorganic silicon source, an organic silicon source, sodium hydroxide and water to prepare an initial raw material silicon solution, and fully stirring;
(2) Preparing an initial raw material aluminum solution: uniformly mixing an aluminum source, sulfuric acid and water under vigorous stirring to prepare an initial raw material aluminum solution, and fully stirring;
(3) Slowly dripping the completely dissolved initial raw material aluminum solution into the initial raw material silicon solution, adding OSDA, and stirring at room temperature for 4-10 hours to obtain sol, wherein the mol composition of the sol is as follows: 18Na 2 O : 96.8~99.9SiO 2 -Inorg-Si : 0.1~3.2SiO 2 -Org-Si :0.5~4Al 2 O 3 : 12SO 4 2- : 4000H 2 O : 16.5~40.7OSDA；
(4) And filling the obtained sol into an autoclave lined with polytetrafluoroethylene for hydrothermal crystallization reaction, wherein the hydrothermal crystallization temperature is 130-190 ℃, and the hydrothermal crystallization time is 5 minutes-48 hours.
3. The method for synthesizing a defective zeolite molecular sieve rich in hydroxy-acid cells according to claim 1, wherein: the zeolite molecular sieve is Beta zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) Preparing an initial raw material silicon solution: under intense stirring, uniformly mixing an inorganic silicon source, an organic silicon source, sodium hydroxide and water to prepare an initial raw material silicon solution, and fully stirring;
(2) Slowly adding an aluminum source and OSDA into an initial raw material silicon solution under intense stirring, continuously and vigorously stirring for 5-120 minutes, and then carrying out high-speed shearing and emulsifying treatment for 10 minutes by adopting a shearing and emulsifying machine to obtain sol, wherein the molar composition of the sol is as follows: 8.9 to 16.4Na 2 O : 26.2~59.6SiO 2 -Inorg-Si : 0.4~3.8SiO 2 -Org-Si : 1Al 2 O 3 : 480~960H 2 O : 10~40OSDA；
(3) And filling the obtained sol into an autoclave lined with polytetrafluoroethylene for hydrothermal crystallization reaction, wherein the hydrothermal crystallization temperature is 120-160 ℃, and the hydrothermal crystallization time is 5 minutes-28 hours.
4. A method of synthesizing a defective zeolite molecular sieve rich in hydroxy-pits according to any one of claims 1 to 3, wherein: the inorganic silicon source is selected from one or more of silica sol, white carbon black, water glass and solid silica gel.
5. A method of synthesizing a defective zeolite molecular sieve rich in hydroxy-pits according to any one of claims 1 to 3, wherein: the alkyl siloxane is methyl siloxane.
6. The method for synthesizing a defective zeolite molecular sieve rich in hydroxy-acid cells according to claim 5, wherein: the methyl siloxane is one or more of dimethyl siloxane, dimethyl dimethoxy silane, dimethyl diethoxy silane and methyl triethoxy silane.
7. A method of synthesizing a defective zeolite molecular sieve rich in hydroxy-pits according to any one of claims 1 to 3, wherein: the aluminum source is one or more of aluminum oxide, aluminum nitrate, sodium metaaluminate and aluminum isopropoxide.
8. A method of synthesizing a defective zeolite molecular sieve rich in hydroxy-acid cells according to claim 2, wherein: the OSDA is one or more of methylamine, ethylamine, propylamine, n-butylamine, tetrapropylammonium hydroxide and tetrapropylammonium bromide.
9. A method of synthesizing a defective zeolite molecular sieve rich in hydroxy-acid cells according to claim 3, wherein: the OSDA is at least one of tetraethyl bromide and tetraethyl ammonium hydroxide.
10. A method of synthesizing a defective zeolite molecular sieve rich in hydroxy-pits according to any one of claims 1 to 3, wherein: and in the step S2, the roasting temperature is 500-600 ℃ and the roasting time is 10 hours.
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