CN113683099A - Method for synthesizing defect type zeolite molecular sieve rich in hydroxyl pits - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 73
- 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 73
- 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 53
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 52
- 239000010457 zeolite Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 47
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 37
- 230000007547 defect Effects 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 57
- 239000010703 silicon Substances 0.000 claims abstract description 57
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 230000002950 deficient Effects 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 125000005376 alkyl siloxane group Chemical group 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- 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
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 14
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 239000011734 sodium Substances 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
- 238000002360 preparation method 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
- 238000004945 emulsification Methods 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
- 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
- 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 2
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 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 4
- 239000001164 aluminium sulphate Substances 0.000 description 4
- 235000011128 aluminium sulphate Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001308 synthesis method 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
- 238000012512 characterization method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 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
- 238000001228 spectrum 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- 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
- 230000001804 emulsifying effect 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
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
-
- 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
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- 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 hydroxyl pits, which comprises the steps of mixing an inorganic silicon source and an organic silicon source serving as mixed silicon sources with an aluminum source and an OSDA template agent to obtain sol, and crystallizing; filtering, drying and roasting the obtained solid to obtain the defective zeolite molecular sieve rich in hydroxyl pits; the organic silicon source is alkyl siloxane. The method introduces alkyl siloxane in the process of constructing the framework by the molecular sieve to form partial Si-C bond connection, and then C is burnt off in the roasting process of the molecular sieve to form a framework point position defect of a single T position of the molecular sieve to form a hydroxyl pit, wherein the point position defect almost has no influence on the crystallinity of the material, and the integrity of the framework of the molecular sieve is maintained to a great extent; the defect degree of the molecular sieve can be relatively accurately controlled by controlling the type and the content of the alkyl siloxane in the synthesis process, so that the defect type zeolite molecular sieve rich in the hydroxyl pits can be obtained.
Description
Technical Field
The invention belongs to the field of synthesis of aluminosilicate zeolite, and particularly relates to a synthesis method of a defect type zeolite molecular sieve rich in hydroxyl pits.
Background
Zeolite molecular sieves are the most widely distributed inorganic microporous materials in nature. After a swedish scientist Cronstedt discovers natural zeolite for the first time in 1756 years, the natural zeolite is widely concerned by researchers due to the characteristics of unique molecular sieving capability, good adsorption performance and the like, and is gradually applied to the actual production life of people. Although natural zeolite has the characteristics of various varieties, wide distribution, large reserves, low cost and the like, the natural zeolite has more impurities and low purity, and the large-scale industrial application is limited, so the artificial synthesis of the zeolite becomes a new direction for people to study. At the end of the 40 s of the 20 th century, the first batch of low-silicon zeolite molecular sieves were successfully prepared by Barrer, an outstanding chemist in the field of molecular sieve synthesis, by using a low-temperature hydrothermal synthesis technology, with a silica-alumina ratio of 1.0-1.5. In 1964, the Y-type molecular sieve with the silicon-aluminum ratio of 1.5-3.0 is successfully synthesized and developed by Breck in the industry, and shows excellent performance in industrial catalysis, thereby promoting the development of artificially synthesized zeolite. Since then, with the development of science and technology and various innovative attempts of researchers, the synthesis methods of zeolite molecular sieves are increasing, and researchers have been exploring the synthesis of zeolite molecular sieves from the conventional hydrothermal synthesis methods which simulate the environment of natural zeolite formation from the beginning to the subsequent solvothermal synthesis methods, dry gel methods, seed crystal assisted synthesis and solvent-free methods.
However, in either synthesis method, it is the ultimate goal to produce nearly perfect or minimally defective molecular sieves. With the continuous and intensive scientific research, scientists find that the defect sites of the molecular sieve framework have certain special properties, such as: the hydroxyl nest has relatively strong acidity due to mutual disturbance of hydrogen bonds with each other, is an important adsorption site in VOC adsorption, and can contain certain metal ions to enable metal heteroatoms to enter a molecular sieve framework; the 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 currently more common method is a method by post-treatment, namely: the zeolite molecular sieve containing defect sites is prepared by a post-modification method of removing partial framework aluminum or silicon of a molecular sieve matrix by soaking in acid/alkali liquor, but how to accurately control the position and the size of the defect sites without damaging the topological structure of the molecular sieve framework is a great challenge in synthesizing the molecular sieve rich in the defect sites.
Disclosure of Invention
In order to fully utilize the special properties of the defect sites of the molecular sieve, the invention provides a method for synthesizing a defect type zeolite molecular sieve rich in hydroxyl pits. The defect degree of the molecular sieve can be relatively accurately controlled by controlling the type and the content of the alkyl siloxane in the synthesis process, so that the defect type zeolite molecular sieve rich in the hydroxyl pits can be obtained.
The technical scheme of the invention is as follows:
a method for synthesizing a defective zeolite molecular sieve rich in hydroxyl pits comprises the following steps:
s1, mixing an inorganic silicon source (Inorg-Si) and an organic silicon source (Org-Si) as a mixed silicon source with an aluminum source and an OSDA template agent to obtain sol, and crystallizing;
s2 is filtered, dried and roasted to obtain the defect zeolite molecular sieve rich in hydroxyl nests;
the organic silicon source is alkyl siloxane, and SiO in the sol2Inorg-Si (SiO in inorganic silicon source)2) With SiO2-Org-Si (SiO in organic silicon source)2) The molar ratio of (A) to (B) is 1: 0.001-0.2.
The zeolite molecular sieve is a ZSM-5 zeolite molecular sieve, a Beta zeolite molecular sieve, an MCM22 zeolite molecular sieve or an SSZ13 zeolite molecular sieve.
The zeolite molecular sieve is a ZSM-5 zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) preparation of initial raw material silicon solution: under vigorous 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) preparation of initial raw material aluminum solution: under the condition of violent stirring, uniformly mixing an aluminum source, sulfuric acid and water to prepare an initial raw material aluminum solution and fully stirring;
(3) slowly dropping an initial raw material aluminum solution completely dissolved into an initial raw material silicon solution, adding OSDA, stirring at room temperature for 4-10 hours to obtain sol, wherein the sol comprises the following molar components:
18Na2O:96.8～99.9SiO2Inorg-Si (SiO in inorganic silicon source)2):0.1～3.2SiO2-Org-Si (SiO in organic silicon source)2):0.5～4Al2O3:12SO4 2-:4000H2O:16.5～40.7OSDA；
(4) Putting the obtained sol into a high-pressure autoclave lined with polytetrafluoroethylene to carry out 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 a Beta zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) preparation of initial raw material silicon solution: under vigorous 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 vigorous stirring, continuously and vigorously stirring for 5-120 minutes, and then carrying out high-speed shearing emulsification treatment for 10 minutes by using a shearing emulsifier to obtain sol, wherein the sol comprises the following molar compositions:
8.9～16.4Na2O:26.2～59.6SiO2Inorg-Si (SiO in inorganic silicon source)2):0.4～3.8SiO2-Org-Si (SiO in organic silicon source)2):1Al2O3:480～960H2O:10～40OSDA；
(3) Putting the obtained sol into a high-pressure autoclave lined with polytetrafluoroethylene to carry out 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.
In the synthesis of the ZSM-5 zeolite molecular sieve, OSDA is one or more of methylamine, ethylamine, propylamine, n-butylamine, tetrapropylammonium hydroxide and tetrapropylammonium bromide.
In the synthesis of the Beta zeolite molecular sieve, OSDA is at least one of tetraethyl bromide and tetraethyl ammonium hydroxide. A
In the step S2, the drying temperature 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, is difficult to control the removal degree, and the framework atoms removed by the post-treatment method are generally flaked to form larger defect vacancies, so that the crystallinity and the framework integrity of the material are damaged to a certain degree. The method utilizes organic silicon sources such as inorganic silicon source and siloxane as mixed silicon source to be mixed and crystallized with a conventional aluminum source and template agent, forms partial Si-C bond connection due to the introduction of organic siloxane as partial silicon source in the process of constructing the framework of the molecular sieve, and then burns off C in the roasting process of the molecular sieve to form the framework point position defect of single T position of the molecular sieve to form the hydroxyl nest. The point position 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. More importantly, the hydroxyl nest formed by the single T-site defect has the most hydrogen bond interference and the most unique chemical property. Therefore, the defect degree of the molecular sieve can be relatively accurately controlled by controlling the type and the content of siloxane in the synthesis process by the method, so that the defect type zeolite molecular sieve rich in the hydroxyl pits can be obtained.
Drawings
Fig. 1 is an XRD spectrum of comparative example D1# and example samples # 1 and # 2.
FIG. 2 is a hydroxyl group infrared spectrum of comparative example D1# and example samples 1-3 #.
FIG. 3 is a hydroxyl radical IR spectrum of comparative example D2# and example Nos. 6# and 9 #.
Detailed Description
Comparative example 1
0.75g NaOH, 50g sodium Silicate (SiO) was weighed260% by mass of Na 210 percent of O) is added into 22.5g of deionized water and stirred evenly by a magnetic stirrer; then 4.28g of aluminium sulphate was completely dissolved in 5g of water, 2.25g of concentrated sulphuric acid (98%) was slowly added; slowly dropping the completely dissolved aluminum sulfate solution into the solution containing sodium silicate, adding 25.9g of tetrapropyl ammonium hydroxide TPAOH, and stirring at room temperature for 6 hours to obtain sol, wherein the molar composition in the sol is as follows: 18Na2O:100SiO2:2.5Al2O3:12SO4 2-:4000H2O is 25.4 TPAOH; putting the obtained sol into a high-pressure kettle lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to be 170 ℃ and the hydrothermal crystallization time to be 26 hours; filtering, drying at 110 deg.C for 8 hr, and calcining at 540 deg.C for 10 hr to obtain crystallized ZSM-5, and recording 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 vigorous stirring, then adding 73.5g of tetraethylammonium hydroxide, continuously and vigorously stirring for 1 hour, and then carrying out high-speed shearing emulsification treatment for 10 minutes by using a shearing emulsifying machine to obtain sol, wherein the molar composition in the sol is as follows: 8.9Na2O:30SiO2:1Al2O3:960H2O15 TEAOH; putting the obtained sol into a high-pressure kettle with a polytetrafluoroethylene lining, wherein the crystallization temperature is 150 ℃, and the hydrothermal crystallization time is 48 hours; filtering, drying at 110 deg.C for 8 hr, and calcining at 540 deg.C for 10 hr to obtain crystallized Beta molecular sieve, and recording as D2 #.
Example 1
0.75g NaOH, 49.8g sodium Silicate (SiO) was weighed260% by mass of Na 210 percent of O) is added into 22.5g of deionized water, 0.36g of methyltriethoxysilane is added and stirred evenly by a magnetic stirrer; then 4.28g of aluminium sulphate was completely dissolved in 5g of water, 2.25g of concentrated sulphuric acid (98%) was slowly added; slowly dropping completely dissolved aluminum sulfate solution into solution containing sodium silicate, adding 25.9g of tetrapropyl ammonium hydroxide TPAOH, stirring at room temperature for 6 hours to obtain sol, and dissolving the solThe medium molar composition is as follows: 18Na2O:99.6SiO2-Inorg-Si:0.4SiO2-Org-Si:2.5Al2O3:12SO4 2-:4000H2O is 25.4 TPAOH; putting the obtained sol into a high-pressure kettle lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to be 170 ℃ and the hydrothermal crystallization time to be 25 hours; filtering the obtained solid, drying at 110 ℃ for 8 hours, and roasting at 540 ℃ for 10 hours to obtain the defective ZM-5 zeolite molecular sieve rich in hydroxyl nests. The product obtained is recorded as sample # 1.
Example 2
0.75g NaOH, 49.25g sodium Silicate (SiO) was weighed260% by mass of Na 210 percent of O) is added into 22.5g of deionized water, 1.34g of methyltriethoxysilane is added and stirred evenly by a magnetic stirrer; then 4.28g of aluminium sulphate was completely dissolved in 5g of water, 2.25g of concentrated sulphuric acid (98%) was slowly added; slowly dropping the completely dissolved aluminum sulfate solution into the solution containing sodium silicate, adding 30.7g of tetrapropyl ammonium hydroxide TPAOH, and stirring at room temperature for 6 hours to obtain sol, wherein the molar composition in the sol is as follows: 18Na2O:98.5SiO2-Inorg-Si:1.5SiO2-Org-Si:2.5Al2O3:12SO4 2-:4000H2O is 30.2 TPAOH; putting the obtained sol into a high-pressure kettle lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to be 170 ℃ and the hydrothermal crystallization time to be 25 hours; filtering the obtained solid, drying at 110 ℃ for 8 hours, and roasting at 540 ℃ for 10 hours to obtain the defective ZM-5 zeolite molecular sieve rich in hydroxyl nests. The product obtained is recorded as sample # 2.
Example 3
0.75g NaOH, 48.6g sodium Silicate (SiO) was weighed260% by mass of Na 210 percent of O) is added into 22.5g of deionized water, 2.50g of methyltriethoxysilane is added and stirred evenly by a magnetic stirrer; then 4.28g of aluminium sulphate was completely dissolved in 5g of water, 2.25g of concentrated sulphuric acid (98%) was slowly added; slowly dropping the completely dissolved aluminum sulfate solution into the solution containing sodium silicate, adding 30.7g of tetrapropyl ammonium hydroxide TPAOH, and stirring at room temperature for 6 hours to obtain sol, wherein the molar composition in the sol is as follows: 18Na2O:97.2SiO2-Inorg-Si:2.8SiO2-Org-Si:2.5Al2O3:12SO4 2-:4000H2O is 30.2 TPAOH; putting the obtained sol into a high-pressure kettle lined with polytetrafluoroethylene, and controlling the hydrothermal crystallization temperature to be 170 ℃ and the hydrothermal crystallization time to be 25 hours; filtering the obtained solid, drying at 110 ℃ for 8 hours, and roasting at 540 ℃ for 10 hours to obtain the defective ZM-5 zeolite molecular sieve rich in hydroxyl nests. The resulting product was designated sample # 3.
Examples 4 to 5
The procedure was as in example 3, except that the organic silicon source and the quality were changed, as shown in Table 1, and the other operations were the same.
TABLE 1 deficient ZM-5 zeolite molecular sieves rich in hydroxyl pits obtained with different organic silicon sources and qualities
| Example numbering | Sample numbering | Kind of organosilicon Source | Mass of organic silicon source |
| Example 4 | 4# | Dimethyldiethoxysilane | 2.22g |
| Example 5 | 5# | Dimethylsiloxane | 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 vigorous stirring, then adding 73.5g of tetraethylammonium hydroxide, continuing to vigorously stir for 1 hour, and then carrying out high-speed shearing emulsification treatment for 10 minutes by using a shearing emulsifier; obtaining sol, wherein the molar composition in the sol is as follows: 8.9Na2O:30SiO2(Inorg-Si):0.6SiO2(Org-Si):1Al2O3:960H2O15 TEAOH; putting the obtained sol into a high-pressure kettle with a polytetrafluoroethylene lining, wherein the crystallization temperature is 150 ℃, and the hydrothermal crystallization time is 48 hours; filtering, drying at 110 deg.C for 8 hr, and calcining at 540 deg.C for 10 hr to obtain the defective Beta zeolite molecular sieve rich in hydroxyl nest. The product obtained is recorded as sample # 6.
Examples 7 to 9
The procedure was the same as in example 6, except that the organic silicon source and the quality were changed, and the other procedures were the same.
TABLE 2 deficient Beta zeolite molecular sieves rich in hydroxyl pits obtained from different organic silicon sources and qualities
| Example numbering | Sample numbering | Kind of organosilicon Source | Mass of organic silicon source |
| Example 7 | 7# | Methyltriethoxysilane | 4.8g |
| Example 8 | 8# | Dimethyldiethoxysilane | 3.2g |
| Example 9 | 9# | Dimethyldimethoxysilane | 2.4g |
Example 10
XRD characterization was performed on the samples obtained in the above examples, taking comparative example D1# and example samples 1#, 2# as examples, and the XRD spectrum is shown in FIG. 1; comparative example D1# and example samples 1-5# the relative crystallinity data is shown in Table 3. The result shows that all samples accord with the structural characteristics of ZSM-5 through XRD analysis, namely, the obtained solid samples are ZSM-5 molecular sieves, and the defect type molecular sieves prepared by introducing the organic silicon source have complete frameworks, so that the relative crystallinity of the samples is not obviously reduced.
TABLE 3 relative crystallinity of different samples
| Sample numbering | Relative degree of crystallinity |
| D1# | 100％ |
| 1# | 97.3％ |
| 2# | 99.1％ |
| 3# | 98.8％ |
| 4# | 99.4％ |
| 5# | 98.9％ |
Example 11
The hydroxyl groups of the samples prepared in the above examples were characterized by infrared, and the hydroxyl groups of comparative example D1# and example samples 1-3# were shown in FIG. 2. The results show that comparative example No. D1 is 3500cm-1The absence of vibration indicates that the sample has no hydroxyl pit, while the sample introduced with the organic silicon source can be at 3500cm-1Clear peak inclusions are seen, which indicates that the samples have abundant hydroxyl pit defect sites, and the degree of material defects is obviously increased along with the increase of the amount of the organic silicon source.
Example 12
Infrared hydroxyl radical characterization was performed on Beta series samples and the hydroxyl radical IR spectra of comparative example D2# and example samples 6# and 9# are shown in FIG. 3. In addition, XRD testing showed that the 6# and 9# defective molecular sieves had intact frameworks. It has the same effect as the ZSM-5 series.
Claims (10)
1. A method for synthesizing a defect type zeolite molecular sieve rich in hydroxyl pits is characterized in that: the method comprises the following steps:
s1, mixing inorganic silicon source Inorg-Si and organic silicon source Org-Si as mixed silicon sources with an aluminum source and an OSDA template agent to obtain sol, and crystallizing;
filtering, drying and roasting the solid obtained from S2 to obtain the defect type zeolite molecular sieve rich in hydroxyl nests;
the organic silicon source is alkyl siloxane, and the organic silicon source isSiO in sol2-Inorg-Si with SiO2-The mole ratio of Org-Si is 1: 0.001-0.2.
2. The method for synthesizing the defective zeolite molecular sieve rich in hydroxyl pits of claim 1, wherein the method comprises the following steps: the zeolite molecular sieve is a ZSM-5 zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) preparation of initial raw material silicon solution: under vigorous 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) preparation of initial raw material aluminum solution: under the condition of violent stirring, uniformly mixing an aluminum source, sulfuric acid and water to prepare an initial raw material aluminum solution and fully stirring;
(3) slowly dropping an initial raw material aluminum solution completely dissolved into an initial raw material silicon solution, adding OSDA, stirring at room temperature for 4-10 hours to obtain sol, wherein the sol comprises the following molar components:
18Na2O:96.8～99.9SiO2-Inorg-Si:0.1～3.2SiO2-Org-Si:0.5～4Al2O3:12SO4 2-:4000H2O:16.5～40.7OSDA；
(4) putting the obtained sol into a high-pressure autoclave lined with polytetrafluoroethylene to carry out 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 the defective zeolite molecular sieve rich in hydroxyl pits of claim 1, wherein the method comprises the following steps: the zeolite molecular sieve is a Beta zeolite molecular sieve, and the S1 specifically comprises the following steps:
(1) preparation of initial raw material silicon solution: under vigorous 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 the initial raw material silicon solution under vigorous stirring, continuing to vigorously stir for 5-120 minutes, and then carrying out high-speed shearing emulsification for 10 minutes by using a shearing emulsifierObtaining the sol, wherein the molar composition in the sol is as follows: 8.9 to 16.4Na2O:26.2～59.6SiO2-Inorg-Si:0.4～3.8SiO2-Org-Si:1Al2O3:480～960H2O:10～40OSDA；
(3) Putting the obtained sol into a high-pressure autoclave lined with polytetrafluoroethylene to carry out hydrothermal crystallization reaction, wherein the hydrothermal crystallization temperature is 120-160 ℃, and the hydrothermal crystallization time is 5 minutes-28 hours.
4. The method for synthesizing the defective molecular sieve rich in hydroxyl pits of claims 1 to 3, wherein the method comprises the following steps: the inorganic silicon source is selected from one or more of silica sol, white carbon black, water glass and solid silica gel.
5. The method for synthesizing the defective molecular sieve rich in hydroxyl pits of claims 1 to 3, wherein the method comprises the following steps: the alkyl siloxane is methyl siloxane.
6. The method for synthesizing the defective zeolite molecular sieve rich in hydroxyl pits of claim 5, wherein the method comprises the following steps: the methyl siloxane is one or more of dimethyl siloxane, dimethyl dimethoxy silane, dimethyl diethoxy silane and methyl triethoxy silane.
7. The method for synthesizing the defective molecular sieve rich in hydroxyl pits of claims 1 to 3, wherein the method comprises the following steps: the aluminum source is one or more of aluminum oxide, aluminum nitrate, sodium metaaluminate and aluminum isopropoxide.
8. The method for synthesizing the defective zeolite molecular sieve rich in hydroxyl pits of claim 2, wherein the method comprises the following steps: the OSDA is one or more of methylamine, ethylamine, propylamine, n-butylamine, tetrapropylammonium hydroxide and tetrapropylammonium bromide.
9. The method for synthesizing the defective zeolite molecular sieve rich in hydroxyl pits of claim 3, wherein the method comprises the following steps: the OSDA is at least one of tetraethyl bromide and tetraethyl ammonium hydroxide.
10. The method for synthesizing the defective molecular sieve rich in hydroxyl pits of claims 1 to 3, wherein the method comprises the following steps: in the step S2, the roasting temperature is 500-600 ℃, and the roasting time is 10 hours.
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