CN108097293A - The synthetic method of the MFI structure zeolite molecular sieve of tin dope and application - Google Patents
The synthetic method of the MFI structure zeolite molecular sieve of tin dope and application Download PDFInfo
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- CN108097293A CN108097293A CN201711314141.0A CN201711314141A CN108097293A CN 108097293 A CN108097293 A CN 108097293A CN 201711314141 A CN201711314141 A CN 201711314141A CN 108097293 A CN108097293 A CN 108097293A
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- silicon source
- synthetic method
- molecular sieve
- mfi
- zeolite molecular
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- 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 37
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 22
- 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 22
- 239000010457 zeolite Substances 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 17
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000001509 sodium citrate Substances 0.000 claims abstract description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 10
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 10
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 210000002966 serum Anatomy 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 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 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 235000014121 butter Nutrition 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000003643 water by type Substances 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- 239000002841 Lewis acid Substances 0.000 description 7
- 150000007517 lewis acids Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 4
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 2
- 229940120503 dihydroxyacetone Drugs 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical compound CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
Synthetic method and application the present invention relates to a kind of MFI structure zeolite molecular sieve of tin dope.Synthetic method is successively by silicon source, sodium hydroxide, tetrapropylammonium hydroxide, water, silicon source is mixed evenly to form gelatinous, the mixed liquor of disodium ethylene diamine tetraacetate and sodium citrate and the aqueous solution of soluble pink salt is added in above-mentioned gel again, after being sufficiently stirred, it is transferred in stainless steel polytetrafluoroethylene (PTFE) hydro-thermal autoclave, in constant temperature oven after crystallization a couple of days, cooled to room temperature, it filters, deionized water is washed three times, when drying 12 16 is small in 80 DEG C of thermostatic drying chambers, then in 550 600 DEG C of 4 6h of Muffle kiln roasting, recycle the NH that mass fraction is 6%4Cl solution exchanges three times, then obtains final products in 550 600 DEG C of 4 6h of Muffle kiln roasting.Crystallinity height, Sn MFI and Sn the Al MFI zeolite molecular sieves of regular appearance can be made in the present invention.This method preparation process is simple, reproducible, is easy to large-scale application.
Description
Technical field
Synthetic method and application the present invention relates to a kind of MFI structure zeolite molecular sieve of tin dope are specially Sn-MFI
The synthetic method of structural zeolite molecular sieve and application.By hydro-thermal method one-step synthesis by the species distribution of Sn in the structure of molecular sieve
In, available for the structure of Sn species in MFI structure molecular sieve and heterogeneous catalysis application, belong to Zeolite synthesis field.
Background technology
In recent years, lewis acid zeolite molecular sieve catalyst due to its shown in some acid catalyzed reactions it is unique excellent
Catalytic performance and get more and more people's extensive concerning.It is mainly carried out at present for its preparation by way of rear synthesis, first
By traditional zeolite molecular sieve containing aluminium（Such as Beta, ZSM-5, MOR etc.）Dealuminzation is carried out using concentrated nitric acid, then passes through atom kind
By the metal of high-valence state such as Ti, Zr, Hf and Sn etc. be rear to be mended in the molecular sieve after dealuminzation leaves the defects of on position the mode of plant, and is obtained
It is applied to some specific catalytic reactions to lewis acidic molecular sieve, however this method is needed using substantial amounts of dense nitre
Acid, end processing sequences are complicated and larger pollution is caused to environment, therefore this method is unfavorable for large-scale promotion；In addition it is existing
It needs to introduce F in the one direct preparation process of step hydro-thermal-The crystallization of molecular sieve is promoted to obtain lewis acid molecule as mineralizer
Sieve, but due to F-A large amount of discharges cause the eutrophication of water body and limit the use of this method.Therefore, exploitation, which has, prepares
The honest and clean lewis acid molecular sieve catalyst of simple process and low cost has important practical significance.Due to the MFI structure of Sn doping
Molecular sieve shows the lactic acid of the conversion high added value such as some biomass molecules such as dihydroxyacetone (DHA) or the process of lactate
Good catalytic activity and it is of interest by people, therefore develop and have that preparation process is simple, favorable reproducibility, and the height being easily achieved
The preparation method of the lewis acid Sn-MFI molecular sieves of catalytic activity has very important application value.Meanwhile in some allusion quotations
In the catalytic process of type, bronsted acid is generally required（Bronsted acid）And lewis acid（Lewis acid）Coordination catalysis, because
This exploitation is also anticipated with the difunctional zeolite molecular sieve catalyst that Bronsted acid and Lewis acid coexist with important reality
Justice.
The content of the invention
Synthetic method and application it is an object of the invention to provide a kind of MFI structure zeolite molecular sieve of tin dope.It should
Sn-MFI structural zeolite molecular sieves containing Sn are by metal Sn by one step of hydrothermal synthesis method（IV）It is introduced into MFI structure molecular sieve
In, synthesis technology is simple, and crystallization time is short, obtains the crystallinity height of sample, is easy to industrial applications.
The MFI structure zeolite molecular sieve of tin dope provided by the invention be with soluble pink salt, disodium ethylene diamine tetraacetate,
Sodium citrate, silicon source and silicon source are raw material by hydro-thermal method one-step synthesis, and Sn contains in Sn-MFI structural zeolite molecular sieve catalysts
It measures as 0.1-5%.
The step of specific synthetic method includes：Successively by silicon source, sodium hydroxide, tetrapropylammonium hydroxide aqueous solution
（TPAOH, mass percentage 30%）, water, silicon source is mixed evenly to form gelatinous, then by disodium ethylene diamine tetraacetate
It adds in above-mentioned gel with the mixed liquor of the aqueous solution and the aqueous solution of soluble pink salt of sodium citrate, after being sufficiently stirred, is transferred to
In stainless steel polytetrafluoroethylene (PTFE) hydro-thermal autoclave, in constant temperature oven after crystallization, cooled to room temperature filters, washing,
It is dry, then in 550-600 DEG C of Muffle kiln roasting 4-6h, use NH4Cl solution exchanges three times, then in 550-600 DEG C of Muffle furnace
Middle roasting.
The step of specific synthetic method of the MFI structure zeolite molecular sieve of tin dope provided by the invention includes:
1) silicon source, sodium hydroxide, tetrapropylammonium hydroxide and water are uniformly mixed, stir 1-3h, then add silicon source solution,
2-3h is stirred, then again adds disodium ethylene diamine tetraacetate and sodium citrate solid and the mixed liquor of water-soluble pink salt and water
Enter in above-mentioned mixed serum, continue to stir 1-2h, obtain mixed serum.
2) above-mentioned slurries are fitted into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, crystallization 2-15 days is subsequently cooled to room temperature, filters, goes
Ion water washing three times, when 80 DEG C of dry 12-16 are small, in 550-600 DEG C of Muffle kiln roasting 4-6h.
3) sample for obtaining above-mentioned roasting utilizes the NH that mass fraction is 4-6%4Cl solution exchanges three times, then 550-600
DEG C Muffle kiln roasting 4-6h and then obtain final products.
Soluble pink salt described in step 1) is Tin tetrachloride pentahydrate or acetylacetone,2,4-pentanedione tin；Silicon source is Ludox, positive silicic acid
Ethyl ester, aerosil, any one in waterglass and sodium metasilicate；Silicon source is preferably aerosil；Silicon source is inclined
Any one in sodium aluminate, aluminium isopropoxide, aluminum nitrate and aluminum sulfate；Silicon source is preferably aluminum nitrate；Disodium ethylene diamine tetraacetate
For complexing agent, sodium citrate is cooperation buffer, and tetrapropylammonium hydroxide is structure directing agent.
Wherein, Sn4+It is complexed with disodium ethylene diamine tetraacetate, Sn4+Molar ratio with disodium ethylene diamine tetraacetate is:1:0.5-10,
Sn4+Molar ratio with sodium citrate is：1:1-10.
The amount of the substance of material in step 1) matches：H2O:SiO2=10-1000；Sn：SiO2=0.01-0.2；NaOH：
SiO2=0.05-2；TPAOH：SiO2=0.1-1；Al：SiO2=0.0-0.5.The whipping temp of step 1) is 25 DEG C -80 DEG C.
Crystallization temperature described in step 2) is 80-200 DEG C.
The present invention provides the MFI structure zeolite molecular sieve of tin dope, Sn-MFI zeolite molecular sieve of the skeleton containing Sn is
The complex compound of metal Sn salt is added in the synthetic system of MFI structure molecular sieve by one step of hydrothermal synthesis method, obtains molecule
Sn-MFI structural zeolite molecular sieve catalysts containing Sn in sieve structure.The present invention is the aggregation of no bulky grain Sn metal oxides
Body.Sn species are introduced into the structure of MFI zeolite molecular sieves, synthesis technology step is simple, and the crystallinity of sample is high, and XRD is shown
Synthetic product is the molecular sieve of MFI type structure, and crystallinity is good.SEM the results show samples are the particle 100nm of elliposoidal
The spherical little particle of left and right, is easy to industrial applications.
Description of the drawings
Fig. 1：The XRD diagram of sample obtained by embodiment 1-5.
Fig. 2：3% Sn-MFI of sample in example 4（Si/Al=160）Scanning electron microscope (SEM) photograph.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated on, but protection scope of the present invention is not limited to this.Implement
The experimental method of actual conditions is not specified in example, usually according to the condition described in normal condition and handbook or according to manufacture
Condition proposed by manufacturer；Common apparatus, material, reagent used etc., are commercially available unless otherwise specified.
Embodiment 1：It is Sn-MFI samples Si/Al=∞ that silicon source synthesis Sn contents are 2% using aerosil
First by 0.60g sodium hydroxides, 17.50g tetrapropylammonium hydroxide, 5.20g aerosils and 10ml deionized waters
It mixes, after stirring 4h at 50 DEG C, by bis- ethylenediamine hydrate tetraacethyl disodiums of 0.35g, the sodium citrate of 0.30g,
0.30g Tin tetrachloride pentahydrates and the solution of 30ml deionized waters are added dropwise in above-mentioned mixed liquor, are further continued for stirring 4h, are transferred to poly-
In tetrafluoroethene reaction kettle, the crystallization 3d in 200 DEG C of constant temperature ovens, then cooled to room temperature, filters, deionized water washing
After three times, being placed in drying in 80 DEG C of thermostatic drying chambers, for 24 hours, after 550 DEG C of Muffle kiln roasting 6h, it is 6% to recycle mass fraction
NH4Cl solution exchanges 3 times, is dried for 24 hours in 80 DEG C of thermostatic drying chambers, then is placed in 550 DEG C of Muffle kiln roasting 6h and obtains
Final products.
A is the XRD of the sample in attached drawing 1, it can be seen that sample display has gone out the feature diffraction of the molecular sieve of typical MFI structure
Peak has higher crystallinity.
Embodiment 2：It is Sn-MFI samples Si/Al=∞ that silicon source prepares that Sn contents are 3% using aerosil
First by 0.80g sodium hydroxides, 17.50g tetrapropylammonium hydroxide, 5.20g aerosils and 10ml deionized waters
It mixes, after stirring 4h at 50 DEG C, by bis- ethylenediamine hydrate tetraacethyl disodiums of 0.50g, the sodium citrate of 0.80g,
0.48g Tin tetrachloride pentahydrates and the solution of 30ml deionized waters are added dropwise in above-mentioned mixed liquor, are further continued for stirring 4h, are transferred to poly-
In tetrafluoroethene reaction kettle, the crystallization 3d in 200 DEG C of constant temperature ovens, then cooled to room temperature, filters, deionized water washing
After three times, being placed in drying in 80 DEG C of thermostatic drying chambers, for 24 hours, after 550 DEG C of Muffle kiln roasting 6h, it is 6% to recycle mass fraction
NH4Cl solution exchanges 3 times, is dried for 24 hours in 80 DEG C of thermostatic drying chambers, then is placed in 550 DEG C of Muffle kiln roasting 6h and obtains
Final products.
B is the XRD of the sample in attached drawing 1, it can be seen that sample display has gone out the feature diffraction of the molecular sieve of typical MFI structure
Peak has higher crystallinity.
Embodiment 3：It is Sn-MFI samples Si/Al=∞ that silicon source synthesis Sn contents are 2% using sodium metasilicate
0.80g sodium hydroxides, 17.50g tetrapropylammonium hydroxide, 4.6g sodium silicate nanahydrates and 10ml deionized waters are mixed first
It is combined, after stirring 4h at 50 DEG C, by bis- ethylenediamine hydrate tetraacethyl disodiums of 0.45g, the sodium citrate of 0.40g, 0.35g
Tin tetrachloride pentahydrate and the solution of 25ml deionized waters are added dropwise in above-mentioned mixed liquor, are further continued for stirring 4h, are transferred to polytetrafluoro
In ethylene reaction kettle, the crystallization 3d in 200 DEG C of constant temperature ovens, then cooled to room temperature, filters, and deionized water is washed three times
Afterwards, being placed in drying in 80 DEG C of thermostatic drying chambers, for 24 hours, after 550 DEG C of Muffle kiln roasting 6h, it is 6% to recycle mass fraction
NH4Cl solution exchanges 3 times, is dried for 24 hours in 80 DEG C of thermostatic drying chambers, then is placed in 550 DEG C of Muffle kiln roasting 6h and obtains most
Finished product.
C is the XRD of the sample in attached drawing 1, it can be seen that sample display has gone out the feature diffraction of the molecular sieve of typical MFI structure
Peak has higher crystallinity.
Embodiment 4：Using aerosil Si/Al=160 are prepared for silicon source（The molal weight ratio of Si and Al）, Sn contents are
3% Sn-MFI samples
First by 0.80g sodium hydroxides, 17.50g tetrapropylammonium hydroxide, 5.20g aerosils and 10ml deionized waters
It mixes, after stirring 4h at 50 DEG C, the ANN aluminium nitrate nonahydrate of 0.25g and the solution of 10ml deionized waters is added in above-mentioned
In mixed liquor, after stirring 2h, by bis- ethylenediamine hydrate tetraacethyl disodiums of 0.50g, the sodium citrate of 0.80g, the hydrations of 0.48g five four
Stannic chloride and the solution of 20ml deionized waters are added dropwise in above-mentioned mixed liquor, are further continued for stirring 4h, are transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, the crystallization 3.5d in 200 DEG C of constant temperature ovens, then cooled to room temperature, filters, and after deionized water washing three times, puts
Drying for 24 hours, after 550 DEG C of Muffle kiln roasting 6h, recycles the NH that mass fraction is 6% in 80 DEG C of thermostatic drying chambers4Cl is molten
Liquid exchanges 3 times, is dried for 24 hours in 80 DEG C of thermostatic drying chambers, then is placed in 550 DEG C of Muffle kiln roasting 6h and obtains final products.
D is the XRD of the sample in attached drawing 1, it can be seen that sample display has gone out the feature diffraction of the molecular sieve of typical MFI structure
Peak has higher crystallinity.Attached drawing 2 is its scanning electron microscope (SEM) photograph, and the sample of synthesis is the little particle of 100 nm or so.
Embodiment 5：Tetraethyl orthosilicate is selected to synthesize Si/Al=80 for silicon source, Sn contents are 2% Sn-MFI samples
First by 0.30g sodium hydroxides, 17.50g tetrapropylammonium hydroxide, 18.0g tetraethyl orthosilicates and 10ml deionized waters
It mixes, after stirring 4h at 60 DEG C, the ANN aluminium nitrate nonahydrate of 0.50g and the solution of 10ml deionized waters is added in above-mentioned
In mixed liquor, after stirring 2h, by bis- ethylenediamine hydrate tetraacethyl disodiums of 0.50g, the sodium citrate of 0.80g, the hydrations of 0.48g five four
Stannic chloride and the solution of 20ml deionized waters are added dropwise in above-mentioned mixed liquor, are further continued for stirring 4h, are transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, the crystallization 3.5d in 200 DEG C of constant temperature ovens, then cooled to room temperature, filters, and after deionized water washing three times, puts
Drying for 24 hours, after 550 DEG C of Muffle kiln roasting 6h, recycles the NH that mass fraction is 6% in 80 DEG C of thermostatic drying chambers4Cl is molten
Liquid exchanges 3 times, is dried for 24 hours in 80 DEG C of thermostatic drying chambers, then is placed in 550 DEG C of Muffle kiln roasting 6h and obtains final products.
E is the XRD of the sample in attached drawing 1, it can be seen that sample display has gone out the feature diffraction of the molecular sieve of typical MFI structure
Peak has higher crystallinity.
Claims (7)
1. the MFI structure zeolite molecular sieve of a kind of tin dope, it is characterised in that it is with soluble pink salt, ethylenediamine tetra-acetic acid two
Sodium, silicon source and silicon source are raw material by hydro-thermal method one-step synthesis, and Sn contents are in Sn-MFI structural zeolite molecular sieve catalysts
0.1-5%,
The step of specific synthetic method includes：Successively by silicon source, sodium hydroxide, tetrapropylammonium hydroxide aqueous solution（TPAOH, matter
It is 30% to measure fraction）, water, silicon source is mixed evenly to form gelatinous, then by disodium ethylene diamine tetraacetate and sodium citrate solid
It is added in the mixed liquor of the aqueous solution of soluble pink salt in above-mentioned gel, after being sufficiently stirred, is transferred to stainless steel polytetrafluoroethylene (PTFE) water
In thermal high reaction kettle, in constant temperature oven after crystallization, cooled to room temperature filters, and washes, dry, then in 550-600
DEG C Muffle kiln roasting 4-6h, uses NH4Cl solution exchanges three times, then in 550-600 DEG C of Muffle kiln roasting.
2. the specific synthetic method of the MFI structure zeolite molecular sieve of the tin dope described in claim 1, it is characterised in that including
The steps:
1) silicon source, sodium hydroxide, tetrapropylammonium hydroxide and water are uniformly mixed, 1-3h is stirred at 25 DEG C ~ 80 DEG C, then added again
Enter silicon source solution, stir 2-3h, then again by disodium ethylene diamine tetraacetate and sodium citrate solid and water-soluble pink salt with
The mixed liquor of water is added in above-mentioned mixed serum, is continued to stir 1-2h, is obtained mixed serum；
2) above-mentioned slurries being fitted into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, 80 ~ 200 DEG C of crystallization 2-15 days are subsequently cooled to room temperature,
It filters, deionized water is washed three times, when 80 DEG C of dry 12-16 are small, in 550-600 DEG C of Muffle kiln roasting 4-6h；
3) sample for obtaining above-mentioned roasting utilizes the NH that mass fraction is 4-6%4Cl solution exchanges three times, then 550-600 DEG C
Muffle kiln roasting 4-6h and then obtain final products.
3. synthetic method described in accordance with the claim 2, it is characterised in that the soluble pink salt described in step 1) is five hydrations
Butter of tin or acetylacetone,2,4-pentanedione tin.
4. synthetic method described in accordance with the claim 2, it is characterised in that in step 1) silicon source for Ludox, ethyl orthosilicate,
Aerosil, any one in waterglass and sodium metasilicate；It is preferred that aerosil.
5. synthetic method described in accordance with the claim 2, it is characterised in that in step 1) silicon source for sodium metaaluminate, aluminium isopropoxide,
Any one in aluminum nitrate and aluminum sulfate；It is preferred that aluminum nitrate.
6. synthetic method described in accordance with the claim 2, it is characterised in that Sn in step 1)4+With disodium ethylene diamine tetraacetate
Molar ratio is:1:0.5 ~ 10, Sn4+Molar ratio with sodium citrate is：1:1~10.
7. synthetic method described in accordance with the claim 2, it is characterised in that the material proportion in step 1)：H2O:SiO2=10~
1000；Sn：SiO2=0.01-0.2；NaOH：SiO2=0.05-2；TPAOH：SiO2=0.1-1；Al：SiO2=0.0-0.5。
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| CN114560474A (en) * | 2022-03-09 | 2022-05-31 | 南京工业大学 | Synthesis method of metal modified M-MFI molecular sieve membrane |
| CN114560475A (en) * | 2022-03-09 | 2022-05-31 | 南京工业大学 | Preparation method of metal modified M-SSZ-13 molecular sieve membrane |
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