CN109264739A - A kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis method of no extra mesoporous template - Google Patents
A kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis method of no extra mesoporous template Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- 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 44
- 239000011148 porous material Substances 0.000 title claims abstract description 40
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000003068 static effect Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 238000003756 stirring Methods 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 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01P2002/70—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
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis methods of no extra mesoporous template.The aqueous solution of micropore template agent is mixed with silicon source, colorless and transparent mixed solution A is stirred to get under room temperature；Mixed solution B containing titanium source and isopropanol is slowly added to mixed solution A, obtains mixed solution C；By mixed solution C, aging removes alcohol until mixed solution C goes completely into powder D at normal temperature；Powder D is added after water in the baking oven for placing it in steady temperature and carries out static crystallization, obtains crystallization product E；Crystallization product E is calcined after centrifuge washing, drying, obtains multistage pore canal nanometer titanium-silicon molecular sieve TS-1.It is simple that the beneficial effects of the invention are as follows preparation methods, high income, and preparation cost is low.
Description
Technical field
The invention belongs to mesoporous material preparation technical fields, are related to a kind of conjunction of multistage pore canal nanometer titanium-silicon molecular sieve TS-1
At method.
Background technique
In the 1980s, Taramasso et al. has successfully synthesized for the first time has identical MFI type topology with ZSM-5
The TS-1 Titanium Sieve Molecular Sieve of new generation of structure, by the transition metals Ti with variable valence feature in the skeleton structure of molecular sieve
It introduces, since there is skeleton titanium species empty 2p track to form the acid site Lewis with the potential for receiving electronics pair, because
And it can effective activation H2O2In oxygen-oxygen double bond form Ti-O-O-H active specy, and then with protonic solvent building high activity
Five-membered ring intermediate realizes effective transmitting of oxygen.Therefore, the appearance of titanium-silicon molecular sieve TS-1 opens up molecular sieve from solid acid catalysis
The field for having opened up selective catalytic oxidation opens the new direction of liquid phase selective oxidation.Titanium-silicon molecular sieve TS-1 is aoxidizing
Application in reaction has the advantage of energy-saving and environmental protection and economy etc., has good application in epoxidation reaction of olefines
Prospect.In METHANOL MEDIUM, H2O2/ TS-1 system catalysis chloropropene Direct Epoxidation prepares the reaction condition temperature of epoxychloropropane
With, and activity with higher, the time for reacting required is very short, and reacting is heterogeneous system, and the loss of catalyst is small, easily with
Product separation.
Traditional its pore size of TS-1 molecular sieve is less than 1nm.Since it is with orderly microcellular structure, so that in activity
The accessibility of the heart reduces, and is limited by duct and transgranular molecular mass-transfer rate is caused to slow down, and causes reactivity worth can not be most
The performance of big degree.And limitation is spread again such that molecular sieve is highly susceptible to the influence of carbon distribution coking, is urged to inhibit
The activity of agent shortens the service life of catalyst.Therefore, in order to eliminate the influence of diffusion, the same of zeolite crystal size is reduced
Shi Qi is transgranular to create multi-stage artery structure, can improve the diffusion of reactant and product molecule.In traditional molecule
It sieves in synthesized gel rubber other than with the presence of micropore directed agents, additional addition soft template or hard template can be in intrinsic zeolites
Additional pore system is generated in skeleton structure.Soft template method is to go to prepare multistage pore canal using the principle of surfactant support layer,
But the surfactant price utilized is costly, and since the influence preparation process of phase separation effect is difficult, synthesis it is more
Grade porous molecular sieve stability is poor, it is difficult to repeat.Hard template rule generally in gel preparation course filling template agent and after pass through
Multi-stage pore canal molecular sieve is made in one step of mode of calcination process.Substance of the high-temperature process containing carbons will will lead to loss of product, at
This is higher, these factors all limit its industrial application to a certain extent.
In conclusion carry out epoxidation with TS-1 titanium molecular sieve catalysis chloropropene has well to produce epoxychloropropane
Application prospect.While spreading raising catalyst activity and stability in molecular sieve crystal by improving, how to control and urge
The preparation cost of agent is a urgent problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of multistage pore canal nanometer Titanium Sieve Molecular Sieve synthesis sides of no extra mesoporous template
Method.
The technical scheme adopted by the invention is that following the steps below:
The first step mixes the aqueous solution of micropore template agent with silicon source, and colorless and transparent mixed solution is stirred to get under room temperature
A；
Mixed solution B containing titanium source and isopropanol is slowly added to mixed solution A, obtains mixed solution C by second step；
Third step will be warming up to 50- after mixed solution C at normal temperature aging 1.5-5 hours with the speed of 1-15 DEG C/min
100 DEG C except alcohol until mixed solution C goes completely into powder D；
Powder D is placed in the small crucible of polytetrafluoroethylene (PTFE) by the 4th step, and is placed on the crystalline substance with polytetrafluoroethyllining lining
Change in kettle, carries out static crystallization in the baking oven for placing it in steady temperature after water is added in kettle, obtain crystallization product E；
Crystallization product E is calcined after centrifuge washing, drying, obtains multistage pore canal provided by the invention by the 5th step
Nanometer titanium-silicon molecular sieve TS-1.
Further, the molar concentration rate of the silicon source, titanium source and micropore template agent is 30-400:1:1.5-10.
Further, the molar concentration rate of silicon source, titanium source and micropore template agent is 100:1:2.
Further, the titanium source is selected from titanium-containing compound that is water-soluble or dissolving in water, the preferably positive fourth of metatitanic acid
Ester；The silicon source is selected from silicon-containing compound that is water-soluble or dissolving in water, preferably silica solution；The micropore template agent
Selected from tetramethylammonium hydroxide (TMAOH), tetraethyl ammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH) and the tetrabutyl
Ammonium hydroxide (TBAOH), preferably tetrapropylammonium hydroxide.
Further, the mixed solution A that the first step obtains stirs 15-100 minutes；It is preferred that stirring 15-60 minutes；It is more excellent
Choosing stirring 60-100 minutes.The second step is that the mixed solution B containing titanium source and isopropanol is slowly added in mixed solution A
To obtain mixed solution C.The third step is by mixed solution C aging 1.5-5 hours (preferably 5 hours) and in 50-100 DEG C
(preferably 80 DEG C) are except alcohol until becoming powder D.4th step is placed in the crystallizing kettle with polytetrafluoroethyllining lining, to kettle
After middle addition water, 130-170 DEG C crystallization 4-72 hours, preferably 150 DEG C crystallization 24 hours.Powder D and water in crystallizing kettle
Mass ratio is 1.25-10:1, preferably 2.5:1.
Further, the addition is in the form of dropwise addition, and speed is 0.01-0.2ml/ minutes, preferably 0.05-
0.2ml/ minutes, more preferably 0.01-0.05ml/ minutes.
Further, the room temperature refers to 15-30 DEG C, preferably 20-25 DEG C.
The evaluation method of TS-1 Titanium Sieve Molecular Sieve of the present invention:
It is anti-in stainless steel under intense agitation (700rpm) that chloropropene liquid phase epoxidation prepares epichlorohydrin reaction
It answers in device and carries out.0.5g catalyst is added in a kettle, accounts for the 2.5wt% of quality of material score.Weigh a certain amount of matter
Hydrogen peroxide solution, the chloropropene solution that score is 30% are measured, a certain amount of methanol solution is then added as reaction dissolvent, solution
Addition in the following proportions, n (ALC): n (H2O2)=2:1, n (CH3OH):n(H2O2)=2:1,40 DEG C of reaction temperature, react into
By the cooling progress chromatography of product after row 1h.
It is simple that the beneficial effects of the invention are as follows preparation methods, high income, and preparation cost is low.
Detailed description of the invention
Fig. 1 is the x-ray diffraction pattern of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 1；
Fig. 2 is the UV-vis figure of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 1；
Fig. 3 is the transmission electron microscope TEM figure of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 1；
Fig. 4 is the N of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 12Physical absorption and graph of pore diameter distribution；
Fig. 5 is the pore-size distribution comparison diagram of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 1-4；
Fig. 6 is the graph of pore diameter distribution of nanometer titanium-silicon molecular sieve TS-1 in embodiment 5.
Specific embodiment
The present invention is described in detail With reference to embodiment.
Embodiment 1
The preparation of multistage pore canal nanometer titanium-silicon molecular sieve TS-1
It takes 10.168g tetrapropylammonium hydroxide to be placed in a beaker, the stirring of 32.045g silica solution is added and obtains solution within 60 minutes
A.It takes 10mL isopropanol to be uniformly mixed with 1.362g tetrabutyl titanate, is added in A and is stirred 3 hours with 0.2ml/ minutes rates, obtained
To solution B.By B solution under room temperature aging 5 hours, and in 80 degree except alcohol until synthesis presoma become powder completely.It will
1.25g powder is placed in the small crucible of polytetrafluoroethylene (PTFE), and is placed in the crystallizing kettle with polytetrafluoroethyllining lining, in kettle
It after 1g water is added, crystallizes 24 hours under the conditions of 150 degree, after taking out washing drying, is roasted 6 hours in 550 degree of air atmospheres.
Fig. 1 is the x-ray diffraction pattern of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 1.Fig. 2 is multistage pore canal in embodiment 1
The UV-vis figure of nanometer titanium-silicon molecular sieve TS-1.Fig. 3 is the transmission electricity of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 1
Mirror TEM figure.Fig. 4 is the N of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 12Physical absorption and graph of pore diameter distribution.
Embodiment 2
The preparation of multistage pore canal nanometer titanium-silicon molecular sieve TS-1
It takes 10.168g tetrapropylammonium hydroxide to be placed in a beaker, the stirring of 32.045g silica solution is added and obtains solution within 60 minutes
A.It takes 10mL isopropanol to be uniformly mixed with 1.362g tetrabutyl titanate, is added in A and is stirred 3 hours with 0.2ml/ minutes rates, obtained
To solution B.By B solution under room temperature aging 5 hours, and in 80 degree except alcohol until synthesis presoma become powder completely.It will
2.5g powder is placed in the small crucible of polytetrafluoroethylene (PTFE), and is placed in the crystallizing kettle with polytetrafluoroethyllining lining, in kettle
It after 1g water is added, crystallizes 24 hours under the conditions of 150 degree, after taking out washing drying, is roasted 6 hours in 550 degree of air atmospheres.
Embodiment 3
The preparation of multistage pore canal nanometer titanium-silicon molecular sieve TS-1
It takes 10.168g tetrapropylammonium hydroxide to be placed in a beaker, the stirring of 32.045g silica solution is added and obtains solution within 60 minutes
A.It takes 10mL isopropanol to be uniformly mixed with 1.362g tetrabutyl titanate, is added in A and is stirred 3 hours with 0.2ml/ minutes rates, obtained
To solution B.By B solution under room temperature aging 5 hours, and in 80 degree except alcohol until synthesis presoma become powder completely.By 5g
Powder is placed in the small crucible of polytetrafluoroethylene (PTFE), and is placed in the crystallizing kettle with polytetrafluoroethyllining lining, to be added in kettle
It after 1g water, crystallizes 24 hours under the conditions of 150 degree, after taking out washing drying, is roasted 6 hours in 550 degree of air atmospheres.
Embodiment 4
The preparation of multistage pore canal nanometer titanium-silicon molecular sieve TS-1
It takes 10.168g tetrapropylammonium hydroxide to be placed in a beaker, the stirring of 32.045g silica solution is added and obtains solution within 60 minutes
A.It takes 10mL isopropanol to be uniformly mixed with 1.362g tetrabutyl titanate, is added in A and is stirred 3 hours with 0.2ml/ minutes rates, obtained
To solution B.By B solution under room temperature aging 5 hours, and in 80 degree except alcohol until synthesis presoma become powder completely.By 10g
Powder is placed in the small crucible of polytetrafluoroethylene (PTFE), and is placed in the crystallizing kettle with polytetrafluoroethyllining lining, to be added in kettle
It after 1g water, crystallizes 24 hours under the conditions of 150 degree, after taking out washing drying, is roasted 6 hours in 550 degree of air atmospheres.Fig. 5
For the pore-size distribution comparison diagram of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 in embodiment 1-4.
Embodiment 5 (comparison)
It takes 28.25g tetrapropylammonium hydroxide to be placed in a beaker stirring with 57.2g deionized water to be uniformly mixed to obtain for 30 minutes
Solution A takes 72.082g tetraethyl orthosilicate to be slowly added dropwise into above-mentioned solution and obtains solution B, and stirring 3 hours complete to silicon source
The 1.178g tetrabutyl titanate being dissolved in 15ml isopropanol in advance is added in the form that 0.2ml/ minutes rates are added dropwise after dissolution
Solution C obtains solution D, and by solution D, aging 5 hours will except alcohol 3 hours under the conditions of being continuously heating to 80 degree under the conditions of 50 degree
This aqueous precursor gel is placed in hydro-thermal static crystallization 72h in the crystallizing kettle with polytetrafluoroethyllining lining, after taking out washing drying, in
It is roasted 6 hours in 550 degree of air atmospheres.
The present invention provides a kind of multistage pore canal nanometer titanium-silicon molecular sieve TS-1, compared to the prior art in meso titanium silica point
Son sieve, does not use additional mesoporous template, forms meso-hole structure by kirkendall growth effects.Its mesoporous pore size master
It to be 2-20nm, preferably 2.5-8nm；It is more preferably 2.8-4.5nm.
It is also an advantage of the present invention that:
1, the present invention utilizes Kirkendall growth effects, is not necessarily to any mesoporous template, only using dry gel method synthesis
Multistage pore canal nanometer titanium-silicon molecular sieve TS-1 containing tetrahedral framework titanium.
2, multistage pore canal nanometer titanium-silicon molecular sieve TS-1 grain diameter provided by the invention is nano particle scope (50-
500nm), intracrystalline diffusion resistance is small, strengthens reaction product diffusion, reduces coking rate, and then extend catalyst life；
3, the pore ratio of multistage pore canal nanometer titanium-silicon molecular sieve TS-1 particle provided by the invention is low, by expanding micropore
To mesoporous scope, it is effectively prevent blockage of the micro orifice phenomenon caused by coking, extends catalyst life.
The above is only not to make limit in any form to the present invention to better embodiment of the invention
System, any simple modification that embodiment of above is made according to the technical essence of the invention, equivalent variations and modification,
Belong in the range of technical solution of the present invention.
Claims (5)
1. a kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis method of no extra mesoporous template, it is characterised in that according to following step
It is rapid to carry out:
The first step mixes the aqueous solution of micropore template agent with silicon source, and colorless and transparent mixed solution A is stirred to get under room temperature；
Mixed solution B containing titanium source and isopropanol is slowly added to mixed solution A, obtains mixed solution C by second step；
Third step will be warming up to 50-100 DEG C after mixed solution C at normal temperature aging 1.5-5 hours with the speed of 1-15 DEG C/min
Except alcohol, until mixed solution C goes completely into powder D；
Powder D is placed in the small crucible of polytetrafluoroethylene (PTFE) by the 4th step, and is placed on the crystallizing kettle with polytetrafluoroethyllining lining
In, after in kettle be added water after place it in steady temperature baking oven in carry out static crystallization, obtain crystallization product E；
Crystallization product E is calcined after centrifuge washing, drying, obtains multistage pore canal nanometer Titanium Sieve Molecular Sieve TS- by the 5th step
1。
2. according to a kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis method of no extra mesoporous template described in claim 1,
Be characterized in that: the molar concentration rate of the silicon source, titanium source and micropore template agent is 30-400:1:1.5-10.
3. according to a kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis method of no extra mesoporous template described in claim 1,
Be characterized in that: the titanium source is selected from titanium-containing compound that is water-soluble or dissolving in water；The silicon source be selected from it is water-soluble or
The silicon-containing compound dissolved in water；The micropore template agent is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl
Ammonium hydroxide and tetrabutylammonium hydroxide.
4. according to a kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis method of no extra mesoporous template described in claim 1,
Be characterized in that: the mixed solution A that the first step obtains stirs 15-100 minutes；The second step is will to contain titanium source and isopropyl
The mixed solution B of alcohol is slowly added in mixed solution A obtain mixed solution C；The third step is by mixed solution C aging
1.5-5 hours and in 50-100 DEG C except alcohol until become powder D；4th step is placed in the crystalline substance with polytetrafluoroethyllining lining
Change kettle in, after in kettle be added water after, 130-170 DEG C crystallization 4-72 hours；The mass ratio of powder D and water is in crystallizing kettle
1.25-10:1。
5. according to a kind of multistage pore canal nanometer titanium silicon molecular sieve synthesis method of no extra mesoporous template described in claim 1,
Be characterized in that: the addition is in the form of dropwise addition, and speed is 0.01-0.2ml/ minutes.
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| CN113353951A (en) * | 2021-07-21 | 2021-09-07 | 中国石油大学(北京) | Hierarchical pore titanium silicalite molecular sieve and preparation method and application thereof |
| CN113426480A (en) * | 2021-05-25 | 2021-09-24 | 武汉理工大学 | Preparation method and catalytic application of organic-inorganic hybrid ZOF-TS-1 molecular sieve |
| CN114345407A (en) * | 2022-01-17 | 2022-04-15 | 江苏扬农化工集团有限公司 | Hierarchical pore TS-1 catalyst and preparation method and application thereof |
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Cited By (4)
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| CN113426480A (en) * | 2021-05-25 | 2021-09-24 | 武汉理工大学 | Preparation method and catalytic application of organic-inorganic hybrid ZOF-TS-1 molecular sieve |
| CN113353951A (en) * | 2021-07-21 | 2021-09-07 | 中国石油大学(北京) | Hierarchical pore titanium silicalite molecular sieve and preparation method and application thereof |
| CN114345407A (en) * | 2022-01-17 | 2022-04-15 | 江苏扬农化工集团有限公司 | Hierarchical pore TS-1 catalyst and preparation method and application thereof |
| CN114345407B (en) * | 2022-01-17 | 2024-04-23 | 江苏扬农化工集团有限公司 | Hierarchical pore TS-1 catalyst and preparation method and application thereof |
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