CN1840473A - Vanadium-substituted silicate molecular sieve and its preparing method - Google Patents

Abstract

The disclosed V-Si molecular sieve with mole composition as (0.001~0.2)VO2:SiO2 belongs to a 3D channel structure with two vertical deca-element rings by every one formed by four ligating atoms and one nine-element ring with four ligating atoms crossed with former two rings.

Description

A kind of V-Si molecular sieve and preparation method thereof

Technical field

The invention relates to a kind of V-Si molecular sieve and preparation method thereof, further say so about a kind of ITH structure V-Si molecular sieve and preparation method thereof.

Background technology

Molecular sieve with ITH structure is the novel molecular sieve material of being developed by Exxon Mobil Corporation at earlier 2000s.This molecular sieve has the three-dimensional open-framework of the duct composition of three cover different diameters.Concrete structure is: the ten-ring that its parallel duct of the first cover cardinal principle is made up of the four-coordination atom constitutes; The second cover duct also is made of the ten-ring that the four-coordination atom is formed, and with first overlap the mutual vertical interlaced in duct; The 3rd cover duct and first, second cover duct are staggered, and the nonatomic ring of being made up of the four-coordination atom constitutes.The diameter of the first cover connection portion, ten-ring duct is 4.8～5.5_, and the diameter of the second cover connection portion, ten-ring duct is 5.0～5.7_, and the diameter of the 3rd cover connection portion, nonatomic ring duct is 4.0～4.9_.

In molecular sieve, introduce and have coordination and the transition element vanadium of the feature of appraising at the current rate, molecular sieve performance and transition metal tool voltinism can be able to be combined and produce the tool effect of uniqueness.Experiment shows, vanadium silicon class zeolite has good catalytic performance in many organic oxidizing reactions, the vanadium ZSM-5 molecular sieve (VS-1) that contains that for example has the MFI structure shows good catalytic performance in many organic oxidation reduction reactions such as toluene oxidation, phenol hydroxylation, xylidine oxidation, oxidation of alkanes, especially show good reaction preference, have a good application prospect.

The synthetic method of molecular sieve with ITH structure by the people such as Boix Teresa, Corma Avelino of ExxonMobil company in August, 2002 open (USP6471941B1) first, and called after ITQ-13.This method is to prepare a kind of reaction mixture that contains quadrivalent element Y, trivalent element X, organic amine (R) and fluorion earlier, with this reaction mixture in autoclave in 120～160 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.Trivalent element wherein is selected from boron, iron, indium, gallium, aluminium, and quadrivalent element Y is selected from silicon, tin, titanium, germanium, and the silicon source is preferably positive tetraethyl orthosilicate, colloidal state SiO ₂, the preferred dihydroxy-hexane diamine of organic amine, fluorochemical is preferably HF.The mole compositing range of its reaction mixture is:

Table 1

Reactant	Available proportioning	Optimum ratio
			YO 2/X 2O 3：	Be at least 5	Be at least 40
H 2O/YO 2：	2～50	5～20
			OH -/YO 2：	0.05～0.7	0.2～0.4
F -/YO 2：	0.1～1	0.4～0.8
			R/YO 2：	0.05～0.7	0.2～0.4

Summary of the invention

Up to now, do not see the report of vanadium silicon as the molecular sieve with ITH structure of backbone element, therefore, one of purpose of the present invention provides a kind of V-Si molecular sieve of the ITH of having structure and the preparation method of this molecular sieve is provided.

V-Si molecular sieve provided by the invention, has the ITH crystalline structure, it is characterized in that this molecular sieve has by the staggered three-dimensional open-framework of forming in two cover ten-ring ducts and a cover nonatomic ring duct, the ten-ring that its parallel duct of the first cover cardinal principle is made up of the four-coordination atom constitutes; The second cover duct also is made of the ten-ring that the four-coordination atom is formed, and with first overlap the mutual vertical interlaced in duct; The 3rd cover duct interlocks with first, second cover duct, and the nonatomic ring of being made up of the four-coordination atom constitutes, and has (0.001～0.2) VO ₂: SiO ₂, preferred (0.01～0.08) VO ₂: SiO ₂The mole of anhydrous oxide form.

V-Si molecular sieve provided by the invention, its X-ray diffraction (XRD) spectrogram has the feature of following table 2 at least.

Table 2

d(_)	Relative intensity (I)
		12.56±0.2	w-vs
11.05±0.2	m-vs
		10.09±0.2	vw-w
8.25±0.2	vw
		7.87±0.2	w-vs
5.51±0.15	w-m
		5.32±0.15	vw-w
4.70±0.15	vw
		4.22±0.15	vw-m
4.14±0.15	vw-w
		3.97±0.1	vw-w
3.91±0.1	vw-m
		3.87±0.1	m-vs
3.76±0.1	m-vs
		3.68±0.1	w-s

In the table, vs=80-100, s=60-80, m=40-60, w=20-40, vw=0-20.

The present invention also provides the preparation method of the V-Si molecular sieve of the above-mentioned ITH of having structure, it is characterized in that this method is water, vanadium source, silicon source, template R and hydrogen fluoride to be formed have the reaction mixture gel that following mole is formed: (0.02～0.7) R: (0.001～0.2) VO ₂: SiO ₂: (0.1～4) HF: (2～50) H ₂O, crystallization is 2 hours to 25 days under 120～200 ℃ condition, perhaps 150～200 ℃ of following crystallization 2 hours～3 days, then 120～140 ℃ of following crystallization 2 hours～3 days, and reclaims product.

Wherein said template R is the dihydroxy-hexane diamine.

Among the preparation method provided by the invention, said silicon source is inorganic silicon source or organosilicon source, preferred silica gel in said inorganic silicon source or silicon sol; Said organosilicon source preferred formula is Si (OR ¹ _n) ₄The organosilicon source, R wherein ¹Be alkyl, n=1～7, wherein more preferably tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters.

Said vanadium source can be inorganic vanadium source or organic vanadium source.Said inorganic vanadium source is selected from vanadic salts, oxyvanadium compound or metavanadic acid, wherein more preferably vanadylic sulfate, vanadium trichloride, vanadic acid sodium, acetic acid vanadium or Vanadium Pentoxide in FLAKES; Said organic vanadium source is the organic vanadium complex compound, as vanadium acetylacetonate (V (C ₅H ₇O ₂) ₃

In the method provided by the invention, when adopting the organosilicon source, preferably silicon source and vanadium source are mixed in the template aqueous solution earlier, and the alcohol that under 30～100 ℃, preferred 50～100 ℃ hydrolysis is produced catches up with and remove, add hydrofluoric preparation process again after catching up with alcohol thoroughly.

In the method provided by the invention, the ITH structure molecular screen that can also add pure silicon is as crystal seed (preparation of the pure silicon molecular sieve of ITH structure can with reference to the associated description among the USP6471941), and its add-on is SiO in the reaction mixture ₂0.5～20% of weight.

The mole composition of said reaction mixture gel is preferably: (0.2～0.4) R: (0.01～0.08) VO ₂: SiO ₂: (0.8～2) HF: (5～20) H ₂O.

Preparation method provided by the invention, can adopt high temperature, cryogenic crystallization process, more particularly be exactly 150～200 ℃ of following crystallization 2 hours～3 days with reaction mixture gel, 120～140 ℃ of following crystallization 2 hours～3 days, this process can obviously shorten the crystallization cycle than the crystallization process of single stage method then.

The process of wherein said recovery product is meant conventional filtration, washing, exsiccant process, and the present invention there is no special requirement to this.

The V-Si molecular sieve that the inventive method provides has the ITH crystalline structure, and the catalyzer that can be used as oxidizing reaction and desulphurization reaction uses; Have good heat and hydrothermal stability, for example after 800 ℃/4h, 100% water vapor are handled down, still can keep the stable of structure.

Description of drawings

Fig. 1 is the preceding X-ray diffraction spectrogram of ITH structure V-Si molecular sieve roasting of embodiment 1 preparation.

Fig. 2 is the X-ray diffraction spectrogram after the ITH structure V-Si molecular sieve roasting of embodiment 1 preparation.

Embodiment

Following embodiment will be described further content of the present invention, but content not thereby limiting the invention.

In each of the embodiments described below, remove special instruction, agents useful for same is commercially available chemically pure reagent.

Among the embodiment, dihydroxy-hexane diamine as template is to make by ion-exchange with the hexamethonium bromide of producing (Tokyo changes into), used ion exchange resin is the strong-basicity styrene series anion exchange resin that Shanghai produces, HCl with 6% soaked 4 hours earlier in exchange column, wash neutrality, soaked 4 hours with about 8% NaOH then, wash neutrality.Form about 10% solution 36.22 the hexamethonium bromide of gram is dissolved in the water, on the resin of handling well, exchange.The solution that exchange is good concentrates under 50 ℃ of conditions with Rotary Evaporators.H with 0.1mol/L ₂SO ₄The solution titration, the dihydroxy-hexane diamine strength of solution of last gained is about 0.3993mol/L.

Among the embodiment, be according to USP6 as the pure silicon ITH structure molecular screen of crystal seed, 471,941B1 embodiment 3 described water silicon than be 7, crystallization time is that 10 days process obtains.

The X-ray diffraction spectral data of sieve sample is collected by a cover Philips diffraction system, be equipped with a kind of super detector, adopt copper K-α radiation, diffraction data is that 0.017 degree progressively scans with 2 θ angles, the θ here is a Bragg angle, and clocking of per step is 35 seconds.

Adopt Rigaku 3271E type Xray fluorescence spectrometer to measure the constituent content of sieve sample.Test process: after the pressed powder pellet moulding, measure the intensity of an elemental characteristic spectral line on Xray fluorescence spectrometer, obtain the content of element with external standard method, wherein the content of v element is expressed as V ₂O ₅

Embodiment 1

The 21.46g tetraethoxy is added in the 72.62g dihydroxy-hexane diamine solution, stirring is complete up to alcohol volatilization wherein, adds the 0.326g vanadylic sulfate again, and last 4 grams 40 that slowly add weigh %HF, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.29R: SiO ₂: 0.02VO ₂: 0.8HF: 10H ₂O, with this gel crystallization 14 days under 170 ℃ of conditions, more after filtration, washing, and under 120 ℃ of conditions dry two hours, obtain sample, its XRD spectra analytical data sees Table 3, and spectrogram is seen Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of: 0.010V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.020VO ₂: SiO ₂, its XRD spectra analytical data sees Table 4, and spectrogram is seen Fig. 2.

After handling under 800 ℃/4h, 100% water vapor, its XRD spectra still has the feature of Fig. 2 with the sample after the roasting, still can keep the stable of structure, illustrates that its hydrothermal stability is good.

Table 3

d(_)	Relative intensity (I)
		12.64	47
11.09	60
		10.21	23
8.32	10
		7.92	47
5.52	29
		5.35	11
4.71	9
		4.23	37
4.15	23
		3.97	25
3.92	39
		3.87	100
3.76	64
		3.68	40

Table 4

d(_)	Relative intensity (I)
		12.64	100
11.14	43
		10.24	24
8.35	8
		7.95	42
5.76	14
		5.55	15
5.36	10
		4.24	7
4.16	8
		3.99	8
3.92	15
		3.88	34
3.78	23
		3.70	17

Embodiment 2

The 21.46g tetraethoxy is added in the 72.62g dihydroxy-hexane diamine solution, stir, add 0.364gV again up to wherein the ethanol and the water volatilization of capacity ₂O ₅, slowly adding 4 grams, 40 heavy %HF at last, stirring forms cogelled, and the cogelled mole of gained consists of 0.29R: SiO ₂: 0.04VO ₂: 0.8HF: 10H ₂O with this gel crystallization 14 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.019V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.038VO ₂: SiO ₂Its XRD spectra analytical data sees Table 5, and spectrogram has the feature of Fig. 2.

Table 5

d(_)	Relative intensity (I)
		12.67	100
11.15	46
		10.22	26
8.39	10
		7.99	50
5.71	17
		5.54	19
5.34	12
		4.23	9
4.15	6
		3.98	8
3.91	12
		3.88	34
3.77	27
		3.72	19

Embodiment 3

With 1.26gVCl ₃Mix with the silicon sol of the heavy % of 20g30, this solution is added among the dihydroxy-hexane diamine solution 100.16g, stir up to forming uniform solution, slowly add 8 grams, 40 heavy %HF at last, stirring forms cogelled, and the cogelled mole of gained consists of 0.4R: SiO ₂: 0.08VO ₂: 1.6HF: 20H ₂O with this gel crystallization 14 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample.Its XRD crystalline phase figure has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.038V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.076VO ₂: SiO ₂Its XRD spectra analytical data sees Table 6.

Table 6

d(_)	Relative intensity (I)
		12.62	100
11.17	49
		10.22	21
8.35	10
		7.98	46
5.74	16
		5.52	13
5.35	11
		4.27	8
4.19	10
		3.99	7
3.93	16
		3.87	34
3.76	29
		3.71	19

Embodiment 4

With 0.32g VCl ₃Mix with the silicon sol of the heavy % of 20g30, this solution is added among the dihydroxy-hexane diamine solution 50.08g, stir up to forming uniform solution, slowly add 9 grams, 40 heavy %HF at last, stirring forms cogelled, and the cogelled mole of gained consists of 0.2R: SiO ₂: 0.02VO ₂: 1.8HF: 5H ₂O with this gel crystallization 16 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample.Its XRD crystalline phase figure has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.009V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.018VO ₂: SiO ₂Its XRD spectra analytical data sees Table 7.

Table 7

d(_)	Relative intensity (I)
		12.61	100
11.14	57
		10.25	29
8.36	8
		7.97	46
5.75	13
		5.54	15
5.33	11
		4.25	9
4.16	7
		3.99	10
3.91	14
		3.88	34
3.78	30
		3.72	23

Embodiment 5

The 21.46g tetraethoxy is added in the 75.12g dihydroxy-hexane diamine solution, stirring adds the 0.652g vanadylic sulfate again up to the water volatilization of all pure and mild capacities, last 4 grams, the 40 heavy %HF that slowly add, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.30R: SiO ₂: 0.04VO ₂: 0.8HF: 10H ₂O with this gel crystallization 15 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample.Its XRD crystalline phase figure has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.018V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.036VO ₂: SiO ₂Its XRD spectra analytical data sees Table 8.

Table 8

d(_)	Relative intensity (I)
		12.59	100
11.25	56
		10.21	29
8.34	14
		7.89	40
5.76	23
		5.51	19
5.35	13
		4.24	7
4.19	14
		4.03	9
3.91	10
		3.88	30
3.77	28
		3.70	19

Embodiment 6

The 32.66g butyl silicate is added in the 100.16g dihydroxy-hexane diamine solution, stirring adds the 3.26g vanadylic sulfate again up to the water volatilization of all pure and mild capacities, last 5 grams, the 40 heavy %HF that slowly add, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.4R: SiO ₂: 0.20VO ₂: 1.0HF: 20H ₂O with this gel crystallization 3 days under 170 ℃ of conditions, after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample.Its XRD crystalline phase figure has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.097V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.194VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Embodiment 7

The 21.46g tetraethoxy is added among the dihydroxy-hexane diamine solution 60.10g, be stirred to the water volatilization of all ethanol and capacity, add 0.316gNaVO ₃2H ₂O, adding quality again is SiO ₂15% pure silicon ITH structure molecular screen as crystal seed, the last 3.6gHF (40wt%) that slowly adds, stir up to forming a kind of cogelled, SiO in the crystal seed ₂The gel that does not count has following mole proportioning: 0.24R: SiO ₂: 0.02VO ₂: 0.72HF: 15H ₂O, with this gel crystallization 3 days under 170 ℃ of conditions, crystallization 1 day under 140 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly gets said crystal.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.010V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.020VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Embodiment 8

The 21.46g tetraethoxy is added among the dihydroxy-hexane diamine solution 60.10g, be stirred to the water volatilization of all pure and mild capacities, add 0.88gV (C ₂H ₇O ₂) ₃, add SiO again ₂The pure silicon ITH structure molecular screen of weight 5% slowly adds 3.6gHF (40wt%) at last as crystal seed, and stirring is a kind of cogelled up to forming, SiO in the crystal seed ₂The gel that does not count has following mole proportioning: 0.24R: SiO ₂: 0.025VO ₂: 0.72HF: 15H ₂O, with this gel crystallization 3 days under 170 ℃ of conditions, crystallization 1 day under 140 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly gets said crystal.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.012V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.024VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Embodiment 9

The positive silicic acid propyl ester of 27.06g is added among the dihydroxy-hexane diamine solution 80.13g, be stirred to the water volatilization of all pure and mild capacities, add 0.4gVOC ₂O ₄, add SiO again ₂The pure silicon ITH structure molecular screen of weight 8% slowly adds 4.8gHF (40wt%) at last as crystal seed, and stirring is a kind of cogelled up to forming, SiO in the crystal seed ₂The gel that does not count has following mole proportioning: 0.32R: SiO ₂: 0.026VO ₂: 0.96HF: 15H ₂O, with this gel crystallization 3 days under 170 ℃ of conditions, crystallization 1 day under 140 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly gets said crystal.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.0103V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.0206VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Embodiment 10

Synthesized gel rubber is identical with embodiment 7, and in gel crystallization 0.5 day under 170 ℃ of conditions, crystallization 2 days under 140 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly gets said crystal with this gel.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.010: SiO with sample ₂, be scaled VO ₂Consist of 0.020VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Embodiment 11

Synthesized gel rubber is identical with embodiment 1, has just added SiO before adding HF ₂The pure silicon ITH structure molecular screen of weight 4%.With this gel crystallization 10 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly get said crystal.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.010V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.020VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Embodiment 12

Synthesized gel rubber is identical with embodiment 2, has just added SiO before adding HF ₂10% pure silicon ITH structure molecular screen of weight.With this gel crystallization 10 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly get said crystal.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.019V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.038VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Embodiment 13

Synthesized gel rubber is identical with embodiment 3, has just added before adding HF that to account for quality be total SiO ₂15% pure silicon ITH structure molecular screen.With this gel crystallization 0.5 day under 170 ℃ of conditions, crystallization 2 days under 140 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly gets said crystal.Its XRD spectra has the feature of Fig. 1.

Behind 5 hours removed template methods of 550 ℃ of following roastings and hydrogen fluoride, the mole by its anhydrous oxide of fluorometric analysis consists of 0.037V with sample ₂O ₅: SiO ₂, be scaled VO ₂Consist of 0.074VO ₂: SiO ₂Spectrogram has the feature of Fig. 2.

Claims (13)

1. a V-Si molecular sieve is characterized in that this molecular sieve has by the staggered three-dimensional open-framework of forming in two cover ten-ring ducts and a cover nonatomic ring duct, and the ten-ring that its parallel duct of the first cover cardinal principle is made up of the four-coordination atom constitutes; The second cover duct also is made of the ten-ring that the four-coordination atom is formed, and with first overlap the mutual vertical interlaced in duct; The 3rd cover duct is staggered with first, second cover duct, and the nonatomic ring of being made up of the four-coordination atom constitutes, and has mole composition of anhydrous oxide as follows: (0.001～0.2) VO ₂: SiO ₂

2. according to the V-Si molecular sieve of claim 1, it is characterized in that its X-ray diffraction spectrogram has the feature of following table at least, vs, s, m, w and vw represent relative intensity in the table, vs=80-100, s=60-80, m=40-60, w=20-40, vw=0-20.

Table d(_) Relative intensity (I) 12.56±0.2 w-vs 11.05±0.2 m-vs 10.09±0.2 vw-w 8.25±0.2 vw 7.87±0.2 w-vs 5.51±0.15 w-m 5.32±0.15 vw-w 4.70±0.15 vw 4.22±0.15 vw-m 4.14±0.15 vw-w 3.97±0.1 vw-w 3.91±0.1 vw-m 3.87±0.1 m-vs 3.76±0.1 m-vs 3.68±0.1 w-s

3. according to the V-Si molecular sieve of claim 1, it is characterized in that the mole of said anhydrous oxide consists of (0.01～0.08) VO ₂: SiO ₂

4. the preparation method of the V-Si molecular sieve of claim 1 is characterized in that water, vanadium source, silicon source, and template R and hydrogen fluoride form has the reaction mixture gel that following mole is formed: (0.02～0.7) R: (0.001～0.2) VO ₂: SiO ₂: (0.1～4) HF: (2～50) H ₂O, 120～200 ℃ of following crystallization 2 hours to 25 days, perhaps 150～200 ℃ of following crystallization 1 hour to 3 days, 120～140 ℃ of crystallization were 1 hour to 3 days then, and reclaim product, and wherein said template R is the dihydroxy-hexane diamine.

5. according to the method for claim 4, wherein said silicon source is silica gel or silicon sol.

6. according to the method for claim 4, wherein said silicon source is that general formula is Si (OR ¹ _n) ₄The organosilicon source, R wherein ¹Be alkyl, n=1～7.

7. according to the method for claim 6, said organosilicon source is selected from tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters.

8. according to the method for claim 4, said vanadium source is selected from vanadic salts, oxyvanadium compound, metavanadic acid or organic vanadium complex compound.

9. according to the method for claim 8, said vanadium source is selected from vanadylic sulfate, vanadium trichloride, vanadic acid sodium, acetic acid vanadium or Vanadium Pentoxide in FLAKES.

10. according to the method for claim 8, said organic vanadium complex compound is a vanadium acetylacetonate.

11., it is characterized in that organosilicon source and vanadium source are mixed in the template aqueous solution, and under 30～100 ℃, catch up with alcohol according to the method for claim 4, catch up with alcohol thoroughly to add hydrogen fluoride in the back, form reaction mixture gel.

12. according to the method for claim 4 or 11, add pure silicon ITH structure molecular screen in the said reaction mixture as crystal seed, its add-on is SiO in the reaction mixture ₂0.5～20 weight %.

13. according to the method for claim 4, the mole of said reaction mixture gel consists of: (0.2～0.4) R: (0.01～0.08) VO ₂: SiO ₂: (0.8～2) HF: (5～20) H ₂O.

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