CN1332882C - Titanium-silicon molecular sieve and preparation method - Google Patents
Titanium-silicon molecular sieve and preparation method Download PDFInfo
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Abstract
The present invention discloses a titanium silicon molecular sieve which is characterized in that the molecular sieve has a three-dimensional pore channel structure comprising two ten-element ring pore channels and one nine-element ring pore channel in a staggered mode, wherein the first pore channel which is roughly parallel comrises a ten-element ring comprising four coordination atoms. The second pore channel also comprises a ten-element ring composed of four coordination atoms and is mutually vertical and staggered with the first pore channel, and the third pore channel is staggered with the first pore channel and the second pore channel and comprises a nine-element ring comprising four coordination atoms. The molar composition of anhydrous oxide is (0.001-0.2)TiO2: SiO2, and the molecular sieve can be used as a catalytic oxidation catalyst.
Description
Technical field
The invention relates to a kind of HTS 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 are made of nine Yuans rings that the four-coordination atom is formed.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_.
HTS is the novel hetero-atom molecular-sieve that early eighties begins to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, and have than the TS-48 of macroporous structure etc.This molecular sieve analog is to many organic oxidizing reactions, for example the reactions such as oxidation of the epoxidation of alkene, aromatic hydrocarbons hydroxylation, pimelinketone oximate, alcohol have excellent catalytic activity and selective paraffin oxidation performance, and they have a good application prospect as redox (redox) type molecular sieve catalyst.
The synthetic method of molecular sieve with ITH structure is by the Boix Teresa of ExxonMobil company, and people such as Corma Avelino are 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.Quadrivalent element Y wherein can be a silicon, 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 the HTS with ITH structure, therefore, one of purpose of the present invention provides a kind of HTS of the ITH of having structure, and two of purpose provides the preparation method of this molecular sieve.
HTS with ITH structure provided by the invention, 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) TiO
2: SiO
2, preferred (0.01～0.08) TiO
2: SiO
2The mole of anhydrous oxide form.
HTS with ITH structure 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) |
| 12.47±0.2 | w-vs |
| 10.98±0.2 | m-vs |
| 10.09±0.2 | vw-w |
| 8.25±0.2 | vw |
| 7.85±0.2 | w-vs |
| 5.51±0.15 | w-m |
| 5.31±0.15 | vw-w |
| 4.68±0.15 | vw |
| 4.21±0.15 | vw-m |
| 4.13±0.15 | vw-w |
| 3.95±0.1 | vw-w |
| 3.90±0.1 | vw-m |
| 3.85±0.1 | m-vs |
| 3.74±0.1 | m-vs |
| 3.66±0.1 | w-s |
In the table, the relative intensity when vs=80-100, s=60-80, m=40-60, w=20-40, vw=0-20, vs, s, m, w and vw represent to be benchmark 100 with the highest peak.
The present invention also provides the preparation method of the HTS of the above-mentioned ITH of having structure, it is characterized in that this method is with water, titanium source, silicon source, template R and hydrogen fluoride form in oxide compound has the reaction mixture that following mole is formed: (0.02～0.7) R: (0.001～0.2) TiO
2: SiO
2: (0.1～4) HF: (2～50) H
2O, and with this reaction mixture crystallization 1 hour to 25 days under 120～200 ℃ condition, perhaps with this reaction mixture 150～170 ℃ of following crystallization 1 hour～3 days, then 120～140 ℃ of following crystallization 1 hour～3 days.
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 titanium source is inorganic ti sources or organic titanium source, the preferred halogenated titanium of said inorganic ti sources, wherein more preferably titanium tetrachloride.It is Ti (OR that said organic titanium source is selected from general formula
2 m)
4The organic titanium source, R wherein
2Be alkyl, m=1～7, wherein more preferably tetraethyl titanate, metatitanic acid orthocarbonate or tetrabutyl titanate.
Among the preparation method provided by the invention, when silicon source and employing organosilicon source, titanium source and organic titanium source, preferably the two is mixed in the template aqueous solution, and catch up with alcohol, catch up with alcohol thoroughly to add hydrogen fluoride in the back 30～100 ℃ of following hydrolysis.
Among the preparation method provided by the invention, the ITH structure molecular screen that can also add pure silicon is as crystal seed, and its add-on is SiO in the reaction mixture
20.5～20 heavy %.
The mole composition of said reaction mixture is preferably: (0.2～0.4) R: (0.01～0.08) TiO
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 150～170 ℃ of following crystallization 1 hour～3 days with reaction mixture, 120～140 ℃ of following crystallization 1 hour～3 days, this process can obviously shorten the crystallization cycle than the crystallization process of single stage method then.
HTS with ITH structure provided by the invention has good heat and hydrothermal stability, for example under 800 ℃/4h, 100% water vapor, still can keep the stable of structure; The catalyzer that can be used as oxidizing reaction uses, and especially has the wide industrial application prospect in the small molecules catalytic oxidation.The preparation method of this molecular sieve provided by the invention adopts HF as mineralizer, particularly makes product preparation have shorter crystallization time with high temperature-low temperature crystallized method.
Description of drawings
Fig. 1 is the preceding X-ray diffraction spectrogram of ITH structure titanium silicon molecular sieve roasting of embodiment 1 preparation.
Fig. 2 is the X-ray diffraction spectrogram after the ITH structure titanium silicon molecular sieve roasting of embodiment 1 preparation.
Fig. 3 is the preceding X-ray diffraction spectrogram of ITH structure titanium silicon molecular sieve roasting of embodiment 2 preparations.
Fig. 4 is the preceding X-ray diffraction spectrogram of ITH structure titanium silicon molecular sieve roasting of embodiment 6 preparations.
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), the strong-basicity styrene series anion exchange resin that used ion exchange resin 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, 471,941 B1 embodiment, 3 described water silicon than be 7, crystallization time is that 10 days process obtains.
The test condition of the X-ray diffraction spectrogram of the molecular sieve of doing: the X-ray diffraction data of being done are 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.
Embodiment 1
The 1.28g tetrabutyl titanate is mixed with the 21.46g tetraethoxy, add in the 72.62g dihydroxy-hexane diamine solution, stir water volatilization, last 4 grams, the 40 heavy %HF that slowly add up to all ethanol and capacity, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.29R: SiO
2: 0.04TiO
2: 0.8HF: 10H
2O, with this gel crystallization 15 days under 140 ℃ 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 accompanying drawing 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 0.039TiO with sample
2: SiO
2, its XRD spectra analytical data sees Table 4, and spectrogram is seen accompanying drawing 2.
Table 3
| d(_) | Relative intensity (I) |
| 12.47 | 42 |
| 10.98 | 53 |
| 10.09 | 20 |
| 8.25 | 9 |
| 7.85 | 48 |
| 5.51 | 29 |
| 5.31 | 11 |
| 4.68 | 8 |
| 4.21 | 37 |
| 4.13 | 21 |
| 3.95 | 20 |
| 3.90 | 39 |
| 3.85 | 100 |
| 3.74 | 58 |
| 3.66 | 37 |
Table 4
| d(_) | Relative intensity (I) |
| 12.56 | 100 |
| 11.04 | 47 |
| 10.20 | 29 |
| 8.32 | 12 |
| 7.93 | 65 |
| 5.74 | 21 |
| 5.54 | 26 |
| 5.33 | 29 |
| 4.70 | 6 |
| 4.23 | 11 |
| 4.14 | 14 |
| 3.98 | 11 |
| 3.91 | 29 |
| 3.86 | 55 |
| 3.76 | 40 |
| 3.69 | 29 |
Embodiment 2
The silicon sol of 0.76g titanium tetrachloride with 20 grams, 30 heavy % mixed, this solution is added among the dihydroxy-hexane diamine solution 72.62g, stir up to forming uniform solution, last 4 grams, the 40 heavy %HF that slowly add, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.29R: SiO
2: 0.04TiO
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 is seen Fig. 3.
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 0.038TiO with sample
2: SiO
2
Embodiment 3
The silicon sol of 1.51g titanium tetrachloride with the heavy % of 20g30 mixed, this solution is added among the dihydroxy-hexane diamine solution 100.16g, stir up to forming uniform solution, last 10 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: 0.08TiO
2: 2.0HF: 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. 3.
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 0.079TiO with sample
2: SiO
2
Embodiment 4
The silicon sol of 0.38g titanium tetrachloride with the heavy % of 20g30 mixed, this solution is added among the dihydroxy-hexane diamine solution 50.08g, stir up to forming uniform solution, last 9 grams, the 40 heavy %HF that slowly add, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.2R: SiO
2: 0.02TiO
2: 1.8HF: 5H
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. 3.
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 0.019TiO with sample
2: SiO
2
1.50g metatitanic acid orthocarbonate is mixed with the 32.66g butyl silicate, add in the 75.12g dihydroxy-hexane diamine solution, stir water volatilization, last 4 grams, the 40 heavy %HF that slowly add up to all ethanol and capacity, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.3R: SiO
2: 0.04TiO
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 0.038TiO with sample
2: SiO
2
Embodiment 6
The 4.8g tetrabutyl titanate is mixed with the positive silicic acid propyl ester of 27.06g, add in the 100.16g dihydroxy-hexane diamine solution, stir water volatilization, last 5 grams, the 40 heavy %HF that slowly add up to all ethanol and capacity, it is cogelled to stir formation, and the cogelled mole of gained consists of 0.4R: SiO
2: 0.15TiO
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 sees Fig. 4.
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 0.148TiO with sample
2: SiO
2
Embodiment 7
The 0.64g tetrabutyl titanate is mixed with the 21.46g tetraethoxy, add among the dihydroxy-hexane diamine solution 60.10g, be stirred to the water volatilization of all ethanol and capacity, having added quality 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: 0.02TiO
2: 0.72HF: 15H
2O, with this gel crystallization 1 day 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 0.018TiO with sample
2: SiO
2
Embodiment 8
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 0.019TiO with sample
2: SiO
2
Embodiment 9
Synthesized gel rubber is identical with embodiment 1, has just added before adding HF that to account for quality be total SiO
24% pure silicon ITH structure molecular screen.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 0.038TiO with sample
2: SiO
2
Synthesized gel rubber is identical with embodiment 2, has just added before adding HF that to account for quality be total SiO
210% pure silicon ITH structure molecular screen.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. 3.
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 0.039TiO with sample
2: SiO
2
Embodiment 11
Synthesized gel rubber is identical with embodiment 2, 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. 3.
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 0.037TiO with sample
2: SiO
2
Claims (14)
1, a kind of HTS 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) TiO
2: SiO
2
2,, it is characterized in that its X-ray diffraction spectrogram has the feature of following table at least, the relative intensity when vs, s, m, w and vw represent to be benchmark 100 with the highest peak in the table according to the HTS of claim 1, vs=80-100, s=60-80, m=40-60, w=20-40, vw=0-20
Table
3,, it is characterized in that the mole of said anhydrous oxide consists of (0.01～0.08) TiO according to the HTS of claim 1
2: SiO
2
4, the preparation method of claim 1 HTS is characterized in that water, titanium source, silicon source, and template R and hydrogen fluoride form in oxide compound has the reaction mixture that following mole is formed: (0.02～0.7) R: (0.001～0.2) TiO
2: SiO
2: (0.1～4) HF: (2～50) H
2O and with this reaction mixture 120～200 ℃ of following crystallization 1 hour to 25 days, perhaps with this reaction mixture 150～170 ℃ of following crystallization 1 hour to 3 days, 120～140 ℃ of crystallization are 1 hour to 3 days then, 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 titanium source is a halogenated titanium.
9, according to the method for claim 8, said halogenated titanium is a titanium tetrachloride.
10, according to the method for claim 4, it is Ti (OR that said titanium source is selected from general formula
2 m)
4The organic titanium source, R wherein
2Be alkyl, m=1～7.
11, according to the method for claim 10, said organic titanium source is selected from tetraethyl titanate, metatitanic acid orthocarbonate or tetrabutyl titanate.
12, according to the method for claim 4, it is characterized in that organosilicon source and organic titanium source are mixed in the template aqueous solution, and catch up with alcohol 30～100 ℃ of following hydrolysis, catch up with alcohol thoroughly to add hydrogen fluoride in the back, stirred the back 150～170 ℃ of following crystallization 1 hour to 3 days, and 120～140 ℃ of crystallization are 1 hour to 3 days then.
13, according to the method for claim 4, 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 heavy %.
14, according to the method for claim 4, the mole of said reaction mixture consists of:
(0.2～0.4)R∶(0.01～0.08)TiO
2∶SiO
2∶(0.8～2)HF∶(5～20)H
2O。
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