CN103708493A - Titanium silicalite molecular sieve with MFI structure and preparation method thereof - Google Patents
Titanium silicalite molecular sieve with MFI structure and preparation method thereof Download PDFInfo
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- CN103708493A CN103708493A CN201310606472.7A CN201310606472A CN103708493A CN 103708493 A CN103708493 A CN 103708493A CN 201310606472 A CN201310606472 A CN 201310606472A CN 103708493 A CN103708493 A CN 103708493A
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- molecular sieve
- quaternary ammonium
- ammonium salt
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Abstract
The invention discloses a titanium silicalite molecular sieve with a MFI structure. The XRD spectra of titanium silicalite molecular sieve comprises the characteristic spectral line of pure silica molecular sieve silicalite-1, and the crystal grains of titanium silicalite molecular sieve are monoclinic system crystal grains or monoclinic system and orthorhombic system intergrowth crystal grains. The preparation method comprises: preparing a reaction mixture of titanium silicalite molecular sieve, organic quaternary ammonium hydroxide, organic quaternary ammonium salt and water according to a weight ratio of 1:(0.01-1):(0.01-0.5):(5-50); transferring the reaction mixture to a high-pressure reaction vessel, performing hydro-thermal processing at 100-200 DEG C for 4-72 h, then filtering, washing, drying and roasting to obtain titanium silicalite molecular sieve with the MFI structure. Titanium silicalite molecular sieve with the MFI structure has relatively strong catalytic oxidation capability compared with titanium silicalite molecular sieve TS-1; and the preparation process of the molecular sieve is simple and is easy for industrialized production.
Description
Technical field
The invention belongs to inorganic chemistry synthesizes and Application in Chemical Engineering technical field, relate to a kind of MFI of having structure titanium silicon molecular sieve and preparation method thereof, exactly, relate to a kind of MFI of having structure, crystallographic system is HTS of oblique system or oblique system and rhombic system symbiosis and preparation method thereof.
Background technology
The transition metal titanium atom with the feature of appraising at the current rate is introduced to framework of molecular sieve, formed HTS.HTS has oxidation-reduction catalysis function and selects shape function, thereby has good directional catalyzing oxidation susceptibility.At present they in the oxidation of saturated alkane, the ammonia oxidation of the oxidation of the epoxidation of alkene, alcohols, ketone and aldehyde and the fields such as hydroxylation of aromatic hydrocarbons have shown good prospects for commercial application.HTS has caused the extensive concern of world catalyticing research person and industry member as the Green Chemistry new catalyst of selective oxidation of new generation.
US 4,410, and first 501 disclose transition metal titanium atom introducing pure silicon molecular sieve (Silicalite-1) skeleton, obtained titanium-silicon molecular sieve TS-1.Its constitutional features is, the same with pure silicon molecular sieve (Silicalite-1) have a MFI topological framework; Yet difference is, titanium-silicon molecular sieve TS-1 belongs to rhombic system, and pure silicon molecular sieve (Silicalite-1) belongs to oblique system.Can fine differentiation rhombic system and oblique system by X-ray diffraction technology (XRD).As US 4,410,501 disclosed Fig. 1 a(Fig.1a) for belonging to the XRD spectra of monoclinic pure silicon molecular sieve (Silicalite-1), it is characterized by 2 θ, be approximately 24.3 ° and 29.3 ° and locate to be shown as double diffraction peak; Fig. 1 b(Fig.1b) for belonging to the XRD spectra of titanium-silicon molecular sieve TS-1 of rhombic system, it is characterized by 2 θ, be approximately 24.3 ° and 29.3 ° and locate to be shown as single diffraction peak.
So far, the constitutional features with MFI structure titanium silicon molecular sieve of all open reports is identical with US 4,410,501 disclosed titanium-silicon molecular sieve TS-1s, its crystal grain rhombic system crystal grain.
Summary of the invention
One of object of the present invention is to provide a kind of MFI of having structure titanium silicon molecular sieve, and its constitutional features is, the characteristic spectral line that its XRD spectra contains pure silicon molecular sieve (Silicalite-1), and its crystal grain is oblique system crystal grain.
Two of object of the present invention is to provide the preparation method of above-mentioned molecular sieve.The technical scheme that realizes this object comprises following operation steps: according to prior art, prepare titanium-silicon molecular sieve TS-1, then further pass through organic quaternary ammonium hydroxide and organic quaternary ammonium salt mixing solutions hydrothermal treatment consists and roasting, obtain product.
Now describe technical scheme of the present invention in detail:
A preparation method with MFI structure titanium silicon molecular sieve, concrete operation step:
The preparation of the first step reaction mixture
By weight titanium-silicon molecular sieve TS-1: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:(0.01 ~ 1): (0.01 ~ 0.5): (5 ~ 50), preparation reaction mixture, described organic quaternary ammonium hydroxide is at least one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH and TBAH, described organic quaternary ammonium salt is at least one in tetramethyl-quaternary ammonium salt, tetraethyl-quaternary ammonium salt, tetrapropyl quaternary ammonium salt and tetrabutyl quaternary ammonium salt, and organic quaternary ammonium salt is villaumite or bromine salt;
Second step hydrothermal treatment consists
The reaction mixture making through upper step is transferred in autoclave, in 100～200 ℃ of hydrothermal treatment consists 4～72 hours, then after filtration, after washing, dry, roasting product.
Compared with prior art, the present invention has following remarkable advantage:
(1) have MFI structure, crystal grain be oblique system or crystal grain be oblique system and the symbiosis of rhombic system crystal HTS, there is complete crystalline structure;
(2) this HTS has the catalyzed oxidation ability stronger than titanium-silicon molecular sieve TS-1;
(3) molecular sieve process is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of molecular sieve, and in figure, a is the XRD spectra of the synthetic titanium-silicon molecular sieve TS-1 of comparative example 1; B is the XRD spectra of the synthetic pure silicon molecular sieve (Silicalite-1) of comparative example 2; C is the XRD spectra of the synthetic HTS of embodiment 1; D is the XRD spectra of the synthetic HTS of embodiment 8.
As we know from the figure, there is strong diffraction peak at 2q=7.8 °, 8.8 °, 23.2 °, 23.8 °, 24.3 ° etc. in diffraction peak position, illustrates that it all has MFI structure; Simultaneously in Fig. 1 in a and Fig. 1 b respectively with US 4,410, the titanium-silicon molecular sieve TS-1s of 501 reports are consistent with the XRD spectra of pure silicon molecular sieve (Silicalite-1); And the XRD spectra of c has similar constitutional features to the XRD spectra of pure silicon molecular sieve (Silicalite-1) in Fig. 1, at 2 θ, be approximately 24.3 ° and 29.3 ° and locate to be shown as double diffraction peak, this illustrates that the crystal grain of resulting HTS is oblique system crystal grain.
embodiment
All embodiment all operate by the operation steps of technique scheme.
Comparative example 1
According to US 4,410, the method for 501 reports has been synthesized titanium-silicon molecular sieve TS-1, and synthesis material silicon source, titanium source and template are respectively tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, and its mol ratio is 1:0.008:0.25.Obtain the XRD spectra of product as shown in Figure 1a, disclosed Fig. 1 b(Fig.1b in contrast US 4,410,501 files), known, the synthetic titanium-silicon molecular sieve TS-1 that obtained.
Comparative example 2
According to the method for comparative example 1, synthesize pure silicon molecular sieve (Silicalite-1), in building-up process, do not added the tetrabutyl titanate as titanium source.Obtain the XRD spectra of product as shown in Figure 1 b, disclosed Fig. 1 a(Fig.1a in contrast US 4,410,501 files), known, the synthetic pure silicon molecular sieve (Silicalite-1) that obtained.
Embodiment 1
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:0.25: 0.01: 35, preparation reaction mixture, tetraethyl ammonium hydroxide and TPAOH that described organic quaternary ammonium hydroxide is is 5:5 according to weight ratio, described organic quaternary ammonium salt is 4-propyl ammonium chloride;
Second step hydrothermal treatment consists
The reaction mixture making through upper step is transferred in autoclave, in 160 ℃ of hydrothermal treatment consists 72 hours, then after filtration, after washing, dry, roasting product.
The XRD spectra of products obtained therefrom is as shown in Fig. 1 c.
Embodiment 2
Except for the following differences, all the other are all with embodiment 1 for implementation process:
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:0.05: 0.25: 15, described organic quaternary ammonium hydroxide is TPAOH, tetraethylammonium bromide and 4-propyl ammonium chloride that described organic quaternary ammonium salt is is 5:5 according to weight ratio;
Second step hydrothermal treatment consists
In 190 ℃ of hydrothermal treatment consists 10 hours.
The XRD spectra of products obtained therefrom and Fig. 1 c are similar.
Embodiment 3
Except for the following differences, all the other are all with embodiment 1 for implementation process:
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:0.01: 0.5: 50, described organic quaternary ammonium hydroxide was tetraethyl ammonium hydroxide, and described organic quaternary ammonium salt is 4-propyl bromide;
Second step hydrothermal treatment consists
In 170 ℃ of hydrothermal treatment consists 48 hours.
The XRD spectra of products obtained therefrom and Fig. 1 c are similar.
Embodiment 4
Except for the following differences, all the other are all with embodiment 1 for implementation process:
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:0.5: 0.5: 50, TBAH and TPAOH that described organic quaternary ammonium hydroxide is is 3:7 according to weight ratio, 4-propyl bromide and tetrabutylammonium chloride that described organic quaternary ammonium salt is is 5:5 according to weight ratio;
Second step hydrothermal treatment consists
In 160 ℃ of hydrothermal treatment consists 48 hours.
The XRD spectra of products obtained therefrom and Fig. 1 c are similar.
Except for the following differences, all the other are all with embodiment 1 for implementation process:
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:0.1: 0.15: 20, described organic quaternary ammonium hydroxide was tetraethyl ammonium hydroxide, and described organic quaternary ammonium salt is tetrabutylammonium chloride;
Second step hydrothermal treatment consists
In 180 ℃ of hydrothermal treatment consists 24 hours.
The XRD spectra of products obtained therefrom and Fig. 1 c are similar.
Embodiment 6
Except for the following differences, all the other are all with embodiment 1 for implementation process:
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:1: 0.15: 50, tetraethyl ammonium hydroxide and TBAH that described organic quaternary ammonium hydroxide is is 7:3 according to weight ratio, 4-propyl bromide and tetrabutylammonium chloride that described organic quaternary ammonium salt is is 3:7 according to weight ratio;
Second step hydrothermal treatment consists
In 170 ℃ of hydrothermal treatment consists 24 hours.
The XRD spectra of products obtained therefrom and Fig. 1 c are similar.
Embodiment 7
Except for the following differences, all the other are all with embodiment 1 for implementation process:
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:0.25: 0.3: 5, described organic quaternary ammonium hydroxide was TPAOH, and described organic quaternary ammonium salt is tetrabutylammonium chloride;
Second step hydrothermal treatment consists
In 110 ℃ of hydrothermal treatment consists 72 hours.
The XRD spectra of products obtained therefrom and Fig. 1 c are similar.
Embodiment 8
Except for the following differences, all the other are all with embodiment 1 for implementation process:
The preparation of the first step reaction mixture
The titanium-silicon molecular sieve TS-1 by weight comparative example 1 being obtained: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:0.1: 0.2: 25, described organic quaternary ammonium hydroxide is TBAH, 4-propyl bromide and tetramethyl ammonium chloride that described organic quaternary ammonium salt is is 5:5 according to weight ratio;
Second step hydrothermal treatment consists
In 180 ℃ of hydrothermal treatment consists 18 hours.
The XRD spectra of products obtained therefrom is as Fig. 1 d, similar with Fig. 1 c, but is 24.3 ° and 29.3 ° of acromions of locating to be shown as broadening at 2 θ, illustrates that crystal grain is oblique system and rhombic system symbiosis crystal grain.
Embodiment 9
With the epoxy of n-hexylene, turn to the catalytic activity that probe reaction is evaluated the product that the present invention obtains.Detailed process is, solvent is methyl alcohol, oxygenant is that concentration is 30.1% hydrogen peroxide, successively HTS, solvent, reactant and oxygenant are added in reactor, stir, reactant: HTS: the weight ratio of solvent is 1:0.03:5, reactant: the mol ratio of oxygenant is 1:1,60 ℃ are reacted 2 hours.It is as shown in the table for result.
Table 1 is depicted as the catalyzed reaction evaluation result of HTS.By analysis, the composition of all HTS is in suitable level, and catalytic performance shows, the titanium-silicon molecular sieve TS-1 that the catalytic activity with MFI structure titanium silicon molecular sieve prepared by the inventive method obtains apparently higher than comparative example 1.
Claims (3)
1. there is a MFI structure titanium silicon molecular sieve, it is characterized in that, the characteristic spectral line that its XRD spectra contains pure silicon molecular sieve Silicalite-1, its crystal grain is oblique system crystal grain.
2. HTS according to claim 1, is characterized in that, its crystal grain is oblique system and rhombic system symbiosis crystal grain.
3. a preparation method for HTS described in claim 1 or 2, is characterized in that operation steps:
The preparation of the first step reaction mixture
By weight titanium-silicon molecular sieve TS-1: organic quaternary ammonium hydroxide: organic quaternary ammonium salt: water is 1:(0.01～1): (0.01～0.5): (5～50) preparation reaction mixture, described organic quaternary ammonium hydroxide is at least one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH and TBAH; Described organic quaternary ammonium salt is at least one in tetramethyl-quaternary ammonium salt, tetraethyl-quaternary ammonium salt, tetrapropyl quaternary ammonium salt and tetrabutyl quaternary ammonium salt;
Second step hydrothermal treatment consists
The reaction mixture making through upper step is transferred in autoclave, in 100～200 ℃ of hydrothermal treatment consists 4～72 hours, then after filtration, after washing, dry, roasting described in there is MFI structure titanium silicon molecular sieve.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130157A (en) * | 2014-07-08 | 2014-11-05 | 华东师范大学 | Method for preparing cyclohexanone-oxime |
| WO2020074586A1 (en) | 2018-10-09 | 2020-04-16 | Basf Se | A molding comprising a zeolitic material having framework type mfi |
| CN114477205A (en) * | 2022-03-01 | 2022-05-13 | 大连捷尔催化材料科技有限公司 | Preparation method and application of MFI molecular sieve containing heteroatom Ti |
| RU2808562C2 (en) * | 2018-10-09 | 2023-11-29 | Басф Се | Molded piece containing zeolite material having mfi frame structure type |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130157A (en) * | 2014-07-08 | 2014-11-05 | 华东师范大学 | Method for preparing cyclohexanone-oxime |
| WO2020074586A1 (en) | 2018-10-09 | 2020-04-16 | Basf Se | A molding comprising a zeolitic material having framework type mfi |
| CN112805272A (en) * | 2018-10-09 | 2021-05-14 | 巴斯夫欧洲公司 | Molded article comprising a zeolitic material having an MFI-type framework |
| RU2808562C2 (en) * | 2018-10-09 | 2023-11-29 | Басф Се | Molded piece containing zeolite material having mfi frame structure type |
| CN114477205A (en) * | 2022-03-01 | 2022-05-13 | 大连捷尔催化材料科技有限公司 | Preparation method and application of MFI molecular sieve containing heteroatom Ti |
| CN114477205B (en) * | 2022-03-01 | 2023-08-04 | 大连捷尔催化材料科技有限公司 | Preparation method and application of MFI molecular sieve containing heteroatom Ti |
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Application publication date: 20140409 |