CN103464196A - Preparation method for immobilized Lewis acid - Google Patents
Preparation method for immobilized Lewis acid Download PDFInfo
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- CN103464196A CN103464196A CN2013103171233A CN201310317123A CN103464196A CN 103464196 A CN103464196 A CN 103464196A CN 2013103171233 A CN2013103171233 A CN 2013103171233A CN 201310317123 A CN201310317123 A CN 201310317123A CN 103464196 A CN103464196 A CN 103464196A
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- lewis acid
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Abstract
The invention discloses a preparation method for immobilized Lewis acid, belonging to the field of catalysis in organic synthesis. The immobilized Lewis acid referred to in the invention comprises Sn-Beta, Ti-Beta, In-Beta, Cu-Beta, Zn-Beta, Cr-Beta, etc. Solid acid with activity of Lewis acid is prepared by reacting a salt solution of a metal with a dealuminated molecular sieve and then carrying out sintering. The invention has the following advantages: raw materials are cheap and easily available, a generation period is short, the preparation method has high yield, the immobilized Lewis acid is easy to separate, reaction conditions are simple, and the immobilized Lewis acid can be extensively applied in the Baeyer-Villiger oxidation reaction, a reaction for preparation of methyl lactate from 1,3-dioxyacetone or a reaction for preparation of fructose from glucose.
Description
Technical field
The invention belongs to catalytic field in organic synthesis, particularly a kind of preparation method of immobilized Lewis acid.
Background technology
In recent years, along with the development of catalysis technique, that catalyst is immobilized, realize being separated into important research contents with substrate simple and easy.In traditional acid catalyst,
sour is immobilized more ripe, is mainly that sulfonic group is connected and obtains with the matrix of load by alkyl chain.Yet can not adopt the method in the building-up process of Lewis acid, so the immobilized technical research of Lewis acid is comparatively backward.(Nature, 2001, the 412:424-425 such as Corma, Davis; PNAS, 2010,107:6164-6168) by tetraethyl orthosilicate, SnCl
4h
2obtain stanniferous molecular sieve (Sn-Beta) after the hydrolysis such as O, crystallization, there is Lewis acidity well.But the manufacturing cycle that this method need to be very long (nearly 40 days).Hermans etc. (Angew.Chem.Int.Ed.2012,51:1 – 5) have improved the method, and the H-Beta of commodity in use is raw material, with salpeter solution, inner Al is removed, and is formed with the deAlBeta of cavity, then by itself and Sn (CH
3cOO)
2grind, under air atmosphere, sintering can obtain stanniferous Beta molecular sieve, and it has saved crystallization process, has shortened greatly manufacturing cycle, however the volatilizable Sn (CH of limitation only
3cOO)
2preparation Sn-Beta, and Sn (CH
3cOO)
2price is higher, inapplicable large-scale preparation.
Summary of the invention
For overcoming the shortcoming and defect of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method of immobilized Lewis acid.This preparation method provides a kind of practical, immobilized preparation of can be used for various metals Lewis acid.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of immobilized Lewis acid comprises the following steps:
The red fuming nitric acid (RFNA) that is 8～16mol/L by the concentration of the H-Beta molecular sieve of 1 weight portion and 5～50 weight portions mixes, take off the aluminium of molecular sieve inside at 50～100 ℃ of lower stirring reaction 1～48h, filter, be washed to neutrality, oven dry dewaters, and obtains dealuminzation molecular sieve (deAlBeta); Then add the slaine of 0.1～10 weight portion and the organic solvent of 5～100 weight portions, stir 10～48h and make slaine be diffused into deAlBeta inside under 10～150 ℃, then filter, washing, roasting, obtain the immobilized Lewis acid that contains metal center.
The H-Beta molecular sieve that described H-Beta molecular sieve is commercially available all kinds;
Described slaine is SnCl
4, TiCl
4, InCl
3, CuCl
2, ZnCl
2, CrCl
3or FeCl
3in a kind of;
Described organic solvent is a kind of in methyl alcohol, ethanol, acetone, toluene, benzene, dimethylbenzene, chloroform, carbon dichloride or ethyl acetate;
Described washing is for using organic solvent washing; Organic solvent used is a kind of in methyl alcohol, ethanol, acetone, toluene, benzene, dimethylbenzene, chloroform, carbon dichloride or ethyl acetate;
Described roasting is under air atmosphere, 400～800 ℃ of sintering 1～20h;
The preparation method's of described immobilized Lewis acid process is suc as formula shown in I:
Formula I;
Wherein,
mean commercially available H-Beta molecular sieve;
mean the dealuminzation molecular sieve;
the catalyst that contain metal center of expression through forming after slaine diffusion, M is Sn, Ti, In, Cu, Zn, a kind of in Cr or Fe; Described metal salt solution is the solution that slaine forms in organic solvent; Described slaine is SnCl
4, TiCl
4, InCl
3, CuCl
2, ZnCl
2, CrCl
3or FeCl
3in a kind of; Described organic solvent is a kind of in methyl alcohol, ethanol, acetone, toluene, benzene, dimethylbenzene, chloroform, carbon dichloride or ethyl acetate.
Described immobilized Lewis acid is prepared by above-mentioned preparation method.
The immobilized Lewis acid that said method obtains can be applied in the reaction of activation carbonyl, and described activation carbonyl reaction is the Baeyer-Villiger oxidation reaction, and 1,3-Dihydroxyacetone prepares the reaction of methyl lactate, and glucose prepares the reaction of fructose.
The present invention has advantages of as follows with respect to prior art: this method raw material is cheap slaine and organic solvent, and not only is confined to Sn (CH
3cOO)
2this kind of slaine, with a wide range of applications, solved problem prepared by immobilized Lewis.
The accompanying drawing explanation
The energy spectrogram that Fig. 1 is Sn-Beta in embodiment 1.
the specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Umber mentioned in embodiment 1～10 is weight portion.
Embodiment 1
Synthesizing of stanniferous molecular sieve (Sn-Beta): be heated to 100 ℃ of reaction 20h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 20 parts of 13M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous SnCl of 10 weight portion
4100 parts of benzene in, 25 ℃ are filtered after stirring 24h, with 1000mL benzene, wash to remove free SnCl
4, 550 ℃ of blowing airs activation 3h, obtain Sn-Beta after cooling.
Contain the synthetic of Ti molecular sieve (Ti-Beta): be heated to 50 ℃ of reaction 48h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 50 parts of 13M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous TiCl of 0.1 weight portion
45 parts of chloroforms in, 10 ℃ are filtered after stirring 48h, by 500 parts of toluene wash to remove free TiCl
4, 400 ℃ of blowing airs activation 20h, obtain Ti-Beta after cooling.
Embodiment 3
Contain the synthetic of In molecular sieve (In-Beta): be heated to 150 ℃ of reaction 1h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 50 parts of 8M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous InCl of 10 weight portion
310 parts of methyl alcohol in, 65 ℃ are filtered after stirring 48h, with 500 parts of chloroforms, wash to remove free InCl
3, 800 ℃ of blowing airs activation 1h, obtain In-Beta after cooling.
Contain the synthetic of Cu molecular sieve (Cu-Beta): be heated to 100 ℃ of reaction 20h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 50 parts of 10M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous CuCl of 5 weight portion
250 parts of ethanol in, 78 ℃ are filtered after stirring 10h, with 500 parts of ethanol, wash to remove free CuCl
2, 700 ℃ of blowing airs activation 2h, obtain Cu-Beta after cooling.
Embodiment 5
Contain the synthetic of Zn molecular sieve (Zn-Beta): be heated to 120 ℃ of reaction 20h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 25 parts of 13M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous ZnCl of 5 weight portion
250 parts of methyl alcohol in, 65 ℃ are filtered after stirring 48h, by 500 parts of methanol wash to remove free InCl
3, 600 ℃ of blowing airs activation 3h, obtain Zn-Beta after cooling.
Contain the synthetic of Cr molecular sieve (Cr-Beta): be heated to 150 ℃ of reaction 1h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 50 parts of 8M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous CrCl of 10 weight portion
3100 parts of methyl alcohol in, 65 ℃ are filtered after stirring 48h, by 500 parts of methanol wash to remove free CrCl
3, 550 ℃ of blowing airs activation 4h, obtain Cr-Beta after cooling.
Embodiment 7
Contain the synthetic of Fe molecular sieve (Fe-Beta): be heated to 150 ℃ of reaction 1h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 50 parts of 8M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous FeCl of 10 weight portion
310 parts of methyl alcohol in, 65 ℃ are filtered after stirring 48h, by 500 parts of methanol wash to remove free FeCl
3, 500 ℃ of blowing airs activation 20h, obtain Fe-Beta after cooling.
Synthesizing of stanniferous molecular sieve (Sn-Beta): be heated to 100 ℃ of reaction 20h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 20 parts of 13M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous SnCl of 0.1 weight portion
45 parts of dimethylphenyl phenyls in, 140 ℃ are filtered after stirring 24h, with 1000mL dimethylbenzene, wash to remove free SnCl
4, 550 ℃ of blowing airs activation 3h, obtain Sn-Beta after cooling.
Embodiment 9
Synthesizing of stanniferous molecular sieve (Sn-Beta): be heated to 100 ℃ of reaction 20h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 20 parts of 13M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous SnCl of 1 weight portion
4100 parts of ethyl acetate in, 40 ℃ are filtered after stirring 24h, with 1000mL ethyl acetate, wash to remove free SnCl
4, 550 ℃ of blowing airs activation 20h, obtain Sn-Beta after cooling.
Synthesizing of stanniferous molecular sieve (Sn-Beta): be heated to 120 ℃ of reaction 2h after getting 1 part of Hydrogen beta-molecular sieve (H-β) and the salpeter solution of 50 parts of 13M mixing.Filter, be washed to neutrality, oven dry dewaters, and obtains the molecular sieve (deAlBeta) of dealuminzation.Then join and be dissolved with the anhydrous SnCl of 9 weight portion
4100 parts of dichloros in, 30 ℃ are filtered after stirring 48h, by the 1000mL washed with dichloromethane to remove free SnCl
4, 550 ℃ of blowing airs activation 20h, obtain Sn-Beta after cooling.
As shown in Figure 1, the testing result data are as shown in table 1 for the energy spectrogram of the Sn-Beta of embodiment 1 preparation, and wherein, in the Sn-Beta molecular sieve, the mass ratio of silicon and tin is 37.87:4.59.
The Sn-Beta's of table 1 embodiment 1 can spectral data
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. the preparation method of an immobilized Lewis acid is characterized in that comprising the following steps:
The red fuming nitric acid (RFNA) that is 8～16mol/L by the concentration of the H-Beta molecular sieve of 1 weight portion and 5～50 weight portions mixes, and at 50～100 ℃ of lower stirring reaction 1～48h, takes off the aluminium of molecular sieve inside, filters, is washed to neutrality, and oven dry dewaters, and obtains the dealuminzation molecular sieve; Then add the slaine of 0.1～10 weight portion and the organic solvent of 5～100 weight portions, stir 10～48h and make slaine be diffused into dealuminzation molecular sieve inside under 10～150 ℃, then filter, washing, roasting, obtain the immobilized Lewis acid that contains metal center.
2. the preparation method of immobilized Lewis acid according to claim 1, it is characterized in that: described H-Beta molecular sieve is commercially available H-Beta molecular sieve.
3. the preparation method of immobilized Lewis acid according to claim 1, it is characterized in that: described slaine is SnCl
4, TiCl
4, InCl
3, CuCl
2, ZnCl
2, CrCl
3or FeCl
3in a kind of.
4. the preparation method of immobilized Lewis acid according to claim 1 is characterized in that: described organic solvent is a kind of in methyl alcohol, ethanol, acetone, toluene, benzene, dimethylbenzene, chloroform, carbon dichloride or ethyl acetate.
5. the preparation method of immobilized Lewis acid according to claim 1 is characterized in that: described washing is for using organic solvent washing; Organic solvent used is a kind of in methyl alcohol, ethanol, acetone, toluene, benzene, dimethylbenzene, chloroform, carbon dichloride or ethyl acetate.
6. the preparation method of immobilized Lewis acid according to claim 1 is characterized in that: described roasting is under air atmosphere, 400～800 ℃ of sintering 1～20h.
7. an immobilized Lewis acid is obtained by the described preparation method of claim 1～6 any one.
8. immobilized Lewis acid claimed in claim 7 is applied in the reaction of activation carbonyl.
9. immobilized Lewis acid according to claim 8 is applied in the reaction of activation carbonyl, it is characterized in that: described activation carbonyl reaction is the Baeyer-Villiger oxidation reaction, 1,3-Dihydroxyacetone prepares a kind of in the reaction of methyl lactate or reaction that glucose prepares fructose.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097293A (en) * | 2017-12-12 | 2018-06-01 | 南开大学 | The synthetic method of the MFI structure zeolite molecular sieve of tin dope and application |
| CN108212207A (en) * | 2018-03-23 | 2018-06-29 | 陕西师范大学 | A kind of catalyzed conversion glucose prepares solid acid catalyst of methyl lactate and preparation method thereof |
| CN111905802A (en) * | 2020-06-15 | 2020-11-10 | 厦门大学 | Method for preparing lactate by using molybdenum-alkali metal/alkaline earth metal modified Lewis acid catalyst |
| CN112551538A (en) * | 2020-12-23 | 2021-03-26 | 中触媒新材料股份有限公司 | Synthesis method of nanoscale Sn-Beta |
| CN114229863A (en) * | 2021-11-30 | 2022-03-25 | 中国矿业大学 | Preparation method of Ti-Beta molecular sieve |
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| JP2009214039A (en) * | 2008-03-11 | 2009-09-24 | Tosoh Finechem Corp | Solid lewis acid catalyst and manufacturing method of diels-alder adduct using this catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097293A (en) * | 2017-12-12 | 2018-06-01 | 南开大学 | The synthetic method of the MFI structure zeolite molecular sieve of tin dope and application |
| CN108212207A (en) * | 2018-03-23 | 2018-06-29 | 陕西师范大学 | A kind of catalyzed conversion glucose prepares solid acid catalyst of methyl lactate and preparation method thereof |
| CN111905802A (en) * | 2020-06-15 | 2020-11-10 | 厦门大学 | Method for preparing lactate by using molybdenum-alkali metal/alkaline earth metal modified Lewis acid catalyst |
| CN111905802B (en) * | 2020-06-15 | 2022-01-18 | 厦门大学 | Method for preparing lactate by using molybdenum-alkali metal/alkaline earth metal modified Lewis acid catalyst |
| CN112551538A (en) * | 2020-12-23 | 2021-03-26 | 中触媒新材料股份有限公司 | Synthesis method of nanoscale Sn-Beta |
| CN114229863A (en) * | 2021-11-30 | 2022-03-25 | 中国矿业大学 | Preparation method of Ti-Beta molecular sieve |
| CN114229863B (en) * | 2021-11-30 | 2023-01-13 | 中国矿业大学 | Preparation method of Ti-Beta molecular sieve |
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