CN106179510A - A kind of mesoporous molecular sieve catalyst containing double acidic sites and preparation method thereof - Google Patents
A kind of mesoporous molecular sieve catalyst containing double acidic sites and preparation method thereof Download PDFInfo
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- CN106179510A CN106179510A CN201610528032.8A CN201610528032A CN106179510A CN 106179510 A CN106179510 A CN 106179510A CN 201610528032 A CN201610528032 A CN 201610528032A CN 106179510 A CN106179510 A CN 106179510A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
The invention discloses a kind of mesoporous molecular sieve catalyst containing double acidic sites, its structure is the product of aluminium containing molecular sieve and silane Sulphonic Acid Functionalized；Preparation method is: form solution A with positive primary amine, second alcohol and water, tetraethyl orthosilicate and aluminium salt is successively added, stirring, prepares Al HMS mesopore molecular sieve；Al HMS is contacted with hydrosulphonyl silane solution, 60 ~ 75oStir 2 ~ 6 h under C, obtain the Al HMS mesopore molecular sieve of hydrosulphonyl silane grafting grafting, be designated as SH Al HMS；By SH Al HMS and hydrogen peroxide room temperature catalytic oxidation, obtain the Al HMS mesopore molecular sieve of silane Sulphonic Acid Functionalized, be designated as SO3H Al HMS, this is the catalyst of the present invention.Present invention have the advantage that in mesopore molecular sieve HMS parent, introduce Al and two kinds of acidic sites of sulfonic group, improve surface acidity bit quantity, surface acid concentration can be improved；Can be by the amount of the different acidic site of regulation to realize the reasonable layout of the overall acid strength of catalyst, to be adapted to different acid catalyzed reaction occasions.
Description
Technical field
The present invention relates to chemical products field of catalyst preparation, be specifically a kind of and containing aluminium ion and silane sulfonic acid bisgallic acid
Mesoporous molecular sieve catalyst of position and preparation method thereof.
Background technology
Acid catalyzed reaction is the important reaction of class in chemical industry, including cracking, alkylation, be esterified, be disproportionated, isomery
The unit processes such as change, polycondensation, dehydration (hydration).Consideration based on environmental conservation, such as concentrated sulphuric acid, phosphoric acid, aluminum chloride etc. pass
System liquid acidic catalyst is the most progressively replaced by solid acids such as aluminosilicate, zeolite, ion exchange resin.But, these are solid
The sour position of body acid often a kind of acidic site, such as zeolite is generally aluminium ion vacant (L acid) or aluminum hydroxyl (B-acid)；Ion
The sour position of exchanger resin is then sulfonic group.
It addition, have been reported that a kind of novel solid acid in recent years, sulfonated for silica gel or pure silicon mesopore molecular sieve surface grafting
The organic inorganic hybridization thing that silane is formed.But, its acidic site is still single sulfonic group.
Therefore, research and develop a kind of catalyst containing many acidic sites class, and then improve surface acidity bit quantity, improve surface acid
Concentration, to be adapted to the catalyst of different acid catalyzed reaction occasions, has been a problem with economy and learning value.
Summary of the invention
In order to overcome in above-mentioned prior art the deficiency that existing solid acid acidic site type is single, the present invention provide a kind of by
The Al mesopore molecular sieve grafted silane sulfonic acid containing metal forms the mesoporous molecular sieve catalyst of double acidic site.
The object of the present invention is achieved like this:
A kind of mesoporous molecular sieve catalyst of pair of acidic site, its structural formula schematically as follows:
The preparation method of the mesoporous molecular sieve catalyst of described pair of acidic site, comprises the steps:
(1), form solution A with positive primary amine, second alcohol and water, tetraethyl orthosilicate and aluminium salt are successively added, stirring, prepare Al-HMS
Mesopore molecular sieve；
(2), Al-HMS prepared by step (1) is contacted with hydrosulphonyl silane solution, 60 ~ 75oStir 2 ~ 6 h under C, obtain sulfydryl
The Al-HMS mesopore molecular sieve of Silane Grafted, is designated as SH-Al-HMS；
(3) SH-Al-HMS, by step (2) prepared and hydrogen peroxide room temperature catalytic oxidation, obtain the Al-HMS of sulfonic silane grafting
Mesopore molecular sieve, is SO3H-Al-HMS, the catalyst of the present invention.
Described positive primary amine is the one of lauryl amine, tetradecy lamine, cetylamine and 18-amine., preferably lauryl amine and cetylamine.
Aluminium salt used is the one in aluminum isopropylate., aluminum nitrate, aluminum sulfate, aluminum chloride, preferably aluminum isopropylate. and nitre
Acid aluminum.
Described hydrosulphonyl silane solution solvent for use is normal octane or toluene.
Described hydrosulphonyl silane is mercaptopropyl trimethoxysilane or mercapto hydroxypropyl methyl dimethoxysilane.
Actively beneficial effect: 1, introduce Al and two kinds of acidic sites of sulfonic group in mesopore molecular sieve HMS parent, improve surface
Acidic site quantity, can improve surface acid concentration；2, can be by the amount of the different acidic site of regulation to realize the overall acid strength of catalyst
Reasonable layout, to be adapted to different acid catalyzed reaction occasions.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further:
A kind of mesoporous molecular sieve catalyst of pair of acidic site, its structural formula schematically as follows:
The preparation method of the mesoporous molecular sieve catalyst of described pair of acidic site, comprises the steps:
(1), form solution A with positive primary amine, second alcohol and water, tetraethyl orthosilicate and aluminium salt are successively added, stirring, prepare Al-HMS
Mesopore molecular sieve；
(2), Al-HMS prepared by step (1) is contacted with hydrosulphonyl silane solution, 60 ~ 75oStir 2 ~ 6 h under C, obtain sulfydryl
The Al-HMS mesopore molecular sieve of Silane Grafted, is designated as SH-Al-HMS；
(3) SH-Al-HMS, by step (2) prepared and hydrogen peroxide room temperature catalytic oxidation, obtain the Al-HMS of sulfonic silane grafting
Mesopore molecular sieve, is SO3The catalyst of the H-Al-HMS present invention.
Described positive primary amine is the one of lauryl amine, tetradecy lamine, cetylamine and 18-amine., preferably lauryl amine and cetylamine.
Aluminium salt used is the one in aluminum isopropylate., aluminum nitrate, aluminum sulfate, aluminum chloride, preferably aluminum isopropylate. and nitre
Acid aluminum.
Hydrosulphonyl silane solution solvent for use is normal octane or toluene.
Described hydrosulphonyl silane is mercaptopropyl trimethoxysilane or mercapto hydroxypropyl methyl dimethoxysilane.
Embodiment 1
(1), 7.0 g 16 primary amine (HDA) are added in the solution being made up of 60 g deionized waters and 22 g ethanol, at 50 DEG C
Lower stirring and dissolving forms solution；20.8 g tetraethyl orthosilicates are rapidly joined, under stirring, has been added dropwise over by 10 g ethanol
Solution B with 3.1 g aluminum isopropylate. compositions；By above-mentioned formation solution stirring 18 h, filter, washing, be dried 24 h at 110 DEG C,
Last 600oC roasting 8 h, obtains Al-HMS；
(2), above-mentioned sample is put in the normal octane solution (100 mL) of the mercaptopropyl trimethoxysilane of 0.2 mol/L,
Stir 3 h at 60 DEG C, with washing with alcohol, filtration, be dried 24 h at 70 DEG C, obtain SH-Al-HMS.
(3), at room temperature, by the above-mentioned sample hydrogen peroxide oxidation of 100 mL30%, with 100 mL deionized water and ethanol
Washing, is acidified with 100mL 10% sulfuric acid solution, the complete drip washing of powder deionized water, is dried 24 h at 70 DEG C, obtains SO3H-
Al-HMS mesopore molecular sieve.
Embodiment 2
(1), 7.0 g 16 primary amine (HDA) are added in the solution being made up of 60 g deionized waters and 22 g ethanol, at 55 DEG C
Lower stirring and dissolving forms solution；20.8 g tetraethyl orthosilicates are rapidly joined, stirring stirring 5 min, be added dropwise over by 10 g
The solution B that ethanol forms with 5.6g aluminum nitrate；By above-mentioned formation solution stirring 16 h, filter, washing, be dried 24 at 110 DEG C
H, finally 600oC roasting 8 h, obtains Al-HMS；
(2), above-mentioned sample is put into the normal octane solution (100 mL) of the mercapto hydroxypropyl methyl dimethoxysilane of 0.2 mol/L
In, at 60 DEG C, stir 3 h, with washing with alcohol, filtration, be dried 24 h at 70 DEG C, obtain SH-Al-HMS.
(3), at room temperature, by the above-mentioned sample hydrogen peroxide oxidation of 100 mL30%, with 100 mL deionized water and ethanol
Washing, is acidified with 100mL 10% sulfuric acid solution, the complete drip washing of powder deionized water, is dried 24 h at 70 DEG C, obtains SO3H-
Al-HMS mesopore molecular sieve.
Embodiment 3
(1), 7.0 g 16 primary amine (HDA) are added in the solution being made up of 60 g deionized waters and 22 g ethanol, at 55 DEG C
Lower stirring and dissolving forms solution；20.8 g tetraethyl orthosilicates are rapidly joined, stirring stirring 5 min, be added dropwise over by 10 g
Isopropanol and the solution B of 4.1 g aluminum isopropylate. composition；By above-mentioned formation solution stirring 14 h, filter, washing, do at 110 DEG C
Dry 24 h, finally 600oC roasting 8 h, obtains Al-HMS；
(2), above-mentioned sample is put in the normal octane solution (100 mL) of the mercaptopropyl trimethoxysilane of 0.2 mol/L,
Stir 3 h at 60 DEG C, with washing with alcohol, filtration, be dried 24 h at 70 DEG C, obtain SH-Al-HMS.
(3), at room temperature, by the above-mentioned sample hydrogen peroxide oxidation of 100 mL30%, with 100 mL deionized water and ethanol
Washing, is acidified with 100mL 10% sulfuric acid solution, the complete drip washing of powder deionized water, is dried 24 h at 70 DEG C, obtains SO3H-
Al-HMS mesopore molecular sieve.
Embodiment 4
(1), 7.0 g 16 primary amine (HDA) are added in the solution being made up of 60 g deionized waters and 22 g ethanol, at 65 DEG C
Lower stirring and dissolving forms solution；20.8 g tetraethyl orthosilicates are rapidly joined, stirring stirring 5 min, be added dropwise over by 10 g
Isopropanol and the solution B of 7.5 g aluminum nitrates composition；By above-mentioned formation solution stirring 12 h, filter, washing, be dried at 110 DEG C
24 h, finally 600oC roasting 8 h, obtains Al-HMS；
(2), above-mentioned sample is put into the normal octane solution (100 mL) of the mercapto hydroxypropyl methyl dimethoxysilane of 0.2 mol/L
In, at 60 DEG C, stir 3 h, with washing with alcohol, filtration, be dried 24 h at 70 DEG C, obtain SH-Al-HMS.
(3), at room temperature, by the above-mentioned sample hydrogen peroxide oxidation of 100 mL30%, with 100 mL deionized water and ethanol
Washing, is acidified with 100mL 10% sulfuric acid solution, the complete drip washing of powder deionized water, is dried 24 h at 70 DEG C, obtains SO3H-
Al-HMS mesopore molecular sieve.
Use the present invention and existing method gained molecular sieve make and sour measuring see table:
| Catalyst | Al+Content (mmol/g) | -SO3H content (mmol/g) | Acid amount (mmol/g) |
| Embodiment 1 | 2.4 | 1.8 | 3.26 |
| Embodiment 2 | 3.2 | 1.5 | 3.32 |
| Embodiment 3 | 2.4 | 1.8 | 3.34 |
| Embodiment 4 | 3.2 | 1.5 | 3.41 |
| Control sample 1 | 2.4 | 0 | 1.51 |
| Control sample 2 | 3.2 | 0 | 1.62 |
| Control sample 3 | 0 | 1.8 | 1.77 |
| Control sample 4 | 0 | 1.5 | 1.43 |
Annotation and supplementary notes:
The control sample 1 and 2 of this table is not introduce sulfonic acid group in above-described embodiment 1 and 2 respectively, the most only carries out first step synthesis and draws
Enter the molecular sieve-4 A l-HMS of Al ion；Control sample 3 and 4 is to be added without Al during synthesis of molecular sieve in above-described embodiment 3 and 4 respectively
Salt, that i.e. synthesize is pure silicon HMS, is re-introduced into sulfonic acid group and the SO that obtains3H-HMS。
Present invention have the advantage that 1, in mesopore molecular sieve HMS parent, introduce Al and two kinds of acidic sites of sulfonic group, carry
High surface acidity bit quantity, can improve surface acid concentration；2, can be overall to realize catalyst by the amount of the different acidic site of regulation
The reasonable layout of acid strength, to be adapted to different acid catalyzed reaction occasions.
Above case study on implementation is merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, in the ken that described field those of ordinary skill is possessed, that is made within the spirit and principles in the present invention is any
Amendment, equivalent replacement and improvement etc., be regarded as the protection domain of the application.
Claims (6)
1. the mesoporous molecular sieve catalyst containing double acidic sites, it is characterised in that structure is:
。
2. the preparation method of the mesoporous molecular sieve catalyst containing double acidic sites as claimed in claim 1, it is characterised in that include
Following steps:
(1), form solution A with positive primary amine, second alcohol and water, tetraethyl orthosilicate and aluminium salt are successively added, stirring, prepare Al-HMS
Mesopore molecular sieve；
(2), Al-HMS prepared by step (1) is contacted with hydrosulphonyl silane solution, 60 ~ 75oStir 2 ~ 6 h under C, obtain sulfydryl silicon
The Al-HMS mesopore molecular sieve of alkane grafting, is designated as SH-Al-HMS；
(3) SH-Al-HMS, by step (2) prepared and hydrogen peroxide room temperature catalytic oxidation, obtain the Al-HMS of sulfonic silane grafting
Mesopore molecular sieve, is SO3H-Al-HMS, the catalyst of the present invention.
3. according to the preparation method of the mesoporous molecular sieve catalyst containing double acidic sites of claims 2, it is characterised in that: described
Positive primary amine is the one of lauryl amine, tetradecy lamine, cetylamine and 18-amine., preferably lauryl amine and cetylamine.
4. according to the preparation method of the mesoporous molecular sieve catalyst containing double acidic sites of claims 2, it is characterised in that: used
Aluminium salt is the one in aluminum isopropylate., aluminum nitrate, aluminum sulfate, aluminum chloride, preferably aluminum isopropylate. and aluminum nitrate.
5. according to the preparation method of the mesoporous molecular sieve catalyst containing double acidic sites of claims 2, it is characterised in that: sulfydryl
Solution of silane solvent for use is normal octane or toluene.
6. according to the preparation method of the mesoporous molecular sieve catalyst containing double acidic sites of claims 2, it is characterised in that: described
Hydrosulphonyl silane be mercaptopropyl trimethoxysilane or mercapto hydroxypropyl methyl dimethoxysilane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605231A (en) * | 2022-03-22 | 2022-06-10 | 广州华园科技有限公司 | Method for preparing 2-tert-butylphenol by liquid-phase alkylation |
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Cited By (2)
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| CN114605231A (en) * | 2022-03-22 | 2022-06-10 | 广州华园科技有限公司 | Method for preparing 2-tert-butylphenol by liquid-phase alkylation |
| CN114605231B (en) * | 2022-03-22 | 2023-08-25 | 广州华园科技有限公司 | Method for preparing 2-tertiary butyl phenol by liquid phase alkylation |
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