CN103464196A - Preparation method for immobilized Lewis acid - Google Patents
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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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- immobilized lewis
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- 239000002841 Lewis acid Substances 0.000 title claims abstract description 29
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 14
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 claims abstract description 3
- 229930091371 Fructose Natural products 0.000 claims abstract description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 3
- 239000005715 Fructose Substances 0.000 claims abstract description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims abstract description 3
- 239000008103 glucose Substances 0.000 claims abstract description 3
- 229940057867 methyl lactate Drugs 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 5
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 239000011636 chromium(III) chloride Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000011973 solid acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 the field of catalysis in organic synthesis, and particularly relates to a preparation method of immobilized Lewis acid.
Background
In recent years, with the progress of catalytic technology, it has become important to support a catalyst and to easily separate the catalyst from a substrate. In the case of the conventional acid-based catalysts,
the immobilization of the acid is mature, and the sulfonic group is mainly connected with a loaded matrix through an alkyl chain. However, this method cannot be used in the synthesis process of Lewis acid, so the research on the immobilization technology of Lewis acid is laggard. Corma, Davis et al (Nature 2001,412:424-4·H2The molecular sieve (Sn-Beta) containing tin is obtained after hydrolysis and crystallization of O and the like, and has good Lewis acidity. However, this method requires a long preparation period (up to 40 days). Hermans et Al (Angew. chem. int. Ed.2012,51: 1-5) improved this process by using commercial H-Beta as the starting material, removing internal Al with nitric acid solution to form a voided Beta with a cavity, and then reacting it with Sn (CH)3COO)2Grinding and sintering in air atmosphere to obtain the Beta molecular sieve containing tin, which omits the crystallization process, greatly shortens the preparation period, but only limits the volatilizable Sn (CH)3COO)2Preparation of Sn-Beta, and Sn (CH)3COO)2The price is high, and the large-scale preparation is not suitable.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of immobilized Lewis acid. The preparation method has strong practicability and can be used for immobilized preparation of various metal Lewis acids.
The purpose of the invention is realized by the following technical scheme: a preparation method of immobilized Lewis acid comprises the following steps:
uniformly mixing 1 part by weight of H-Beta molecular sieve and 5-50 parts by weight of concentrated nitric acid with the concentration of 8-16 mol/L, stirring and reacting at 50-100 ℃ for 1-48H to remove aluminum in the molecular sieve, filtering, washing with water to be neutral, drying and removing water to obtain an aluminum-removed molecular sieve (deAlBeta); then adding 0.1-10 parts by weight of metal salt and 5-100 parts by weight of organic solvent, stirring for 10-48 h at 10-150 ℃ to enable the metal salt to diffuse into the deAlBeta, and then filtering, washing and roasting to obtain the immobilized Lewis acid containing the metal center.
The H-Beta molecular sieve is commercially available H-Beta molecular sieves of all kinds;
the metal salt is SnCl4，TiCl4，InCl3，CuCl2，ZnCl2，CrCl3Or FeCl3One of (1);
the organic solvent is one of methanol, ethanol, acetone, toluene, benzene, xylene, chloroform, carbon dichloride or ethyl acetate;
the washing is washing by using an organic solvent; the organic solvent is one of methanol, ethanol, acetone, toluene, benzene, xylene, chloroform, carbon dichloride or ethyl acetate;
the roasting is carried out for 1-20 h at 400-800 ℃ in an air atmosphere;
the process of the preparation method of the immobilized Lewis acid is shown as a formula I:
Formula I;
wherein,
represents a commercially available H-Beta molecular sieve;
represents a dealuminized molecular sieve;the supported Lewis acid containing a metal center is formed after metal salt diffusion, and M is one of Sn, Ti, In, Cu, Zn, Cr or Fe; the metal salt solution is formed by metal salt in an organic solvent; the metal salt is SnCl4，TiCl4，InCl3，CuCl2，ZnCl2，CrCl3Or FeCl3One of (1); the organic solvent is one of methanol, ethanol, acetone, toluene, benzene, xylene, chloroform, carbon dichloride or ethyl acetate.
The immobilized Lewis acid is prepared by the preparation method.
The immobilized Lewis acid obtained by the method can be applied to the reaction of activating carbonyl, wherein the reaction of activating carbonyl is Baeyer-Villiger oxidation reaction, the reaction of preparing methyl lactate from 1, 3-dihydroxyacetone and the reaction of preparing fructose from glucose.
Compared with the prior art, the invention has the following advantages: the raw materials of the method are cheap metal salt and organic solvent, not onlyLimited to Sn (CH)3COO)2The metal salt has wide applicability and solves the problem of preparation of immobilized Lewis.
Drawings
FIG. 1 is an energy spectrum of Sn-Beta in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The parts mentioned in examples 1 to 10 are parts by weight.
Example 1
Synthesis of tin-containing molecular sieves (Sn-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) and 20 parts of 13M nitric acid solution are mixed and heated to 100 ℃ for reaction for 20 hours. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then adding into the solution 10 weight portions of anhydrous SnCl4100 parts of benzene (D), stirred at 25 ℃ for 24h, filtered and washed with 1000mL of benzene to remove free SnCl4And introducing air at 550 ℃ for activation for 3h, and cooling to obtain Sn-Beta.
Example 2
Synthesis of Ti-containing molecular sieve (Ti-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) and 50 parts of 13M nitric acid solution are mixed and heated to 50 ℃ for reaction for 48 hours. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then added to a solution of 0.1 part by weight of anhydrous TiCl45 parts of chloroform, stirred at 10 ℃ for 48 hours, filtered and washed with 500 parts of toluene to remove free TiCl4And introducing air to activate for 20h at 400 ℃, and cooling to obtain the Ti-Beta.
Example 3
Synthesis of In-containing molecular sieves (In-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) is mixed with 50 parts of 8M nitric acid solution and then heated to 150 ℃ for reaction for 1 hour. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then added to a solution of 10 parts by weight of anhydrous InCl 310 parts of methanol, stirred at 65 ℃ for 48h, filtered and washed with 500 parts of chloroform to remove free InCl3And introducing air for activation for 1h at 800 ℃, and cooling to obtain the In-Beta.
Example 4
Synthesis of Cu-containing molecular sieves (Cu-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) is mixed with 50 parts of 10M nitric acid solution and then heated to 100 ℃ for reaction for 20 hours. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then added to a solution of 5 parts by weight of anhydrous CuCl 250 parts of ethanol, stirring at 78 ℃ for 10h, filtering, washing with 500 parts of ethanol to remove free CuCl2And introducing air for activation for 2h at 700 ℃, and cooling to obtain the Cu-Beta.
Example 5
Synthesis of Zn-containing molecular sieves (Zn-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) and 25 parts of 13M nitric acid solution are mixed and heated to 120 ℃ for reaction for 20 hours. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then adding the mixture to a solution of 5 parts by weight of anhydrous ZnCl 250 parts of methanol, stirred at 65 ℃ for 48h, filtered and washed with 500 parts of methanol to remove free InCl3And introducing air for activation for 3h at the temperature of 600 ℃, and cooling to obtain Zn-Beta.
Example 6
Synthesis of Cr-containing molecular sieves (Cr-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) is mixed with 50 parts of 8M nitric acid solution and then heated to 150 ℃ for reaction for 1 hour. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then added into a solution of 10 parts by weight of anhydrous CrCl3100 parts of methanol, stirred at 65 ℃ for 48h, filtered and washed with 500 parts of methanol to remove free CrCl3And introducing air at 550 ℃ for activation for 4h, and cooling to obtain the Cr-Beta.
Example 7
Synthesis of Fe-containing molecular sieves (Fe-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) is mixed with 50 parts of 8M nitric acid solution and then heated to 150 ℃ for reaction for 1 hour. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then adding into a solution containing 10 parts by weight of anhydrous FeCl 310 parts of methanol, stirred at 65 ℃ for 48 hours, filtered and washed with 500 parts of methanol to remove free FeCl3And introducing air for activation for 20h at 500 ℃, and cooling to obtain Fe-Beta.
Example 8
Synthesis of tin-containing molecular sieves (Sn-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) and 20 parts of 13M nitric acid solution are mixed and heated to 100 ℃ for reaction for 20 hours. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then adding into a solution of 0.1 weight part of anhydrous SnCl45 parts of xylene, stirred at 140 ℃ for 24h, filtered and washed with 1000mL of xylene to remove free SnCl4And introducing air at 550 ℃ for activation for 3h, and cooling to obtain Sn-Beta.
Example 9
Synthesis of tin-containing molecular sieves (Sn-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) and 20 parts of 13M nitric acid solution are mixed and heated to 100 ℃ for reaction for 20 hours. Filtering, washing with water to neutrality, drying and removing water to obtain the dealuminized molecular sieve (deAlBeta). Then adding into the solution 1 weight part of anhydrous SnCl4100 parts of ethyl acetate, stirred at 40 ℃ for 24h, filtered and washed with 1000mL of ethyl acetate to remove free SnCl4And introducing air at 550 ℃ for activation for 20h, and cooling to obtain Sn-Beta.
Example 10
Synthesis of tin-containing molecular sieves (Sn-Beta): 1 part of hydrogen type beta molecular sieve (H-beta) and 50 parts of 13M nitric acid solution are mixed and heated to 120 ℃ for reaction for 2 hours. Filtering, washing with water to neutrality, dryingWater to obtain a dealuminated molecular sieve (deAlBeta). Then adding into 9 parts by weight of anhydrous SnCl4100 parts of dichloro-benzene, stirred at 30 ℃ for 48h, filtered and washed with 1000mL of dichloromethane to remove free SnCl4And introducing air at 550 ℃ for activation for 20h, and cooling to obtain Sn-Beta.
The energy spectrum of Sn-Beta prepared in example 1 is shown in FIG. 1, and the data of the detection result is shown in Table 1, wherein the mass ratio of silicon to tin in the Sn-Beta molecular sieve is 37.87: 4.59.
TABLE 1 energy spectrum data of Sn-Beta of example 1
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of immobilized Lewis acid is characterized by comprising the following steps:
uniformly mixing 1 part by weight of H-Beta molecular sieve and 5-50 parts by weight of concentrated nitric acid with the concentration of 8-16 mol/L, stirring and reacting at 50-100 ℃ for 1-48H to remove aluminum in the molecular sieve, filtering, washing with water to be neutral, drying and removing water to obtain an aluminum-removed molecular sieve; then adding 0.1-10 parts by weight of metal salt and 5-100 parts by weight of organic solvent, stirring at 10-150 ℃ for 10-48 h to enable the metal salt to diffuse into the dealuminized molecular sieve, and then filtering, washing and roasting to obtain the immobilized Lewis acid containing the metal center.
2. The preparation method of the immobilized Lewis acid as claimed in claim 1, which is characterized in that: the H-Beta molecular sieve is a commercially available H-Beta molecular sieve.
3. The preparation method of the immobilized Lewis acid as claimed in claim 1, which is characterized in that: the metal salt is SnCl4，TiCl4，InCl3，CuCl2，ZnCl2，CrCl3Or FeCl3One kind of (1).
4. The preparation method of the immobilized Lewis acid as claimed in claim 1, which is characterized in that: the organic solvent is one of methanol, ethanol, acetone, toluene, benzene, xylene, chloroform, carbon dichloride or ethyl acetate.
5. The preparation method of the immobilized Lewis acid as claimed in claim 1, which is characterized in that: the washing is washing by using an organic solvent; the organic solvent is one of methanol, ethanol, acetone, toluene, benzene, xylene, chloroform, carbon dichloride or ethyl acetate.
6. The preparation method of the immobilized Lewis acid as claimed in claim 1, which is characterized in that: the roasting is carried out for 1-20 h at 400-800 ℃ in an air atmosphere.
7. An immobilized Lewis acid obtained by the preparation method of any one of claims 1 to 6.
8. Use of the immobilized Lewis acid of claim 7 in a reaction to activate a carbonyl group.
9. The use of the immobilized Lewis acid of claim 8 in a reaction to activate a carbonyl group, wherein: the activated carbonyl reaction is one of Baeyer-Villiger oxidation reaction, reaction for preparing methyl lactate from 1, 3-dihydroxyacetone or reaction for preparing fructose from glucose.
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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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261011A (en) * | 1999-12-29 | 2000-07-26 | 中国科学院上海有机化学研究所 | Solid-carried catalyst using bentonite as carrier, its preparing process and its application |
| 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 |
| CN101638455A (en) * | 2009-03-06 | 2010-02-03 | 大连海事大学 | Method for preparing petroleum resin by using supported AlCl3 catalyst |
-
2013
- 2013-07-25 CN CN2013103171233A patent/CN103464196A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261011A (en) * | 1999-12-29 | 2000-07-26 | 中国科学院上海有机化学研究所 | Solid-carried catalyst using bentonite as carrier, its preparing process and its application |
| 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 |
| CN101638455A (en) * | 2009-03-06 | 2010-02-03 | 大连海事大学 | Method for preparing petroleum resin by using supported AlCl3 catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 康自华等: "杂原子Sn-β分子筛的脱铝补位两步法制备、表征及其催化环己酮Baeyer-Villiger氧化性能", 《催化学报》 * |
| 韩巧凤，等: "《催化材料导论》", 31 March 2013, 化学工业出版社 * |
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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