CN110180603A - A kind of preparation method and products thereof of porous amino-acid modified molecular sieve - Google Patents
A kind of preparation method and products thereof of porous amino-acid modified molecular sieve Download PDFInfo
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- CN110180603A CN110180603A CN201910469120.9A CN201910469120A CN110180603A CN 110180603 A CN110180603 A CN 110180603A CN 201910469120 A CN201910469120 A CN 201910469120A CN 110180603 A CN110180603 A CN 110180603A
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- molecular sieve
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- allyl
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- -1 amino-acid modified molecular sieve Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- 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 27
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 150000001413 amino acids Chemical class 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 10
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000000643 oven drying Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000002732 mesitylenes Chemical class 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
The invention discloses a kind of preparation methods and products thereof of porous amino-acid modified molecular sieve, amino acid ligand containing double bonds is caused by thermal initiator, under nitrogen protection, it is grafted on the MCFs molecular sieve surface with double bond, due to " ink ampuliform " pore structure feature of MCFs molecular sieve, internal pore structure can be made to form " microreactor ", the characteristics of by porous molecular screen larger aperture and specific surface area, keep catalyst highly enriched in molecular sieve surface, make full use of the activated centre of catalyst, form high concentration region reaction, increase the mass transfer of substrate and product, and it is easily recycled catalyst and product separation, to be easier to industrial applications.
Description
Technical field
The present invention relates to a kind of preparation methods and products thereof of porous amino-acid modified molecular sieve, belong to functional molecular sieve skill
Art field.
Background technique
Chinese patent CN107880220A the study found that amino acid ligand can be grafted on Surfaces of Polystyrene Microparticles, but
It is that it is limited by polystyrene microsphere specific surface area, load capacity is lower, so that the conversion ratio of corresponding reaction is not high, and should
Microballoon can be swollen in organic solvent, influence its reaction result.
Therefore, the present invention has synthesized a kind of porous amino-acid modified molecular sieve, and amino acid ligand containing double bonds is connect
Branch can be such that internal pore structure is formed " micro- in MCFs molecular sieve surface due to " ink ampuliform " pore structure feature of MCFs molecular sieve
Reactor " the characteristics of by porous molecular screen larger aperture and specific surface area, keeps catalyst highly enriched in molecular sieve surface,
The activated centre of catalyst is made full use of, high concentration region reaction is formed, increases the mass transfer of substrate and product, and be easily recycled
It is separated using catalyst and product, since molecular sieve of the invention is inorganic carrier, it will not be made to occur in organic solvent molten
It is swollen, to be easier to industrial applications.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of preparation sides of porous amino-acid modified molecular sieve
Method.
Another object of the present invention is: providing a kind of porous amino-acid modified zeolite product of above method preparation.
The object of the invention is realized by following proposal: a kind of preparation method of porous amino-acid modified molecular sieve will contain
The amino acid ligand of double bond is caused by thermal initiator, under nitrogen protection, is grafted on the MCFs molecular sieve table with double bond
Face makes internal pore structure form " microreactor ", by porous point in conjunction with " ink ampuliform " pore structure feature of MCFs molecular sieve
The characteristics of son sieve larger aperture and specific surface area, keeps catalyst highly enriched in molecular sieve surface, make full use of the work of catalyst
Property center, formed high concentration region reaction, increase substrate and product mass transfer, include the following steps:
Step 1, at room temperature, by 2.2 grams of Pluronic P123(EO20PO70EO20, Mav=5800) it is dissolved in 75 milliliters
In 1.6 mol/L aqueous hydrochloric acid solutions, the Pluronic P123 is its molecule of polyoxyethylene-poly-oxypropylene polyoxyethylene
Formula are as follows: PEO-PPO-PEO；
Step 2 is gradually added 23 milligrams of ammonium fluorides in step 1, and 3.0 gram 1,3,5- trimethylbenzenes stir 1-2 hours；
Step 3,3.75 grams of ethyl orthosilicates and quality are slowly added dropwise in the solution of step 2 being 0.29-0.41 grams has
The silane of allyl continues stirring 20 hours；
Above-mentioned solution is transferred in the crystallizing kettle with polytetrafluoroethyllining lining by step 4, is placed in 90-110 DEG C of baking oven
Middle crystallization 24-48 hours；
Crystallizing kettle is taken out and is cooled to room temperature rear filtering and washing, and obtained white solid is dispersed in second by step 5
In alcohol, 80 degree are filtered after reflux 8-20 hours, and this process was repeated three times, then dry 8 ~ 20 small in 50 ~ 80 DEG C of vacuum drying ovens
When, obtain the MCFs molecular sieve with allyl；
Step 6, allyl MCFs is evenly dispersed with toluene solution, and addition quality is 0.10-0.20 grams of ammonia containing double bonds
Base acid ligand, stirs evenly, and azodiisobutyronitrile is then added, and is passed through nitrogen on one side, is evacuated together with vacuum pump, removes system
In air, so that reaction process is in nitrogen protection state；
Reaction temperature is risen to 50-80 DEG C by step 7, and stirring rate is 300-400 revs/min, after stirring 12-24 hours, is taken out
Filter obtains white solid, is put into 50-80 DEG C of oven drying to get porous amino-acid modified molecular sieve.
The aperture of the porous amino-acid modified molecular sieve is about 12-15 nanometers, and hole holds about 1.12-2.20 cubes li
Rice/gram, specific surface area is about 350-600 meters squared per gram.
Silane described in step 3 with vinyl is allyltrimethoxysilanis and allyltriethoxysilane
One of, the quality of the silane with allyl is 0.29-0.41.
Amino acid ligand described in step 6 is the amino acid ligand with vinyl.
The present invention provides a kind of porous amino-acid modified molecular sieve, is prepared according to any of the above-described the method.
The present invention has a characteristic that
(1) raw material used in the present invention is commercially available, from a wealth of sources to be easy to get；
(2) amino acid ligand is grafted to porous molecular screen surface by the present invention, is kept catalyst highly enriched in molecular sieve surface, is borrowed
The characteristics of helping porous molecular screen larger aperture and specific surface area highly utilizes the activated centre of catalyst, forms high concentration region
Reaction increases the mass transfer of substrate and product, makes Immobilized homogenous catalyst, is easily recycled catalyst and product separation, from
And it is easier to industrial applications.
(3) since molecular sieve of the invention is inorganic carrier, it will not be made to be swollen in organic solvent.
Specific embodiment
Be described in detail combined with specific embodiments below: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and specific operation process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
A kind of porous amino-acid modified molecular sieve is caused amino acid ligand containing double bonds by thermal initiator, in nitrogen
Under protection, it is grafted on the MCFs molecular sieve surface with double bond, in conjunction with " ink ampuliform " pore structure feature of MCFs molecular sieve, is made
Internal pore structure forms " microreactor ", the characteristics of by porous molecular screen larger aperture and specific surface area, make catalyst point
Son sieve apparent height enrichment, makes full use of the activated centre of catalyst, forms high concentration region reaction, increases substrate and product
Mass transfer, preparation step are as follows:
Step 1, at room temperature, by 2.0 grams of P123(EO20PO70EO20, MW=5800) it is dissolved in 75 milliliter of 1.6 mol/L
In HCL aqueous solution；
Step 2, is then added 23 milligrams of ammonium fluorides and 3.0 gram 1 in step 1, and 3,5- trimethylbenzenes stir 1 hour；
3.75 grams of ethyl orthosilicates and 0.41 gram of allyl ethyl triethoxy silicane are slowly added dropwise in step 3 in the solution of step 2
Alkane continues to stir 20 h；
Solution is transferred to 24 h of crystallization in the baking oven for be placed in the crystallizing kettle with polytetrafluoroethyllining lining 100 DEG C by step 4；
Step 5 filters after being cooled to room temperature from crystallizing kettle taking-up, washs, obtain white solid, be dispersed in ethyl alcohol
In, 80 degree are filtered after reflux 12 hours, and this process was repeated three times, then dry 12 hours in 70 DEG C of vacuum drying ovens, is had
There is the MCFs molecular sieve of allyl；
1.0 grams of allyl MCFs are dispersed in toluene solution by step 6, and 0.10 gram of amino acid ligand is added, and stirring is equal
It is even, azodiisobutyronitrile is then added, is passed through nitrogen on one side, is evacuated together with vacuum pump, the air in removing system makes to react
Process is in nitrogen protection state；
Reaction temperature is risen to 70 DEG C by step 7, and stirring rate is 350 revs/min, and after stirring 24 hours, suction filtration obtains white
Solid is put into 70 DEG C of oven dryings to get porous amino-acid modified molecular sieve, and aperture is 14.5 nanometers, and Kong Rongwei 1.86 is vertical
Square centimetre/gram, specific surface area are 429 meters squared per grams.
The structure of amino acid ligand is as follows:
。
Embodiment 2
A kind of porous amino-acid modified molecular sieve, preparation step are as follows:
Step 1, at room temperature, by 2.0 grams of P123(EO20PO70EO20, MW=5800) it is dissolved in 75 milliliter of 1.6 mol/L
In HCL aqueous solution；Then,
Step 2 is gradually added 23 milligrams of ammonium fluorides and 3.0 gram 1,3,5- trimethylbenzenes, after stirring 1 hour in step 1；
3.75 grams of ethyl orthosilicates and 0.41 gram of allyl ethyl triethoxy silicane are slowly added dropwise in step 3 in the solution of step 2
Alkane continues to stir 20 h；
Above-mentioned solution is transferred to crystallization in the baking oven for be placed in the crystallizing kettle with polytetrafluoroethyllining lining 100 DEG C by step 4
24 h；
Step 5 filters after being cooled to room temperature from crystallizing kettle taking-up, washs, obtain white solid, be dispersed in ethyl alcohol
In, 80 DEG C are filtered after reflux 12 hours, and this process was repeated three times, then dry 12 hours in 70 DEG C of vacuum drying ovens, is had
There is the MCFs molecular sieve of allyl；
Step 6, by 1.0 grams of allyl MCFs it is evenly dispersed with toluene solution in, 0.15 gram of amino acid ligand is added, stirring is equal
It is even, azodiisobutyronitrile is then added, is passed through nitrogen on one side, is evacuated together with vacuum pump, the air in removing system makes to react
Process is in nitrogen protection state；
Reaction temperature is risen to 70 DEG C by step 7, and stirring rate is 350 revs/min, and after stirring 24 hours, suction filtration obtains white
Solid is put into 70 degree of oven dryings to get porous amino-acid modified molecular sieve, and aperture is 13.1 nanometers, and Kong Rongwei 1.37 is vertical
Square centimetre/gram, specific surface area are 358 meters squared per grams.
The structure of amino acid ligand is as follows:
。
Embodiment 3
A kind of porous amino-acid modified molecular sieve, preparation step are as follows:
Step 1, at room temperature, by 2.0 grams of P123(EO20PO70EO20, MW=5800) it is dissolved in 75 milliliter of 1.6 mol/L
In HCL aqueous solution；Then,
Step 2 is gradually added 23 milligrams of ammonium fluorides and 3.0 gram 1,3,5- trimethylbenzenes, after stirring 1 hour in step 1；
3.75 grams of ethyl orthosilicates and 0.41 gram of allyl ethyl triethoxy silicane are slowly added dropwise in step 3 in the solution of step 2
Alkane continues to stir 20 h；
Above-mentioned solution is transferred in the crystallizing kettle with polytetrafluoroethyllining lining by step 4, is placed in crystallization in 100 DEG C of baking oven
24 h；
Step 5 filters after being cooled to room temperature from crystallizing kettle taking-up, washs, obtain white solid, be dispersed in ethyl alcohol
In, 80 DEG C are filtered after reflux 12 hours, and this process was repeated three times, then dry 12 hours in 70 DEG C of vacuum drying ovens, is had
There is the MCFs molecular sieve of allyl；
1.0 grams of allyl MCFs are dispersed in toluene solution by step 6, and 0.20 gram of amino acid ligand is added, and stirring is equal
It is even, azodiisobutyronitrile is then added, is passed through nitrogen on one side, is evacuated together with vacuum pump, the air in removing system makes to react
Process is in nitrogen protection state；
Reaction temperature is risen to 70 DEG C by step 7, and stirring rate is 350 revs/min, and after stirring 24 hours, suction filtration obtains white
Solid is put into 70 DEG C of oven dryings to get porous amino-acid modified molecular sieve, and aperture is 12.8 nanometers, and Kong Rongwei 1.12 is vertical
Square centimetre/gram, specific surface area are 303 meters squared per grams.
The structure of amino acid ligand is as follows:
。
Comparative example
Step 1, at room temperature, by 2.0 grams of P123(EO20PO70EO20, MW=5800) it is dissolved in 75 milliliter of 1.6 mol/L
In HCL aqueous solution；Then.
Step 2, is gradually added 23 milligrams of ammonium fluorides and 3.0 gram 1 in step 1, and 3,5- trimethylbenzenes stir 1 hour
Afterwards, 3.75 grams of ethyl orthosilicates and 0.41 gram of allyltriethoxysilane are slowly added dropwise, continue to stir 20 h；
Step 2 solution is transferred in the baking oven for be placed in the crystallizing kettle with polytetrafluoroethyllining lining 100 DEG C brilliant by step 3
Change 24 h；
Step 5 filters after being cooled to room temperature from crystallizing kettle taking-up, washs, obtain white solid, be dispersed in ethyl alcohol
In, 80 DEG C are filtered after reflux 12 hours, and this process was repeated three times, then dry 12 hours in 70 DEG C of vacuum drying ovens, is had
There is the MCFs molecular sieve of allyl, aperture is 15.0 nanometers, and 2.20 cubic centimetre/gram of Kong Rongwei, specific surface area is 602 squares
Rice/gram.
Claims (8)
1. a kind of preparation method of porous amino-acid modified molecular sieve, which is characterized in that by amino acid ligand containing double bonds
Caused by thermal initiator, under nitrogen protection, the MCFs molecular sieve surface with double bond is grafted on, in conjunction with MCFs molecular sieve
" ink ampuliform " pore structure feature makes internal pore structure form " microreactor ", by porous molecular screen larger aperture and Bi Biao
The characteristics of area, keeps catalyst highly enriched in molecular sieve surface, makes full use of the activated centre of catalyst, forms high concentration region
Domain reaction, increases the mass transfer of substrate and product, includes the following steps:
Step 1, at room temperature, by 2.2 grams of Pluronic P123(EO20PO70EO20, Mav=5800) it is dissolved in 75 milliliter 1.6
In mol/L aqueous hydrochloric acid solution；
Step 2 is gradually added 23 milligrams of ammonium fluorides in step 1, and 3.0 gram 1,3,5- trimethylbenzenes stir 1-2 hours；
Step 3,3.75 grams of ethyl orthosilicates and quality are slowly added dropwise in the solution of step 2 being 0.29-0.41 grams has
The silane of allyl continues stirring 20 hours；
Above-mentioned solution is transferred in the crystallizing kettle with polytetrafluoroethyllining lining by step 4, is placed in 90-110 DEG C of baking oven
Middle crystallization 24-48 hours；
Crystallizing kettle is taken out and is cooled to room temperature rear filtering and washing, and obtained white solid is dispersed in second by step 5
In alcohol, 80 DEG C are filtered after reflux 8-20 hours, and this process was repeated three times, then dry 8 ~ 20 small in 50 ~ 80 DEG C of vacuum drying ovens
When, obtain the MCFs molecular sieve with allyl；
Step 6, allyl MCFs is evenly dispersed with toluene solution, and addition quality is 0.10-0.20 grams of ammonia containing double bonds
Base acid ligand, stirs evenly, and azodiisobutyronitrile is then added, and is passed through nitrogen on one side, is evacuated together with vacuum pump, removes system
In air, so that reaction process is in nitrogen protection state；
Reaction temperature is risen to 50-80 DEG C by step 7, and stirring rate is 300-400 revs/min, after stirring 12-24 hours, is taken out
Filter obtains white solid, is put into 50-80 degree oven drying to get porous amino-acid modified molecular sieve.
2. the preparation method of porous amino-acid modified molecular sieve according to claim 1, which is characterized in that porous amino acid
The aperture of modified molecular screen is 12-15 nanometers, Kong Rongwei 1.12-2.20 cubic centimetre/gram, and specific surface area is 350-600 squares
Rice/gram.
3. the preparation method of porous amino-acid modified molecular sieve according to claim 1, which is characterized in that described in step 3
The silane with allyl be one of allyltrimethoxysilanis and allyltriethoxysilane.
4. the preparation method of porous amino-acid modified molecular sieve according to claim 1, which is characterized in that described in step 6
Amino acid ligand be the amino acid ligand with vinyl.
5. the preparation method of porous amino-acid modified molecular sieve according to any one of claims 1 to 4, which is characterized in that
Preparation step is as follows:
Step 1, at room temperature, by 2.0 grams of P123(EO20PO70EO20, MW=5800) it is dissolved in the HCl of 75 milliliter of 1.6 mol/L
In aqueous solution；
Step 2, is then added 23 milligrams of ammonium fluorides and 3.0 gram 1 in step 1, and 3,5- trimethylbenzenes stir 1 hour；
3.75 grams of ethyl orthosilicates and 0.41 gram of allyl ethyl triethoxy silicane are slowly added dropwise in step 3 in the solution of step 2
Alkane continues to stir 20 h；
Solution is transferred to 24 h of crystallization in the baking oven for be placed in the crystallizing kettle with polytetrafluoroethyllining lining 100 DEG C by step 4；
Step 5 filters after being cooled to room temperature from crystallizing kettle taking-up, washs, obtain white solid, be dispersed in ethyl alcohol
In, 80 degree are filtered after reflux 12 hours, and this process was repeated three times, then dry 12 hours in 70 DEG C of vacuum drying ovens, is had
There is the MCFs molecular sieve of allyl；
1.0 grams of allyl MCFs are dispersed in toluene solution by step 6, and 0.10 gram of amino acid ligand is added, and stirring is equal
It is even, azodiisobutyronitrile is then added, is passed through nitrogen on one side, is evacuated together with vacuum pump, the air in removing system makes to react
Process is in nitrogen protection state；
Reaction temperature is risen to 70 DEG C by step 7, and stirring rate is 350 revs/min, and after stirring 24 hours, suction filtration obtains white
Solid is put into 70 DEG C of oven dryings to get porous amino-acid modified molecular sieve, and aperture is 14.5 nanometers, and Kong Rongwei 1.86 is vertical
Square centimetre/gram, specific surface area are 429 meters squared per grams.
6. the preparation method of porous amino-acid modified molecular sieve according to any one of claims 1 to 4, which is characterized in that
Preparation step is as follows:
Step 1, at room temperature, by 2.0 grams of P123(EO20PO70EO20, MW=5800) it is dissolved in the HCl of 75 milliliter of 1.6 mol/L
In aqueous solution；Then,
Step 2 is gradually added 23 milligrams of ammonium fluorides and 3.0 gram 1,3,5- trimethylbenzenes, after stirring 1 hour in step 1；
3.75 grams of ethyl orthosilicates and 0.41 gram of allyl ethyl triethoxy silicane are slowly added dropwise in step 3 in the solution of step 2
Alkane continues to stir 20 h；
Above-mentioned solution is transferred to crystallization in the baking oven for be placed in the crystallizing kettle with polytetrafluoroethyllining lining 100 DEG C by step 4
24 h；
Step 5 filters after being cooled to room temperature from crystallizing kettle taking-up, washs, obtain white solid, be dispersed in ethyl alcohol
In, 80 DEG C are filtered after reflux 12 hours, and this process was repeated three times, then dry 12 hours in 70 DEG C of vacuum drying ovens, is had
There is the MCFs molecular sieve of allyl；
Step 6, by 1.0 grams of allyl MCFs it is evenly dispersed with toluene solution in, 0.15 gram of amino acid ligand is added, stirring is equal
It is even, azodiisobutyronitrile is then added, is passed through nitrogen on one side, is evacuated together with vacuum pump, the air in removing system makes to react
Process is in nitrogen protection state；
Reaction temperature is risen to 70 DEG C by step 7, and stirring rate is 350 revs/min, and after stirring 24 hours, suction filtration obtains white
Solid is put into 70 degree of oven dryings to get porous amino-acid modified molecular sieve, and aperture is 13.1 nanometers, and Kong Rongwei 1.37 is vertical
Square centimetre/gram, specific surface area are 358 meters squared per grams.
7. the preparation method of porous amino-acid modified molecular sieve according to any one of claims 1 to 4, which is characterized in that
Preparation step is as follows:
Step 1, at room temperature, by 2.0 grams of P123(EO20PO70EO20, MW=5800) it is dissolved in the HCl of 75 milliliter of 1.6 mol/L
In aqueous solution；Then,
Step 2 is gradually added 23 milligrams of ammonium fluorides and 3.0 gram 1,3,5- trimethylbenzenes, after stirring 1 hour in step 1；
3.75 grams of ethyl orthosilicates and 0.41 gram of allyl ethyl triethoxy silicane are slowly added dropwise in step 3 in the solution of step 2
Alkane continues to stir 20 h；
Above-mentioned solution is transferred in the crystallizing kettle with polytetrafluoroethyllining lining by step 4, is placed in crystallization in 100 DEG C of baking oven
24 h；
Step 5 filters after being cooled to room temperature from crystallizing kettle taking-up, washs, obtain white solid, be dispersed in ethyl alcohol
In, 80 DEG C are filtered after reflux 12 hours, and this process was repeated three times, then dry 12 hours in 70 DEG C of vacuum drying ovens, is had
There is the MCFs molecular sieve of allyl；
1.0 grams of allyl MCFs are dispersed in toluene solution by step 6, and 0.20 gram of amino acid ligand is added, and stirring is equal
It is even, azodiisobutyronitrile is then added, is passed through nitrogen on one side, is evacuated together with vacuum pump, the air in removing system makes to react
Process is in nitrogen protection state；
Reaction temperature is risen to 70 DEG C by step 7, and stirring rate is 350 revs/min, and after stirring 24 hours, suction filtration obtains white
Solid is put into 70 DEG C of oven dryings to get porous amino-acid modified molecular sieve, and aperture is 12.8 nanometers, and Kong Rongwei 1.12 is vertical
Square centimetre/gram, specific surface area are 303 meters squared per grams.
8. a kind of porous amino-acid modified molecular sieve, it is characterised in that -7 any the methods are prepared according to claim 1.
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