CN113117751A - Metal organic framework composite material and preparation method thereof - Google Patents
Metal organic framework composite material and preparation method thereof Download PDFInfo
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- CN113117751A CN113117751A CN201911418210.1A CN201911418210A CN113117751A CN 113117751 A CN113117751 A CN 113117751A CN 201911418210 A CN201911418210 A CN 201911418210A CN 113117751 A CN113117751 A CN 113117751A
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- 239000000463 material Substances 0.000 title claims abstract description 99
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- 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 48
- 239000002131 composite material Substances 0.000 claims abstract description 47
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000003141 primary amines Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 239000013084 copper-based metal-organic framework Substances 0.000 abstract description 25
- 239000002253 acid Substances 0.000 abstract description 10
- 241000269350 Anura Species 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- 229910021536 Zeolite Inorganic materials 0.000 description 21
- 239000010457 zeolite Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000013148 Cu-BTC MOF Substances 0.000 description 4
- 239000013177 MIL-101 Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013147 Cu3(BTC)2 Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001238 wet grinding Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
- C08G65/3255—Ammonia
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Abstract
The invention relates to a metal organic framework composite material and a preparation method thereof, wherein copper salt, trimesic acid, deionized water and amine substances are mixed according to a proportion to obtain a metal organic framework material prepolymer; mixing a silicon source, pseudo-boehmite, a phosphoric acid solution and deionized water in proportion to obtain a mesoporous molecular sieve precursor; and finally, placing the metal organic framework material prepolymer and the mesoporous molecular sieve precursor into a closed reactor, stirring and reacting at a certain temperature, and obtaining the metal organic framework composite material after centrifugal separation, washing and drying. In the composite material prepared by the invention, an interpenetrating structure is formed by the SAPO mesoporous molecular sieve and the copper-based metal organic framework material, the framework strength of the material is enhanced, and the total acid content is improved.
Description
Technical Field
The invention belongs to the field of metal organic framework materials, and particularly relates to a metal organic framework composite material and a preparation method thereof.
Background
Metal organic boneThe rack material is an emerging porous material, and has a larger specific surface area, a controllable pore size, a controllable pore volume and an assembly mode compared with the traditional porous material (activated carbon, alumina and molecular sieve), so that the rack material is concerned. Copper-based metal organic framework material Cu3(BTC)2Also called HKUST-1, has high specific surface area and pore volume and a large number of unsaturated active sites, so that the catalyst is widely applied to the technical fields of adsorption, separation, catalysis and the like. However, HKUST-1 binds easily to water molecules, resulting in a decrease in the number of unsaturated active sites and in the stability of the backbone. In addition, HKUST-1 has weak acidity, especially has limited active sites of B acid centers, which also restricts the scale application of the HKUST-1 in heterogeneous catalytic reactions (such as polyether amine synthesis).
CN105562059A discloses a molecular sieve using metal organic framework material as template and its preparation method. The molecular sieve is prepared by grinding zeolite raw powder by a wet method to obtain zeolite particles with the average particle size of less than or equal to 0.3 mu m; dispersing zeolite particles in the form of colloidal particles in a solvent to obtain a zeolite sol gel; and (2) uniformly mixing the zeolite sol gel and the metal organic framework material MIL-101, carrying out closed reaction on the uniformly mixed solution under the vacuum condition, and drying and calcining after the reaction is finished to obtain the metal-doped zeolite molecular sieve. The residual metal or metal oxide after roasting the metal organic framework material as the template agent plays a role of a bracket, the strength of the molecular sieve is enhanced, and meanwhile, the molecular sieve has specific catalytic activity. However, in the process of roasting and degrading the metal organic framework material, the organic ligand component generates macromolecular carbon deposition through polycondensation reaction, which easily causes the blockage of zeolite sol gel pore channels, namely the specific surface area, the open pore size and the pore number of the generated metal-doped zeolite molecular sieve are obviously reduced. In addition, the metal organic framework material MIL-101 belongs to a coordination polymer with high added value, is only used as a template agent for roasting treatment, and is not beneficial to industrial popularization and use no matter from the aspects of economy, specific surface area, pore volume and the like.
CN107597190A discloses a preparation method for assembling a metal organic framework film on the surface of zeolite molecular sieve crystal grains and an application thereof, wherein the preparation method comprises the following steps: firstly, adding metal cobalt salt, aromatic carboxylic acid, a molecular sieve and an organic solvent into a container, fully mixing and stirring for reaction, and then carrying out purification and vacuum drying treatment to obtain a precursor of a zeolite molecular sieve crystal grain surface assembled metal organic framework membrane material; and then, putting the precursor into a closed device for steam-assisted crystallization reaction, and finally, taking the product for purification and drying treatment to obtain the zeolite molecular sieve grain surface assembled metal organic framework membrane material. The metal organic framework material is only simply loaded on the surface of zeolite molecular sieve crystal grains, and organic combination between the zeolite molecular sieve crystal grains is not realized, so that the metal organic framework material falls off after being used for many times, and the activity of a membrane material is reduced. In addition, although the water vapor assisted crystallization can accelerate the generation process of the membrane material, most metal organic framework materials are easy to cause unstable framework structures or even collapse in the presence of water vapor, so that the metal organic framework membrane assembled on the surface of the zeolite molecular sieve crystal grains prepared by the method is easy to cause the reduction of the physicochemical properties of the components of the metal organic framework materials.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a metal organic framework composite material and a preparation method thereof. In the composite material prepared by the invention, an interpenetrating structure is formed by the SAPO mesoporous molecular sieve and the copper-based metal organic framework material, the framework strength of the material is enhanced, and the total acid content is improved.
The preparation method of the metal organic framework composite material provided by the invention comprises the following steps:
(1) mixing copper salt, trimesic acid, deionized water and amine substances according to a ratio, and stirring at room temperature to react to obtain a metal organic framework material prepolymer;
(2) mixing a silicon source, pseudo-boehmite, a phosphoric acid solution and deionized water according to a ratio, and stirring and reacting at a certain temperature to obtain a mesoporous molecular sieve precursor;
(3) placing the metal organic framework material prepolymer and the mesoporous molecular sieve precursor into a closed reactor, stirring and reacting at a certain temperature, centrifugally separating, washing and drying to obtain the metal organic framework composite material.
In the step (1), the copper salt is at least one selected from copper nitrate trihydrate, copper sulfate pentahydrate, copper chloride dihydrate and the like, and the copper nitrate trihydrate is preferred. The amine substance is selected from amino functional groups (-NH)2) The primary amine species at the end of the carbon chain may be at least one of triethylamine, isobutylamine, polyetheramine D-230, etc., preferably polyetheramine D-230.
In the step (1), the mass ratio of the copper salt, the trimesic acid, the deionized water and the amine substance is 1: (0.1-1): (10-100): (0.01 to 0.1), preferably 1: (0.4-0.6): (30-50): (0.03-0.06). The stirring speed is 200-350 rpm, and the stirring time is 1-5 h.
In the step (2), the silicon source is at least one selected from silica sol, tetraethyl orthosilicate, silicon powder and the like, and silica sol is preferred. The mass concentration of the phosphoric acid solution is 85 percent. The mass ratio of the silicon source, the pseudo-boehmite, the phosphoric acid solution and the deionized water is 1: (0.8-3.9): (1-5): (10-30), preferably 1: (1.6-2.5): (1.9-3.3): (15-20). The reaction temperature is 140-160 ℃; the stirring speed is 400 rpm-600 rpm, and the stirring time is 1 h-4 h.
In the step (3), the mass ratio of the mesoporous molecular sieve precursor to the metal organic framework material prepolymer is 1: (1 to 10), preferably 1: (6-8). The closed reactor is at least one selected from an enamel stirred tank reactor, a polytetrafluoroethylene stirred tank reactor, a nylon stirred tank reactor and the like. The stirring temperature is 180-260 ℃, preferably 210-240 ℃. The stirring speed is 300rpm to 500rpm, and the stirring time is 10h to 50h, preferably 20h to 30 h. Deionized water is adopted for washing, and repeated washing is carried out for multiple times. The drying temperature is 170-200 ℃, and the drying time is 10-15 h.
The metal organic framework composite material is prepared by the method. In the prepared composite material, the content of the mesoporous molecular sieve is 10-50 percent and the content of the metal organic framework material is 50-90 percent based on the total mass of the material. The specific surface area of the composite material is800m2/g～900m2(ii)/g, total pore volume of 0.85cm3/g～1.09 cm3Per g, the average pore diameter is 6.5nm to 8.3nm, and the crushing strength is 1.5MPa to 2.5 MPa.
The metal organic framework composite material prepared by the invention can be applied to the technical field of heterogeneous catalysis, improves the activity and selectivity of the metal organic framework composite material in heterogeneous catalytic reaction, and is particularly suitable for catalyzing amination to synthesize polyether amine with the molecular weight less than 1000. Before use, the composite material prepared by the invention is reduced, and the reduction process comprises the following steps: before testing, the catalyst is dried for 1-3 h at 80-120 ℃, and then reduced for 1-3 h at 200-220 ℃ under the condition of 50-70 mL/min hydrogen flow rate.
The composite material prepared by the invention is used for synthesizing polyetheramine, 1g to 7g of reduced catalyst, 200g to 400g of polypropylene glycol and 15g to 40g of liquid ammonia are taken to react for 0.5h to 4h under the conditions of the reaction temperature of 140 ℃ to 200 ℃, the hydrogen partial pressure of 0.1MPa to 1MPa and the reaction total pressure of 3MPa to 6MPa, the conversion rate of raw materials is more than 95 percent, and the selectivity of primary amine products is more than 98 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, firstly, amine substances are introduced into the metal organic framework material prepolymer, and on one hand, the amine substances can effectively crosslink the mesoporous molecular sieve and the metal organic framework material prepolymer, so that the framework strength of the composite material is enhanced and the pore structure is modified; on the other hand, the formation of single-sheet layered silicon-aluminum substances which are not beneficial to the stability of the composite material can be controlled through an induction effect, and the stability of the material is enhanced.
(2) The mesoporous molecular sieve and the metal organic framework material in the composite material form an interpenetrating network structure, so that the stability of the metal organic framework material is effectively improved, a novel 'super cage' structure is generated in the process of interpenetrating the structure of the mesoporous molecular sieve and the metal organic framework material, and the pore volume and the pore size of the composite material are improved.
(3) SAPO mesoporous molecular sieve containing silicon and aluminum components is introduced into the metal organic framework material unit to form an interpenetrating network structure, so that the total acid content is improved, and the distribution is more uniform.
(4) The preparation method disclosed by the invention is simple in preparation process, simple and convenient to operate, energy-saving and environment-friendly, does not need special processing equipment, and is suitable for industrial production.
Drawings
Fig. 1 to 5 are nitrogen adsorption-desorption isotherms of the copper-based metal-organic framework material, the composite materials prepared in example 1, example 6, comparative example 1 and comparative example 3;
FIG. 6 is a thermogravimetric plot (TG) of copper-based metal organic framework materials, composites prepared in example 1 and comparative example 1;
fig. 7 to 11 are Scanning Electron Micrographs (SEM) of the copper-based metal organic framework material, the composite materials prepared in example 1, example 6, comparative example 1 and comparative example 3.
Detailed Description
The composite material of the present invention, its preparation and use are further illustrated by the following examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
Example 1
And (3) mixing 20g of copper nitrate trihydrate, 10g of trimesic acid, 800g of deionized water and 1g of polyetheramine D-230, and stirring at the temperature of 20 ℃ and the rpm of 200 for 1h to obtain the copper-based metal organic framework material prepolymer. 50g of silica sol, 105g of pseudo-boehmite, 115g of phosphoric acid solution with the mass concentration of 85% and 900g of deionized water are mixed, and stirred and reacted at the temperature of 150 ℃ for 3.5 hours at the speed of 550rpm to obtain a mesoporous molecular sieve precursor. Placing the mesoporous molecular sieve precursor and the copper-based metal organic framework material prepolymer in a closed reaction kettle according to the mass ratio of 1:7, and stirring and reacting at 225 ℃ and 450rpm for 24 hours. And centrifugally separating the obtained mixture, repeatedly washing the mixture by deionized water, and drying the mixture at 180 ℃ for 12 hours to obtain the composite material.
Example 2
And (3) mixing 20g of copper nitrate trihydrate, 8g of trimesic acid, 600g of deionized water and 0.6g of polyetheramine D-230, and stirring at the temperature of 25 ℃ and the rpm of 260 for 3 hours to obtain the copper-based metal organic framework material prepolymer. 50g of silica sol, 80g of pseudo-boehmite, 95g of phosphoric acid solution with the mass concentration of 85 percent and 750g of deionized water are mixed, and stirred and reacted for 1h at 140 ℃ and 400rpm to obtain a mesoporous molecular sieve precursor. Placing the mesoporous molecular sieve precursor and the copper-based metal organic framework material prepolymer in a closed reaction kettle according to the mass ratio of 1:6, and stirring and reacting at 210 ℃ and 300rpm for 20 hours. And centrifuging the obtained mixture, repeatedly washing the mixture by deionized water, and drying the mixture for 10 hours at 170 ℃ to obtain the composite material.
Example 3
20g of copper nitrate trihydrate, 12g of trimesic acid, 1000g of deionized water and 1.2g of polyetheramine D-230 are mixed and stirred at the temperature of 30 ℃ and the rpm of 350 for 5 hours to obtain the copper-based metal organic framework material prepolymer. 50g of silica sol, 125g of pseudo-boehmite, 165g of phosphoric acid solution with the mass concentration of 85 percent and 1000g of deionized water are mixed, and stirred and reacted at the temperature of 160 ℃ and the rpm of 600 for 4 hours to obtain a mesoporous molecular sieve precursor. Placing the mesoporous molecular sieve precursor and the copper-based metal organic framework material prepolymer in a closed reaction kettle according to the mass ratio of 1:8, and stirring and reacting at 240 ℃ for 30 hours at 500 rpm. And centrifugally separating the obtained mixture, repeatedly washing the mixture by using deionized water, and drying the mixture for 15 hours at the temperature of 200 ℃ to obtain the composite material.
Example 4
In example 1, copper sulfate pentahydrate was used instead of copper nitrate trihydrate, and the other reaction conditions and material composition were unchanged to obtain a composite material.
Example 5
In example 1, copper chloride dihydrate was used instead of copper nitrate trihydrate, and the other reaction conditions and material composition were unchanged to obtain a composite material.
Example 6
In example 1, triethylamine was used instead of polyetheramine D-230, and other reaction conditions and material compositions were unchanged to obtain a composite material.
Example 7
In example 1, isobutylamine was used in place of polyetheramine D-230, and the other reaction conditions and material composition were unchanged to obtain a composite material.
Example 8
In example 1, tetraethyl orthosilicate was used instead of silica sol, and other reaction conditions and material compositions were unchanged to obtain a composite material.
Example 9
In example 1, silica powder was used instead of silica sol, and other reaction conditions and material compositions were unchanged to obtain a composite material.
Example 10
In example 1, the stirring reaction temperature of the mixture of the metal organic framework material prepolymer and the mesoporous molecular sieve precursor was raised to 260 ℃, the reaction time was 10 hours, and other reaction conditions and material compositions were unchanged, to obtain a composite material.
Example 11
In example 1, the stirring reaction temperature of the mixture of the metal organic framework material prepolymer and the mesoporous molecular sieve precursor was reduced to 180 ℃, the reaction time was 50 hours, and other reaction conditions and material compositions were unchanged, to obtain a composite material.
Comparative example 1
In example 1, polyetheramine D-230 was omitted and the other reaction conditions and material composition were unchanged to give a composite material.
Comparative example 2
In example 1, the copper-based metal organic framework material prepolymer was suction filtered, repeatedly washed with deionized water, and dried at 120 ℃ for 12 hours to obtain copper-based metal organic framework material powder. The composite material is obtained by replacing the copper-based metal organic framework material prepolymer with copper-based metal organic framework material powder and keeping other reaction conditions and material compositions unchanged.
Comparative example 3
In example 1, mesoporous molecular sieve powder was used in place of the mesoporous molecular sieve precursor, and the composite material was obtained without changing other reaction conditions and material composition.
Comparative example 4
According to the method described in CN105562059A, the metal chromium organic framework material MIL-101 is prepared by a hydrothermal method. The zeolite colloid was prepared by mechanical wet milling. The zeolite raw powder is alternately washed by absolute ethyl alcohol and deionized water for 1 time and then dried in a vacuum oven at 80 ℃ for 24 hours. The zeolite particles were dispersed in the form of colloidal particles in solvent water to obtain a zeolite sol gel having a solid content of 15 wt%. The zeolite colloid is filled in the metal-organic framework material. Mixing zeolite sol gel with solid content of 15 wt% and metal chromium organic framework material MIL-101 according to a mass ratio of 8: 1, and reacting for 2.5 hours in a vacuum closed way at 90-95 ℃ under the condition of slow uniform stirring. And then, after molding and vacuum drying, roasting for 3 hours at 400 ℃ in an argon protective gas atmosphere with the flow rate of 5mL/min to obtain the chromium-doped zeolite molecular sieve N.
Comparative example 5
According to the method described in CN107597190A, firstly, 0.747 g of cobalt acetate, 0.5 g of terephthalic acid and 2.5 g Y are added into a beaker, 60g N is added, N-Dimethylformamide (DMF) is stirred in a magnetic stirrer in a water bath at 40 ℃ for carrying out self-assembly reaction for 4 hours, and then the precursor of the zeolite molecular sieve crystal grain surface assembly metal organic framework membrane material is obtained by suction filtration, washing with hot DMF and hot ethanol respectively and vacuum drying. The precursor material is placed into a polytetrafluoroethylene lining of 20ml, then the lining of 20ml is placed into a lining of 100ml which is added with 5g of water in advance, then the lining of 100ml is placed into a closed reaction kettle, and the reaction kettle is placed into an oven for steam assisted crystallization at 200 ℃ for 4h to synthesize the zeolite molecular sieve crystal grain surface assembly metal organic framework membrane material. And (3) carrying out first solvent hot washing treatment on the crystallized and synthesized material at 60 ℃ by using DMF (dimethyl formamide), taking the filter cake, sequentially carrying out washing and hot washing treatment, carrying out second suction filtration treatment at 60 ℃ by using ethanol, sequentially washing the filter cake, and carrying out vacuum drying treatment at 80 ℃ to obtain the zeolite molecular sieve crystal grain surface assembled metal organic framework membrane material O.
Test example 1
The physical and chemical properties of the composite materials of examples 1 to 11 and comparative examples 1 to 5 were measured, and the results are shown in Table 1. The specific surface area, pore volume and average pore diameter were determined by an adsorption apparatus model ASAP 2020, Micromeritics, USA, at a test temperature of-196 deg.C, and the samples were degassed at 120 deg.C for 10h before the test, and the results were calculated by the Brunauer-Emmett-Teller (BET) method. The acid amount and acid strength are determined by Nicolet 5DX type Fourier transform infrared spectrometerSamples at 14.71X 106Pressing into tablet under Pa, placing in infrared tank, vacuumizing to 133.3 × 10 at 500 deg.C-4Pa, adsorbing pyridine at room temperature, heating to 200 ℃ after balancing, vacuumizing for 0.5h, cooling to room temperature, and carrying out infrared spectrum determination. And (3) carrying out suction filtration on the copper-based metal organic framework material prepolymer, repeatedly washing with deionized water, and drying at 120 ℃ for 12h to obtain copper-based metal organic framework material powder serving as a reference agent.
TABLE 1 physicochemical Properties of the composites prepared in the examples and comparative examples
As shown in Table 1, the composite material prepared by the invention has good physicochemical properties, the average pore diameter is 6.5 nm-8.3 nm on the premise of keeping a certain specific surface area and pore volume, and the N of the copper-based metal organic framework material and the composite material is shown in figures 1-52According to an adsorption-desorption curve, the copper-based metal organic framework material is a microporous material, and the composite material contains a hysteresis ring, namely the composite material is a mesoporous material. In addition, as can be seen from the thermogravimetric curve of fig. 6, the composite material prepared by the present invention has good heat resistance stability. The scanning electron micrographs in fig. 7 to fig. 11 show that the appearance of the interpenetrating structure of the mesoporous molecular sieve and the copper-based metal-organic framework material is changed from octahedron to ellipse, and the separation phenomenon of the mesoporous molecular sieve and the copper-based metal-organic framework material is not seen in the samples in the examples due to the crosslinking effect of the polyetheramine D-230. On the other hand, the sample of comparative example 1 has no polyetheramine D-230, so the combination effect of the mesoporous molecular sieve and the copper-based metal-organic framework material is not good, and the sample of comparative example 3 only uses the metal-organic framework material as the template agent and does not form an interpenetrating structure.
Test example 2
The catalytic effect of the copper-based metal organic framework materials, the composites of examples 1-11 and comparative examples 1-5 on the synthesis of polyetheramine (D-230) from polypropylene glycol (230) was determined. Before testing, the catalysts prepared in the examples were dried at 100 ℃ for 1h and reduced at 220 ℃ for 2h under a hydrogen flow rate of 60mL/min to complete the catalyst reduction. 300g of polypropylene glycol (average molecular weight 230), 30g of liquid ammonia and 5g of reduction catalyst are added into a high-pressure reaction kettle and reacted for 2 hours under the conditions of reaction temperature of 160 ℃, hydrogen partial pressure of 0.5MPa and total reaction pressure of 4.5 MPa. The test results are shown in Table 2.
TABLE 2 catalytic Effect of catalysts prepared in examples and comparative examples
As can be seen from Table 2, the composite material prepared by the invention has good catalytic activity and selectivity in the catalytic amination reaction of polyether amine synthesized by polypropylene glycol. The composite material prepared by the invention has moderate acid amount and acid distribution, is beneficial to the generation of the main reaction of the polyether amine, and inhibits the occurrence of side reactions including coking and cracking. Meanwhile, the composite material prepared by the invention still keeps higher reactivity and selectivity after half a year, and the polypropylene glycol conversion rate and the main product D-230 selectivity of the sample in example 1 after half a year are still kept at 98.1% and 98.7%, which shows that the active center in the composite material plays a role for a long time, and the composite material has longer service life. This provides space for the raw material polypropylene glycol and its reaction intermediate products to diffuse in the inner and outer surfaces of the catalyst. The mesoporous molecular sieve in the composite material and the copper-based metal organic framework material form an interpenetrating network structure, the polyetheramine D-230 further plays a crosslinking role, the acid amount and the acid distribution of the composite material are effectively regulated and controlled, and a high-quality polyetheramine product is favorably generated.
Claims (14)
1. The preparation method of the metal organic framework composite material is characterized by comprising the following steps:
(1) mixing copper salt, trimesic acid, deionized water and amine substances according to a ratio, and stirring at room temperature to react to obtain a metal organic framework material prepolymer;
(2) mixing a silicon source, pseudo-boehmite, a phosphoric acid solution and deionized water according to a ratio, and stirring and reacting at a certain temperature to obtain a mesoporous molecular sieve precursor;
(3) placing the metal organic framework material prepolymer and the mesoporous molecular sieve precursor into a closed reactor, stirring and reacting at a certain temperature, centrifugally separating, washing and drying to obtain the metal organic framework composite material.
2. The method of claim 1, wherein: in the step (1), the copper salt is selected from at least one of copper nitrate trihydrate, copper sulfate pentahydrate and copper chloride dihydrate, and is preferably copper nitrate trihydrate.
3. The method of claim 1, wherein: in step (1), the amine is selected from amino functional groups (-NH)2) The primary amine species at the end of the carbon chain is preferably at least one of triethylamine, isobutylamine, and polyetheramine D-230.
4. The method of claim 1, wherein: in the step (1), the mass ratio of the copper salt, the trimesic acid, the deionized water and the amine substance is 1: (0.1-1): (10-100): (0.01 to 0.1), preferably 1: (0.4-0.6): (30-50): (0.03-0.06).
5. The method of claim 1, wherein: in the step (2), the silicon source is at least one selected from silica sol, tetraethyl orthosilicate and silicon powder, and the silica sol is preferred.
6. The method of claim 1, wherein: in the step (2), the mass ratio of the silicon source, the pseudo-boehmite, the phosphoric acid solution and the deionized water is 1: (0.8-3.9): (1-5): (10-30), preferably 1: (1.6-2.5): (1.9-3.3): (15-20).
7. The method of claim 1, wherein: in the step (2), the reaction temperature is 140-160 ℃; the stirring speed is 400 rpm-600 rpm, and the stirring time is 1 h-4 h.
8. The method of claim 1, wherein: in the step (3), the mass ratio of the mesoporous molecular sieve precursor to the metal organic framework material prepolymer is 1: (1 to 10), preferably 1: (6-8).
9. The method of claim 1, wherein: in the step (3), the stirring temperature is 180-260 ℃, preferably 210-240 ℃; the stirring speed is 300rpm to 500rpm, and the stirring time is 10h to 50h, preferably 20h to 30 h; the drying temperature is 170-200 ℃, and the drying time is 10-15 h.
10. A metal organic framework composite material, characterized in that it is prepared by a process according to any one of claims 1 to 9.
11. The composite material of claim 10, wherein: based on the total mass of the material, the content of the mesoporous molecular sieve is 10-50 percent, and the content of the metal organic framework material is 50-90 percent; the specific surface area of the composite material is 800m2/g～900m2(ii)/g, total pore volume of 0.85cm3/g～1.09 cm3Per g, the average pore diameter is 6.5nm to 8.3nm, and the crushing strength is 1.5MPa to 2.5 MPa.
12. Use of a composite material according to claim 10 or 11, characterized in that the catalytic amination synthesizes polyetheramines having a molecular weight of less than 1000.
13. Use according to claim 12, characterized in that: before use, the composite material prepared by the invention is reduced, and the reduction process comprises the following steps: before testing, the catalyst is dried for 1-3 h at 80-120 ℃, and then reduced for 1-3 h at 200-220 ℃ under the condition of 50-70 mL/min hydrogen flow rate.
14. Use according to claim 12, characterized in that: 1g to 7g of reduced catalyst, 200g to 400g of polypropylene glycol and 15g to 40g of liquid ammonia are taken to react for 0.5h to 4h under the conditions of the reaction temperature of 140 ℃ to 200 ℃, the hydrogen partial pressure of 0.1MPa to 1MPa and the reaction total pressure of 3MPa to 6MPa, the conversion rate of the raw materials is more than 95 percent, and the selectivity of the primary amine product is more than 98 percent.
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