CN116216752A - Preparation method of porous carbonate with high specific surface area - Google Patents
Preparation method of porous carbonate with high specific surface area Download PDFInfo
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- CN116216752A CN116216752A CN202310189901.9A CN202310189901A CN116216752A CN 116216752 A CN116216752 A CN 116216752A CN 202310189901 A CN202310189901 A CN 202310189901A CN 116216752 A CN116216752 A CN 116216752A
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- carbonate
- porous
- specific surface
- surface area
- salt
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 238000009423 ventilation Methods 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 5
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 5
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical group O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 claims description 4
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 claims description 4
- 159000000008 strontium salts Chemical class 0.000 claims description 4
- 239000003937 drug carrier Substances 0.000 claims description 3
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims description 3
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940047908 strontium chloride hexahydrate Drugs 0.000 claims description 3
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical group O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 claims description 3
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 claims description 2
- 229940067460 calcium acetate monohydrate Drugs 0.000 claims description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 claims description 2
- 229940052299 calcium chloride dihydrate Drugs 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 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 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940087646 methanolamine Drugs 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 239000002904 solvent Substances 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 4
- 239000002981 blocking agent Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000000352 supercritical drying Methods 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 52
- 239000001095 magnesium carbonate Substances 0.000 description 48
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 48
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 229940116318 copper carbonate Drugs 0.000 description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- RZEKVGVHFLEQIL-UHFFFAOYSA-N celecoxib Chemical compound C1=CC(C)=CC=C1C1=CC(C(F)(F)F)=NN1C1=CC=C(S(N)(=O)=O)C=C1 RZEKVGVHFLEQIL-UHFFFAOYSA-N 0.000 description 1
- 229960000590 celecoxib Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 thermal insulation Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/186—Strontium or barium carbonate
- C01F11/187—Strontium carbonate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/186—Strontium or barium carbonate
- C01F11/188—Barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to the field of porous material manufacturing, and particularly relates to a preparation method of porous carbonate with a high specific surface area. The method comprises the following steps: (1) preparation of a carbonate oligomer sol solution, (2) preparation of a carbonate oligomer gel, and (3) preparation of porous carbonate. The invention takes common metal salt with lower price as an initiator, organic alcohol with low dielectric constant as a solvent, organic amine with electron pushing effect as a blocking agent, and prepares a carbonate oligomer gel precursor with polymerization and crosslinking capability, and the gel precursor can prepare a porous material with large specific surface area through supercritical drying. The method has universality, can be used for preparing porous phosphate, sulfate and other materials with large specific surface area, and has good popularization value.
Description
Technical Field
The invention belongs to the field of porous material manufacturing, and particularly relates to a preparation method of porous carbonate with a high specific surface area.
Background
Porous materials are widely used as industrial catalysts, catalyst supports, separators, adsorbents, thermal insulation, sewage and exhaust gas treatment, and filtration liquidsAnd gaseous, lightweight building materials, NO in the atmosphere X The method can be used for treating automobile exhaust such as chemical compounds and sulfur dioxide, eliminating carbon dioxide and water in a spacecraft, improving soil in agriculture, and fixing fillers and chromatograms in cement, rubber, plastic and paper industry.
The carbonate has the advantages of no smell, no toxicity, good biocompatibility and the like, and has wide development prospect. Compared with the conventional carbonate, the porous carbonate has the characteristics of rich pore canal structure, higher specific surface area, excellent adsorption performance and the like, and has very attractive potential application in the fields of environmental protection and drug delivery. For example, in the medical field, mesoporous carbonate is used for improving the solubility of a poorly soluble drug celecoxib, so that the bioavailability and sustained release performance of the drug are obviously improved; in the environment protection field, porous carbonate is used for adsorbing Cu in wastewater 2+ Post-adsorption Cu 2+ The removal rate is as high as 99%.
The core parameters of porous material performance are high specific surface area and controlled porosity, however, to date, it has remained a challenge to produce a porous magnesium carbonate with a large specific surface area and adjustable porosity.
At present, there are two main methods for producing porous carbonates. The organic surfactant is used as the surface crystallization of the template, and the other is the non-classical crystallization of the colloid intermediate, ions are mainly used as precursors in the synthesis process of the two modes, electrostatic interaction is adopted among the ions, the crystallization growth mode is followed, the crystallization nucleation process has randomness, the controllability is poor, the obtained product has a macroporous structure, and the specific surface area is low. For example, patent CN101391783a reports a microemulsion method for preparing hollow and porous magnesium carbonate with a surfactant as a soft template agent, and the magnesium carbonate is in a nano rod shape and has a smaller specific surface.
Both patent CN109071252a and patent CN104837772a report a sol-gel process for preparing highly porous magnesium carbonate, which uses magnesium oxide or magnesium hydroxide as an initiator, and reacts under a certain temperature and pressure condition in an alcohol solution to generate an alkoxide gel precursor of magnesium, the gel precursor needs to be treated at a high temperature to obtain porous magnesium carbonate, and the obtained porous material is non-pure magnesium carbonate, which is a mixture containing 10% -20% magnesium oxide and 80% -90% magnesium carbonate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of porous carbonate with high specific surface, which takes common metal salt with lower price as an initiator, takes organic alcohol with low dielectric constant as a solvent, takes organic amine with electron pushing effect as a blocking agent, and introduces CO under the conditions of normal temperature and normal pressure 2 The gas can obtain pure carbonate oligomer gel precursor which is blocked by organic amine and has polymerization and crosslinking capability, and the gel precursor can obtain pure porous carbonate material without high-temperature treatment after supercritical drying.
In order to achieve the technical effects, the technical scheme adopted by the invention is as follows: the preparation method of the porous carbonate with high specific surface area comprises the following steps:
(1) Preparation of carbonate oligomer sol solution: adding a certain amount of metal salt into a container, fully dissolving in an organic solvent with low dielectric constant, controlling the concentration of the metal salt to be 0.01-0.5mol/L, adding an organic amine end capping agent, controlling the molar ratio of the organic amine to the metal salt to be 5:1-500:1, stirring at normal temperature and normal pressure, and introducing CO 2 Stopping ventilation after reacting for a period of time, and standing to obtain a carbonate oligomer sol solution;
(2) Preparation of carbonate oligomer gel: placing the obtained carbonate oligomer sol solution in an open way, aging for several days under normal pressure and a certain temperature, concentrating by adopting a high-speed centrifuge, and dispersing again for removing substances after concentrating to obtain pure carbonate oligomer gel;
(3) Preparation of porous carbonate: drying the obtained carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous carbonate.
Further, the metal salt in the step (1) is one of magnesium salt, calcium salt, barium salt, strontium salt and copper salt.
Further, the magnesium salt is one of magnesium chloride hexahydrate, magnesium sulfate heptahydrate, magnesium nitrate hexahydrate and magnesium acetate tetrahydrate.
Further, the calcium salt is one of calcium chloride dihydrate, calcium nitrate tetrahydrate and calcium acetate monohydrate.
Further, the barium salt is barium chloride dihydrate.
Further, the strontium salt is strontium chloride hexahydrate.
Further, the copper salt is one of copper chloride dihydrate, copper sulfate pentahydrate and copper nitrate trihydrate.
Further, the low dielectric constant organic solvent in the step (1) is one of methanol, ethanol, isopropanol, propylene glycol and glycerol.
Further, the organic amine in the step (1) is one of diethylamine, triethylamine, ethanolamine, tributylamine and methanolamine.
Further, the reaction time in the step (1) is 10-60min.
Further, the temperature in the step (2) is 5-40 ℃, and the aging period is 1-10 days.
The invention provides a porous carbonate with a high specific surface, which is prepared by the method.
The invention provides a carrier, which comprises porous carbonate prepared by the method.
The invention provides application of porous carbonate with high specific surface, and the porous carbonate can be used as a drug carrier in the field of medicine and an adsorbent in the field of environment.
The invention also provides a preparation method of the porous magnesium carbonate with the high specific surface, which comprises the following steps: 1) Preparation of magnesium carbonate oligomer sol solution: adding a certain amount of magnesium salt into a beaker, fully dissolving in an organic solvent with low dielectric constant, and controlling the concentration of the magnesium salt to be
0.01-0.5mol/L, adding an organic amine end capping agent, wherein the mol ratio of organic amine to magnesium salt is 5:
1-500:1, CO is introduced under normal temperature and pressure 2 Stopping ventilation after reacting for a period of time, and standing to obtain clear transparent blue light magnesium carbonate oligomerSol solution.
2) Preparation of magnesium carbonate oligomer gel: placing the obtained magnesium carbonate oligomer sol solution in an open way, aging for several days at normal pressure and a certain temperature, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure carbonate oligomer gel.
3) Preparation of porous magnesium carbonate: drying the obtained magnesium carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous magnesium carbonate material.
Further, the magnesium salt in the step 1) is one of magnesium chloride hexahydrate, magnesium sulfate heptahydrate, magnesium nitrate hexahydrate and magnesium acetate tetrahydrate.
Further, the low dielectric constant organic solvent in the step 1) is one of methanol, ethanol and isopropanol, the organic amine in the step 1) is one of diethylamine, triethylamine and ethanolamine, the reaction time in the step 1) is 10-60min, the temperature in the step 2) is 5-40 ℃, and the aging days are 1-10 days.
The beneficial effects of the invention are as follows: 1) The invention provides an inorganic ion oligomer sol-gel method, which uses common metal salt with lower price as an initiator, organic alcohol with low dielectric constant as a solvent, organic amine with electron pushing effect as a blocking agent, so as to prepare a carbonate oligomer gel precursor with polymerization and crosslinking capability, wherein the gel precursor can be used for preparing porous materials with large specific surface area through supercritical drying, and the method has universality and can be used for preparing porous phosphate and sulfate with large specific surface area; 2) The porous magnesium carbonate prepared by the invention has large specific surface area and adjustable porosity, and can be used as a drug carrier in the field of medicine and an adsorbent in the field of environment.
Description of the drawings
FIG. 1 is a flow chart of the preparation of magnesium carbonate according to the present invention;
FIG. 2 is a diagram of the tyndall effect of magnesium carbonate oligomer sol;
FIG. 3 shows the isothermal adsorption and desorption curve of porous magnesium carbonate material nitrogen and BJH pore size distribution;
FIG. 4 is an XRD pattern of a porous magnesium carbonate material;
FIG. 5 is a scanning electron microscope of porous magnesium carbonate;
FIG. 6 is a transmission electron microscope image of a porous magnesium carbonate material;
Detailed Description
Example 1
Adding 0.01mol of magnesium chloride hexahydrate into a beaker, fully dissolving in 50ml of ethanol, adding 1mol of triethylamine end-capping agent, and introducing CO at normal temperature and pressure 2 And stopping ventilation after reacting for 30min, and standing to obtain clear transparent bluish light magnesium carbonate oligomer sol solution, as shown in figure 2. And (3) placing the obtained magnesium carbonate oligomer sol solution in an open way, aging for 5 days at normal temperature and normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure magnesium carbonate oligomer gel. Drying the magnesium carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous magnesium carbonate material. As shown in FIG. 3, the specific surface area and porosity analyzer were used to obtain the adsorption-desorption curve of the sample, and the specific surface area of the sample was 689.3m as calculated by BET method 2 The pore diameter distribution diagram shows that the diameter of the material pores is between 2.0nm and 140nm, which indicates that the porous magnesium carbonate has a mesoporous and macroporous structure at the same time, and the material with the mesopores and macropores has great application potential in the fields of macromolecular drug loading, transmission, adsorption separation and the like.
The porous magnesium carbonate prepared by the patent of the embodiment has the purity reaching 99.8 percent through plasma emission spectrum, a spectrometer, a thermogravimetric analyzer and the like, and is high-purity magnesium carbonate.
Example 2
Adding 0.01mol of magnesium chloride hexahydrate into a beaker, fully dissolving in 50ml of ethanol, adding 3mol of triethylamine end-capping agent, and introducing CO at normal temperature and pressure 2 And (3) stopping ventilation after reacting for 20min, and standing to obtain a clear transparent bluish light magnesium carbonate oligomer sol solution. Placing the obtained magnesium carbonate oligomer sol solution in an open way, aging for 5 days at normal temperature and normal pressure, concentrating by a high-speed centrifuge, concentrating, and concentratingThe solvent was redispersed 3 times to remove impurities, resulting in a pure magnesium carbonate oligomer gel. Drying the obtained magnesium carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous magnesium carbonate material, wherein the specific surface area of the porous magnesium carbonate is 821.5m 2 /g。
Example 3
Adding 0.02mol of magnesium acetate tetrahydrate into a beaker, fully dissolving in 50ml of methanol, adding 1mol of triethylamine end-capping agent, and introducing CO at normal temperature and pressure 2 And (3) stopping ventilation after reacting for 60min, and standing to obtain a clear transparent bluish light magnesium carbonate oligomer sol solution. Placing the obtained magnesium carbonate oligomer sol solution in an open way, aging for 3 days at 37 ℃ and normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure magnesium carbonate oligomer gel. Drying the obtained magnesium carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous magnesium carbonate material, wherein the specific surface area of the porous magnesium carbonate is 513.6m 2 /g。
Example 4
Adding 0.005mol of magnesium nitrate hexahydrate into a beaker, fully dissolving the magnesium nitrate hexahydrate into 40ml of methanol, adding 0.1mol of ethanolamine end-capping agent, introducing CO2 gas at normal temperature and normal pressure, stopping ventilation after reacting for 20min, and standing to obtain a clear transparent bluish-light magnesium carbonate oligomer sol solution. Placing the obtained magnesium carbonate oligomer sol solution in an open way, aging for 2 days at the temperature of 10 ℃ and under normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure magnesium carbonate oligomer gel. Drying the obtained magnesium carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous magnesium carbonate material, wherein the specific surface area of the porous magnesium carbonate is 215.3m 2 /g。
Example 5
Adding 0.005mol of magnesium nitrate hexahydrate into a beaker, fully dissolving in 40ml of methanol, adding 0.1mol of diethylamine end-capping agent, introducing CO2 gas at normal temperature and normal pressure, reacting for 20min, stopping ventilation, and standing to obtain clear and transparent bluish-light magnesium carbonateOligomer sol solution. Placing the obtained magnesium carbonate oligomer sol solution in an open way, aging for 2 days at the temperature of 10 ℃ and under normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure magnesium carbonate oligomer gel. Drying the obtained magnesium carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous magnesium carbonate material, wherein the specific surface area of the porous magnesium carbonate is 457.9m 2 /g。
Example 6
Adding 0.01mol of calcium nitrate tetrahydrate into a beaker, fully dissolving the calcium nitrate tetrahydrate into 50ml of ethanol, adding 1mol of triethylamine end-capping agent, introducing CO2 gas at normal temperature and normal pressure, stopping the aeration after reacting for 20min, and standing to obtain the calcium carbonate oligomer sol solution. Placing the obtained calcium carbonate oligomer sol solution in an open way, aging for 8 days at normal temperature and normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure calcium carbonate oligomer gel. Drying the calcium carbonate oligomer gel under supercritical carbon dioxide to obtain porous calcium carbonate material with specific surface area of 325.6m 2 /g。
Example 7
Adding 0.01mol of barium chloride dihydrate into a beaker, fully dissolving the barium chloride dihydrate into 50ml of ethanol, adding 1mol of triethylamine end-capping agent, introducing CO2 gas at normal temperature and normal pressure, stopping the aeration after reacting for 30min, and standing to obtain the barium carbonate oligomer sol solution. And (3) placing the obtained barium carbonate oligomer sol solution in an open way, aging for 4 days at normal temperature and normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure barium carbonate oligomer gel. Drying the obtained barium carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain a porous barium carbonate material, wherein the specific surface area of the porous barium carbonate is 218.4m 2 /g。
Example 8
Adding 0.01mol of strontium chloride hexahydrate into a beaker, fully dissolving in 50ml of ethanol, adding 1mol of triethylamine end-capping agent, and introducing at normal temperature and normal pressureCO in 2 Stopping ventilation after reacting for 30min, and standing to obtain strontium carbonate oligomer sol solution. And (3) placing the obtained strontium carbonate oligomer sol solution in an open way, aging for 5 days at normal temperature and normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure strontium carbonate oligomer gel. Drying the obtained strontium carbonate oligomer gel under supercritical carbon dioxide to obtain porous strontium carbonate material with specific surface area of 437.1m 2 /g。
Example 9
Adding 0.01mol of cupric chloride dihydrate into a beaker, fully dissolving in 50ml of ethanol, adding 1mol of triethylamine end-capping agent, and introducing CO at normal temperature and pressure 2 And (3) stopping ventilation after reacting for 30min, and standing to obtain the copper carbonate oligomer sol solution. And (3) placing the obtained copper carbonate oligomer sol solution in an open way, aging for 5 days at normal temperature and normal pressure, concentrating by adopting a high-speed centrifuge, and dispersing the concentrated solution for 3 times by adopting a solvent to remove impurities so as to obtain the pure copper carbonate oligomer gel. Drying the copper carbonate oligomer gel under supercritical carbon dioxide to obtain porous copper carbonate material with specific surface area of 245.8m 2 /g。
Claims (10)
1. A method for preparing a porous carbonate with a high specific surface area, which is characterized by comprising the following steps:
(1) Preparation of carbonate oligomer sol solution: adding a certain amount of metal salt into a container, fully dissolving in an organic solvent with low dielectric constant, controlling the concentration of the metal salt to be 0.01-0.5mol/L, adding an organic amine end capping agent, controlling the molar ratio of the organic amine to the metal salt to be 5:1-500:1, stirring at normal temperature and normal pressure, and introducing CO 2 Stopping ventilation after reacting for a period of time, and standing to obtain a carbonate oligomer sol solution;
(2) Preparation of carbonate oligomer gel: placing the carbonate oligomer sol solution in an open way, aging for several days under normal pressure and a certain temperature, adopting a high-speed centrifuge to centrifugally concentrate, dispersing and removing impurities after concentrating, and obtaining pure carbonate oligomer gel;
(3) Preparation of porous carbonate: drying the carbonate oligomer gel under the condition of supercritical carbon dioxide to obtain the porous carbonate.
2. The method for preparing the porous carbonate with high specific surface area according to claim 1, wherein the method comprises the following steps: the metal salt in the step (1) is one of magnesium salt, calcium salt, barium salt, strontium salt and copper salt.
3. The method for preparing the porous carbonate with high specific surface area according to claim 2, wherein the method comprises the following steps: the magnesium salt is one of magnesium chloride hexahydrate, magnesium sulfate heptahydrate, magnesium nitrate hexahydrate and magnesium acetate tetrahydrate; the calcium salt is one of calcium chloride dihydrate, calcium nitrate tetrahydrate and calcium acetate monohydrate; the barium salt is barium chloride dihydrate; the strontium salt is strontium chloride hexahydrate; the copper salt is one of copper chloride dihydrate, copper sulfate pentahydrate and copper nitrate trihydrate.
4. A method for preparing a porous carbonate with a high specific surface area according to any one of claims 1 to 3, wherein: the low dielectric constant organic solvent in the step (1) is an organic alcohol, preferably the organic alcohol is one of methanol, ethanol, isopropanol, propylene glycol and glycerol.
5. A method for preparing a porous carbonate with a high specific surface area according to any one of claims 1 to 3, wherein: the organic amine in the step (1) is one of diethylamine, triethylamine, ethanolamine, tributylamine and methanolamine.
6. A method for preparing a porous carbonate with a high specific surface area according to any one of claims 1 to 3, wherein: the reaction time in the step (1) is 10-60min.
7. A method for preparing a porous carbonate with a high specific surface area according to any one of claims 1 to 3, wherein: the temperature in the step (2) is 5-40 ℃, and the aging days are 1-10 days.
8. A high specific surface area porous carbonate, characterized in that it is prepared by the method of any one of claims 1-7.
9. A support comprising a porous carbonate prepared by the method of any one of claims 1-7.
10. The use of a porous carbonate with a high specific surface area, characterized in that the porous carbonate can be used as a drug carrier in the pharmaceutical field and as an adsorbent in the environmental field.
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| US20150298984A1 (en) * | 2012-12-06 | 2015-10-22 | Disruptive Materials Ab | Anhydrous, amorphous and porous magnesium carbonates and methods of production thereof |
| CN109071252A (en) * | 2016-04-04 | 2018-12-21 | 破坏性材料公司 | Highly porous magnesium carbonate and its production method |
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| US20150298984A1 (en) * | 2012-12-06 | 2015-10-22 | Disruptive Materials Ab | Anhydrous, amorphous and porous magnesium carbonates and methods of production thereof |
| CN109071252A (en) * | 2016-04-04 | 2018-12-21 | 破坏性材料公司 | Highly porous magnesium carbonate and its production method |
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