CN115321572A - Efficient preparation method of environment-friendly spherical-like nano calcium carbonate - Google Patents
Efficient preparation method of environment-friendly spherical-like nano calcium carbonate Download PDFInfo
- Publication number
- CN115321572A CN115321572A CN202210998626.0A CN202210998626A CN115321572A CN 115321572 A CN115321572 A CN 115321572A CN 202210998626 A CN202210998626 A CN 202210998626A CN 115321572 A CN115321572 A CN 115321572A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- suspension
- nano calcium
- carbonization
- environment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 180
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims abstract description 75
- 239000000725 suspension Substances 0.000 claims abstract description 57
- 239000011575 calcium Substances 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000008213 purified water Substances 0.000 claims abstract description 17
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 16
- 239000012066 reaction slurry Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000029087 digestion Effects 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 238000009423 ventilation Methods 0.000 claims abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 17
- 239000000292 calcium oxide Substances 0.000 claims description 14
- 238000013329 compounding Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical group 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 6
- -1 ammonium ions Chemical class 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 102000004169 proteins and genes Human genes 0.000 claims description 6
- 108090000623 proteins and genes Proteins 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001202 Inulin Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- 229940029339 inulin Drugs 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 3
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 3
- 229920005553 polystyrene-acrylate Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007789 sealing Methods 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 45
- 239000000047 product Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229910052791 calcium Inorganic materials 0.000 description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- 239000012528 membrane Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000005273 aeration Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000013717 Houttuynia Nutrition 0.000 description 1
- 240000000691 Houttuynia cordata Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008946 yang xin Substances 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
-
- 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
- C01P2006/16—Pore diameter
-
- 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
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to an efficient preparation method of environment-friendly spherical-like nano calcium carbonate, which comprises the following steps: the method comprises the following steps of digestion and aging: adding purified water or distilled water into CaO, heating, sealing, stirring, digesting, sealing, standing, and aging to obtain refined Ca (OH) 2 A suspension; the refined Ca (OH) 2 Sieving the suspension to remove impurities to obtain Ca (OH) 2 A suspension; and (2) carbonizing: ca (OH) 2 Adding the suspension, the spherulite or calcite crystal form control agent and the template agent into a carbonization reactor, and adding CO 2 And N 2 The mixed gas enters the bottom of the carbonization reactor through a microporous gas disperser in a microaeration mode to carry out carbonization reaction, and when the pH of the reaction slurry is =6.5 to 7.0, the ventilation is stopped, and the carbonization reaction is finished; thirdly, centrifugally filtering, washing and drying the carbonized reaction slurry, and then grinding to obtain the spheroidal nano calcium carbonate product. The invention has simple process and easy industrial popularization, and the obtained productThe nano calcium carbonate particles are uniform and have good performance.
Description
Technical Field
The invention relates to the technical field of inorganic powder preparation, in particular to a high-efficiency preparation method of environment-friendly spherical nano calcium carbonate.
Background
The nano calcium carbonate is a novel superfine solid powder material, and the particle size of the nano calcium carbonate is between 1 to 100nm. Because of the ultra-fining of the nano calcium carbonate particles, the crystal structure and the surface electronic structure of the nano calcium carbonate particles are changed, and the quantum size effect, the small size effect, the surface effect and the macroscopic quantum effect which are not possessed by the common calcium carbonate are generated. At present, the most mature application of nano calcium carbonate is in the plastic industry, mainly used for high-end plastic products, and can effectively improve the rheological property of plastic master batch and enable the plastic master batch to have better formability. When used as plastic filler, the product can toughen and reinforce, increase the flexural modulus, flexural strength and dimensional stability of the product, and improve the thermal deformation temperature and plastic hysteresis. The nano calcium carbonate in the ink industry also shows excellent dispersibility, transparency and glossiness, and super-good absorptivity and self-drying property of the ink, so that the applicability of the nano calcium carbonate is greatly improved.
The synthesis of nano calcium carbonate materials with controllable morphology and structure is a hot point of research in the calcium carbonate industry. Calcite, aragonite, vaterite are 3 crystal forms of calcium carbonate, wherein vaterite is unstable and readily converts to calcite. But the vaterite nano calcium carbonate has higher specific surface area, good solubility, dispersibility, wear resistance and lower density, thereby having good application prospect in the fields of paper making, rubber, printable ink, coating, food additive, sealant and materials.
At present, the documents for preparing the spherical nano calcium carbonate are more reported, and most of the spherical nano calcium carbonate is prepared by adopting a double decomposition method and using soluble calcium salt and carbonate as raw materials. For example, in patent CN109133137A, glycerol is used as a crystal form control agent, and sodium carbonate, potassium carbonate, ammonium bicarbonate and calcium acetate or calcium chloride are used to react to prepare ellipsoidal micro-nano calcium carbonate. Cabernet-heartleaf houttuynia herb (inorganic salt industry, 2014,46 (04): 25-28) adopts calcium chloride and sodium carbonate to prepare the spherical vaterite phase nano calcium carbonate in an ethanol-water system. Yangxin (nuclear chemistry and radiochemistry, 2012,34 (06): 337-340) uses sodium polystyrene sulfonate as a crystal form control agent, and synthesizes spherical nano calcium carbonate by using sodium carbonate and calcium chloride. However, the nano calcium carbonate prepared by the method has the defects of uneven particle size, poor dispersibility, easy agglomeration and CO 2 Low utilization rate, high energy consumption, environmental protection of products and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a simple and easily-popularized method for efficiently preparing environment-friendly spherical-like nano calcium carbonate.
In order to solve the problems, the invention provides a high-efficiency preparation method of environment-friendly spherical-like nano calcium carbonate, which comprises the following steps:
the method comprises the following steps of digestion and aging:
adding purified water or distilled water with the mass being 11 to 41 times of that of CaO into CaO, heating to 50 to 90 ℃, hermetically stirring and digesting for 3 to 6 hours, and hermetically standing and aging for 20 to 48 hours to obtain refined Ca (OH) 2 A suspension; the refined Ca (OH) 2 Sieving the suspension through a 200 to 500-mesh sieve to remove Ca (OH) 2 Solid impurities in the suspension to obtain Ca (OH) with the concentration of 3 to 10wt percent 2 A suspension;
and (2) carbonizing:
the Ca (OH) with the concentration of 3 to 10wt percent 2 Adding the suspension, the spherulite or calcite crystal form control agent and the template agent into a carbonization reactor, and adding CO 2 And N 2 The mixed gas enters the bottom of the carbonization reactor through a micropore gas disperser in a way of micro gas flow to carry out carbonization reaction, and the gas passes through Ca (OH) 2 Suspension, part of CO 2 And Ca (OH) 2 Reacting to form calcium carbonate, residual CO 2 And N 2 The mixed gas of (2) is discharged from the top of the carbonization reactor; stopping ventilation when the pH of the reaction slurry is =6.5 to 7.0, and ending the carbonization reaction;
thirdly, centrifugally filtering and washing the carbonized reaction slurry, drying for 24 hours at 120 ℃, and then grinding to obtain the spheroidal nano calcium carbonate product.
The aragonite or calcite crystal form control agent in the step II is a compound of polyol or polyol and other crystal form control agents, and the addition amount of the aragonite or calcite crystal form control agent is 0.01 to 8wt% of the dry basis mass of calcium hydroxide.
The polyalcohol refers to one or a mixture of more of ethylene glycol, glycerol and pentaerythritol.
The compounding of the polyhydric alcohol and other crystal form control agents refers to any one of compounding of the polyhydric alcohol and inorganic matters containing ammonia molecules, ammonium ions and nitric acid, compounding of the polyhydric alcohol and organic matters containing amino acids, proteins and sucrose, and compounding of the polyhydric alcohol and polymers containing polystyrene sulfonate, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polycarboxylic acid, carboxymethyl inulin, dendritic macromolecules and calixarene.
The compounding of the polyhydric alcohol and other crystal form control agents in the step II is one or a mixture of more of monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, diisopropanolamine, 2-amino-2-methyl-1, 3-propanediol, tris (hydroxymethyl) aminomethane, sodium tripolyphosphate, amino acid, protein, sucrose, zinc chloride, magnesium chloride and barium chloride.
The template agent is one or a mixture of silicon dioxide, zinc oxide, titanium dioxide, polystyrene and polymethyl methacrylate, and the addition amount of the template agent is 1 to 99wt% of the dry basis mass of calcium hydroxide.
The step is in the second 2 And N 2 Of the mixed gas of (2) 2 The volume concentration of the gas is 25 to 50 percent.
The carbonization reaction condition in the second step is that the stirring rotating speed is 300 to 1000 r/min, the carbonization temperature is 15 to 50 ℃, and CO is used 2 The flow rate is 100 to 300mL/min, N 2 The flow rate was 300mL/min.
The carbonization reactor comprises a cylindrical shell I without a bottom; the top of the shell I is respectively provided with a residual unreacted mixed gas outlet and Ca (OH) 2 A mixed liquid inlet of the suspension, the crystal form control agent and the template agent, and CaCO arranged at the lower part of the side surface 3 A suspension outlet; and a stirring device is arranged in the shell I along the vertical direction, and the bottom of the shell I is connected with the top of the micropore gas disperser.
The microporous gas disperser comprises a funnel-shaped shell II; the lower part of the side surface of the shell II is provided with CO 2 And N 2 With CaCO in the carbonization reactor 3 The outlet direction of the suspension is opposite; the top of the shell II is provided with a connecting part with the carbonization reactorThe gas supply film forms an included angle alpha with the central axis of the carbonization reactor, and 0 o ≤α＜90 o (ii) a The section of the air supply film is T-shaped, wherein a through hole is formed in the vertical part, and a plurality of micropores with the diameter of 0.1 to 10000 mu m are annularly and uniformly distributed on the surface of the horizontal part.
Compared with the prior art, the invention has the following advantages:
1. the invention takes calcium oxide and carbon dioxide as raw materials, adds a crystal form control agent and a template agent to control the structure and the appearance of nano calcium carbonate, and adopts a microporous air supply film and a rotary micro-airflow carbonization method to synthesize (quasi) spherical nano calcium carbonate. Not only can fix the carbon dioxide, but also improves the uniformity, the dispersibility and the stability of the calcium carbonate particles.
2. The polyol crystal form control agent is beneficial to formation of the spherulite (metastable setting) or the calcite, the control agent can increase the interfacial energy of the calcite and the spherulite, the alcohol hydroxyl directional adsorption reduces the adsorption site density, and is the most possible mechanism for improving the mineral interfacial energy, and the number of solvent hydrogen bonds determines CO 3 -2 Degree of freedom, low degree of symmetry and CO 3 -2 Non-parallel spherulitic or calcite formation.
3. The invention combines the characteristics of polyhydroxyl alcohol and inorganic salt crystal form control to synthesize (quasi-) spherical nano calcium carbonate, and the calcium carbonate has the advantages of better specific surface area, lower contact area, better solubility, dispersibility and wear resistance.
4. The invention utilizes the template agent to prepare the nano calcium carbonate, synthesizes the hollow spherical nano calcium carbonate, has porous structure which can improve the light scattering coefficient and the thermal insulation performance of paper, and can be used for paper filler and coating pigment.
5. According to the carbonization reactor, the gas disperser with the micropores is connected with the carbonization reactor, carbon dioxide is introduced into the carbonization reactor through the micropore gas supply membrane for carbonization, and the carbonization and ventilation mode has the functions of stirring and centrifuging at the same time, so that the carbonization process is more efficient, the energy consumption is low, the stability of equipment is improved, and the generated nano calcium carbonate particles are more uniform.
6. The method for preparing the nano calcium carbonate by using the calcium oxide and the carbon dioxide as raw materials has simple reaction process conditions, can realize continuous operation, and is easy for industrial popularization.
7. The invention takes carbon dioxide as a raw material, effectively converts carbon resource into a life requirement product, realizes emission reduction benefit and economic benefit, and meets the relative requirements of carbon peak reaching and carbon neutralization.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of a carbonization reactor in the present invention.
In the figure: 1-mixed gas inlet; 2-mixed gas outlet; 3-inlet of mixed liquid; 4-CaCO 3 A suspension outlet; 5-microporous gas disperser; 6-a stirring device; 7-carbonization reactor.
FIG. 2 is a schematic top view of the microporous disperser of the present invention.
Fig. 3 is a front view of the air supply membrane of the present invention.
FIG. 4 is a SEM image of example 2 of the present invention. Wherein: the resolution of the left image is 1.00 mu m; the resolution of the right image is 500nm.
FIG. 5 is a SEM image of example 6 of the present invention. Wherein: the resolution of the left image is 1.00 mu m; the resolution of the right image is 400nm.
Figure 6 is an XRD pattern of example 2 of the present invention.
Figure 7 is an XRD pattern of example 6 of the present invention.
Detailed Description
An efficient preparation method of environment-friendly spherical-like nano calcium carbonate comprises the following steps:
the method comprises the following steps of digestion and aging:
adding purified water or distilled water with the mass being 11 to 41 times of that of CaO into CaO, heating to 50 to 90 ℃, hermetically stirring and digesting for 3 to 6 hours, and hermetically standing and aging for 20 to 48 hours to obtain refined Ca (OH) 2 A suspension; the refined Ca (OH) 2 Sieving the suspension through a 200 to 500-mesh sieve to remove Ca (OH) 2 After the solid impurities in the suspension are diluted with water, ca (OH) is determined according to GBT7476-87 2 To an accurate concentration of3 to 10wt% of Ca (OH) 2 (ii) a suspension.
The method comprises the following steps:
ca (OH) with the concentration of 3 to 10wt percent 2 Adding the suspension, 0.01 to 8wt% of an aragonite or calcite crystal form control agent (calculated by the dry mass of calcium hydroxide) and 1 to 99wt% of a template agent (calculated by the dry mass of calcium hydroxide) into a carbonization reactor, and adding CO 2 And N 2 The mixed gas enters the bottom of the carbonization reactor through a micropore gas disperser 5 in a micro gas flow mode to carry out carbonization reaction, and CO 2 And N 2 Of the mixed gas of (2) 2 The volume concentration of the gas is 25 to 50 percent; the carbonization reaction conditions are that the stirring speed is 300 to 1000 r/min, the carbonization temperature is 15 to 50 ℃, and CO is 2 The flow rate is 100 to 300mL/min, N 2 The flow rate was 300mL/min. Gas passing Ca (OH) 2 Suspension, part of CO 2 And Ca (OH) 2 Reacting to form calcium carbonate and residual CO 2 And N 2 The mixed gas of (2) is discharged from the top of the carbonization reactor; and when the pH of the reaction slurry is =6.5 to 7.0, stopping ventilation, and ending the carbonization reaction.
Wherein: the spherulite or calcite crystal form control agent refers to polyol or the composition of the polyol and other crystal form control agents.
The polyalcohol refers to one or more of ethylene glycol, glycerol and pentaerythritol.
The compounding of the polyhydric alcohol and other crystal form control agents refers to any one of compounding of the polyhydric alcohol and an inorganic substance containing ammonia molecules, ammonium ions and nitric acid, compounding of the polyhydric alcohol and an organic substance containing amino acid, protein and sucrose, and compounding of the polyhydric alcohol and a polymer containing polystyrene sulfonate, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polycarboxylic acid, carboxymethyl inulin, dendritic macromolecules and calixarene. Preferably: monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, diisopropanolamine, 2-amino-2-methyl-1, 3-propanediol, tris (hydroxymethyl) aminomethane, sodium tripolyphosphate, amino acid, protein, sucrose, zinc chloride, magnesium chloride and barium chloride.
The template agent is one or a mixture of more of silicon dioxide, zinc oxide, titanium dioxide, polystyrene and polymethyl methacrylate.
Thirdly, centrifugally filtering the carbonized reaction slurry, washing the reaction slurry for at least 3 times by using ethanol, ethyl acetate, purified water or distilled water, pouring out washing supernatant, drying the washing supernatant for 24 hours at 120 ℃, and then grinding the washing supernatant to obtain the spheroidal nano calcium carbonate product.
As shown in FIGS. 1 to 3, the carbonization reactor 7 comprises a cylindrical and bottomless shell I; the top of the shell I is respectively provided with a residual unreacted mixed gas outlet 2 and Ca (OH) 2 A mixed liquid inlet 3 for the suspension, the crystal form control agent and the template agent, and CaCO arranged at the lower part of the side surface 3 A suspension outlet 4; a stirring device 6 is arranged in the shell I along the vertical direction, and the bottom of the shell I is connected with the top of the micropore gas disperser 5.
The microporous gas disperser 5 comprises a funnel-shaped shell II; the lower part of the side surface of the shell II is provided with CO 2 And N 2 The mixed gas inlet 1 of (2), the mixed gas inlet 1 and CaCO in the carbonization reactor 7 3 The direction of the suspension outlet 4 is opposite; the top of the shell II is provided with an air supply film connected with the carbonization reactor 7, and the air supply film and the center shaft of the carbonization reactor 7 form an included angle alpha of 0 o ≤α＜90 o (ii) a The air supply membrane is made of stainless steel, glass or other inorganic materials, the cross section of the air supply membrane is T-shaped, a through hole is formed in the vertical part, and a plurality of micropores with the diameters of 0.1 to 10000 mu m are annularly and uniformly distributed on the surface of the horizontal part.
In fig. 2, the arrows are the gas flow direction, the gas diffuses from the center of the gas supply film to the periphery, and the gas flows out along the tangent line of the gas supply film and at a certain angle with the horizontal direction, so that the rotary micro gas flow is formed. When the included angle is 0 o In this case, the micropore channels are parallel to the central axis of the carbonization reactor 7.
Embodiment 1 a method for efficiently preparing environment-friendly spherical-like nano calcium carbonate, comprising the following steps:
the method comprises the following steps of digestion and aging:
weighing 12.91 g CaO, adding 412.75g purified water, heating to 90 deg.C, sealing, stirring, digesting for 4 h, sealing, standing, aging for 20 h to obtain refined Ca (OH) 2 Sieving the suspension with 200 mesh sieve to remove Ca (OH)) 2 Solid impurities in the suspension to give 3.8wt% Ca (OH) 2 And (3) suspension.
And (2) carbonizing:
3.8wt% Ca (OH) was weighed 2 100 g of suspension, adding Ca (OH) 2 The suspension, 0.019 g (0.5 wt%) of ethylene glycol and 0.019 g (0.5 wt%) of polystyrene were charged into a carbonization reactor, gas was supplied by a stainless steel membrane having a pore size of 5 μm, and CO was supplied 2 The flow rate is 150 mL/min, N 2 The flow rate is 300mL/min, and the two gases are mixed and then enter the bottom of the carbonization reactor. In the experimental process, the stirring speed is 800 r/min, and the carbonization temperature is 25 ℃. When the reaction slurry pH =7.0, the aeration was stopped and the carbonization reaction was ended.
The CaCO after carbonization 3 Filtering the slurry, washing with ethanol and purified water for 3 times, pouring off the supernatant, drying at 120 deg.C for 24 hr, and grinding to obtain 4.88 g calcium carbonate product.
The obtained calcium carbonate product is analyzed by a scanning electron microscope, the shape of the nano calcium carbonate is spherical, and the average grain diameter of the nano calcium carbonate is 50nm. The specific surface area (BET) of the nano calcium carbonate is 20 m 2 /g。
Embodiment 2 a method for efficiently preparing environment-friendly spherical-like nano calcium carbonate, comprising the following steps:
the method comprises the following steps of digestion and aging: weighing 6.02 g CaO, adding 101.84 g purified water, heating to 60 deg.C, sealing, stirring, digesting for 6 h, sealing, standing, aging for 24 h to obtain refined Ca (OH) 2 Suspending, sieving with 200 mesh sieve to remove Ca (OH) 2 Solid impurities in the suspension to obtain 7wt% Ca (OH) 2 And (3) suspension.
And (2) carbonizing:
weighing 7wt% Ca (OH) 2 104.19 g of suspension, adding Ca (OH) 2 The suspension, triethanolamine (0.1094 g, 1.5 wt.%), and polystyrene (0.0729 g, 1 wt.%) are fed into a carbonization reactor, and gas is supplied through a nickel membrane with a pore size of 0.2um, and CO is supplied through the nickel membrane 2 The flow rate is 100 mL/min, N 2 The flow rate is 300mL/min, and the two gases are mixed and then enter the bottom of the carbonization reactor. In the experimental process, the stirring speed is 1000 r/min, and the carbonization temperature is 15 ℃. When the reaction slurry pH =7.0, the aeration was stopped and the carbonization reaction was ended.
The CaCO after carbonization 3 Filtering the slurry, washing with ethanol and purified water for 3 times, pouring off the washing supernatant, drying at 120 deg.C for 24 hr, and grinding to obtain 9.37 g calcium carbonate product.
The obtained calcium carbonate product is analyzed by a scanning electron microscope, the shape of the nano calcium carbonate is spherical (as shown in figure 4), and the average particle size of the nano calcium carbonate is 69nm. The specific surface area (BET) of the nano calcium carbonate is 31 m 2 The crystalline form is calcite as analyzed by XRD (figure 6).
Embodiment 3 a method for efficiently preparing environment-friendly spherical-like nano calcium carbonate, comprising the following steps:
the method comprises the following steps of digestion and aging: weighing 6.02 g CaO, adding 245g purified water, heating to 50 deg.C, sealing, stirring, digesting for 3 hr, sealing, standing, aging for 48 hr to obtain refined Ca (OH) 2 Suspending, sieving with 200 mesh sieve to remove Ca (OH) 2 Solid impurities in the suspension to obtain 3wt% Ca (OH) 2 And (3) suspension.
And (2) carbonizing:
weighing 3wt% Ca (OH) 2 100 g of suspension, adding Ca (OH) 2 The suspension, diethanolamine 0.003 g (0.1 wt%) and polymethyl methacrylate 0.03 g (1 wt%) were charged into a carbonization reactor, and gas was supplied through a stainless steel membrane having a pore size of 25 μm, and CO was supplied 2 The flow rate is 300mL/min, N 2 The flow rate is 300mL/min, and the two gases are mixed and then enter the bottom of the carbonization reactor. In the experimental process, the stirring speed is 300 r/min, and the carbonization temperature is 50 ℃. When the reaction slurry pH =7.0, the aeration was stopped and the carbonization reaction was ended.
The CaCO after carbonization 3 Filtering the slurry, washing with ethanol and purified water for 3 times, pouring off the supernatant, drying at 120 deg.C for 24 hr, and grinding to obtain 3.86 g calcium carbonate product.
The obtained calcium carbonate product is analyzed by a scanning electron microscope, the shape of the nano calcium carbonate is spherical, and the average grain diameter of the nano calcium carbonate is 30nm. The specific surface area (BET) of the nano calcium carbonate is 25 m 2 /g。
Embodiment 4 a method for efficiently preparing environment-friendly spherical-like nano calcium carbonate, comprising the following steps:
the method comprises the following steps of digestion and aging:
weighing 10 g CaO, adding 115.71g purified water, heating to 800 deg.C, sealing, stirring, digesting for 4 h, sealing, standing, aging for 24 h to obtain refined Ca (OH) 2 Suspending, sieving with 200 mesh sieve to remove Ca (OH) 2 Solid impurities in the suspension, to obtain 10wt% Ca (OH) 2 And (3) suspension.
And (2) carbonizing:
weighing 10wt% Ca (OH) 2 100 g of suspension, adding Ca (OH) 2 The suspension, 0.5 g (5 wt%) of tris (hydroxymethyl) aminomethane and 0.5 g (5 wt%) of polystyrene were charged into a carbonization reactor, and gas was supplied through a stainless steel membrane having a pore diameter of 30 μm, and CO was supplied 2 The flow rate is 150 mL/min, N 2 The flow rate is 300mL/min, and the two gases are mixed and then enter the bottom of the carbonization reactor. In the experimental process, the stirring speed is 800 r/min, and the carbonization temperature is 20 ℃. When the reaction slurry pH =7.0, the aeration was stopped and the carbonization reaction was ended.
The CaCO after carbonization 3 Filtering the slurry, washing with ethanol and purified water for 3 times, pouring off the washing supernatant, drying at 120 deg.C for 24 hr, and grinding to obtain 12.85g calcium carbonate product.
The obtained calcium carbonate product is analyzed by a scanning electron microscope, the shape of the nano calcium carbonate is spherical, and the average grain diameter of the nano calcium carbonate is 40nm. The specific surface area (BET) of the nano calcium carbonate is 22 m 2 /g。
Embodiment 5 a method for efficiently preparing environment-friendly spherical-like nano calcium carbonate, comprising the following steps:
the method comprises the following steps of digestion and aging: weighing 8.41 g CaO, adding 142.33g purified water, heating to 80 deg.C, sealing, stirring, digesting for 4 h, sealing, standing, aging for 24 h to obtain refined Ca (OH) 2 Suspending, sieving with 200 mesh sieve to remove Ca (OH) 2 Solid impurities in the suspension to obtain 7wt% Ca (OH) 2 And (3) suspension.
The method comprises the following steps:
weighing 7wt% Ca (OH) 2 100 g of suspension, adding Ca (OH) 2 The suspension, 0.035 g (0.5 wt%) of 2-amino-2-methyl-1, 3-propanediol and 0.07g (1 wt%) of polystyrene were charged into a carbonization reactor, and the pores were utilizedStainless steel membrane with diameter of 5um for supplying CO 2 The flow rate is 150 mL/min, N 2 The flow rate is 300mL/min, and the two gases are mixed and then enter the bottom of the carbonization reactor. In the experimental process, the stirring speed is 800 r/min, and the carbonization temperature is 25 ℃. When the reaction slurry pH =7.0, the aeration was stopped and the carbonization reaction was ended.
Thirdly, the carbonized CaCO 3 Filtering the slurry, washing with ethanol and purified water for 3 times, pouring off the supernatant, drying at 120 deg.C for 24 hr, and grinding to obtain 9g calcium carbonate product.
The obtained calcium carbonate product is analyzed by a scanning electron microscope, the shape of the nano calcium carbonate is spherical, and the average grain diameter of the nano calcium carbonate is 35nm. The specific surface area (BET) of the nano calcium carbonate is 27m 2 /g。
Embodiment 6 a method for efficiently preparing environment-friendly spherical-like nano calcium carbonate, comprising the following steps:
the method comprises the following steps of digestion and aging:
weighing 8.41 g CaO, adding 142.33g purified water, heating to 80 deg.C, sealing, stirring, digesting for 4 h, sealing, standing, aging for 24 h to obtain refined Ca (OH) 2 Suspending, sieving with 200 mesh sieve to remove Ca (OH) 2 Solid impurities in the suspension to obtain 7wt% Ca (OH) 2 And (3) suspension.
The method comprises the following steps:
weighing the prepared 7wt% Ca (OH) 2 100 g of suspension, adding Ca (OH) 2 The suspension, 0.035 g (0.5 wt%) of 2-amino-2-methyl-1, 3-propanediol and 0.07g (1 wt%) of polystyrene were charged into a carbonization reactor, and gas was supplied through a stainless steel membrane having a pore diameter of 5 μm, and CO was supplied 2 The flow rate is 150 mL/min, N 2 The flow rate is 300mL/min, and the two gases are mixed and then enter the bottom of the carbonization reactor. In the experimental process, the stirring speed is 800 r/min, and the carbonization temperature is 25 ℃. When the reaction slurry pH =7.0, the aeration was stopped and the carbonization reaction was ended.
Thirdly, the carbonized CaCO containing the functional filler 3 Filtering the slurry, washing with ethanol and purified water for 3 times, pouring off the supernatant, drying at 120 deg.C for 24 hr, and grinding to obtain 9.20 g calcium carbonate product.
Scanning the obtained calcium carbonate productThe morphology of the product was spherical as determined by electron microscopy (see FIG. 5), the product had an average particle size of 84 nm and a specific surface area (BET) of 23 m 2 The crystalline form is calcite as analyzed by XRD (figure 7).
Claims (10)
1. An efficient preparation method of environment-friendly spherical-like nano calcium carbonate comprises the following steps:
the method comprises the following steps of digestion and aging:
adding purified water or distilled water with the mass being 11 to 41 times of that of CaO into CaO, heating to 50 to 90 ℃, hermetically stirring and digesting for 3 to 6 hours, and hermetically standing and aging for 20 to 48 hours to obtain refined Ca (OH) 2 A suspension; the refined Ca (OH) 2 Sieving the suspension through a 200 to 500-mesh sieve to remove Ca (OH) 2 Solid impurities in the suspension to obtain Ca (OH) with the concentration of 3 to 10wt percent 2 A suspension;
and (2) carbonizing:
the Ca (OH) with the concentration of 3 to 10wt percent 2 Adding the suspension, the spherulite or calcite crystal form control agent and the template agent into a carbonization reactor, and adding CO 2 And N 2 The mixed gas enters the bottom of a carbonization reactor (7) through a microporous gas disperser (5) in a micro-gas flow mode to carry out carbonization reaction, and the gas passes through Ca (OH) 2 Suspension, part of CO 2 And Ca (OH) 2 Reacting to form calcium carbonate, residual CO 2 And N 2 The mixed gas of (2) is discharged from the top of the carbonization reactor; stopping ventilation when the pH of the reaction slurry is =6.5 to 7.0, and finishing the carbonization reaction;
thirdly, centrifugally filtering and washing the carbonized reaction slurry, drying for 24 hours at 120 ℃, and then grinding to obtain the spheroidal nano calcium carbonate product.
2. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 1, which is characterized in that: the aragonite or calcite crystal form control agent in the second step is a compound of polyol or polyol and other crystal form control agents, and the addition amount of the aragonite or calcite crystal form control agent is 0.01 to 8wt% of the dry basis mass of calcium hydroxide.
3. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 2, which is characterized in that: the polyalcohol refers to one or more of ethylene glycol, glycerol and pentaerythritol.
4. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 2, which is characterized in that: the compounding of the polyhydric alcohol and other crystal form control agents refers to any one of compounding of the polyhydric alcohol and an inorganic substance containing ammonia molecules, ammonium ions and nitric acid, compounding of the polyhydric alcohol and an organic substance containing amino acid, protein and sucrose, and compounding of the polyhydric alcohol and a polymer containing polystyrene sulfonate, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polycarboxylic acid, carboxymethyl inulin, dendritic macromolecules and calixarene.
5. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 4, characterized by comprising the following steps: the compounding of the polyhydric alcohol and other crystal form control agents in the step II is one or a mixture of more of monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, diisopropanolamine, 2-amino-2-methyl-1, 3-propanediol, tris (hydroxymethyl) aminomethane, sodium tripolyphosphate, amino acid, protein, sucrose, zinc chloride, magnesium chloride and barium chloride.
6. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 1, which is characterized in that: the template agent in the second step is one or a mixture of silicon dioxide, zinc oxide, titanium dioxide, polystyrene and polymethyl methacrylate, and the addition amount of the template agent is 1 to 99wt% of the dry basis weight of calcium hydroxide.
7. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 1, characterized by comprising the following steps: the step of adding CO 2 And N 2 CO in the mixed gas 2 The volume concentration of the gas is 25 to 50 percent.
8. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 1, which is characterized in that: the carbonization reaction condition in the second step is that the stirring rotating speed is 300 to 1000 r/min, the carbonization temperature is 15 to 50 ℃, and CO is used 2 The flow rate is 100 to 300mL/min, N 2 The flow rate was 300mL/min.
9. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 1, which is characterized in that: the carbonization reactor (7) comprises a cylindrical shell I without a bottom; the top of the shell I is respectively provided with a residual unreacted mixed gas outlet (2) and Ca (OH) 2 A mixed liquid inlet (3) of the suspension, the crystal form control agent and the template agent, and CaCO is arranged at the lower part of the side surface 3 A suspension outlet (4); and a stirring device (6) is arranged in the shell I along the vertical direction, and the bottom of the shell I is connected with the top of the micropore gas disperser (5).
10. The efficient preparation method of the environment-friendly spherical-like nano calcium carbonate as claimed in claim 1, which is characterized in that: the microporous gas disperser (5) comprises a funnel-shaped shell II; the lower part of the side surface of the shell II is provided with CO 2 And N 2 The mixed gas inlet (1) of (1) and CaCO in the carbonization reactor (7) 3 The direction of the suspension outlet (4) is opposite; the top of the shell II is provided with a gas supply film connected with the carbonization reactor, and the gas supply film and the center shaft of the carbonization reactor (7) form an included angle alpha of 0 o ≤α＜90 o (ii) a The section of the air supply film is T-shaped, wherein a through hole is formed in the vertical part, and a plurality of micropores with the diameter of 0.1 to 10000 mu m are annularly and uniformly distributed on the surface of the horizontal part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210998626.0A CN115321572B (en) | 2022-08-19 | 2022-08-19 | Efficient preparation method of environment-friendly spherical nano calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210998626.0A CN115321572B (en) | 2022-08-19 | 2022-08-19 | Efficient preparation method of environment-friendly spherical nano calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115321572A true CN115321572A (en) | 2022-11-11 |
| CN115321572B CN115321572B (en) | 2024-02-06 |
Family
ID=83926425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210998626.0A Active CN115321572B (en) | 2022-08-19 | 2022-08-19 | Efficient preparation method of environment-friendly spherical nano calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115321572B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375070A (en) * | 2023-03-06 | 2023-07-04 | 湖北工业大学 | Liquid phase mineralization grinding synergistic SiO 2 Method for preparing high-activity calcium carbonate by PAMAM |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04292414A (en) * | 1991-03-20 | 1992-10-16 | Maruo Calcium Co Ltd | Method for growing particle of vaterite-type calcium carbonate and controlling its shape |
| JP2007070164A (en) * | 2005-09-07 | 2007-03-22 | Nittetsu Mining Co Ltd | Silica-calcium carbonate composite particle, its producing method and pigment, filler or paper containing it |
| CN202369409U (en) * | 2011-07-26 | 2012-08-08 | 中国中材国际工程股份有限公司 | Reactor for synthesizing nano calcium carbonate micro powder |
| CN102701255A (en) * | 2012-06-21 | 2012-10-03 | 石家庄市红日钙业有限公司 | Method for high-concentration carbonization production of spherical nano calcium carbonate |
| CN105502462A (en) * | 2015-12-22 | 2016-04-20 | 东莞理工学院 | Device and method for preparing nanometer calcium carbonate through micropore pipe |
| CN107337225A (en) * | 2017-04-20 | 2017-11-10 | 广西民族大学 | A kind of preparation method of nanometer of elliposoidal calcium carbonate granule |
| CN109809457A (en) * | 2019-03-21 | 2019-05-28 | 广西碳酸钙产业化工程院有限公司 | Regular spherical calcium carbonate and its preparation process |
| CN111268712A (en) * | 2018-12-04 | 2020-06-12 | 天津大学 | Method for preparing nano calcium carbonate by using crystal form control agent for regulation and control |
| CN113307295A (en) * | 2021-06-25 | 2021-08-27 | 安徽前江超细粉末科技有限公司 | Method for producing nano calcium carbonate by using kiln gas with low carbon dioxide concentration |
-
2022
- 2022-08-19 CN CN202210998626.0A patent/CN115321572B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04292414A (en) * | 1991-03-20 | 1992-10-16 | Maruo Calcium Co Ltd | Method for growing particle of vaterite-type calcium carbonate and controlling its shape |
| JP2007070164A (en) * | 2005-09-07 | 2007-03-22 | Nittetsu Mining Co Ltd | Silica-calcium carbonate composite particle, its producing method and pigment, filler or paper containing it |
| CN202369409U (en) * | 2011-07-26 | 2012-08-08 | 中国中材国际工程股份有限公司 | Reactor for synthesizing nano calcium carbonate micro powder |
| CN102701255A (en) * | 2012-06-21 | 2012-10-03 | 石家庄市红日钙业有限公司 | Method for high-concentration carbonization production of spherical nano calcium carbonate |
| CN105502462A (en) * | 2015-12-22 | 2016-04-20 | 东莞理工学院 | Device and method for preparing nanometer calcium carbonate through micropore pipe |
| CN107337225A (en) * | 2017-04-20 | 2017-11-10 | 广西民族大学 | A kind of preparation method of nanometer of elliposoidal calcium carbonate granule |
| CN111268712A (en) * | 2018-12-04 | 2020-06-12 | 天津大学 | Method for preparing nano calcium carbonate by using crystal form control agent for regulation and control |
| CN109809457A (en) * | 2019-03-21 | 2019-05-28 | 广西碳酸钙产业化工程院有限公司 | Regular spherical calcium carbonate and its preparation process |
| CN113307295A (en) * | 2021-06-25 | 2021-08-27 | 安徽前江超细粉末科技有限公司 | Method for producing nano calcium carbonate by using kiln gas with low carbon dioxide concentration |
Non-Patent Citations (1)
| Title |
|---|
| 陈银霞;赵改青;王晓波;: "聚合物控制碳酸钙晶型、形貌的研究", 化学进展, vol. 21, no. 7, pages 1619 - 1625 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375070A (en) * | 2023-03-06 | 2023-07-04 | 湖北工业大学 | Liquid phase mineralization grinding synergistic SiO 2 Method for preparing high-activity calcium carbonate by PAMAM |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115321572B (en) | 2024-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3392099B2 (en) | Method for producing silica-calcium carbonate composite particles, and composition or structure containing the particles | |
| CN109809457B (en) | Regular spherical calcium carbonate and preparation process thereof | |
| CN101475759A (en) | Practical method for preparing high thixotropy surface treating nano calcium carbonate | |
| CN101318684A (en) | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation | |
| CN106517285A (en) | Method for preparing bar-shaped nanometer calcium carbonate | |
| CN101993104A (en) | Novel method for producing superfine calcium carbonate by using carbide slag as raw material | |
| CN111333096A (en) | Production process of ultrafine calcium carbonate powder | |
| CN109809458B (en) | Rugby-shaped calcium carbonate and preparation process thereof | |
| CN1232443C (en) | Ultrafine modified aluminium hydroxide and its preparation | |
| CN101318685A (en) | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone activation of activation tank | |
| CN1429772A (en) | Method for preparing calcium carbonate with actual forms | |
| CN109867986A (en) | A kind of macromolecule modified nanometer calcium carbonate new product family | |
| CN115321572A (en) | Efficient preparation method of environment-friendly spherical-like nano calcium carbonate | |
| CN113666380B (en) | Preparation method of spherical silicon dioxide | |
| JP3910503B2 (en) | Method for producing basic magnesium carbonate | |
| CN114291835B (en) | Preparation method of large-small cubic dispersion precipitated calcium carbonate | |
| CN112299465A (en) | Synthetic method of modified porous calcium carbonate | |
| CN1200049C (en) | Method for preparing high-white ness nano calcium carbide | |
| CN108190935B (en) | Preparation method of strip-shaped and sheet-shaped calcium carbonate ultrafine particles | |
| CN114921851A (en) | Calcium carbonate whisker prepared by carbide slag carbonization and preparation method thereof | |
| CN102285676B (en) | Method for preparing nano calcium carbonate from epoxypropane saponification waste water by chlorhydrin method | |
| CN110128851B (en) | Preparation method of hydrophobic nano calcium carbonate | |
| CN110407212B (en) | High-dispersity nano carbonate gel as well as preparation method and application thereof | |
| CN115321845B (en) | Preparation method of large-particle calcium hydroxide with regular shape | |
| JP4065703B2 (en) | Method for producing spherical porous calcium carbonate having a plate-like structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240401 Address after: 256200 Sun Zhen Shi Jia Cun Nan, Zouping City, Binzhou City, Shandong Province Patentee after: Zouping Shengchang calcium Industry Co.,Ltd. Country or region after: China Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Country or region before: China |
|
| TR01 | Transfer of patent right |