CN117303426A - Preparation method of calcium carbonate with high specific surface area - Google Patents
Preparation method of calcium carbonate with high specific surface area Download PDFInfo
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- CN117303426A CN117303426A CN202311350692.8A CN202311350692A CN117303426A CN 117303426 A CN117303426 A CN 117303426A CN 202311350692 A CN202311350692 A CN 202311350692A CN 117303426 A CN117303426 A CN 117303426A
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 267
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 54
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 53
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 53
- 239000000725 suspension Substances 0.000 claims abstract description 51
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 22
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 22
- 239000004571 lime Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000008103 glucose Substances 0.000 claims abstract description 13
- 235000019738 Limestone Nutrition 0.000 claims abstract description 11
- 230000005587 bubbling Effects 0.000 claims abstract description 11
- 239000006028 limestone Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 239000002455 scale inhibitor Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 26
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 4
- 102100025991 Betaine-homocysteine S-methyltransferase 1 Human genes 0.000 claims description 3
- 101000933413 Homo sapiens Betaine-homocysteine S-methyltransferase 1 Proteins 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- STNSYZSNIYTNMI-UHFFFAOYSA-N azane;[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound N.OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O STNSYZSNIYTNMI-UHFFFAOYSA-N 0.000 claims description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 29
- 230000001105 regulatory effect Effects 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 5
- 239000004021 humic acid Substances 0.000 description 5
- -1 organic acid salt Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- JQGRPPCZXQJUAF-UHFFFAOYSA-N decanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCCCCCC(O)=O JQGRPPCZXQJUAF-UHFFFAOYSA-N 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of calcium carbonate with high specific surface area, which comprises the following steps: (1) Calcining limestone to obtain lime, placing the lime in slaked water added with glucose to obtain calcium hydroxide suspension, and filtering to remove waste residues for later use; (2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, introducing carbon dioxide mixed gas, adding a mixed solution containing phosphate and a scale inhibitor when the gel point is reached, and continuing to react until the conductivity of the whole system is 0.6us/cm, thereby obtaining nano calcium carbonate slurry; (3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) to obtain a nano calcium carbonate product with high specific surface area. The nano calcium carbonate prepared by the method has the advantages of high specific surface area, good dispersibility and the like, is simple in preparation process, is easy to realize industrial production, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of calcium carbonate preparation, in particular to a preparation method of calcium carbonate with high specific surface area.
Background
Calcium carbonate is the most abundant inorganic biomaterial in nature, and exists in different structures: calcite, vanadate and aragonite. Most sources of calcium carbonate consist mainly of calcite, which is the most stable phase in other polycrystalline phases, according to thermodynamics. The calcium carbonate has the advantages of simple synthesis, no toxicity, good biocompatibility, large surface area, low cost and the like, and is widely applied to the medical fields of buildings, bone cements, dental implants, stents and the like. In addition, calcium carbonate is strongly demanded as an abrasive, an absorbent and a filler in paper, plastics, rubber, paint and adhesives to improve the rheological properties and mechanical properties of the products.
Fillers in the fields of rubber, ink, silicone sealant and the like generally include carbon black, white carbon black, calcium carbonate, magnesium carbonate, dolomite powder and the like. Calcium carbonate has a lower price and higher filling rate than other fillers (e.g., white carbon black). Meanwhile, the nano calcium carbonate with high specific surface area can also improve the properties of rubber, such as hardness, tensile strength, wear resistance and the like.
In order to obtain nano calcium carbonate products with higher specific surface area, related industry professionals have made much research work on the preparation process and method thereof.
Du Nianjun and Sun Yongfeng to synthesize the nano calcium carbonate with high specific surface area. Analyzing nano calcium carbonate by using a BET specific surface area tester and a TEM transmission electron microscope, wherein the primary particle diameter is 10-20 nm, and the specific surface area is 100-120 m 2 And/g. Adding chelating agent before carbonization, adding polyol during carbonization, adding a compound agent of organic acid salt and inorganic acid ester when the conductivity is rapidly reduced, carrying out surface modification, drying and crushing to obtain the high-specific-surface nano calcium carbonate.
Liu Haidi, zhao Rongfang and Chen Yunfa are prepared by adding humic acid into calcium hydroxide suspension for carbonization, and calcium carbonate with high specific surface area is successfully synthesized. By adopting BET, XRD and SEM, the specific surface area, pore distribution and particle morphology analysis in the reaction process of the calcium carbonate are adopted, and the humic acid is found to change the microcrystalline morphology of the calcium carbonate while changing the specific surface area of the calcium carbonate product, and the morphology of the calcium carbonate particles is changed from a spheroid shape to a rod shape and then a cuboid shape along with the increase of the dosage of the humic acid; with the increase of the amount of humic acid, the specific surface area of the obtained calcium carbonate is obviously increased, and the average pore diameter is reduced with the increase of the amount of humic acid.
Chinese patent CN111606344B discloses a method for preparing nano calcium carbonate with high specific surface area, comprising the following steps: 1) Adding urea into calcium hydroxide suspension, stirring and mixing, regulating the pH value with ammonia water to obtain slurry A, heating the slurry A to 35-40 ℃ and keeping constant temperature, introducing mixed gas of carbon dioxide and nitrogen, stopping introducing the mixed gas after the pH value of the slurry A is 6.5-7, and continuing stirring for 1-2 hours to obtain slurry B; 2) Heating the slurry B to 80-90 ℃ under stirring, keeping the temperature, adding a composite modifier, keeping the temperature for 2-5 hours to obtain nano calcium carbonate suspension, and finally filtering and freeze-drying to obtain nano calcium carbonate. The method has complex process flow, difficult industrialization and poor economic benefit.
Chinese patent CN112811456a discloses a nano calcium carbonate with high specific surface area and its preparation method, which comprises the following steps in sequence: (1) Introducing calcium hydroxide slurry with the temperature of 20-25 ℃ into a carbonization reactor, continuously adding a nucleating agent, then introducing high-pressure pure carbon dioxide gas, and stirring at a high speed to generate calcium carbonate crystal nucleus; (2) The temperature of the carbonization reactor is controlled below 35 ℃, calcium hydroxide slurry with the temperature of 10-15 ℃ is fed into the carbonization reactor, a crystal nucleus growth control agent is continuously added, pure carbon dioxide gas is introduced, and the mixture is stirred at a low speed, so that the nano calcium carbonate slurry with high specific surface area is prepared. The high-pressure pure carbon dioxide used by the method has high cost, high industrial cost and low economic benefit, can generate a large amount of tail gas, and does not accord with the environment-friendly concept of green pollution-free.
Chinese patent CN104059390B discloses a modified calcium carbonate with a high specific surface area, which is characterized in that it is prepared from the following raw materials in parts by weight: 90-95 parts of calcium carbonate, 4-6 parts of methyl methacrylate, 5-7 parts of melamine resin, 3-4 parts of propylene glycol sebacate polyester, 2-3 parts of coconut shell activated carbon, 2-3 parts of fly ash, 1-1.5 parts of ammonium bicarbonate, 2-3 parts of turpentine, 801-2 parts of polysorbate and 2.5-3.5 parts of modified titanium dioxide, and finally obtaining the modified calcium carbonate with high surface area. The modifier used in the method has the advantages of numerous components, high cost, complex process and difficult popularization.
Chinese patent CN109453733a discloses a high specific surface area modified calcium carbonate filter material, a preparation method thereof and a composite material, the preparation method of the high specific surface area modified calcium carbonate filter material comprises: (1) Placing a calcium carbonate filter material into a low-temperature plasma generator; (2) introducing an action gas; (3) And starting the low-temperature plasma generator, adjusting discharge voltage, and performing plasma treatment. Finally, the prepared calcium carbonate has small powder size and large specific surface area. The plasma generator used in the method has high industrial cost and low economic benefit.
Chinese patent CN115872432a discloses a method for preparing spherical calcium carbonate and increasing specific surface area by regulating and modifying. The method comprises the following steps: (1) sodium carbonate and calcium chloride are used as raw materials; (2) CMC is crystal form regulator and modifier, and adopts ultrasonic assistance to prepare spherical calcium carbonate finally. The method has high cost in industry by adopting ultrasonic waves, and is not suitable for popularization.
In summary, the existing preparation process of the nano calcium carbonate with high specific surface area has the problems that the calcium carbonate is easy to agglomerate and the production cost is high.
Disclosure of Invention
Aiming at the problems, the invention provides the preparation method of the high specific surface area calcium carbonate, and the prepared nano calcium carbonate has the advantages of high specific surface area, good dispersibility and the like, is simple in preparation process, is easy to realize industrial production, and has good application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of calcium carbonate with high specific surface area comprises the following steps:
(1) Calcining limestone to obtain lime, placing the lime in slaked water added with glucose to obtain calcium hydroxide suspension, and filtering to remove waste residues for later use;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, introducing carbon dioxide mixed gas, adding a mixed solution containing phosphate and a scale inhibitor when the gel point is reached, and continuing to react until the conductivity of the whole system is 0.6us/cm, thereby obtaining nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) to obtain a nano calcium carbonate product with high specific surface area.
Preferably, in the step (1), the addition amount of glucose is 0.10-0.30% of the dry content of calcium hydroxide.
Preferably, in the step (1), the calcination temperature is 1300-1600 ℃ and the time is 150-300 min.
Preferably, in the step (1), a 140-170 mesh screen is adopted for filtration.
Preferably, in the step (2), the concentration of carbon dioxide is 25-35%, and the flow rate is 1-4 m 3 /h。
Preferably, in the step (2), the phosphate is one or more of sodium dihydrogen phosphate, trisodium phosphate and disodium hydrogen phosphate, and the addition amount is 0.20-0.40% of the dry basis content of the calcium carbonate.
Preferably, in the step (2), the scale inhibitor is organic phosphoric acid, and the addition amount is 0.30-0.60% of the dry content of calcium carbonate.
Preferably, the organic phosphonic acid is one or more of ATMP, HEDP, EDTMPS, DTPMPA, PBTCA, BHMT.
Preferably, in the step (2), the temperature of the suspension is adjusted to 18-23 ℃ before introducing the carbon dioxide mixed gas.
Preferably, in the step (3), the drying temperature is 90-150 ℃ and the time is 10-22 h.
The preparation method of the invention has the following principle:
1. adding sugar into slaked water, and dissociating OH from calcium hydroxide solution - With Ca 2+ Dissociated Ca 2+ Forming a complex with the added saccharide, inhibiting the crystal growth of calcium hydroxide, reducing the whole particle size, and dissolving small-particle calcium hydroxide quickly during carbonization to obtain carbonic acidThe calcium intermediate is more, which is favorable for forming high-specific-surface nano calcium carbonate.
2. On the premise of preparing the small-particle calcium hydroxide, a large amount of nano calcium carbonate intermediates are formed in the early stage of carbonization, and the growth of the intermediates is inhibited to form the nano calcium carbonate with high specific surface. PO in phosphate 4 3- Providing coordination electrons with CaCO with methylenephosphonic acid groups or O=P-O-structural units in the scale inhibitor structure 3 Ca in the surface lattice 2+ The ions are chelated to form coordination chemical bonds and are firmly adsorbed on the surface of the crystal, and the adsorption preferentially occurs at active growth points on the surface of the crystal, so that the growth of the crystal is inhibited, and the electrostatic force between the nano calcium carbonate crystals is reduced, thereby achieving the dispersing effect.
Compared with the prior art, the invention has the advantages that:
1. the nano calcium carbonate prepared by the invention has the advantages of high specific surface area, good dispersibility and the like, has simple preparation process, is easy to realize industrial production, and has good application prospect.
2. The phosphate and the scale inhibitor used in the invention have wide sources, low cost and safe use in industrial production.
Drawings
FIG. 1 is a scanning electron microscope photograph of a calcium carbonate product prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of a calcium carbonate product prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope photograph of a calcium carbonate product prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope photograph of a calcium carbonate product prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope photograph of the calcium carbonate product prepared in comparative example 1 of the present invention;
FIG. 6 is a scanning electron microscope photograph of a calcium carbonate product prepared in comparative example 2 of the present invention;
FIG. 7 is a scanning electron microscope photograph of a calcium carbonate product prepared in comparative example 3 of the present invention;
FIG. 8 is a scanning electron microscope photograph of a calcium carbonate product prepared in comparative example 4 of the present invention.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments.
Example 1
The preparation method of the nano calcium carbonate with high specific surface area comprises the following steps:
(1) Placing limestone at 1300 ℃ for calcination for 300min to obtain lime, placing the lime in slaking water added with 0.10% glucose of calcium hydroxide dry basis content to obtain calcium hydroxide suspension, removing waste residues of the calcium hydroxide suspension through a 140-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 5%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 18 ℃, then introducing carbon dioxide mixed gas with the concentration of 25% and the flow rate of 2%, adding a mixed solution containing trisodium phosphate with the dry content of 0.20% of calcium carbonate, ATMP with the dry content of 0.30% of calcium carbonate and HEDP compound when the gel point is reached, continuously reacting until the conductivity of the whole system is 0.6us/cm, immediately stopping introducing gas, and stopping the reaction to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 90 ℃ for 22 hours to obtain the nano calcium carbonate product with high specific surface area.
Example 2
The preparation method of the nano calcium carbonate with high specific surface area comprises the following steps:
(1) Placing limestone at 1400 ℃ for calcination for 250min to obtain lime, placing the lime in slaking water added with 0.30% glucose of calcium hydroxide dry basis content to obtain calcium hydroxide suspension, removing waste residues of the calcium hydroxide suspension through a 170-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 6%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 20 ℃, then introducing carbon dioxide mixed gas with the concentration of 28% and the flow of 2.5%, adding a mixed solution containing trisodium phosphate with the dry basis content of 0.30% of calcium carbonate, a disodium hydrogen phosphate compound and a EDTMPS, DTPMPA, PBTCA compound with the dry basis content of 0.45% of calcium carbonate when the gel point, continuously reacting until the conductivity of the whole system is 0.6us/cm, immediately stopping introducing gas, and stopping the reaction to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 100 ℃ for 20 hours to obtain the nano calcium carbonate product with high specific surface area.
Example 3
The preparation method of the nano calcium carbonate with high specific surface area comprises the following steps:
(1) Placing limestone at 1500 ℃ for calcination for 200min to obtain lime, placing the lime in slaking water added with 0.20% glucose of calcium hydroxide dry basis content to obtain calcium hydroxide suspension, removing waste residues of the calcium hydroxide suspension through a 150-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 8%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 23 ℃, then introducing carbon dioxide mixed gas with the concentration of 35% and the flow of 1%, adding a mixed solution containing sodium dihydrogen phosphate with the dry content of 0.40% of calcium carbonate and ATMP with the dry content of 0.60% of calcium carbonate when the gel point is reached, continuously reacting until the conductivity of the whole system is 0.6us/cm, immediately stopping introducing gas, and stopping reacting to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 150 ℃ for 10 hours to obtain the nano calcium carbonate product with high specific surface area.
Example 4
The preparation method of the nano calcium carbonate with high specific surface area comprises the following steps:
(1) Placing limestone at 1600 ℃ for calcination for 150min to obtain lime, placing the lime in slaking water added with 0.15% glucose of calcium hydroxide dry basis content to obtain calcium hydroxide suspension, removing waste residues of the calcium hydroxide suspension through a 140-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 7%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 19.5 ℃, then introducing carbon dioxide mixed gas with the concentration of 30% and the flow rate of 3%, adding a mixed solution containing sodium dihydrogen phosphate and disodium hydrogen phosphate compound with the dry basis content of 0.25% and ATMP and BHMT compound with the dry basis content of 0.375% into the gel point, continuously reacting until the conductivity of the whole system is 0.6us/cm, immediately stopping introducing gas, and stopping the reaction to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 120 ℃ for 12 hours to obtain the nano calcium carbonate product with high specific surface area.
Comparative example 1
The preparation method of the nano calcium carbonate comprises the following steps:
(1) Placing limestone at 1500 ℃ for calcination for 200min to obtain lime, placing the lime into slaked water to obtain calcium hydroxide suspension, removing waste residues of the calcium hydroxide suspension through a 150-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 8%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 23 ℃, then introducing carbon dioxide mixed gas with the concentration of 35% and the flow of 1%, adding a mixed solution containing sodium dihydrogen phosphate with the dry content of 0.40% of calcium carbonate and ATMP with the dry content of 0.60% of calcium carbonate when the gel point is reached, continuously reacting until the conductivity of the whole system is 0.6us/cm, immediately stopping introducing gas, and stopping reacting to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 150 ℃ for 10 hours to obtain the nano calcium carbonate product with high specific surface area.
Comparative example 2
(1) Placing limestone at 1500 ℃ for calcination for 200min to obtain lime, placing the lime in slaking water added with 0.20% glucose of calcium hydroxide dry basis content to obtain calcium hydroxide suspension, removing waste residues of the calcium hydroxide suspension through a 150-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 8%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 23 ℃, then introducing carbon dioxide mixed gas with the concentration of 35% and the flow of 1%, adding sodium dihydrogen phosphate solution with the dry content of 0.40% of calcium carbonate when the gel point is reached, continuously reacting until the conductivity of the whole system is 0.6us/cm, immediately stopping introducing gas, and stopping reacting to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 150 ℃ for 10 hours to obtain the nano calcium carbonate product with high specific surface area.
Comparative example 3
(1) Placing limestone at 1500 ℃ for calcination for 200min to obtain lime, placing the lime in slaking water added with 0.20% glucose of calcium hydroxide dry basis content to obtain calcium hydroxide suspension, removing waste residues of the calcium hydroxide suspension through a 140-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 8%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 23 ℃, then introducing carbon dioxide mixed gas with the concentration of 35% and the flow of 1%, adding ATMP solution with the dry content of 0.60% of calcium carbonate when the gel point is reached, continuously reacting until the conductivity of the whole system is 0.6us/cm, immediately stopping introducing gas, and stopping reacting to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 150 ℃ for 10 hours to obtain the nano calcium carbonate product with high specific surface area.
Comparative example 4
(1) Placing limestone at 1500 ℃ for calcination for 200min to obtain lime, placing the lime in slaked water to obtain calcium hydroxide suspension, removing waste residues from the calcium hydroxide suspension through a 150-mesh screen, and finally adding water to adjust the solid content of the calcium hydroxide suspension to 8%;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, regulating the temperature of the suspension to 23 ℃, then introducing carbon dioxide mixed gas with the concentration of 35% and the flow of 1%, immediately stopping introducing gas when the conductivity of the whole system is 0.6us/cm, and stopping the reaction to obtain nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) at 150 ℃ for 10 hours to obtain the nano calcium carbonate product with high specific surface area.
1. Performance test experiments
1. The high-specific-surface nano calcium carbonate prepared in examples 1 to 4 and the nano calcium carbonate powder prepared in comparative examples 1 to 4 were detected by a scanning electron microscope, and the detection results are shown in fig. 1 to 8.
As can be seen from FIGS. 1 to 4, the high-specific-surface nano calcium carbonate prepared in examples 1 to 4 of the invention has regular morphology, good dispersibility, small particles and an average particle diameter of about 35 nm;
as can be seen from FIGS. 5 to 8, the nano calcium carbonate prepared in comparative examples 1 to 4 has serious agglomeration, large particles and an average particle diameter of 76nm.
2. The specific surface area, whiteness and pH value of the nano calcium carbonate prepared in examples 1 to 4 and comparative examples 1 to 4 were measured according to GB/T19587-2017/ISO 9277:2010, GB/T23774-2009 and GB/T23769-2009 by using a specific surface area meter, a whiteness meter and a pH meter, and the measurement results are shown in Table 1:
table 1 test results
| Sample of | Specific surface area/m 2 /g | Whiteness/% | pH/% |
| Example 1 | 74.76 | 98.11 | 8.95 |
| Example 2 | 75.32 | 98.24 | 8.83 |
| Example 3 | 76.92 | 98.88 | 8.56 |
| Example 4 | 72.54 | 98.15 | 8.35 |
| Comparative example 1 | 20.46 | 88.48 | 8.24 |
| Comparative example 2 | 22.21 | 88.53 | 8.46 |
| Comparative example 3 | 20.78 | 89.12 | 8.21 |
| Comparative example 4 | 19.45 | 87.56 | 8.67 |
As is clear from Table 1, the nano calcium carbonate obtained in examples 1 to 4 of the present invention has a higher specific surface area and whiteness than those obtained in comparative examples 1 to 4, and the pH value does not change much.
Comparative example 1 on the basis of example 3, no glucose is added into the digestive water, and the specific surface area and whiteness of the prepared calcium carbonate product are obviously reduced.
Comparative example 4 on the basis of example 3, the specific surface area and whiteness of the prepared calcium carbonate product are greatly reduced without adding the mixed solution containing sodium dihydrogen phosphate and ATMP.
Comparative example 2 and comparative example 3 are added with sodium dihydrogen phosphate and ATMP respectively on the basis of comparative example 4, the specific surface area and whiteness of the prepared calcium carbonate product are improved to a certain extent, but a great difference exists between the calcium carbonate product and the calcium carbonate product in comparison with example 3.
2. Application experiment
The nano calcium carbonate of the above examples 1 to 4 and comparative examples 1 to 4 were prepared into rubber according to the raw materials and the mass fraction formula of the following table 2, and the performance test was performed, and the test results are shown in table 3.
TABLE 2 raw materials and mass parts of rubber
| Raw materials | Mass fraction,% |
| Styrene-butadiene rubber | 90 |
| Sulfur, sulfur and its preparation method | 1 |
| Stearic acid | 0.5 |
| Promoter CZ | 2 |
| Zinc oxide | 5 |
| Anti-aging agent 4010 | 0.4 |
| Calcium carbonate prepared in examples 1 to 4 or comparative examples 1 to 4 | 45 |
Table 3 results of application of examples and comparative examples table
From the above application comparison experiment results, the tensile strength, 100% set tensile strength, elongation at break and tear strength of examples 1 to 4 are all superior to those of comparative examples 1 to 4.
Comparative example 1 on the basis of example 3, no glucose was added to the digested water, and the indexes of the rubber made of the prepared calcium carbonate product were all significantly reduced.
Comparative example 4 on the basis of example 3, the indexes of rubber prepared from the prepared calcium carbonate product are greatly reduced without adding the mixed solution containing sodium dihydrogen phosphate and ATMP.
Comparative examples 2 and 3, to which sodium dihydrogen phosphate and ATMP were added on the basis of comparative example 4, respectively, improved the respective indexes of rubber made of the prepared calcium carbonate product to a certain extent, but there was still a great difference from example 3.
The nano calcium carbonate product prepared by the method has the advantages of high specific surface area, high whiteness, good dispersibility, excellent processing performance, and stronger reinforcing performance and tear resistance after rubber is filled.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The preparation method of the calcium carbonate with high specific surface area is characterized by comprising the following steps of:
(1) Calcining limestone to obtain lime, placing the lime in slaked water added with glucose to obtain calcium hydroxide suspension, and filtering to remove waste residues for later use;
(2) Transferring the calcium hydroxide suspension obtained in the step (1) into a bubbling reaction tower, introducing carbon dioxide mixed gas, adding a mixed solution containing phosphate and a scale inhibitor when the gel point is reached, and continuing to react until the conductivity of the whole system is 0.6us/cm, thereby obtaining nano calcium carbonate slurry;
(3) And (3) filtering, washing and drying the nano calcium carbonate slurry obtained in the step (2) to obtain a nano calcium carbonate product with high specific surface area.
2. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (1), the addition amount of glucose is 0.10-0.30% of the dry content of calcium hydroxide.
3. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (1), the calcination temperature is 1300-1600 ℃ and the time is 150-300 min.
4. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (1), a 140-170 mesh screen is adopted for filtering.
5. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (2), the concentration of carbon dioxide is 25-35%, and the flow is 1-4 m 3 /h。
6. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (2), the phosphate is one or more of sodium dihydrogen phosphate, trisodium phosphate and disodium hydrogen phosphate, and the addition amount is 0.20-0.40% of the dry content of the calcium carbonate.
7. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (2), the scale inhibitor is organic phosphoric acid, and the addition amount is 0.30-0.60% of the dry content of calcium carbonate.
8. The method for producing a high specific surface area calcium carbonate according to claim 7, wherein: the organic phosphoric acid is one or more of ATMP, HEDP, EDTMPS, DTPMPA, PBTCA, BHMT.
9. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (2), the temperature of the suspension is adjusted to 18-23 ℃ before introducing the carbon dioxide mixed gas.
10. The method for producing a high specific surface area calcium carbonate according to claim 1, characterized in that: in the step (3), the drying temperature is 90-150 ℃ and the time is 10-22 h.
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