CN114291835A - Preparation method of precipitated calcium carbonate with dispersed size and cube - Google Patents
Preparation method of precipitated calcium carbonate with dispersed size and cube Download PDFInfo
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- CN114291835A CN114291835A CN202111664054.4A CN202111664054A CN114291835A CN 114291835 A CN114291835 A CN 114291835A CN 202111664054 A CN202111664054 A CN 202111664054A CN 114291835 A CN114291835 A CN 114291835A
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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 266
- 229940088417 precipitated calcium carbonate Drugs 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 59
- 239000000725 suspension Substances 0.000 claims abstract description 58
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 52
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 52
- 239000004571 lime Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 23
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007873 sieving Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 14
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000008117 stearic acid Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 238000007127 saponification reaction Methods 0.000 claims abstract description 12
- 238000004381 surface treatment Methods 0.000 claims abstract description 12
- 235000021357 Behenic acid Nutrition 0.000 claims abstract description 10
- 229940116226 behenic acid Drugs 0.000 claims abstract description 10
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 8
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 8
- 159000000009 barium salts Chemical class 0.000 claims abstract description 7
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 7
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 7
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 23
- 239000001569 carbon dioxide Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 14
- 239000000920 calcium hydroxide Substances 0.000 claims description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 13
- 235000012255 calcium oxide Nutrition 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
- 230000005484 gravity Effects 0.000 claims description 9
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 1
- 239000000565 sealant Substances 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 11
- 239000000945 filler Substances 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000011085 pressure filtration Methods 0.000 abstract description 4
- 230000003014 reinforcing effect Effects 0.000 abstract description 4
- 238000009423 ventilation Methods 0.000 abstract 2
- 235000010216 calcium carbonate Nutrition 0.000 description 56
- 229910021532 Calcite Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 6
- 235000019738 Limestone Nutrition 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000004590 silicone sealant Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-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
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 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
- 238000003763 carbonization Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010797 grey water Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 pharmaceutical Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- 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
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of precipitated calcium carbonate with cubic dispersion and size, which comprises the steps of adding a crystal form control agent compounded by sodium hexametaphosphate or sodium pyrophosphate and soluble barium salt into lime slurry, stopping ventilation when the pH value is 8.0 through carbonation reaction, and obtaining a rod-shaped precipitated calcium carbonate suspension; adding a crystal form control agent into the lime slurry, and stopping ventilation when the pH value of a reaction system is 7.5 to obtain cubic precipitated calcium carbonate suspension; mixing the rod-shaped precipitated calcium carbonate suspension and the cubic precipitated calcium carbonate suspension in proportion, adding behenic acid, mixing uniformly, performing surface treatment by using stearic acid saponification liquid, performing pressure filtration, drying, and sieving to obtain the large and small cubic dispersed precipitated calcium carbonate powder. The precipitated calcium carbonate prepared by the method has the advantages of monodisperse morphology, smooth large particle diameter surface, low oil absorption value and the like; the nano calcium carbonate has better compatibility when being used as a filler of a sealant product, and greatly improves the flow property of the sealant while ensuring the reinforcing property of the small-vertical-diameter nano calcium carbonate.
Description
Technical Field
The invention relates to the technical field of inorganic materials, in particular to a preparation method of precipitated calcium carbonate with dispersed large and small cubes.
Background
Precipitated calcium carbonate is an inorganic material that is precipitated by a chemical reaction. Precipitated calcium carbonate is widely used as a filler or extender in various industries, such as paper, paint, plastic, polymer, food material, pharmaceutical, cosmetic, and the like. Precipitated calcium carbonate produced by precipitation has three amorphous forms, calcite, aragonite and vaterite, wherein calcite is the most thermodynamically stable crystal form at room temperature and pressure, aragonite is semi-stable, and vaterite is unstable and becomes stable calcite at the final stage of mineralization, and aragonite and vaterite are also converted to more stable calcite in the industry. Of these three crystalline forms, the only industrially scalable forms are aragonite, which belongs to the orthorhombic (acicular) crystal structure, and calcite, which is in the hexagonal-rhombohedral structure and can be any of 300 different forms. In precipitated calcium carbonate, rhombohedral (cubic), truncated prismatic, beveled (rhombohedral), spherical and chain-like agglomerates, etc. may occur.
Precipitated calcium carbonate can be produced in various ways, such as lime soda, double decomposition and carbonation, the latter being the only process in which precipitated calcium carbonate is considered as the main product, PCC being a by-product in both lime soda and double decomposition, in all processes limestone raw material being used directly or indirectly as a calcium source. Nowadays, heterogeneous (gas-solid-liquid) carbonation is the most common method for producing precipitated calcium carbonate by introducing CO2The mixed gas is bubbled into the lime slurry suspension to produce precipitated calcium carbonate.
At present, in the sealant, nano calcium carbonate (precipitated calcium carbonate with the particle size of less than 100 nm) is mainly used as a filling material, the filling of the nano calcium carbonate can greatly improve the viscosity and tensile strength of the sealant, but the excellent strength of the sealant is endowed, and meanwhile, the thixotropy and the fluidity are greatly damaged, one part of various industrial solutions is to add more expensive thixotropic agents and plasticizers, the other part is to add ground limestone (GCC) to adjust the rheological property, the ground limestone has low specific surface area and low oil absorption value, so the high shear viscosity is reduced, the extrusion time is reduced, and the high shear viscosity is in conflict with the effect of the nano calcium carbonate to a certain extent. In addition, the heavy calcium carbonate greatly reduces the storage time of the sealant due to the hydrophilic surface. Precipitated calcium carbonate is more advantageous than natural and ground calcium carbonate relative to ground calcium carbonate. For example, it has unique characteristics of submicron particle size, organized crystalline form, narrow particle size distribution range and high purity. If the heavy calcium carbonate is replaced by the large cubic calcite precipitated calcium carbonate with low specific surface area in the filler, whether the nano calcium carbonate can be reinforced and the thixotropy and the fluidity are improved simultaneously is a more meaningful research. Aragonite calcium carbonate is easy to be converted into calcite due to instability, but similar reports are mostly made on research on rock mineral or biomineralization, and the industrial method for converting aragonite into calcite and the application effect after conversion are rarely reported. The aragonite calcium carbonate, which is prepared industrially, is relatively stable, and the conversion of aragonite into calcite requires a special treatment method.
Patent CN104087029B discloses a preparation method of special active calcium carbonate for silicone sealant, which mainly comprises mixing nano calcium carbonate and rodlike calcium carbonate slurry through gradation, carrying out secondary surface treatment, and then carrying out filter pressing and drying to obtain mixed powder of nano cube and rodlike calcium carbonate. The powder obtained by the method is simple to mix and does not relate to crystal form transformation.
Patent CN110451545A discloses a preparation method of rod-like calcium carbonate for PE breathable films, limestone is calcined at 1100-1250 ℃ to become quicklime, the quicklime is digested to obtain Ca (OH)2, and the refined Ca (OH)2 is prepared into Ca (OH)2 suspension with the specific gravity of 1.030-1.050; conveying the Ca (OH)2 suspension into a carbonation reaction kettle, adding a tetrasodium pyrophosphate solution, starting stirring, introducing a mixed gas containing carbon dioxide, adding tween-20 when the pH value of a reaction system is reduced to 10.5, continuing the reaction until the pH value of the reaction system is reduced to 6.5-7.0, and finishing the carbonation reaction to obtain calcium carbonate slurry; aging the calcium carbonate slurry at 60-80 deg.C for 5-8 hr, performing surface treatment with sodium stearate, drying, pulverizing, grading, and packaging to obtain rod-shaped calcium carbonate. The rod-shaped calcium carbonate prepared by the method is relatively stable and does not have the phenomenon of being converted into calcite.
Patent CN107445188A discloses a preparation method of rod-like precipitated calcium carbonate, in which limestone is calcined and then digested to obtain lime slurry; placing the lime slurry into a carbonation reaction tower, starting stirring, controlling the temperature of a reaction system to be 40-80 ℃, controlling the concentration of carbon dioxide in mixed gas to be 5-15 vol% within 0-30min in the early stage of reaction, and controlling the flow rate to be 2-4m3The concentration of carbon dioxide in the mixed gas introduced into the later stage of the carbonation reaction is 25-40 vol%, the flow rate is 4-6m3/h, when the pH value of the reaction system reaches 7.5, the introduction of the gas is stopped, and the carbonation reaction is terminated to obtain a precipitated calcium carbonate suspension; and dehydrating and drying the precipitated calcium carbonate suspension to obtain the rod-shaped precipitated calcium carbonate. The rod-shaped calcium carbonate prepared by the method exists as stable powder and does not relate to the conversion from rod shape to cubic shape.
CN106430272A discloses a preparation method of rod-shaped aragonite calcium carbonate, which comprises the following steps of (1) crushing limestone, calcining at 900-1400 ℃ for 2-7 h, and digesting the calcined limestone with a grey-water mass ratio of 1: 3-8 to obtain lime slurry; (2) sieving the lime slurry obtained in the step (1) by using a sieve of 80-100 meshes, filtering and deslagging, and adding water to adjust the solid content of the lime slurry to 7-20% to obtain refined lime slurry for later use; (3) controlling the temperature of the refined lime slurry to be 30-60 ℃, adding a composite crystal form control agent which is 0.5-2.0% of the mass of calcium hydroxide in the lime slurry, then conveying the mixture to a carbonization tower, starting stirring, introducing kiln gas to perform carbonation reaction until the pH value is 8.0, stopping introducing the gas, and terminating the carbonation reaction to obtain a precipitated calcium carbonate suspension; the composite crystal form control agent comprises three components, wherein the first component is polycarboxylic acid and/or polycarboxylic acid soluble salt, and the second component is one or more of calcium chloride, barium chloride, zinc chloride, calcium nitrate, barium nitrate, zinc nitrate, calcium sulfate, barium sulfate and zinc sulfate; the third component is one or a combination of more of polyethylene glycol, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and OP-10; the first component in the composite crystal form control agent is as follows: a second component: the mass ratio of the third component is 1: 1.5-2: 0.2-0.5; (4) and (4) dehydrating and drying the precipitated calcium carbonate suspension obtained in the step (3) according to a conventional method to obtain the rod-shaped aragonite calcium carbonate. The rod-shaped calcium carbonate prepared by the method exists as stable powder and does not relate to the conversion from rod shape to cubic shape.
CN108299811A discloses a preparation method of a calcium carbonate rod-shaped nanoparticle composite material, which comprises the steps of dispersing calcium oxide particles in deionized water, adding a composite surfactant, uniformly stirring, treating feed liquid under microwave, introducing the feed liquid into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, spraying the feed liquid under an ultrasonic condition, carrying out centrifugal separation on the feed liquid by the revolution, taking clear liquid, carrying out high-speed centrifugation, washing with deionized water, drying, and carrying out fusion and coextrusion on the obtained calcium carbonate rod-shaped nanoparticles and polycaprolactone to obtain the calcium carbonate rod-shaped nanoparticle composite material. The method is to prepare rod-shaped particles and mix the rod-shaped particles with the polymer, and does not relate to the transformation of the rod shape into the cubic shape.
CN201911403399.7 discloses a preparation method of hollow rod-shaped calcium carbonate, which comprises the steps of firstly weighing calcium oxide and dissolving the calcium oxide in water to prepare raw material calcium hydroxide slurry; then adding D-sodium gluconate and introducing CO2Gas reaction and carbonation are carried out to obtain product slurry; and (3) after the product slurry is subjected to suction filtration and washing, vacuum drying is carried out on the separated solid product, and finally the solid product is taken out and ground into powder, so that the hollow rod-shaped calcium carbonate can be obtained. The hollow rod-shaped calcium carbonate prepared by the method is not converted into cubic calcite-type calcium carbonate.
It has been reported that aragonite prepared from shellfish, ore, metathesis is converted to calcite by heating with DTA-TG (SAYOKO yoshiooka et al, Geochemical Journal vol.19, pp.24lto 249,1985), and the study of water loss accompanied by crystal transformation during heating did not characterize the sample by XRD.
In summary, the industry has less research on the conversion method of the rod-shaped aragonite type into the cubic calcite type, the application of the rod-shaped aragonite type to downstream application after conversion is less, and some foreign reports are only on the research of the conversion of the marine organism aragonite and are staying in experimental research. In order to obtain cubic precipitated calcium carbonate with good dispersibility, a method which is simple to operate and can be industrially produced is required.
Disclosure of Invention
The invention provides a preparation method of precipitated calcium carbonate with dispersed size and cube, aiming at the problems of nano calcium carbonate used in a sealant, such as the increase of the fluidity and the great reduction of the viscosity and the storage stability of the sealant due to the doping of heavy calcium carbonate. The precipitated calcium carbonate prepared by the method has the advantages of monodisperse morphology, smooth large particle diameter surface, low oil absorption value and the like; the nano calcium carbonate has better compatibility when being used as a filler of a sealant product, and greatly improves the flow property of the sealant while ensuring the reinforcing property of the small-vertical-diameter nano calcium carbonate.
In order to achieve the above object, the present invention adopts the following technical principles:
since the precipitated calcium carbonate in stick form is generally relatively stable, the commercially produced precipitated calcium carbonate in stick form is generally used directly in products for downstream applications. In the process of carbonating lime slurry, rod-shaped calcium carbonate can be in a metastable state by adjusting crystal form control, and in the subsequent heat treatment process, aragonite rod-shaped calcium carbonate in the metastable state overcomes internal energy and gradually changes into more stable calcite type cubic bodies by unit cell expansion in a hot state. In the heat treatment process, aragonite in a metastable state is dissolved in preference to cubic calcite, through the action of dissolution and recrystallization, the surface of cubic nano calcium carbonate grows gradually according to Ostwald ripening, the rod-shaped structure overcomes the internal energy of particles at high temperature, and the phase change is rapidly formed in the presence of calcite crystal nuclei and is converted into stable large-particle calcite.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of precipitated calcium carbonate with cubic dispersion and size comprises the following steps:
s1, slaking and reacting the quicklime, sieving, refining and mixing into lime slurry with the specific gravity of 1.040-1.050, and aging for 12-24h for later use;
s2, adding a crystal form control agent into the lime slurry, wherein the crystal form control agent is prepared by compounding sodium hexametaphosphate or sodium pyrophosphate with soluble barium salt, introducing carbon dioxide mixed gas into the lime slurry, stopping introducing the gas when the pH value of a reaction system is 8.0, and finishing the carbonation reaction to obtain a rod-shaped precipitated calcium carbonate suspension;
s3, adding a crystal form control agent into the lime slurry, wherein the crystal form control agent is one or more of sodium dodecyl sulfate, dodecyl trimethyl betaine and sodium polystyrene sulfonate; introducing carbon dioxide mixed gas into the lime slurry, stopping introducing the gas when the pH of the reaction system is 7.5, and finishing the carbonation reaction to obtain a cubic precipitated calcium carbonate suspension;
s4, mixing the rod-shaped precipitated calcium carbonate suspension obtained in the step S2 and the cubic precipitated calcium carbonate suspension obtained in the step S3 in proportion, adding behenic acid, uniformly mixing, heating to 90-95 ℃, and maintaining for 1.0 hour to obtain large and small cubic dispersed precipitated calcium carbonate suspensions;
s5, performing surface treatment on the precipitated calcium carbonate suspension through stearic acid saponification liquid, performing filter pressing, drying and sieving to obtain the precipitated calcium carbonate powder with cubic dispersion.
Preferably, the addition amount of the crystal form control agent in the step S2 is 0.3-1.5% of the dry content of calcium hydroxide.
Preferably, the mass ratio of the sodium hexametaphosphate or sodium pyrophosphate to the soluble barium salt in the step S2 is 4-10: 1.
Preferably, the soluble barium salt is barium chloride or/and barium nitrate.
Preferably, the addition amount of the crystal form control agent in the step S3 is 0.1-0.4% of the dry content of calcium hydroxide.
Preferably, the carbonation reaction in the step S2 controls the initial carbonation temperature of the lime slurry to be 45.0-55.0 ℃, the concentration of the carbon dioxide mixed gas to be 15-18% and the inflow rate to be 2.0-3.0m3/h。
Preferably, the carbonation reaction in the step S3 controls the initial carbonation temperature of the lime slurry to be 18.0-23.0 ℃, the concentration of the carbon dioxide mixed gas to be 30-33% and the inflow rate to be 2.0-3.0m 3/h.
Preferably, the dosage of the behenic acid is 0.5-0.8% of the dry mass of the calcium carbonate.
Preferably, the dosage of the stearic acid saponification liquid is 3.0-3.5% of the dry mass of the calcium carbonate. The stearic acid saponification liquid is prepared from 15% of sodium hydroxide in stearic acid by mass.
Preferably, the surface modification in step S5 is performed by stirring at a temperature of 90-95 ℃ and a rotation speed of 2500-.
Preferably, the mass ratio of the rod-shaped precipitated calcium carbonate suspension to the cubic precipitated calcium carbonate suspension is 1: 1-10.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the method utilizes the characteristic that the rod-shaped aragonite type precipitated calcium carbonate is unstable, and controls the rod-shaped forming process, so that the aragonite mixed with the nano calcium carbonate can be quickly converted into calcite at a lower temperature.
2. The preparation process of the product is accompanied by an accelerated curing stage, so that the dispersibility of the nano calcium carbonate is improved, the surface of the calcium carbonate is smoother, and the subsequent surface treatment and coating are more sufficient.
3. The precipitated calcium carbonate prepared by the method has the advantages of monodisperse morphology, smooth large particle diameter surface, low oil absorption value and the like; the nano calcium carbonate has better compatibility when being used as a filler of a sealant product, and greatly improves the flow property of the sealant while ensuring the reinforcing property of the small-vertical-diameter nano calcium carbonate.
4. The method has low production cost and is suitable for industrial production, and the prepared precipitated calcium carbonate has better processing performance when being used as the sealant filler, because the precipitated calcium carbonate with larger water absorption is substituted for heavy calcium carbonate, the storage stability of the sealant is greatly improved, the sealant is endowed with excellent bonding performance and tensile strength, and the flowing performance is improved.
Drawings
FIG. 1 is a 50000 SEM image of the precipitated calcium carbonate product in stick form obtained in example 1.
FIG. 2 is a 50000 SEM image of the size cubic dispersion precipitated calcium carbonate product obtained in example 1.
FIG. 3 is a 50000 SEM image of the cubic dispersion of the precipitated calcium carbonate product of example 1.
FIG. 4 is an XRD pattern of a mixture of the rod-shaped precipitated calcium carbonate suspension and the cubic precipitated calcium carbonate suspension of example 1 in proportion and after conversion.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of precipitated calcium carbonate with cubic dispersion and size comprises the following steps:
s1, slaking and reacting quicklime and water according to the ratio of 1:6, sieving, refining and mixing into lime slurry with the specific gravity of 1.050, and aging for 12 hours for later use;
s2 adding 0.5 percent of sodium hexametaphosphate and 0.1 percent of barium chloride in the dry basis content of calcium hydroxide into the lime slurry, controlling the temperature of the lime slurry at 50 ℃ and controlling the temperature at 2.0m3Introducing 16% carbon dioxide mixed gas in the reaction system for h, stopping introducing the gas when the pH value of the reaction system is 8.0, and finishing the carbonation reaction to obtain a rod-shaped precipitated calcium carbonate suspension;
s3 adding dodecyl trimethyl betaine with calcium hydroxide dry basis content of 0.3% into lime slurry, controlling the temperature of the lime slurry at 20 deg.C and 2.0m3Introducing 33% carbon dioxide mixed gas in per hour until the pH value of the reaction system is 7.5, stopping introducing the gas, and finishing the carbonation reaction to obtain cubic precipitated calcium carbonate suspension;
s4, mixing the rod-shaped precipitated calcium carbonate suspension obtained in the S2 and the cubic precipitated calcium carbonate suspension obtained in the S3 according to the mass ratio of 4: 6, mixing, adding docosanoic acid with the mass of 0.5 percent of the dry basis mass of calcium carbonate, uniformly mixing, heating to 90 ℃, and maintaining for 1.0 hour to obtain large and small cubic dispersed precipitated calcium carbonate suspension;
s5, performing surface treatment on the precipitated calcium carbonate suspension by stearic acid saponification liquid with calcium carbonate dry basis mass of 3.0%, press filtering, drying, and sieving to obtain large and small cubic dispersed precipitated calcium carbonate powder.
The rod-shaped precipitated calcium carbonate obtained in step S2 of example 1 and the large and small cubic dispersed precipitated calcium carbonate obtained in step S4 were subjected to scanning electron microscope and X-ray diffraction detection, and the measurement results are shown in fig. 1 to 4. As is apparent from FIG. 1, the rod-like precipitated calcium carbonate prepared by the method of the present invention has the advantages of regular shape, uniform size and good dispersibility. As is apparent from FIGS. 2 and 3, the method of the present invention produces a mixture of precipitated calcium carbonate with two different morphologies, namely, a large cube in which the rod shape is changed and a small cube in which the small cube is obtained in the step S3, and the product has good dispersibility. As can be seen from the XRD pattern of fig. 4, the mixed product of the rod-shaped precipitated calcium carbonate prepared in S2 and the cubic precipitated calcium carbonate prepared in S3 comprised aragonite and calcite, and was completely converted into calcite after adding behenic acid and heating. The rod-shaped precipitated calcium carbonate was converted into large cubic precipitated calcium carbonate in cubic precipitated calcium carbonate by combining scanning electron micrographs and XRD.
Example 2
A preparation method of precipitated calcium carbonate with cubic dispersion and size comprises the following steps:
s1, slaking and reacting quicklime and water according to the ratio of 1:8, sieving, refining and blending into lime slurry with the specific gravity of 1.050, and aging for 20 hours for later use;
s2 adding sodium pyrophosphate of 1.0 percent and barium nitrate of 0.2 percent of the dry content of calcium hydroxide into the lime slurry, controlling the temperature of the lime slurry at 45 ℃ and controlling the temperature at 3.0m3Introducing 18 percent carbon dioxide mixed gas into the reaction system for h, stopping introducing the gas when the pH value of the reaction system is 8.0, and finishing the carbonation reaction to obtain a rod-shaped precipitated calcium carbonate suspension;
s3 adding sodium polystyrene sulfonate with calcium hydroxide dry basis content of 0.3% into lime slurry, controlling the temperature of the lime slurry at 20 ℃ at 2.5m3Introducing 30% carbon dioxide mixed gas, stopping introducing gas when the pH of the reaction system is 7.5, and finishing the carbonation reaction to obtain cubic precipitated calcium carbonate suspension;
s4, mixing the rod-shaped precipitated calcium carbonate suspension obtained in the S2 and the cubic precipitated calcium carbonate suspension obtained in the S3 according to the mass ratio of 1: 4, mixing, adding behenic acid accounting for 0.6 percent of the dry basis weight of the calcium carbonate, uniformly mixing, heating to 95 ℃, and maintaining for 1.0 hour to obtain large and small cubic dispersed precipitated calcium carbonate suspension;
s5, performing surface treatment on the precipitated calcium carbonate suspension by stearic acid saponification liquid with 3.2 percent of the dry basis weight of calcium carbonate, performing pressure filtration, drying and sieving to obtain the large and small cubic dispersed precipitated calcium carbonate powder.
Example 3
A preparation method of precipitated calcium carbonate with cubic dispersion and size comprises the following steps:
s1, slaking and reacting quicklime and water according to the mass ratio of 1:9, sieving, refining and blending into lime slurry with the specific gravity of 1.040, and aging for 24 hours for later use;
s2 adding 0.8 percent of sodium hexametaphosphate and 0.2 percent of barium chloride in the dry basis content of calcium hydroxide into the lime slurry, controlling the temperature of the lime slurry at 55 ℃ and controlling the temperature at 2.0m3Introducing 15% carbon dioxide mixed gas in the reaction system for h, stopping introducing the gas when the pH value of the reaction system is 8.0, and finishing the carbonation reaction to obtain a rod-shaped precipitated calcium carbonate suspension;
s3 adding sodium dodecyl sulfate with the dry content of calcium hydroxide being 0.4% to the lime slurry, controlling the temperature of the lime slurry at 20 ℃ and 3.0m3Introducing 30% carbon dioxide mixed gas, stopping introducing gas when the pH of the reaction system is 7.5, and finishing the carbonation reaction to obtain cubic precipitated calcium carbonate suspension;
s4, mixing the rod-shaped precipitated calcium carbonate suspension obtained in the S2 and the cubic precipitated calcium carbonate suspension obtained in the S3 according to the mass ratio of 1:9, mixing, adding docosanoic acid with the mass of 0.8 percent of the dry basis of calcium carbonate, uniformly mixing, heating to 90 ℃, and maintaining for 1.0 hour to obtain large and small cubic dispersed precipitated calcium carbonate suspension;
s5, performing surface treatment on the precipitated calcium carbonate suspension by stearic acid saponification liquid with 3.5 percent of the dry basis weight of calcium carbonate, performing pressure filtration, drying and sieving to obtain the large and small cubic dispersed precipitated calcium carbonate powder.
Example 4
A preparation method of precipitated calcium carbonate with cubic dispersion and size comprises the following steps:
s1, slaking and reacting quicklime and water according to the mass ratio of 1:7, sieving, refining and blending into lime slurry with the specific gravity of 1.040, and aging for 24 hours for later use;
s2 adding 0.5 percent sodium hexametaphosphate and 0.3 percent barium chloride of the dry content of calcium hydroxide into the lime slurry, controlling the temperature of the lime slurry at 55 ℃ and controlling the temperature at 2.0m3Introducing 18 percent carbon dioxide mixed gas into the reaction system for h, stopping introducing the gas when the pH value of the reaction system is 8.0, and finishing the carbonation reaction to obtain a rod-shaped precipitated calcium carbonate suspension;
s3 adding sodium dodecyl sulfate 0.2% and sodium polystyrene sulfonate 0.2% of the dry content of calcium hydroxide into lime slurry, controlling the temperature of the lime slurry at 20 ℃ and controlling the temperature at 3.0m3Introducing 33% carbon dioxide mixed gas in per hour until the pH value of the reaction system is 7.5, stopping introducing the gas, and finishing the carbonation reaction to obtain cubic precipitated calcium carbonate suspension;
s4, mixing the rod-shaped precipitated calcium carbonate suspension obtained in the S2 and the cubic precipitated calcium carbonate suspension obtained in the S3 according to the mass ratio of 1: 4, mixing, adding docosanoic acid with the mass of 0.6 percent of the dry basis of calcium carbonate, uniformly mixing, heating to 90 ℃, and maintaining for 1.0 hour to obtain large and small cubic dispersed precipitated calcium carbonate suspension;
s5, performing surface treatment on the precipitated calcium carbonate suspension by stearic acid saponification liquid with 3.3 percent of the dry basis weight of calcium carbonate, performing pressure filtration, drying and sieving to obtain the large and small cubic dispersed precipitated calcium carbonate powder.
Comparative example 1
S1, slaking and reacting the quicklime, sieving, refining and mixing into lime slurry with the specific gravity of 1.050, and aging for 12 hours for later use;
s2, controlling the temperature of the lime slurry at 20 ℃, introducing 30 percent carbon dioxide mixed gas at 3.0m3/h, stopping introducing the gas when the pH of a reaction system is 7.5, and finishing the carbonation reaction to obtain a cubic precipitated calcium carbonate suspension;
s3, mixing the cubic precipitated calcium carbonate suspension obtained in the step S2 with ground calcium carbonate according to the mass ratio of 6: 4, mixing.
S4: and (3) carrying out surface treatment on the precipitated calcium carbonate suspension by using a 3.5% stearic acid saponification solution, carrying out filter pressing, drying and sieving to obtain cubic precipitated calcium carbonate powder.
Comparative example 2
S1, slaking and reacting the quicklime, sieving, refining and mixing into lime slurry with the specific gravity of 1.040, and aging for 12 hours for later use;
s2, controlling the temperature of the lime slurry at 20 ℃, introducing 33 percent carbon dioxide mixed gas at 2.0m3/h, stopping introducing the gas when the pH of the reaction system is 7.5, and finishing the carbonation reaction to obtain a cubic precipitated calcium carbonate suspension;
s3: and (3) carrying out surface treatment on the precipitated calcium carbonate suspension by using a 3.5% stearic acid saponification solution, carrying out filter pressing, drying and sieving to obtain cubic precipitated calcium carbonate powder.
The precipitated calcium carbonates obtained in the above examples and comparative examples were used to prepare silicone sealants according to the formulations shown in table 1 in a conventional manner. And (3) performing mechanical property test and storage property test on the sealant according to the standard GB/T13477-2017, wherein the test results are shown in the table 2.
Table 1: the precipitated calcium carbonate prepared by the invention is applied to PVC product formula
| Raw materials | Parts by mass |
| 2w107 resin | 35 |
| 8w107 resin | 45 |
| Filler (A)Precipitated calcium carbonate) | 100 |
| 100cP silicone oil | 5 |
| D20 | 2 |
| KH550 | 0.3 |
| KH560 | 3 |
| D80 | 0.06 |
Table 2: performance test result of applying precipitated calcium carbonate to silicone sealant
As can be seen from Table 2, the large and small cubic dispersion precipitated calcium carbonate prepared by the invention has excellent reinforcing effect when being filled in silicone sealant, and compared with the sealant in which heavy calcium carbonate is added as filler after being filled, the sealant has the advantages of higher viscosity, higher strength, obviously better fluidity, better flow property and better storage property.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (10)
1. A preparation method of precipitated calcium carbonate with cubic dispersion and size is characterized by comprising the following steps: the method comprises the following steps:
s1, slaking and reacting the quicklime, sieving, refining and mixing into lime slurry with the specific gravity of 1.040-1.050, and aging for 12-24h for later use;
s2, adding a crystal form control agent into the lime slurry, wherein the crystal form control agent is prepared by compounding sodium hexametaphosphate or sodium pyrophosphate with soluble barium salt, introducing carbon dioxide mixed gas into the lime slurry, stopping introducing the gas when the pH value of a reaction system is 8.0, and finishing the carbonation reaction to obtain a rod-shaped precipitated calcium carbonate suspension;
s3, adding a crystal form control agent into the lime slurry, wherein the crystal form control agent is one or more of sodium dodecyl sulfate, dodecyl trimethyl betaine and sodium polystyrene sulfonate; introducing carbon dioxide mixed gas into the lime slurry, stopping introducing the gas when the pH of the reaction system is 7.5, and finishing the carbonation reaction to obtain a cubic precipitated calcium carbonate suspension;
s4, mixing the rod-shaped precipitated calcium carbonate suspension obtained in the step S2 and the cubic precipitated calcium carbonate suspension obtained in the step S3 in proportion, adding behenic acid, uniformly mixing, heating to 90-95 ℃, and maintaining for 1.0 hour to obtain large and small cubic dispersed precipitated calcium carbonate suspensions;
s5, performing surface treatment on the precipitated calcium carbonate suspension through stearic acid saponification liquid, performing filter pressing, drying and sieving to obtain the precipitated calcium carbonate powder with cubic dispersion.
2. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: the addition amount of the crystal form control agent in the step S2 is 0.3-1.5% of the dry content of the calcium hydroxide.
3. The process for the preparation of cubic large precipitated calcium carbonate according to claim 2, characterized in that: in the step S2, the mass ratio of the sodium hexametaphosphate or sodium pyrophosphate to the soluble barium salt is 4-10: 1.
4. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: the soluble barium salt is barium chloride or/and barium nitrate.
5. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: the addition amount of the crystal form control agent in the step S3 is 0.1-0.4% of the dry content of the calcium hydroxide.
6. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: step S2, the carbonation reaction controls the initial carbonation temperature of the lime slurry to be 45.0-55.0 ℃, the concentration of the carbon dioxide mixed gas to be 15-18 percent, and the inflow rate to be 2.0-3.0m3/h。
7. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: step S3, the carbonation reaction controls the initial carbonation temperature of the lime slurry to be 18.0-23.0 ℃, the concentration of the carbon dioxide mixed gas to be 30-33%, and the inflow rate to be 2.0-3.0m3/h。
8. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: the dosage of the behenic acid is 0.5 to 0.8 percent of the mass of the calcium carbonate dry base; the dosage of the stearic acid saponification liquid is 3.0-3.5% of the dry mass of the calcium carbonate.
9. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: the surface modification in the step S5 is to stir at the temperature of 90-95 ℃ and the rotation speed of 2500-.
10. The process for the preparation of cubic large precipitated calcium carbonate according to claim 1, characterized in that: the mass ratio of the rod-shaped precipitated calcium carbonate suspension to the cubic precipitated calcium carbonate suspension is 1: 1-10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115557524A (en) * | 2022-09-23 | 2023-01-03 | 广西华纳新材料股份有限公司 | High-whiteness and high-dispersibility nano calcium carbonate and preparation method thereof |
| CN117682544A (en) * | 2024-02-04 | 2024-03-12 | 山东宇信纳米科技有限公司 | Preparation method and application of composite crystal form nano calcium carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0431316A (en) * | 1990-05-28 | 1992-02-03 | Maruo Calcium Co Ltd | Monodispersed plate calcium carbonate and production thereof |
| CN106517285A (en) * | 2016-11-21 | 2017-03-22 | 广西华纳新材料科技有限公司 | Method for preparing bar-shaped nanometer calcium carbonate |
| CN109810294A (en) * | 2019-01-07 | 2019-05-28 | 卢氏国嵩莱纳米科技有限公司 | A kind of preparation method of the high-end nanometer calcium carbonate of butyl rubber product |
| WO2020010689A1 (en) * | 2018-07-12 | 2020-01-16 | 广西华纳新材料科技有限公司 | Preparation method for nanoprecipitated calcium carbonate having core-shell structure |
-
2021
- 2021-12-31 CN CN202111664054.4A patent/CN114291835B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0431316A (en) * | 1990-05-28 | 1992-02-03 | Maruo Calcium Co Ltd | Monodispersed plate calcium carbonate and production thereof |
| CN106517285A (en) * | 2016-11-21 | 2017-03-22 | 广西华纳新材料科技有限公司 | Method for preparing bar-shaped nanometer calcium carbonate |
| WO2020010689A1 (en) * | 2018-07-12 | 2020-01-16 | 广西华纳新材料科技有限公司 | Preparation method for nanoprecipitated calcium carbonate having core-shell structure |
| CN109810294A (en) * | 2019-01-07 | 2019-05-28 | 卢氏国嵩莱纳米科技有限公司 | A kind of preparation method of the high-end nanometer calcium carbonate of butyl rubber product |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115557524A (en) * | 2022-09-23 | 2023-01-03 | 广西华纳新材料股份有限公司 | High-whiteness and high-dispersibility nano calcium carbonate and preparation method thereof |
| CN117682544A (en) * | 2024-02-04 | 2024-03-12 | 山东宇信纳米科技有限公司 | Preparation method and application of composite crystal form nano calcium carbonate |
| CN117682544B (en) * | 2024-02-04 | 2024-05-24 | 山东宇信纳米科技有限公司 | Preparation method and application of composite crystal form nano calcium carbonate |
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