CN112441605B - Preparation method of vermicular precipitated calcium carbonate - Google Patents
Preparation method of vermicular precipitated calcium carbonate Download PDFInfo
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- CN112441605B CN112441605B CN202011516408.6A CN202011516408A CN112441605B CN 112441605 B CN112441605 B CN 112441605B CN 202011516408 A CN202011516408 A CN 202011516408A CN 112441605 B CN112441605 B CN 112441605B
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- strontium
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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 117
- 229940088417 precipitated calcium carbonate Drugs 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 59
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 22
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims abstract description 9
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 9
- 238000007796 conventional method Methods 0.000 claims abstract description 9
- 230000005484 gravity Effects 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 16
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 16
- 239000004571 lime Substances 0.000 claims description 16
- 239000008267 milk Substances 0.000 claims description 16
- 210000004080 milk Anatomy 0.000 claims description 16
- 235000013336 milk Nutrition 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 5
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 5
- WTNNIXSCSYFNFP-UHFFFAOYSA-N strontium;dicyanide Chemical compound [Sr+2].N#[C-].N#[C-] WTNNIXSCSYFNFP-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 3
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 3
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 3
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- LWNKHILEJJTLCI-UHFFFAOYSA-J calcium;magnesium;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mg+2].[Ca+2] LWNKHILEJJTLCI-UHFFFAOYSA-J 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 35
- 230000029087 digestion Effects 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HDMXIELEUKTYFR-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC HDMXIELEUKTYFR-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of vermicular precipitated calcium carbonate, which comprises the steps of carrying out digestion reaction on quick lime, and adjusting specific gravity to obtain a calcium hydroxide suspension; adding salt of magnesium, strontium or barium element or compound thereof serving as a crystal form control agent into the suspension, stirring and mixing uniformly, adding into a carbonization tower, introducing mixed gas containing carbon dioxide to perform calcium carbonate reaction until the pH value is reduced to 9.0, and stopping carbonation to obtain PCC suspension; slowly adding phosphoric acid solution into the PCC suspension until the pH value is reduced to 7.0, stopping the reaction, standing, and then carrying out filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain the vermicular precipitated calcium carbonate powder. The method controls the final end point of the reaction by adding the salt of magnesium, strontium or barium or the compound thereof as a crystal form control agent, and adjusts the final pH value by using phosphoric acid, so that the obtained vermicular precipitated calcium carbonate has the advantages of high purity, high whiteness, high specific surface area and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of vermicular precipitated calcium carbonate.
Background
Calcium carbonate is used as an environment-friendly inorganic material and has wide application. Because the calcium carbonate raw material is low in acquisition cost, the production cost is mature compared with the related technology, and the calcium carbonate is used as the filler, so that the mechanical property, the appearance effect and the structure adjustment of the product can be improved, the cost of the product is greatly reduced, and the like, and the calcium carbonate can be applied to the fields of rubber, plastics, papermaking, printing ink, plastics and the like. The calcium carbonate is applied to coatings, sealants and the like, and calcium carbonate particles with good dispersion can form a good space site structure, so that the anti-sagging performance and the mechanical property of products are improved, and the calcium carbonate has important significance in automotive coatings, building adhesives and the like. The calcium carbonate is applied to paper making, plastics and the like, not only can the mechanical property of products be improved, but also the advantages of the calcium carbonate in whiteness can be fully shown, and the products can be conveniently colored; and part of special shapes, such as spherical calcium carbonate, can be applied to printing ink, lubricating oil and the like because of better wear resistance. At present, the shapes of precipitated calcium carbonate on the market mainly include cubic, spherical, spindle-shaped, chain-shaped, needle-shaped and sheet-shaped shapes, and the preparation methods or processes of precipitated calcium carbonate with different shapes can be different. The application fields of calcium carbonate with different morphologies are gradually explored, and the research and preparation of calcium carbonate with various morphologies have important significance. At present, precipitated calcium carbonate of various morphologies has been studied and is being applied to industrial production in a mature manner.
Patent CN107555459A discloses a preparation method of nano spindle precipitated calcium carbonate, which is characterized in that limestone is calcined, digested and refined, then a mixture of a composite crystal form control agent sodium bis (2-ethylhexyl) succinate sulfonate and zinc sulfate with the mass ratio of 1-3:1 is added, CO is introduced2Adding sodium polyacrylate, sodium polymethacrylate, maleic acid-acrylic acid copolymer sodium salt and other dispersing agents when the mixture is carbonated to the conductivity of 1.0-2.0 mS/cm to obtain the nano spindle precipitated calcium carbonate. The sodium sulfosuccinate is added in the method, so that more bubbles are generated during carbonation, the materials in the carbonation tower overflow during carbonation, and accidents are easily caused during pilot plant test or industrial production. In addition, the method is complicated in adding a crystal form control agent, a dispersing agent and the like, and is not favorable for the stability of the product. The morphology of the calcium carbonate prepared by the method is not vermicular calcium carbonate.
Patent CN111153424A discloses a method for preparing pinecone-shaped calcium carbonate, which comprises dissolving a certain amount of anhydrous calcium chloride in deionized water to prepare solutions with different concentrations, and then adding 2% of crystal form control agent to form a solution A; dissolving a certain amount of anhydrous sodium carbonate in deionized water to prepare solutions with different concentrations, and adding a certain amount of anhydrous ethanol solution to form a solution B; and (3) placing the solution A and the solution B in a constant-temperature water bath at 45 ℃, stirring for 0.5h, quickly pouring the constant-temperature solution B into the solution A, stirring strongly for 2h, and performing centrifugal separation, suction filtration, washing, drying and grinding to obtain the pinecone-shaped calcium carbonate powder. The method uses double decomposition method to prepare the pinecone-shaped calcium carbonate, the preparation conditions are harsh, the industrial production is difficult, and the prepared calcium carbonate is non-worm-shaped.
The patent CN110366539A provides a calcium carbonate with small particle size and easy dispersion in polymer and a preparation method thereof, wherein the content of calcium carbonate and magnesium carbonate is 12000-120000 ppm, and the specific surface area is 60-120 m2/g，(104) The crystallite size of the surface is 20-50 nm, and the particles are connected into a chain shape. The method is an invention of Japan industrial company, adds a proper amount of magnesium hydroxide before carbonating to prepare chain calcium carbonate, and dehydrates and dries after surface treatment to obtain the chain calcium carbonate which has good dispersion and good elongation when being applied to rubber. However, the morphology prepared by the method is calcite chain-shaped and is not vermicular calcium carbonate.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention aims to provide a preparation method of vermicular precipitated calcium carbonate. The method controls the final end point of the reaction by adding the salt of magnesium, strontium or barium or the compound thereof as a crystal form control agent, and adjusts the final pH value by using phosphoric acid, so that the obtained vermicular precipitated calcium carbonate has the advantages of high purity, high whiteness, high specific surface area and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing vermicular precipitated calcium carbonate, comprising the following steps:
(1) slaking and reacting quicklime to obtain lime milk, and adjusting the specific gravity of the lime milk to 1.045-1.065 to obtain a calcium hydroxide suspension;
(2) adding salt of magnesium, strontium or barium element or compound thereof serving as a crystal form control agent into the calcium hydroxide suspension, stirring and mixing uniformly, adding into a carbonization tower, introducing mixed gas containing carbon dioxide for carbonation reaction, and stopping carbonation until the pH value is reduced to 9.0 to obtain PCC suspension;
(3) slowly adding phosphoric acid solution into the PCC suspension until the pH value is reduced to 7.0, stopping the reaction, standing for 10-30min, and then carrying out filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain vermicular precipitated calcium carbonate powder.
Further, the crystal form control agent is one or a combination of more of magnesium chloride, magnesium oxide, magnesium hydroxide, calcium magnesium hydroxide, strontium chloride, strontium oxide, strontium nitrate, strontium cyanide, barium chloride, barium oxide, barium nitrate and barium acetate.
Furthermore, the dosage of the crystal form control agent is 0.2-0.5mol per 15kg of calcium hydroxide suspension, and the crystal form control agent is prepared into the calcium hydroxide suspension with water to have the concentration of 1-8 mol/L. Preferably, the crystal form control agent consists of 0.1mol of magnesium chloride and 0.2mol of strontium chloride; or 0.4mol of magnesium bicarbonate and 0.1mol of barium chloride; or 0.5mol of strontium nitrate and 0.3mol of strontium cyanide.
Further, the mass concentration of the phosphoric acid is 5%.
Further, the adding speed of the phosphoric acid is 200-300 ml/min.
Further, the initial carbonization temperature of the calcium hydroxide suspension in the carbonation reaction process is 20.0-24.0 ℃, the concentration of the carbon dioxide mixed gas is 30-33%, and the gas inlet flow is 2.0-2.4m3The stirring frequency was 20 Hz.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. according to the method, the salt of magnesium, strontium or barium or the compound thereof is used as a crystal form control agent to form carbonate, the application effect of calcium carbonate is not influenced, phosphoric acid is added in the later stage of reaction to control PH, the accurate control means of the carbonation end point is realized, the liquid phase residual substance is treated in the later stage, the product is more stable, calcium phosphate with smaller particles can be formed, the defect of the surface of calcium carbonate is favorably filled, the obtained calcium carbonate is vermiform in appearance, high in purity, high in whiteness and high in specific surface area, and the obtained calcium carbonate has potential application prospects in the fields of papermaking, plastics, rubber, medical treatment, biological pharmacy, daily chemicals and the like.
2. The method adopts the traditional bubbling carbonation process, has simple process and mature technology, and is beneficial to the industrialized application of the vermicular calcium carbonate; the adopted crystal form control agent is easy to obtain and low in price, and the use of the crystal form control agent does not have any pollution, environmental protection and safety problems.
Drawings
FIG. 1 is a 150000 SEM image of the vermicular precipitated calcium carbonate product obtained in example 1.
FIG. 2 is a 100000 SEM image of the vermicular precipitated calcium carbonate product made in example 1.
FIG. 3 is a 10000-fold SEM image of the vermicular precipitated calcium carbonate product made in example 1.
FIG. 4 is a 150000 SEM image of the vermicular precipitated calcium carbonate product obtained in example 2.
Figure 5 is a 100000 SEM image of the vermicular precipitated calcium carbonate product made in example 2.
Figure 6 is a 100000 SEM image of the vermicular precipitated calcium carbonate product made in example 3.
Figure 7 is a 100000 SEM image of the vermicular precipitated calcium carbonate product made in example 4.
FIG. 8 is a 100000 SEM image of the vermicular precipitated calcium carbonate product of example 5.
Figure 9 is a 100000 SEM image of the non-vermicular precipitated calcium carbonate product made in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Example 1
A method for preparing vermicular precipitated calcium carbonate, comprising the following steps:
(1) slaking and reacting quicklime to obtain lime milk, and regulating the specific gravity of the lime milk to 1.050 to obtain calcium hydroxide suspension;
(2) taking 15kg of calcium hydroxide suspension, adding 0.1mol of magnesium chloride and 0.2mol of strontium chloride into the suspension to prepare a solution with a cation molar concentration of 1mol/L as a crystal form control agent, uniformly stirring and mixing the solution, adding the solution into a carbonization tower, controlling the stirring speed to be 20Hz and the carbonization starting temperature to be 21.0 ℃, introducing carbon dioxide mixed gas with the concentration of 30 percent into the suspension, wherein the flow rate is 2.0m3Stopping until the pH drops to 9.0Carbonating to obtain PCC suspension;
(3) adding a phosphoric acid solution with the mass concentration of 5% into the PCC suspension at the speed of 220ml/min until the pH value is reduced to 7.0, stopping the reaction, standing for 10min, and then carrying out filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain the vermicular precipitated calcium carbonate powder.
The precipitated calcium carbonate powder prepared in this example is detected by scanning electron microscopy under different multiples, and the detection results are shown in fig. 1, fig. 2, and fig. 3, and it can be seen from the figures that the prepared calcium carbonate powder is vermiform, and has the characteristics of regular morphology, uniform particle size distribution, and good dispersibility.
Example 2
A method for preparing vermicular precipitated calcium carbonate, comprising the following steps:
(1) slaking and reacting quicklime to obtain lime milk, and regulating the specific gravity of the lime milk to 1.060 to obtain calcium hydroxide suspension;
(2) taking 15kg of calcium hydroxide suspension, adding 0.3mol of magnesium oxide into the suspension to prepare a solution with the concentration of 3mol/L as a crystal form control agent, uniformly stirring and mixing the solution, adding the solution into a carbonization tower, controlling the stirring speed to be 20Hz and the carbonization starting temperature to be 23.0 ℃, introducing carbon dioxide mixed gas with the concentration of 31 percent into the suspension, wherein the flow rate is 2.0m3Stopping carbonation until the pH drops to 9.0 to obtain a PCC suspension;
(3) adding 5% phosphoric acid solution into the PCC suspension at a rate of 250ml/min until the pH value is reduced to 7.0, stopping the reaction, standing for 20min, and performing filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain the vermicular precipitated calcium carbonate powder.
The precipitated calcium carbonate powder prepared in this example is detected by scanning electron microscopy under different multiples, and the detection result is shown in fig. 4 and 5, and it can be seen from the figure that the prepared calcium carbonate powder is vermiform, and has the characteristics of regular morphology, uniform particle size distribution, and good dispersibility.
Example 3
A method for preparing vermicular precipitated calcium carbonate, comprising the following steps:
(1) slaking and reacting quicklime to obtain lime milk, and adjusting the specific gravity of the lime milk to 1.065 to obtain calcium hydroxide suspension;
(2) taking 15kg of calcium hydroxide suspension, adding 0.4mol of magnesium bicarbonate and 0.1mol of barium chloride into the suspension to prepare a solution with a cation concentration of 5mol/L as a crystal form control agent, uniformly stirring and mixing the solution, adding the solution into a carbonization tower, controlling the stirring rate to be 20Hz and the carbonization starting temperature to be 24 ℃, introducing a carbon dioxide mixed gas with the concentration of 33 percent into the suspension, wherein the flow rate is 2.2m3Stopping carbonation until the pH drops to 9.0 to obtain a PCC suspension;
(3) adding phosphoric acid solution with mass concentration of 5% into the PCC suspension at the speed of 280ml/min until the pH value is reduced to 7.0, stopping the reaction, standing for 30min, and then carrying out filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain the vermicular precipitated calcium carbonate powder.
The precipitated calcium carbonate powder prepared in the embodiment is detected by a scanning electron microscope, and the detection result is shown in fig. 6, and it can be seen from the figure that the prepared calcium carbonate powder is vermiform, regular in morphology, uniform in particle size distribution and good in dispersibility.
Example 4
A method for preparing vermicular precipitated calcium carbonate, comprising the following steps:
(1) slaking and reacting quicklime to obtain lime milk, and regulating the specific gravity of the lime milk to 1.060 to obtain calcium hydroxide suspension;
(2) taking 15kg of calcium hydroxide suspension, adding 0.5mol of strontium nitrate and 0.3mol of strontium cyanide into the suspension to prepare a solution with a cation concentration of 8mol/L as a crystal form control agent, uniformly stirring and mixing the solution, adding the solution into a carbonization tower, controlling the stirring rate to be 20Hz and the carbonization starting temperature to be 20 ℃, introducing 32 percent carbon dioxide mixed gas into the suspension, wherein the flow rate is 2.0m3Stopping carbonation until the pH drops to 9.0 to obtain a PCC suspension;
(3) adding phosphoric acid solution with mass concentration of 5% into the PCC suspension at a speed of 240ml/min until the pH value is reduced to 7.0, stopping the reaction, standing for 10min, and then carrying out filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain the vermicular precipitated calcium carbonate powder.
The precipitated calcium carbonate powder prepared in this example is detected by a scanning electron microscope, and the detection result is shown in fig. 7, and it can be seen from the figure that the prepared calcium carbonate powder is vermiform, regular in morphology, uniform in particle size distribution, and good in dispersibility.
Example 5
A method for preparing vermicular precipitated calcium carbonate, comprising the following steps:
(1) slaking and reacting quicklime to obtain lime milk, and regulating the specific gravity of the obtained lime milk to 1.055 to obtain calcium hydroxide suspension;
(2) taking 15kg of calcium hydroxide suspension, adding 0.3mol of barium nitrate and 0.3mol of barium acetate into the suspension to prepare a solution with the cation concentration of 6mol/L as a crystal form control agent, uniformly stirring and mixing the solution, adding the solution into a carbonization tower, controlling the stirring rate to be 20Hz and the carbonization starting temperature to be 20 ℃, introducing 32 percent carbon dioxide mixed gas into the suspension, wherein the flow rate is 2.3m3Stopping carbonation until the pH drops to 9.0 to obtain a PCC suspension;
(3) adding phosphoric acid solution with mass concentration of 5% into the PCC suspension at a speed of 240ml/min until the pH value is reduced to 7.0, stopping the reaction, standing for 10min, and then carrying out filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain the vermicular precipitated calcium carbonate powder.
The precipitated calcium carbonate powder prepared in this example is detected by a scanning electron microscope, and the detection result is shown in fig. 8, and it can be seen from the figure that the prepared calcium carbonate powder is vermiform, regular in morphology, uniform in particle size distribution, and good in dispersibility.
Comparative example 1
(1) Slaking quicklime to prepare lime milk, and preparing the lime milk with the specific gravity of 1.060;
(2) taking 15kg of the calcium hydroxide suspension prepared in the S1; adding into a carbonization tower, stirring well at a stirring speed of 20Hz, controlling the carbonization starting temperature to be 21.0 ℃, and introducing 30% of dioxide into the suspensionCarbon mixed gas with a flow rate of 2m3Stopping carbonation until the pH drops to 7.0 to obtain a PCC suspension;
(3) and then carrying out filter pressing, drying, crushing and grading on the suspension to obtain precipitated calcium carbonate powder.
The precipitated calcium carbonate powder prepared by the example is detected by a scanning electron microscope, and the detection result is shown in fig. 9, wherein the precipitated calcium carbonate prepared by the conventional method is not vermiform and has irregular appearance.
TABLE 1 detection data of vermicular precipitated calcium carbonate
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| CaCO3Ingredients (a) of | 98.3 | 98.5 | 97.4 | 96.8 | 98.2 | 95.4 |
| Whiteness degree% | 96.8 | 96.2 | 95.4 | 96.3 | 95.6 | 94.1 |
| BET, m2/g | 32.44 | 29.31 | 27.20 | 30.02 | 30.51 | 23.63 |
The detection results of the vermicular precipitated calcium carbonate prepared in this example are shown in table 1, and it can be seen from the detection results that the obtained precipitated calcium carbonate has high purity, whiteness and specific surface area.
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 (2)
1. A method for preparing vermicular precipitated calcium carbonate, which is characterized by comprising the following steps: the method comprises the following steps:
(1) slaking and reacting quicklime to obtain lime milk, and adjusting the specific gravity of the lime milk to 1.045-1.065 to obtain a calcium hydroxide suspension;
(2) adding salt of magnesium, strontium or barium element or compound thereof serving as a crystal form control agent into the calcium hydroxide suspension, stirring and mixing uniformly, adding into a carbonization tower, introducing mixed gas containing carbon dioxide for carbonation reaction, and stopping carbonation until the pH value is reduced to 9.0 to obtain PCC suspension;
(3) slowly adding phosphoric acid solution into the PCC suspension until the pH value is reduced to 7.0, stopping the reaction, standing for 10-30min, and then carrying out filter pressing, drying, crushing and grading on the suspension according to a conventional method to obtain vermicular precipitated calcium carbonate powder;
the crystal form control agent is one or a combination of more of magnesium chloride, magnesium oxide, magnesium hydroxide, calcium magnesium hydroxide, strontium chloride, strontium oxide, strontium nitrate, strontium cyanide, barium chloride, barium oxide, barium nitrate and barium acetate;
the dosage of the crystal form control agent is 0.1-0.8mol added into every 15kg of calcium hydroxide suspension, and the crystal form control agent is prepared into the calcium hydroxide suspension with the concentration of 1-8mol/L by water;
the mass concentration of the phosphoric acid solution is 5%; the adding speed of the phosphoric acid solution is 200-300 ml/min;
the initial carbonization temperature of the calcium hydroxide suspension in the carbonation reaction process is 20.0-24.0 ℃, the concentration of the carbon dioxide mixed gas is 30-33%, and the gas inlet flow is 2.0-2.4m3The stirring frequency was 20 Hz.
2. The process for the preparation of vermicular precipitated calcium carbonate according to claim 1, characterized in that: the crystal form control agent consists of 0.1mol of magnesium chloride and 0.2mol of strontium chloride; or 0.4mol of magnesium bicarbonate and 0.1mol of barium chloride; or 0.5mol of strontium nitrate and 0.3mol of strontium cyanide.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4152397A (en) * | 1978-03-17 | 1979-05-01 | Uhde Gmbh | Method for the conversion of phosphate rock containing magnesium into phosphoric acid and a mixture of magnesium and calcium carbonates |
| CN101565198A (en) * | 2009-05-26 | 2009-10-28 | 建德市双超钙业有限公司 | Production method of nano calcium carbonate special for organosilicon |
| CN101570343A (en) * | 2009-06-11 | 2009-11-04 | 福建省万旗非金属材料有限公司 | Method for preparing nanometer calcium carbonate special for water soluble ink by wet method |
| CN102124061A (en) * | 2008-08-13 | 2011-07-13 | Omya发展股份公司 | Process to prepare precipitated calcium carbonate implementing low charge acrylate and/or maleinate-containing polymer |
| CN107445188A (en) * | 2017-09-18 | 2017-12-08 | 广西华纳新材料科技有限公司 | A kind of preparation method of rod-like precipitates calcium carbonate |
-
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- 2020-12-21 CN CN202011516408.6A patent/CN112441605B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4152397A (en) * | 1978-03-17 | 1979-05-01 | Uhde Gmbh | Method for the conversion of phosphate rock containing magnesium into phosphoric acid and a mixture of magnesium and calcium carbonates |
| CN102124061A (en) * | 2008-08-13 | 2011-07-13 | Omya发展股份公司 | Process to prepare precipitated calcium carbonate implementing low charge acrylate and/or maleinate-containing polymer |
| CN101565198A (en) * | 2009-05-26 | 2009-10-28 | 建德市双超钙业有限公司 | Production method of nano calcium carbonate special for organosilicon |
| CN101570343A (en) * | 2009-06-11 | 2009-11-04 | 福建省万旗非金属材料有限公司 | Method for preparing nanometer calcium carbonate special for water soluble ink by wet method |
| CN107445188A (en) * | 2017-09-18 | 2017-12-08 | 广西华纳新材料科技有限公司 | A kind of preparation method of rod-like precipitates calcium carbonate |
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