CN115558316A - Low-alkalinity calcium carbonate and preparation process thereof - Google Patents
Low-alkalinity calcium carbonate and preparation process thereof Download PDFInfo
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- CN115558316A CN115558316A CN202210964296.3A CN202210964296A CN115558316A CN 115558316 A CN115558316 A CN 115558316A CN 202210964296 A CN202210964296 A CN 202210964296A CN 115558316 A CN115558316 A CN 115558316A
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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 319
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 155
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000003763 carbonization Methods 0.000 claims abstract description 76
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Substances CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002002 slurry Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 33
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 33
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 33
- 230000029087 digestion Effects 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000292 calcium oxide Substances 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 9
- 239000004571 lime Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 229920001661 Chitosan Polymers 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910021532 Calcite Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000011362 coarse particle Substances 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229960004424 carbon dioxide Drugs 0.000 description 33
- 235000011116 calcium hydroxide Nutrition 0.000 description 28
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 235000012255 calcium oxide Nutrition 0.000 description 11
- 235000012254 magnesium hydroxide Nutrition 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 2
- 239000002370 magnesium bicarbonate Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002686 lithotriptor Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a low alkalinity calcium carbonate and a preparation process thereof, wherein the pH value of the low alkalinity calcium carbonate is less than 8.0, the surface of the low alkalinity calcium carbonate is coated with a chitosan-acetic anhydride material, and the preparation process of the low alkalinity calcium carbonate comprises the following steps: step S1, digestion: adding water to the CaO obtained by the lime kiln for digestion to generate calcium hydroxide; step S2, carbonization: introducing carbon dioxide into the calcium hydroxide suspension, and adding a crystal form regulator to obtain calcium carbonate slurry; step S3, aging: standing the prepared calcium carbonate slurry until the pH value of the calcium carbonate slurry is stable; step S4, secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry until the pH value of the slurry is less than 7.2; step S5, surface modification: synthesizing chitosan-acetic anhydride modified calcium carbonate; step S6, dewatering and drying: and (3) quickly injecting the calcium carbonate slurry subjected to surface modification into a high-speed running centrifugal machine for dehydration, and then drying.
Description
Technical Field
The invention relates to the technical field of calcium carbonate, in particular to low-alkalinity calcium carbonate and a preparation process thereof.
Background
The calcium carbonate has wide application, can be used as a filling and modifying material, is used in the industries of adhesives, papermaking, plastics, rubber, paint, food processing, pharmacy and the like, and has close relation with the daily life of people. The source of alkalinity in calcium carbonate is free base that is produced during the manufacturing process for some reason. The free alkali refers to a substance existing in the form of calcium hydroxide or calcium oxide instead of being converted into calcium carbonate in the production of calcium carbonate, and the alkalinity is too high, so that the free alkali can react with other plasticizers of plastics to cause the problems of brittleness, yellowing and the like of the plastics. The addition of the free alkali in food and rubber can cause alkalinity change and affect the performance of a final finished product, and the free alkali is an important technical index in calcium carbonate products and must be strictly controlled in production.
The calcium carbonate has high alkalinity, the digestion of the quicklime is incomplete, and the calcium carbonate generated during the carbonization takes fine particles as crystal nuclei and is deposited on the crystal nuclei to form calcium carbonate coated calcium oxide particles. The calcium oxide crystal is cubic and the calcium carbonate crystal is rhombohedral, the intercrystalline angles of the two crystals are different, and different expansion coefficients are generated after the temperature is raised, so that the crystal grains are broken, the calcium oxide is dissociated, and the calcium oxide is alkaline. When the carbonization reaches the end point, the pH is = 8-10, and the basic calcium carbonate is alkaline and cannot be damaged. The basic calcium carbonate is not changed, the next procedure is carried out, and after the basic calcium carbonate enters the rotary dryer, the basic calcium carbonate is decomposed into calcium hydroxide and calcium carbonate at the increased temperature, so that the alkalinity is higher.
The current production method of calcium carbonate which is commonly used in industry is to introduce carbon dioxide into calcium hydroxide suspension for carbonization, then to dehydrate, dry, depolymerize and screen to obtain the finished product of calcium carbonate, the pH value of calcium carbonate powder prepared by the carbonization method is usually between 9.5 and 10.5, and the pH value of the product is difficult to be reduced below 9.0 even under the condition that the production process conditions are perfect and calcium hydroxide is completely acidified by carbon dioxide.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides low-alkalinity calcium carbonate and a preparation process thereof, and solves the problem of high alkalinity of the existing calcium carbonate.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a low alkalinity calcium carbonate and a preparation process thereof, comprising the following steps:
step S1, digestion: adding water into CaO obtained by a lime kiln to digest, so as to generate calcium hydroxide and a small amount of magnesium hydroxide, wherein the amount of the water for digestion is 6-8 times of the mass of the powder, and the digestion temperature is 75-90 ℃;
step S2, carbonization: firstly, preparing a calcium hydroxide suspension, then introducing carbon dioxide into the calcium hydroxide suspension, keeping the pressure of the carbon dioxide at 0.2MPa, the concentration of the carbon dioxide at 25-30%, the carbonization time at 10-14h, the carbonization mass increment rate at 22-25%, adding a crystal form regulator, and detecting that the crystal form of a product is calcite type calcium carbonate to obtain calcium carbonate slurry;
step S3, aging: standing and aging the prepared calcium carbonate slurry for 8-12h until the pH value of the calcium carbonate slurry is stable;
step S4, secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry until the pH value of the slurry is less than 7.2;
step S5, surface modification: synthesizing chitosan-acetic anhydride modified calcium carbonate, firstly putting the calcium carbonate slurry obtained in the step (1) into a beaker, performing dispersion treatment for 20min at the rotating speed of 500r/min to form calcium carbonate suspension, secondly adding 0.1% of acetic anhydride (calculated by absolute dry mass of calcium carbonate) into the calcium carbonate suspension, putting the beaker into a water bath kettle, stirring and reacting at the speed of 500r/min for 60min after the temperature of the suspension reaches 50 ℃, then filtering reaction liquid, collecting solid powder, and further washing unreacted acetic anhydride by using distilled water; finally, dispersing the washed solid powder into distilled water with the same volume, adding 5 percent (calculated by the absolute dry mass of calcium carbonate) of chitosan, magnetically stirring and reacting for 2 hours at 50 ℃ at 500r/min, and filtering reaction liquid to obtain chitosan-acetic anhydride modified calcium carbonate slurry;
step S6, dewatering and drying: and (5) injecting the surface-modified calcium carbonate slurry obtained in the step (S5) into a centrifuge for dehydration until no slurry is thrown out for removal to obtain calcium carbonate particles, then drying, carrying out secondary deep drying on the calcium carbonate particles through hot air, finally separating the calcium carbonate from the hot air, and sieving to remove coarse particles to obtain the finished product low-alkalinity calcium carbonate with the pH value lower than 8.0.
Preferably, the digestion water meets the following requirements: the suspended matter is less than or equal to 20mg/L, the transparency is more than or equal to 30CM, the hydrochloric acid insoluble matter is less than or equal to 10mg/L, the ferric oxide is less than or equal to 10mg/L, and the magnesium oxide is less than or equal to 100mg/L.
Preferably, the carbon dioxide gas concentration is prepared by mixing high-purity carbon dioxide with nitrogen or inert gas according to a certain proportion.
Preferably, the crystal form regulator is one of ethanol and sodium citrate, when ethanol is selected, the volume fraction of the ethanol in a water/ethanol solution system is 20-35%, the product is calcite type calcium carbonate, the calcite belongs to a trigonal system, the characteristic morphology is rhombohedral, the thermodynamics is most stable, and when sodium citrate is selected, the addition amount of the sodium citrate is 0.1-0.3% of the solution.
Preferably, the carbonization temperature is 50-75 ℃, and the secondary carbonization temperature is 35-60 ℃.
Preferably, the carbonization mass increase rate formula is:
wherein M1 represents the mass of the powder before carbonization, and M2 represents the mass of the dried powder after carbonization.
The principle is as follows: in the process of generating calcium carbonate by calcium hydroxide carbonization, although the gas environment with higher carbonization rate is slow under the condition of low-concentration carbon dioxide gas, the low-concentration gas environment is favorable for the strength development of a carbonized test block, because the external calcium hydroxide is quickly carbonized under the condition of high-concentration carbon dioxide, the carbon dioxide gas is not easy to enter the calcium hydroxide at the later stage, and the carbonization is not uniform, the carbonization concentration is 25-30 percent in the invention; in the carbonization process, a crystal form modifier is added to ensure that the crystal form of calcium carbonate is calcite, the lithotriptor belongs to a trigonal crystal system, the characteristic morphology is rhombohedral, the thermodynamics is most stable, and the calcium carbonate is prevented from being heated and decomposed; in the dehydration process, the residual water in the filter cake is reduced to the maximum extent, and the magnesium bicarbonate dissolved in the calcium carbonate slurry is thrown away along with the water to the maximum extent; the acetic anhydride and the chitosan are coated on the surface of the calcium carbonate, so that the calcium carbonate has good dispersibility and smaller average particle size, mainly because the surface of the calcium carbonate is coated with a layer of chitosan, the dispersibility of the calcium carbonate particles is favorably improved, the electropositivity of the modified calcium carbonate is higher than that of the calcium carbonate, the chitosan also contains residual amino and hydroxyl, and the addition of the modified calcium carbonate into the material is favorable for improving the physical strength performance of the material.
(III) advantageous effects
The invention provides low-alkalinity calcium carbonate and a preparation process thereof, and the low-alkalinity calcium carbonate has the following beneficial effects: the preparation process of the low-alkalinity calcium carbonate obtains the low-alkalinity calcium carbonate with the pH value less than 8 through digestion, carbonization, aging and secondary carbonization, slowly carbonizes to expand the carbonization effect from inside to outside by controlling the carbonization concentration, avoids the phenomenon that the carbonization is not uniform because the calcium carbonate wraps the calcium hydroxide, removes the magnesium hydroxide in the calcium carbonate through dehydration, can reduce the alkalinity, maintains the dryness of the calcium carbonate through the dehydration property of the acetic anhydride by wrapping the surface of the calcium carbonate with acetic anhydride and chitosan, increases the dispersibility and the potential of the calcium carbonate through the chitosan, and improves the retention rate of the calcium carbonate on materials when the calcium carbonate is used as a filling and modifying material.
Detailed Description
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.
The purity of acetic anhydride used by the invention is more than 98 percent and is purchased from Nanjing reagent mall company, chitosan (CS, deacetylation is more than 87 percent) is purchased from national medicine group chemical reagent company, and the water used in the test process is distilled water.
Example 1
The invention provides a technical scheme that: a low-alkalinity calcium carbonate and a preparation process thereof, wherein the pH value of the low-alkalinity calcium carbonate is less than 8.0, the surface of the low-alkalinity calcium carbonate is coated with chitosan-acetic anhydride, and the preparation process of the low-alkalinity calcium carbonate comprises the following steps:
step S1, digestion: adding water to the CaO obtained by the lime kiln for digestion to generate calcium hydroxide and a small amount of magnesium hydroxide, wherein the reaction is as follows:
CaO+H 2 O→Ca(OH)2 △H＜0
MgO+H2O→Mg(OH)2 △H＜0
the solubility of calcium hydroxide in water is higher than that of magnesium hydroxide, the water consumption for digestion is 6-8 times of the mass of the powder, and the digestion temperature is 70-90 ℃;
step S2, carbonization: firstly, preparing a calcium hydroxide suspension, introducing carbon dioxide into the calcium hydroxide suspension, keeping the pressure of the carbon dioxide at 0.2MPa, the concentration of the carbon dioxide at 30%, the carbonization time at 10-14h and the carbonization mass increase rate at 22-25%, adding ethanol to ensure that the volume fraction of the ethanol in a water/ethanol solution system is 20%, and detecting that the crystal form of a product is calcite type calcium carbonate to obtain calcium carbonate slurry;
step S3, aging: standing the prepared calcium carbonate slurry until the pH value of the calcium carbonate slurry is stable;
step S4, secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry until the pH value of the slurry is less than 7.2;
step S5, surface modification: synthesizing chitosan-acetic anhydride modified calcium carbonate, firstly, putting the calcium carbonate slurry obtained in the step 1 into a beaker, performing dispersion treatment for 20min at the rotating speed of 500r/min to form calcium carbonate suspension, secondly, adding 0.1% of acetic anhydride (calculated by absolute dry mass of calcium carbonate) into the calcium carbonate suspension, putting the beaker into a water bath kettle, stirring and reacting at the speed of 500r/min for 60min after the temperature of the suspension reaches 50 ℃, then filtering reaction liquid, collecting solid powder, and further washing away unreacted acetic anhydride by using distilled water; finally, dispersing the washed solid powder into distilled water with the same volume, adding 5 percent (calculated by the absolute dry mass of calcium carbonate) of chitosan, magnetically stirring and reacting for 2 hours at 50 ℃ at 500r/min, and filtering reaction liquid to obtain chitosan-acetic anhydride modified calcium carbonate slurry;
step S6, dewatering and drying: and (3) quickly injecting the calcium carbonate slurry subjected to surface modification into a high-speed running centrifugal machine for dehydration until no slurry is thrown out, so that the aim of reducing the residue of magnesium ions in the product to the maximum extent is fulfilled, and then drying.
Further, the digestion water satisfies the following requirements: the suspended matter is less than or equal to 20mg/L, the transparency is more than or equal to 30CM, the hydrochloric acid insoluble matter is less than or equal to 10mg/L, the ferric oxide is less than or equal to 10mg/L, the magnesium oxide is less than or equal to 100mg/L, and the carbon dioxide gas concentration is prepared by mixing high-purity carbon dioxide and nitrogen or inert gas according to a certain proportion.
Further, the carbonization temperature is 50-75 ℃, and the secondary carbonization temperature is 35-60 ℃.
Further, the carbonization mass increase rate formula is as follows:
wherein M1 represents the mass of the powder before carbonization, and M2 represents the mass of the dried powder after carbonization.
Example 2
The invention provides a technical scheme that: a low-alkalinity calcium carbonate and a preparation process thereof, wherein the pH value of the low-alkalinity calcium carbonate is less than 8.0, the surface of the low-alkalinity calcium carbonate is coated with chitosan-acetic anhydride, and the preparation process of the low-alkalinity calcium carbonate comprises the following steps:
step S1, digestion: adding water into CaO obtained by a lime kiln to digest to generate calcium hydroxide and a small amount of magnesium hydroxide, wherein the amount of the water for digestion is 6-8 times of the mass of the powder, and the digestion temperature is 70-90 ℃;
step S2, carbonization: firstly, preparing calcium hydroxide suspension, then introducing carbon dioxide into the calcium hydroxide suspension, keeping the pressure of the carbon dioxide at 0.2MPa, the concentration of the carbon dioxide at 25%, the carbonization time at 10-14h, the increase rate of the carbonization mass at 22-25%, adding 0.1% of sodium citrate, and detecting that the crystal form of a product is calcite type calcium carbonate to obtain calcium carbonate slurry;
s3, aging: standing the prepared calcium carbonate slurry until the pH value of the calcium carbonate slurry is stable;
step S4, secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry until the pH value of the slurry is less than 7.2;
step S5, surface modification: synthesizing chitosan-acetic anhydride modified calcium carbonate, firstly, putting the calcium carbonate slurry obtained in the step 1 into a beaker, performing dispersion treatment for 20min at the rotating speed of 500r/min to form calcium carbonate suspension, secondly, adding 0.1% of acetic anhydride (calculated by absolute dry mass of calcium carbonate) into the calcium carbonate suspension, putting the beaker into a water bath kettle, stirring and reacting at the speed of 500r/min for 60min after the temperature of the suspension reaches 50 ℃, then filtering reaction liquid, collecting solid powder, and further washing away unreacted acetic anhydride by using distilled water; finally, dispersing the washed solid powder into distilled water with the same volume, adding 5 percent (calculated by the absolute dry mass of calcium carbonate) of chitosan, magnetically stirring and reacting for 2 hours at 50 ℃ at 500r/min, and filtering reaction liquid to obtain chitosan-acetic anhydride modified calcium carbonate slurry;
step S6, dewatering and drying: and (3) quickly injecting the calcium carbonate slurry subjected to surface modification into a high-speed running centrifugal machine for dehydration until no slurry is thrown out, so that the aim of reducing the residue of magnesium ions in the product to the maximum extent is fulfilled, and then drying.
Further, the digestion water satisfies the following requirements: the suspended matter is less than or equal to 20mg/L, the transparency is more than or equal to 30CM, the hydrochloric acid insoluble matter is less than or equal to 10mg/L, the ferric oxide is less than or equal to 10mg/L, the magnesium oxide is less than or equal to 100mg/L, and the carbon dioxide gas concentration is prepared by mixing high-purity carbon dioxide and nitrogen or inert gas according to a certain proportion.
Further, the carbonization temperature is 50-75 ℃, and the secondary carbonization temperature is 35-60 ℃.
Further, the carbonization mass increase rate formula is as follows:
wherein M1 represents the mass of the powder before carbonization, and M2 represents the mass of the powder after carbonization.
Example 3
The invention provides a technical scheme that: a low-alkalinity calcium carbonate and a preparation process thereof, wherein the pH value of the low-alkalinity calcium carbonate is less than 8.0, the surface of the low-alkalinity calcium carbonate is coated with chitosan-acetic anhydride, and the preparation process of the low-alkalinity calcium carbonate comprises the following steps:
step S1, digestion: adding water into CaO obtained by a lime kiln to digest to generate calcium hydroxide and a small amount of magnesium hydroxide, wherein the amount of the water for digestion is 6-8 times of the mass of the powder, and the digestion temperature is 70-90 ℃;
step S2, carbonization: firstly, preparing a calcium hydroxide suspension, introducing carbon dioxide into the calcium hydroxide suspension, keeping the pressure of the carbon dioxide at 0.2MPa, the concentration of the carbon dioxide at 30%, the carbonization time at 10-14h, the increase rate of the carbonization mass at 22-25%, adding 0.2% of sodium citrate, and detecting that the crystal form of a product is calcite calcium carbonate to obtain calcium carbonate slurry;
step S3, aging: standing the prepared calcium carbonate slurry until the pH value of the calcium carbonate slurry is stable;
step S4, secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry until the pH value of the slurry is less than 7.2;
step S5, surface modification: synthesizing chitosan-acetic anhydride modified calcium carbonate, firstly, putting the calcium carbonate slurry obtained in the step (1) into a beaker, performing dispersion treatment for 20min at the rotating speed of 500r/min to form calcium carbonate suspension, secondly, adding 0.1% of acetic anhydride (calculated by absolute dry mass of calcium carbonate) into the calcium carbonate suspension, putting the beaker into a water bath kettle, stirring and reacting at the speed of 500r/min for 60min after the temperature of the suspension reaches 50 ℃, then filtering reaction liquid, collecting solid powder, and further washing unreacted acetic anhydride by using distilled water; finally, dispersing the washed solid powder into distilled water with the same volume, adding 5 percent (calculated by the absolute dry mass of calcium carbonate) of chitosan, magnetically stirring and reacting for 2 hours at 50 ℃ at 500r/min, and filtering reaction liquid to obtain chitosan-acetic anhydride modified calcium carbonate slurry;
step S6, dewatering and drying: and (3) quickly injecting the calcium carbonate slurry subjected to surface modification into a high-speed running centrifugal machine for dehydration until no slurry is thrown out, so that the aim of reducing the residue of magnesium ions in the product to the maximum extent is fulfilled, and then drying.
Further, the digestion water satisfies the following requirements: the suspended matter is less than or equal to 20mg/L, the transparency is more than or equal to 30CM, the hydrochloric acid insoluble matter is less than or equal to 10mg/L, the ferric oxide is less than or equal to 10mg/L, the magnesium oxide is less than or equal to 100mg/L, and the carbon dioxide gas concentration is prepared by mixing high-purity carbon dioxide and nitrogen or inert gas according to a certain proportion.
Further, the carbonization temperature is 50-75 ℃, and the secondary carbonization temperature is 35-60 ℃.
Further, the carbonization quality is increasedThe formula of the addition rate is as follows:
wherein M1 represents the mass of the powder before carbonization, and M2 represents the mass of the dried powder after carbonization.
The working principle is as follows: although the carbonization rate of calcium hydroxide is higher and the concentration gas environment is slow under the condition of low-concentration carbon dioxide gas, the low-concentration gas environment is beneficial to the strength development of the carbonized test block. The carbonization gradually expands from the outside to the inside of the test block, and under the condition of high-concentration carbon dioxide, the external calcium hydroxide is quickly carbonized, so that carbon dioxide gas is not easy to enter the inside of the test block at the later stage, so that the carbonization of the test block is not uniform, and finally, when the test block is pressed, the force is mainly born by the periphery of the test block, the actual pressed surface of the test block is reduced, and the compressive strength is reduced; the residual water in the filter cake is reduced to the maximum extent, and simultaneously the magnesium bicarbonate dissolved in the calcium carbonate slurry is thrown out along with the water to the maximum extent; caO obtained by a lime kiln is digested by adding water to generate calcium hydroxide and a small amount of magnesium hydroxide, the solubility of the calcium hydroxide in water is larger than that of the magnesium hydroxide, for example, the solubility in water at 20 ℃, mg (OH) 2 is 5X 10 < -4 > mol/L, ca (OH) 2 is 6.9X 10 < -3 > mol/L, and the magnesium hydroxide in lime milk is difficult to remove because the ionic properties of calcium and magnesium are similar and the calcium and the magnesium are difficult to dissolve in water. In order to obtain lime milk with fine particle size and high dispersion, the digestion reaction is carried out at a higher temperature.
Examples of the experiments
The carbonization mass increase rate is calculated through an experimental example, the carbonization mass increase rate is an important index for representing the carbonization degree of calcium hydroxide, and the calculation formula is as follows:
wherein M1 represents the mass of the powder before carbonization, M2 represents the mass of the powder after carbonization, the increase rates of the carbonization mass obtained in examples 1 to 3 were respectively: 22.8%, 23.6% and 24.1%.
And (3) alkalinity detection: data measurements were performed on the low-basicity nano calcium carbonate obtained in examples 1 to 3 and the comparative example, which is a commercially available calcium carbonate, to obtain the following table.
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Average particle diameter (μm) | 8-12 | 6-11 | 6-14 | 14-20 |
| Aspect ratio | 14-17 | 15-21 | 12-17 | 10-20 |
| Alkalinity of | 7.6 | 7.5 | 7.4 | 8.6 |
And (3) characterizing a chemical structure: major chemical bonding of modified calcium carbonate and calcium carbonate using FT-IR and XPSCharacterizing the structure to obtain: compared with calcium carbonate, the modified calcium carbonate is removed of methylene (-CH) on chitosan 2 ) At 2920cm -1 And 2870cm -1 1154cm outside the peak of the stretching vibration -1 The absorption peak is the stretching vibration peak of the C-N bond, which indicates that the chitosan is coated on the surface of the calcium carbonate; 1053cm -1 The absorption peak is 0-Ca stretching vibration peak of carboxyl oxygen and calcium, which shows the formation of calcium acetate, and the characterization further shows that N element in the chitosan mainly exists in a C-NH structure, and the binding energy is about 399eV.
Physical structure characterization: the modified calcium carbonate obtained in example 1 and the dispersibility of calcium carbonate were characterized to obtain: compared with calcium carbonate, the modified calcium carbonate has good dispersibility, smaller particle size, uniform dispersion and obviously improved agglomeration phenomenon, the average particle size of the modified calcium carbonate is 8.15 mu m, the particle size distribution range is 0.5-20 mu m, and the particle size distribution range is obviously lower than the average particle size (16.4 mu m) and the particle size distribution range (0.1-100 mu m) of the calcium carbonate, so that the acetic anhydride and chitosan modification can effectively prevent the agglomeration of carbonic anhydride particles.
In conclusion, the calcium carbonate with low alkalinity and the preparation process thereof obtain the calcium carbonate with low alkalinity of which the pH value is less than 8 through digestion, carbonization, aging and secondary carbonization, the carbonization effect is expanded from inside to outside through controlling the carbonization concentration and slow carbonization, the phenomenon that the carbonization is not uniform because the calcium carbonate wraps calcium hydroxide is avoided, the alkalinity can be reduced by removing magnesium hydroxide in the calcium carbonate through dehydration, acetic anhydride and chitosan are wrapped on the surface of the calcium carbonate, the dryness of the calcium carbonate is kept through the dehydration property of the acetic anhydride, the dispersibility and the potential of the calcium carbonate are increased through the chitosan, so that the retention rate of the calcium carbonate on materials is improved when the calcium carbonate is used as a filling and modifying material, and the problem of high alkalinity of the existing calcium carbonate is solved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A low-alkalinity calcium carbonate and a preparation process thereof are characterized in that: the pH value of the low-alkalinity calcium carbonate is less than 8.0, the surface of the low-alkalinity calcium carbonate is coated with a chitosan-acetic anhydride material, and the preparation process of the low-alkalinity calcium carbonate comprises the following steps:
step S1, digestion: adding water into CaO obtained by a lime kiln to digest, so as to generate calcium hydroxide and a small amount of magnesium hydroxide, wherein the amount of the water for digestion is 6-8 times of the mass of the powder, and the digestion temperature is 75-90 ℃;
step S2, carbonization: firstly, preparing a calcium hydroxide suspension, introducing carbon dioxide into the calcium hydroxide suspension, keeping the pressure of the carbon dioxide at 0.2MPa, the concentration of the carbon dioxide at 25-30%, the carbonization time at 10-14h, the carbonization mass increase rate at 22-25%, adding a crystal form regulator, and detecting that the crystal form of a product is calcite calcium carbonate to obtain calcium carbonate slurry;
s3, aging: standing and aging the prepared calcium carbonate slurry for 8-12h until the pH value of the calcium carbonate slurry is stable;
step S4, secondary carbonization: introducing carbon dioxide into the aged nano calcium carbonate slurry until the pH value of the slurry is less than 7.2;
step S5, surface modification: synthesizing chitosan-acetic anhydride modified calcium carbonate, firstly putting the calcium carbonate slurry obtained in the step (1) into a beaker, performing dispersion treatment for 20min at the rotating speed of 500r/min to form calcium carbonate suspension, secondly adding 0.1% of acetic anhydride into the calcium carbonate suspension, putting the beaker into a water bath, stirring and reacting for 60min at the speed of 500r/min after the temperature of the suspension reaches 50 ℃, then filtering reaction liquid, collecting solid powder, and further washing unreacted acetic anhydride by using distilled water; finally, dispersing the washed solid powder into distilled water with the same volume, adding 5% of chitosan, magnetically stirring and reacting for 2 hours at 50 ℃ at 500r/min, and filtering the reaction solution to obtain chitosan-acetic anhydride modified calcium carbonate slurry;
s6, dewatering and drying: and (5) injecting the surface-modified calcium carbonate slurry obtained in the step (S5) into a centrifuge for dehydration until no slurry is thrown out for removal to obtain calcium carbonate particles, then drying, carrying out secondary deep drying on the calcium carbonate particles through hot air, finally separating the calcium carbonate from the hot air, and sieving to remove coarse particles to obtain the finished product low-alkalinity calcium carbonate with the pH value lower than 8.0.
2. The low alkalinity calcium carbonate and the preparation process thereof according to claim 1, wherein: the digestion water meets the following requirements: the suspended matter is less than or equal to 20mg/L, the transparency is more than or equal to 30CM, the hydrochloric acid insoluble matter is less than or equal to 10mg/L, the ferric oxide is less than or equal to 10mg/L, and the magnesium oxide is less than or equal to 100mg/L.
3. The low alkalinity calcium carbonate and the preparation process thereof according to claim 1, characterized in that: the carbon dioxide gas concentration is prepared by mixing high-purity carbon dioxide and nitrogen or inert gas according to a certain proportion.
4. The low alkalinity calcium carbonate and the preparation process thereof according to claim 1, characterized in that: the crystal form regulator is one of ethanol and sodium citrate, when ethanol is selected, the volume fraction of the ethanol in a water/ethanol solution system is 20-35%, the product is calcite type calcium carbonate, the calcite belongs to a trigonal system, the characteristic morphology is rhombohedral, the thermodynamics is most stable, and when sodium citrate is selected, the addition amount of the sodium citrate is 0.1-0.3% of the solution.
5. The low alkalinity calcium carbonate and the preparation process thereof according to claim 1, wherein: the carbonization temperature is 50-75 ℃, and the secondary carbonization temperature is 35-60 ℃.
6. The low alkalinity calcium carbonate and the preparation process thereof according to claim 1, characterized in that: the carbonization mass increase rate formula is as follows:
wherein M1 represents the mass of the powder before carbonization, and M2 represents the mass of the powder after carbonization.
7. The low alkalinity calcium carbonate and the preparation process thereof according to claim 1, characterized in that: the deacetylation of the chitosan is more than 88 percent.
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