CN107935013B - Method for preparing superfine calcium carbonate nano powder - Google Patents
Method for preparing superfine calcium carbonate nano powder Download PDFInfo
- Publication number
- CN107935013B CN107935013B CN201711180403.9A CN201711180403A CN107935013B CN 107935013 B CN107935013 B CN 107935013B CN 201711180403 A CN201711180403 A CN 201711180403A CN 107935013 B CN107935013 B CN 107935013B
- Authority
- CN
- China
- Prior art keywords
- precipitate
- ammonium bicarbonate
- slurry
- deionized water
- water solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Paper (AREA)
- Fertilizers (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention adopts a rapid precipitation method to prepare the superfine calcium carbonate, controls the particle size of particles by controlling the concentration of reactants, a solvent, reaction time, injection speed and stirring speed, and reduces the probability of collision and combination among nano particles by rapidly adding a large amount of deionized water to dilute the precipitate after reaction, thereby ensuring that the nano particles have good monodispersity. The invention adopts the processes of secondary aging and secondary carbonization, adds glucose and serine in the secondary carbonization, and reduces the pH value of the calcium carbonate product by controlling the dosage of the glucose and the serine.
Description
Technical Field
The invention belongs to the field of calcium carbonate material preparation, and particularly relates to a method for preparing nano calcium carbonate.
Background
The calcium carbonate is widely used in the industries of rubber, plastics, coating, papermaking, printing ink, sizing agent DIAN, sealant and the like, and can also be applied to the industries of toothpaste, food, medicine, word materials, building materials, chemical fibers and the like. The nano calcium carbonate has small particle size, large specific surface area and excellent performance compared with common calcium carbonate. The nano calcium carbonate with the grain diameter of 10-100nm has the reinforcing effect on rubber, plastics and the like; the reinforcing effect of the superfine calcium carbonate with the particle size of 5-20nm is equivalent to that of the white carbon black. However, the nano calcium carbonate prepared in the prior art is mostly micron and submicron size, and the ultra-small size nano calcium carbonate is difficult to obtain.
The prior art method for preparing calcium carbonate comprises the following steps: the method comprises the steps of an intermittent bubbling type carbonization method, an intermittent stirring type carbonization method, a continuous spraying type carbonization method, a hypergravity reaction crystallization method and the like, wherein the methods all need to adopt specific equipment, and the control of the particle size and the pH value of the calcium carbonate is difficult to guarantee.
Disclosure of Invention
The technical scheme of the invention is to overcome the defects of the prior art and provide the superfine, monodisperse and low-pH-value calcium carbonate nano powder.
The invention provides a method for preparing superfine calcium carbonate nano powder, which comprises the following steps:
1) crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry;
2) adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution;
3) under rapid and violent stirring, rapidly spraying the primary aged slurry and the ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed to generate white precipitate, wherein the reaction temperature is 20-30 ℃, and the reaction time is 2-3 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization;
5) filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
The concentration of calcium in the primary aged slurry is 0.05mol/L-0.1 mol/L.
The speed of injecting the primary aged slurry and the ammonium bicarbonate alcohol water solution into the reactor is 40L/h-100L/h.
In the step 3), the stirring speed is 2000rpm-3000 rpm.
The dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
In the step 3), the adding amount of ammonium bicarbonate is controlled, so that the pH value of the reaction system is 9-9.5 when the precipitation reaction is ended. The ammonium bicarbonate aqueous solution is prepared by reacting excessive carbon dioxide with an ammonium carbonate solution.
In step 4), the weight of glucose and serine added is 0.5% and 0.01% of the weight of the solid precipitate, respectively.
The invention adopts a rapid precipitation method to prepare the superfine calcium carbonate, controls the quantity of initial crystal nuclei in a reaction system by controlling the concentration of reactants and a solvent, controls the flowing state of liquid in a solution by controlling the spraying speed and the stirring speed, and controls the nucleation speed, the quantity of the crystal nuclei and the particle size of particles.
The reaction time of the invention is limited to 2-3min, and a large amount of deionized water is rapidly added to dilute the precipitate after the reaction, so that the distance between particles is rapidly increased, and the collision and combination probability between the nanoparticles is greatly reduced, thereby ensuring that the prepared nanoparticles have good monodispersity, the particle size of the calcium carbonate precursor formed after primary carbonization is about 3-5nm, and the particle size of the final product calcium carbonate is about 12-15 nm.
The invention adopts the processes of secondary aging and secondary carbonization, adds glucose and serine in the secondary carbonization, and reduces the pH value of the calcium carbonate product by controlling the dosage of the glucose and the serine, so that the pH value of the product is stabilized within the range of 7-8.
The invention has the beneficial effects that: the method prepares the superfine calcium carbonate nano powder by controlling the conditions of the precipitation reaction, does not use a surfactant in the precipitation reaction, has quick reaction, short period, simplicity and convenience, and can control the pH value of the product by secondary carbonization.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L;
2) adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 2
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 1 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 3
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 4 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 4
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.1 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 5
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.03 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 6
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.2 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 7
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 40L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 8
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 80L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 9
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, quickly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 100L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 10
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 120L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 11
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, quickly spraying the primary aged slurry and ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed of 30L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 12
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 2000rpm, rapidly spraying the once-aged slurry and ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 13
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 1500rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 14
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 4000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction time is 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 15
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) An aqueous ammonium bicarbonate solution was prepared.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and the ammonium bicarbonate aqueous solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of the ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 16
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, quickly spraying the primary aged slurry and ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction time is 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.3% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 17
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.8% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 18
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.005% of the weight of the solid precipitate, respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 19
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.02% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 20
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 9.5 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction time is 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 21
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 8.5 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction time is 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
Example 22
1) Crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry, wherein the concentration of calcium in the primary aged slurry is 0.05 mol/L. (ii) a
2) Adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution; wherein the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate water solution.
3) Under the stirring of 3000rpm, rapidly spraying the primary aged slurry and ammonium bicarbonate alcohol water solution into a reactor at the same speed of 60L/h to generate white precipitate, and controlling the addition amount of ammonium bicarbonate so as to ensure that the pH value of a reaction system is 10 when the precipitation reaction is ended, the reaction temperature is 20-30 ℃, and the reaction is carried out for 2 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization; wherein the added weight of glucose and serine is 0.5% and 0.01% of the weight of the solid precipitate respectively.
5) Filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) and mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder.
The morphology and properties of the products obtained in examples 1 to 22 are given in the following table
Claims (2)
1. A method for preparing superfine calcium carbonate nano powder is characterized by comprising the following steps: the method comprises the following steps:
1) crushing limestone, sieving, adding deionized water for digestion, and performing primary aging to obtain primary aged slurry;
2) adding absolute ethyl alcohol into the ammonium bicarbonate water solution to obtain an ammonium bicarbonate alcohol water solution;
3) under rapid and violent stirring, rapidly spraying the primary aged slurry and the ammonium bicarbonate alcohol aqueous solution into a reactor at the same speed to generate white precipitate, wherein the reaction temperature is 20-30 ℃, and the reaction time is 2-3 min; quickly adding a large amount of deionized water to dilute the precipitate, and performing secondary aging on the slurry;
4) after secondary aging, filtering, washing and dehydrating, re-dispersing the obtained solid precipitate in deionized water, simultaneously adding glucose and serine into the slurry, and introducing carbon dioxide for secondary carbonization;
5) filtering, washing and drying the slurry subjected to secondary carbonization to obtain a precipitate;
6) mixing the precipitate with n-butanol, and performing azeotropic distillation and dehydration under reduced pressure to obtain white ultra-small scale nano calcium carbonate powder;
the concentration of calcium in the primary aged slurry is 0.05mol/L-0.1 mol/L;
in the step 3), the stirring speed is 2000rpm-3000 rpm;
the dosage of the absolute ethyl alcohol is 5-8% of the volume of the ammonium bicarbonate aqueous solution;
in the step 4), the adding weight of the glucose and the serine is respectively 0.5 percent and 0.01 percent of the weight of the solid precipitate;
the speed of injecting the primary aged slurry and the ammonium bicarbonate alcohol water solution into the reactor is 40L/h-100L/h.
2. The method of claim 1, wherein: in the step 3), the adding amount of ammonium bicarbonate is controlled, so that the pH value of the reaction system is 9-9.5 when the precipitation reaction is ended.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711180403.9A CN107935013B (en) | 2017-11-17 | 2017-11-17 | Method for preparing superfine calcium carbonate nano powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711180403.9A CN107935013B (en) | 2017-11-17 | 2017-11-17 | Method for preparing superfine calcium carbonate nano powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107935013A CN107935013A (en) | 2018-04-20 |
| CN107935013B true CN107935013B (en) | 2020-08-28 |
Family
ID=61930873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711180403.9A Active CN107935013B (en) | 2017-11-17 | 2017-11-17 | Method for preparing superfine calcium carbonate nano powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107935013B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116675240B (en) * | 2023-06-21 | 2023-11-10 | 广西科学院 | Preparation method of mildew-proof antibacterial superfine active precipitated calcium carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986408A (en) * | 2006-12-22 | 2007-06-27 | 武汉大学 | Preparing process fibrous nano alumina powder |
| CN101318684A (en) * | 2008-06-28 | 2008-12-10 | 福建省万旗非金属材料有限公司 | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation |
| CN102126736A (en) * | 2011-01-19 | 2011-07-20 | 刘先黎 | Method for preparing nano-calcium carbonate powder by using soluble carbonate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365190B (en) * | 2016-08-26 | 2019-01-11 | 石家庄市东升钙业有限公司 | The preparation method of medicine fermentation calcium carbonate |
| CN107032383A (en) * | 2017-04-25 | 2017-08-11 | 井陉县天顺钙业有限公司 | The method for reducing precipitated calcium carbonate free alkali and pH value |
-
2017
- 2017-11-17 CN CN201711180403.9A patent/CN107935013B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986408A (en) * | 2006-12-22 | 2007-06-27 | 武汉大学 | Preparing process fibrous nano alumina powder |
| CN101318684A (en) * | 2008-06-28 | 2008-12-10 | 福建省万旗非金属材料有限公司 | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation |
| CN102126736A (en) * | 2011-01-19 | 2011-07-20 | 刘先黎 | Method for preparing nano-calcium carbonate powder by using soluble carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107935013A (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108467053B (en) | Preparation method of pompon calcium carbonate nano mixed crystal particles | |
| CN101225245A (en) | Method for preparing core-shell silicon dioxide coated nano calcium carbonate | |
| CN111777089A (en) | Preparation method of high-purity vaterite type calcium carbonate microspheres | |
| CN108516582B (en) | Preparation method of high-weather-resistance nano rutile titanium dioxide | |
| CN111592025B (en) | Preparation method of chrysanthemum-shaped micron calcium carbonate | |
| CN102249281A (en) | Lensing spherical vaterite calcium carbonate crystal with high purity and preparation method thereof | |
| CN105417565A (en) | Cubic CaCO3 and SiO2 composite particles and preparing method thereof | |
| CN110028074B (en) | Preparation method of spherical silicon dioxide | |
| CN103896284B (en) | A kind of monodisperse silica nano particle and preparation method thereof | |
| US4049781A (en) | Method of preparing loosely aggregated 200-500 millimicron silica | |
| CN105152231B (en) | The preparation method of anode material of lithium battery cobalt hydroxide | |
| CN107935013B (en) | Method for preparing superfine calcium carbonate nano powder | |
| KR101727983B1 (en) | Nano precipitation calcium carbonates | |
| CN107758718B (en) | Method for preparing superfine calcium carbonate nano powder from calcite | |
| CN108190935B (en) | Preparation method of strip-shaped and sheet-shaped calcium carbonate ultrafine particles | |
| CN110128851B (en) | Preparation method of hydrophobic nano calcium carbonate | |
| CN113104877A (en) | Preparation method and application of superfine dolomite | |
| CN112142087A (en) | Process for preparing regular spherical calcium carbonate by calcium chloride and ammonia water solution carbonization method | |
| CN111533951B (en) | Preparation method of aluminum silicate-white carbon black composite filler | |
| CN107117639B (en) | A kind of method that ultrasonic wave added prepares vaterite-type calcium carbonate nanometer package assembly | |
| CN112645382B (en) | Preparation method of nano titanium dioxide, nano titanium dioxide and application | |
| CN110203956B (en) | Method for preparing vaterite-phase-containing calcium carbonate by using calcium ethylene glycol wet ball milling | |
| CN104071849A (en) | Method both for preparation of iron oxide black and combined production of ammonium sulfate | |
| CN114291836A (en) | Calcium carbonate crystal form control agent, application thereof and preparation method of cubic calcium carbonate | |
| CN113651349B (en) | Method for preparing stable spherical vaterite phase calcium carbonate in organic medium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200731 Address after: 474650 Changling Industrial Park, Nanhedian, Nanzhao County, Nanyang City, Henan Province Applicant after: Nanyang Zhongrui Micro Powder Technology Co., Ltd Address before: 315400 room 1, 315, international business center, China Plastics City, Ningbo, Zhejiang, Yuyao Applicant before: NINGBO PLASTIC METAL PRODUCT Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |