CN111777089A - Preparation method of high-purity vaterite type calcium carbonate microspheres - Google Patents
Preparation method of high-purity vaterite type calcium carbonate microspheres Download PDFInfo
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- CN111777089A CN111777089A CN201910271454.5A CN201910271454A CN111777089A CN 111777089 A CN111777089 A CN 111777089A CN 201910271454 A CN201910271454 A CN 201910271454A CN 111777089 A CN111777089 A CN 111777089A
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- 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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- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to a method for preparing high-purity vaterite type calcium carbonate microspheres by using calcium sulfate raw materials, which comprises the following steps: 1) grinding a calcium sulfate raw material to obtain a powder raw material; 2) mixing the powder raw material obtained in the step 1) with a leaching aid, placing the mixture into a reaction container with a stirrer for reaction, and after the reaction is finished, carrying out solid-liquid separation on a reaction product to obtain filtrate rich in calcium ions and a solid product; 3) mixing the filtrate obtained in the step 2) with ammonia water, and introducing CO2And (3) reacting the gas in a reaction vessel with stirring, controlling the process conditions to obtain the high-purity vaterite type calcium carbonate microspheres, and further recovering the filtrate for leaching the calcium sulfate raw material. The calcium carbonate microsphere material is non-toxic and safe, has fine particles, has the characteristics of high whiteness, good fluidity and the like, and can be applied to the industries of rubber, plastics, chemical engineering and the like.
Description
Technical Field
The invention relates to a preparation method of high-purity vaterite type calcium carbonate microspheres, in particular to a method for preparing the high-purity vaterite type calcium carbonate microspheres from calcium sulfate raw materials without adding a crystal form control agent, and belongs to the field of inorganic functional materials and chemical materials.
Background
Calcium carbonate is an important inorganic chemical filler, is widely applied to industries such as rubber, plastics, coating, papermaking, printing ink, sealant and the like, and can also be applied to industries such as toothpaste, food, medicine, building materials, chemical industry and the like. Calcium carbonate has three crystal forms, calcite, aragonite and vaterite, wherein the calcite structure is the most stable, aragonite is the second, and vaterite is the least stable.
Compared with the common calcium carbonate, the spherical calcium carbonate has the special properties of large surface area, good dispersibility, small density, good solubility, good smoothness, fluidity and the like, and can improve the covering rate, whiteness, adhesive force, washing resistance, stain resistance and the like of the material; the reinforcing effect of the superfine spherical calcium carbonate with the particle size of 1-10 mu m is equivalent to that of white carbon black. However, the spherical calcium carbonate prepared in the prior reports is large in size, and the addition of a crystal form control agent is generally required.
The invention patent with the patent number of CN107162032A discloses a method for preparing vaterite type calcium carbonate nano-particles by ultrasonic assistance. The method uses calcium nitrate or calcium chloride as a main raw material, uses ethylene glycol monobutyl ether as a crystal form control agent and a morphology control agent, and initiates reaction through ultrasonic action to finally obtain the calcium carbonate nano-particles. The whole process takes an analytically pure medicament as a raw material, a crystal form and a morphology control agent are added, the reaction needs to be carried out by means of the action of ultrasonic waves, the cost of the raw material and equipment of the process is high, and the large-scale industrial production of the process is not utilized.
The invention patent No. CN107128963A discloses a method for preparing spherical vaterite calcium carbonate with concentrated particle size distribution by utilizing electric furnace slag, which comprises the step of reacting leaching solution obtained by mixing and reacting electric furnace slag and ammonium chloride solution with ammonia water and carbon dioxide in a microwave radial state to obtain the vaterite type spherical calcium carbonate. The method takes solid waste as a main raw material, and the prepared spherical calcium carbonate has uniform appearance. The method needs microwave action in the preparation process, has higher requirements on preparation process equipment, and the prepared calcium carbonate particles have larger particle size and cannot meet the requirements of ultrafine calcium carbonate.
In conclusion, the existing preparation process of the vaterite-type calcium carbonate microspheres has the problems of high raw material cost, complex preparation process, need of adding a crystal form control agent and the like, so the invention provides a novel method for preparing high-purity vaterite-type calcium carbonate microspheres at low temperature and normal pressure by using a calcium sulfate raw material without adding the crystal form control agent aiming at the defects of the preparation method of the vaterite-type calcium carbonate microspheres.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of high-purity vaterite type calcium carbonate microspheres, which is low in temperature and normal in pressure, easy to realize industrially, and good in applicability, wherein a calcium sulfate raw material does not need to be added with a crystal form control agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of high-purity vaterite type calcium carbonate microspheres comprises the following steps:
1) grinding the calcium sulfate raw material to obtain calcium sulfate powder with the average particle size of 60-180 meshes;
2) mixing the calcium sulfate powder obtained in the step 1) with a leaching aid, placing the mixture in a reaction container with stirring, and reacting for 30-120 min under the conditions of normal pressure and 30-120 ℃ to obtain a reaction product;
3) and (3) carrying out suction filtration, washing and drying on the reaction product obtained in the step 2) to obtain filtrate rich in calcium ions and a solid reaction product.
4) Taking a certain volume of filtrate rich in calcium ions, adding a certain amount of ammonia water, and introducing CO at a certain speed2Reacting the gas for 30-180 min under the conditions of normal pressure and 30-100 ℃ to obtain a reaction product;
5) carrying out suction filtration, washing and drying on the reaction product obtained in the step 4) to obtain a vaterite type calcium carbonate microsphere material; the filtrate is recycled for leaching the calcium sulfate raw material.
The calcium sulfate raw materials in the step 1) mainly comprise natural gypsum, gypsum tailings, industrial byproduct gypsum and the like; in the step 2), the leaching auxiliary agent is one or more of ammonium acetate, ammonium chloride and ammonium sulfate; the concentration of the leaching auxiliary agent is 2-12 mol/L; the addition amount of the leaching aid is 5-20 mL/g.
The concentration of calcium ions in the filtrate rich in calcium ions in the step 4) is 3-25 g/L, and the concentration of the calcium ions in the solution is adjusted by adding industrial water or calcium chloride and calcium acetate powder; the addition amount of the ammonia water is 3-15 mL/100 mL; the stirring speed is 50-400 r/min; CO 22The flow rate is 30-250 mL/min.
The crystal form of the calcium carbonate microsphere prepared by the method is a vaterite type, the morphology is spherical, the content of calcium carbonate is more than 99.9 percent, the diameter of the particle is 0.3-1.5 mu m, and the whiteness is more than 98.
The method for preparing the high-purity vaterite-type calcium carbonate microspheres has the following beneficial effects: 1) the raw material used in the invention is calcium sulfate, which is easy to obtain and low in price; 2) the whole preparation process is carried out at low temperature and normal pressure, and is safe; 3) no crystal form control agent is needed to be added, and the preparation cost is low; 4) the leaching auxiliary agent is a neutral auxiliary agent, so that the equipment cannot be corroded, the auxiliary agent can be recycled, and the equipment investment is low; 5) the purity of the prepared calcium carbonate microsphere material can reach more than 99.9 percent, the whiteness is more than 98, and the particle diameter is 0.3-2 mu m on the premise of reducing the dosage of chemical additives and shortening the production period by using the method.
Drawings
Fig. 1 is an XRD pattern of the vaterite-type calcium carbonate microspheres prepared in example 1.
Fig. 2 is an SEM image of the vaterite-type calcium carbonate microspheres prepared in example 1.
Detailed Description
The invention relates to a preparation method of a high-purity vaterite-type calcium carbonate microsphere, which comprises the following steps.
1) The calcium sulfate raw material is ground to obtain calcium sulfate powder with the average granularity of 60-180 meshes.
Wherein, the calcium sulfate raw materials in the step 1) mainly comprise natural gypsum, gypsum tailings, industrial byproduct gypsum and the like.
2) Mixing the calcium sulfate powder obtained in the step 1) with a leaching aid, placing the mixture in a reaction container with stirring, and reacting for 30-120 min under the conditions of normal pressure and 30-120 ℃ to obtain a reaction product.
Wherein, the leaching auxiliary agent in the step 2) is one or more of ammonium acetate, ammonium chloride and ammonium sulfate; the concentration of the leaching auxiliary agent is 2-12 mol/L; the addition amount of the leaching aid is 5-20 mL/g.
3) And (3) carrying out suction filtration, washing and drying on the reaction product obtained in the step 2) to obtain filtrate rich in calcium ions and a solid reaction product.
4) Taking a certain volume of calcium-rich ionsAdding a certain amount of ammonia water into the filtrate, and introducing CO at a certain speed2Reacting the gas for 30-180 min under the conditions of normal pressure and 30-100 ℃ to obtain a reaction product.
Wherein, the concentration of calcium ions in the filtrate rich in calcium ions in the step 4) is 3-25 g/L, and the concentration of the calcium ions in the solution is adjusted by adding industrial water or calcium chloride and calcium acetate powder; the addition amount of the ammonia water is 3-15 mL/100 mL; the stirring speed is 50-400 r/min; CO 22The flow rate is 30-250 mL/min.
5) Carrying out suction filtration, washing and drying on the reaction product obtained in the step 4) to obtain a vaterite type calcium carbonate microsphere material; the filtrate is recycled for leaching the calcium sulfate raw material.
The prepared calcium carbonate microsphere has a vaterite crystal form, a spherical shape, a calcium carbonate content of more than 99.9%, a particle diameter of 0.3-2 μm and a whiteness of more than 98.
The technical solution of the present invention is further described in detail by the following specific examples in conjunction with the accompanying drawings.
Example 1:
the calcium sulfate raw material in the embodiment is phosphogypsum, and the phosphogypsum comprises the following main chemical components in percentage by weight: SO (SO)338%，CaO32%，SiO27%, the other 23%; the specific process comprises the following steps:
1) taking 50g of the phosphogypsum powder, preparing 650 mL of 9.5 mol/L ammonium chloride solution, then pouring the phosphogypsum powder into the ammonium chloride solution, stirring and reacting at 90 ℃ for 110 min, and after the reaction is finished, performing suction filtration to obtain filtrate and solid reactant;
2) 500 mL of the filtrate is taken, 29.4 g of calcium chloride powder and 45 mL of ammonia water are added into the solution, and CO is introduced2Gas, stirring and reacting at 85 deg.C for 95 min, CO2The flow rate of (2) is 210 mL/min, and the stirring speed is 400 r/min; stopping introducing CO after the reaction is finished2Gas, and carrying out suction filtration, washing and drying on a reaction product to obtain a calcium carbonate microsphere product;
3) the content of the vaterite in the obtained calcium carbonate microsphere product is 100 percent, the morphology is spherical, the particle diameter is 0.3-1.5 mu m, and the whiteness is 98.6.
Example 2
The calcium sulfate raw material in the embodiment is gypsum tailings, and the main chemical components of the gypsum tailings are as follows by weight percent: SO (SO)324%，CaO20 %，SiO223%，Al2O36%，Fe2O33%, and the other 24%; the specific process comprises the following steps:
1) taking 20g of the gypsum tailing powder, preparing 240 mL of 4.5 mol/L ammonium acetate solution, then pouring the gypsum tailing powder into the ammonium acetate solution, stirring and reacting at 75 ℃ for 55 min, and after the reaction is finished, performing suction filtration to obtain filtrate and a solid reactant;
2) 200 mL of the filtrate was taken, 3.6 g of calcium chloride powder and 18 mL of ammonia water were added to the solution, and CO was introduced2Gas, stirring and reacting at 55 deg.C for 70 min, CO2The flow rate of (2) is 85 mL/min, and the stirring speed is 250 r/min; stopping introducing CO after the reaction is finished2Gas, and carrying out suction filtration, washing and drying on a reaction product to obtain a calcium carbonate microsphere product;
3) the content of the vaterite in the obtained calcium carbonate microsphere product is 100 percent, the morphology is spherical, the particle diameter is 0.4-2 mu m, and the whiteness is 98.4.
Claims (5)
1. A preparation method of high-purity vaterite type calcium carbonate microspheres comprises the following steps:
1) grinding the calcium sulfate raw material to obtain calcium sulfate powder with the average particle size of 60-180 meshes;
2) mixing the calcium sulfate powder obtained in the step 1) with a leaching aid, placing the mixture in a reaction container with stirring, and reacting for 30-120 min under the conditions of normal pressure and 30-120 ℃ to obtain a reaction product;
3) and (3) carrying out suction filtration, washing and drying on the reaction product obtained in the step 2) to obtain filtrate rich in calcium ions and a solid reaction product.
2. A preparation method of high-purity vaterite type calcium carbonate microspheres comprises the following steps:
1) taking a certain volume of filtrate rich in calcium ionsAdding a certain amount of ammonia water, and introducing CO at a certain speed2Reacting the gas for 30-180 min under the conditions of normal pressure and 30-100 ℃ to obtain a reaction product;
2) carrying out suction filtration, washing and drying on the reaction product obtained in the step 1) to obtain a vaterite type calcium carbonate microsphere material; the filtrate is recycled for leaching the calcium sulfate raw material.
3. The method of claim 1, wherein:
the calcium sulfate raw materials in the step 1) mainly comprise natural gypsum, gypsum tailings, industrial byproduct gypsum and the like; in the step 2), the leaching auxiliary agent is one or more of ammonium acetate, ammonium chloride and ammonium sulfate; the concentration of the leaching auxiliary agent is 2-12 mol/L; the addition amount of the leaching aid is 5-20 mL/g.
4. The method of claim 2, wherein:
the concentration of calcium ions in the filtrate rich in calcium ions in the step 1) is 3-25 g/L, and the concentration of the calcium ions in the solution is adjusted by adding industrial water or calcium chloride and calcium acetate powder; the addition amount of the ammonia water is 3-15 mL/100 mL; the stirring speed is 50-400 r/min; CO 22The flow rate is 30-250 mL/min.
5. The production method according to claims 1 to 4, characterized in that:
the preparation process of the high-purity vaterite-type calcium carbonate microspheres does not add any crystal form control agent, can use solid waste as a raw material, and is completed at low temperature and normal pressure; the crystal form of the calcium carbonate microsphere is a vaterite type, the morphology is spherical, the content of calcium carbonate is more than 99.9%, the diameter of the particle is 0.3-2 mu m, and the whiteness is more than 98.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620331A (en) * | 2021-07-08 | 2021-11-09 | 浙江大学 | CO (carbon monoxide)2Method for preparing nanosphere aragonite calcium carbonate by mineralizing carbide slag |
| KR20220124998A (en) * | 2021-03-04 | 2022-09-14 | 현대오일뱅크 주식회사 | Method for producing inorganic compounds using desulfurization gypsum for reduction of greenhouse gas emissions |
| CN115215364A (en) * | 2022-07-12 | 2022-10-21 | 西安建筑科技大学 | Ammonia still waste liquid solidified CO 2 And method for synthesizing vaterite calcium carbonate |
| CN115246652A (en) * | 2021-04-28 | 2022-10-28 | 中国科学院过程工程研究所 | Preparation method of calcium carbonate with controllable purity and nano-microstructure |
| CN115448346A (en) * | 2022-08-11 | 2022-12-09 | 中南大学 | Preparation method of superfine light calcium carbonate |
| CN116375444A (en) * | 2023-04-20 | 2023-07-04 | 中南大学 | Preparation method of improved phosphogypsum-microorganism cement filler |
| CN116395729A (en) * | 2022-12-22 | 2023-07-07 | 浙江大学 | Fly ash building material utilization method based on vaterite dissolution and recrystallization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993105A (en) * | 2010-12-10 | 2011-03-30 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
| CN103922378A (en) * | 2014-04-22 | 2014-07-16 | 华东理工大学 | Method for preparing high-purity metastable vaterite calcium carbonate from gypsum |
| CN104876252A (en) * | 2015-04-14 | 2015-09-02 | 华东理工大学 | Method for preparing calcium carbonate by using ammonia carbonization-calcium conversion two-step method through low-temperature conversion |
| CN105731512A (en) * | 2016-01-27 | 2016-07-06 | 湖北工业大学 | Method and device for preparing vaterite calcium carbonate powder and coproducing ammonium chloride |
-
2019
- 2019-04-04 CN CN201910271454.5A patent/CN111777089A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993105A (en) * | 2010-12-10 | 2011-03-30 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
| CN103922378A (en) * | 2014-04-22 | 2014-07-16 | 华东理工大学 | Method for preparing high-purity metastable vaterite calcium carbonate from gypsum |
| CN104876252A (en) * | 2015-04-14 | 2015-09-02 | 华东理工大学 | Method for preparing calcium carbonate by using ammonia carbonization-calcium conversion two-step method through low-temperature conversion |
| CN105731512A (en) * | 2016-01-27 | 2016-07-06 | 湖北工业大学 | Method and device for preparing vaterite calcium carbonate powder and coproducing ammonium chloride |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220124998A (en) * | 2021-03-04 | 2022-09-14 | 현대오일뱅크 주식회사 | Method for producing inorganic compounds using desulfurization gypsum for reduction of greenhouse gas emissions |
| KR102558419B1 (en) * | 2021-03-04 | 2023-07-20 | 에이치디현대오일뱅크 주식회사 | Method for producing inorganic compounds using desulfurization gypsum for reduction of greenhouse gas emissions |
| CN115246652A (en) * | 2021-04-28 | 2022-10-28 | 中国科学院过程工程研究所 | Preparation method of calcium carbonate with controllable purity and nano-microstructure |
| CN115246652B (en) * | 2021-04-28 | 2023-12-12 | 中国科学院过程工程研究所 | Preparation method of calcium carbonate with controllable purity and nano-microstructure |
| CN113620331A (en) * | 2021-07-08 | 2021-11-09 | 浙江大学 | CO (carbon monoxide)2Method for preparing nanosphere aragonite calcium carbonate by mineralizing carbide slag |
| CN113620331B (en) * | 2021-07-08 | 2022-06-10 | 浙江大学 | CO (carbon monoxide)2Method for preparing nanosphere aragonite calcium carbonate by mineralizing carbide slag |
| CN115215364A (en) * | 2022-07-12 | 2022-10-21 | 西安建筑科技大学 | Ammonia still waste liquid solidified CO 2 And method for synthesizing vaterite calcium carbonate |
| CN115448346A (en) * | 2022-08-11 | 2022-12-09 | 中南大学 | Preparation method of superfine light calcium carbonate |
| CN115448346B (en) * | 2022-08-11 | 2024-03-12 | 中南大学 | Preparation method of superfine light calcium carbonate |
| CN116395729A (en) * | 2022-12-22 | 2023-07-07 | 浙江大学 | Fly ash building material utilization method based on vaterite dissolution and recrystallization |
| CN116395729B (en) * | 2022-12-22 | 2023-11-03 | 浙江大学 | Fly ash building material utilization method based on vaterite dissolution and recrystallization |
| CN116375444A (en) * | 2023-04-20 | 2023-07-04 | 中南大学 | Preparation method of improved phosphogypsum-microorganism cement filler |
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