CN112279288A - Continuous preparation method of modified calcium sulfate - Google Patents
Continuous preparation method of modified calcium sulfate Download PDFInfo
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- CN112279288A CN112279288A CN202011215097.XA CN202011215097A CN112279288A CN 112279288 A CN112279288 A CN 112279288A CN 202011215097 A CN202011215097 A CN 202011215097A CN 112279288 A CN112279288 A CN 112279288A
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- calcium sulfate
- coupling agent
- modified calcium
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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
- C01F11/46—Sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/005—Preparing or treating the raw materials
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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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
A continuous preparation method of modified calcium sulfate comprises the following steps: (1) crushing natural gypsum mixed raw ore to obtain gypsum mixed raw ore powder; (2) preparing the natural gypsum mixed raw ore powder obtained in the step (1) into natural gypsum mixed raw ore slurry, adding a composite flotation agent into the natural gypsum mixed raw ore slurry, and performing flotation to obtain water-containing flotation gypsum powder; (3) and (3) drying the water-containing flotation gypsum powder obtained in the step (2), adding a modifier while the water-containing flotation gypsum powder is hot after drying, and mixing and stirring to obtain the modified calcium sulfate. The preparation method has the advantages of wide raw material source, simple preparation method and low production cost, and the obtained modified calcium sulfate product has high whiteness, good toughness, rigidity and compatibility.
Description
Technical Field
The invention relates to a preparation method of modified calcium sulfate, in particular to a continuous preparation method for preparing modified calcium sulfate by utilizing natural gypsum greenore.
Background
Calcium sulfate is a common inorganic substance, and is favored in various fields such as medical treatment, construction, food, aviation, ships, plastics, and the like, and has a wide range of applications. With the rapid development of socioeconomic performance in recent years, the demand of calcium sulfate is increasing, and higher requirements on the quality of calcium sulfate are provided.
There are two main methods for preparing calcium sulfate. One is to obtain calcium sulfate by chemical synthesis using industrial by-products such as calcium chloride or calcium-containing by-products such as phosphogypsum, etc. produced in the manufacture of organic acids. The method has the advantages of high cost, low production efficiency and unstable product quality, and can generate a large amount of industrial wastewater in the production process to cause serious environmental pollution. Alternatively, the calcium sulfate powder is prepared by grinding and pulverizing natural gypsum ore, and removing particulate impurities such as soil and fine sand by simple dissolving, filtering, and drying. Although the preparation method has low production cost and little environmental pollution, most of the prepared calcium sulfate can not be directly used and needs to be modified and purified again because of complex impurities in the natural gypsum ore and unsatisfactory impurity removal effect.
CN109610004A discloses a method for modifying the surface of calcium sulfate whiskers, which comprises the following steps: (1) preparing a surface modifier: under the condition of stirring, dripping a toluene solution containing an acrylate compound and chloroplatinic acid into a toluene solution containing hydrogen-containing silicone oil, carrying out grafting reaction, and removing the toluene to obtain a surface modifier; (2) and (2) adding the surface modifier prepared in the step (1) into the dried anhydrous calcium sulfate whisker, and stirring for reaction to complete the modification of the surface of the calcium sulfate whisker. The calcium sulfate whisker used in the method has high price, the preparation condition of the surface modifier is complex and difficult to control, and the method is not suitable for large-scale production.
CN108003386A discloses a modified calcium sulfate whisker and a preparation method and application thereof. The preparation method of the modified calcium sulfate whisker comprises the steps of firstly preparing an aqueous solution of a silane coupling agent and adjusting the pH value to 4-5; then mixing the calcium sulfate whisker with the calcium sulfate whisker, and controlling the temperature to be 80-90 ℃ for reaction; and finally reacting the modified calcium sulfate with a copolymer of ethylene and maleic anhydride at the temperature of 60-90 ℃ in the presence of water to obtain the modified calcium sulfate. The calcium sulfate whisker raw material used in the method is expensive, 2 times of modification is carried out, acetic acid is required to strictly control the pH value of the solution in the 1 st modification, the 2 nd modification uses the copolymer of ethylene and maleic anhydride, the modification process is complex, the product improvement effect is not obvious after a plurality of modifiers are used, and the production cost is increased.
CN102219930B discloses a calcium sulfate whisker surface modification process, which comprises the following steps: drying the calcium sulfate whisker in an oven by hot air, standing at room temperature, and cooling to obtain dry calcium sulfate whisker; adding liquid paraffin and an aluminate coupling agent LS-821 into an ultrasonic oscillator for mixing; adding the dried calcium sulfate whiskers into an ultrasonic oscillator, and mixing and modifying for 6-10 min; and airing the obtained mixture at room temperature for 7-9 h, and drying at 85-95 ℃ to obtain the modified calcium sulfate whisker. The calcium sulfate whisker raw material used in the method is also expensive, and the processes of high-temperature drying, standing and cooling are carried out for multiple times, so that the heat energy in the modification process is not fully utilized, certain energy loss is caused, and the time is consumed.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a continuous preparation method of modified calcium sulfate, which has the advantages of wide raw material source, simple preparation method, low production cost, high whiteness and good toughness, rigidity and compatibility.
The technical scheme adopted for solving the technical problems is that the continuous preparation method of the modified calcium sulfate comprises the following steps:
(1) crushing the natural gypsum mixed raw ore to obtain natural gypsum mixed raw ore powder;
(2) preparing the natural gypsum mixed raw ore powder obtained in the step (1) into natural gypsum mixed raw ore slurry, adding a composite flotation agent into the natural gypsum mixed raw ore slurry, and performing flotation to obtain water-containing flotation gypsum powder;
(3) drying the water-containing flotation gypsum powder obtained in the step (2), and after the drying is finished,
adding the modifier while the calcium sulfate is hot, mixing and stirring to obtain the modified calcium sulfate.
Further, in the step (1), the particle size of the natural gypsum mixed raw ore powder is 5000-7000 meshes, preferably 5500-6500 meshes.
Further, in the step (2), the composite flotation agent is formed by mixing polyoxybutylene alcohol dithiophosphate and alkyl dithiocarbonate.
Further, in the composite flotation agent, the weight ratio of the polyoxybutylene alcohol dithiophosphate to the alkyl dithiocarbonate is 3-5: 1.
Further, in the step (2), the addition amount of the composite flotation agent is 0.01-0.1% of the weight of the natural gypsum mixed raw ore slurry, and preferably 0.03-0.08%.
Further, in the step (3), the drying mode is electromagnetic drying, the drying temperature is 200-240 ℃, and the drying time is 1-2 hours.
Further, in the step (3), the modifier is one or more of an aluminate coupling agent, a silane coupling agent and mesoporous magnesium silicate.
Further, in the step (3), the aluminate coupling agent is one or more of aluminate coupling agent F-1, aluminate coupling agent LS-821, aluminate coupling agent HY-133, aluminate coupling agent HY-988 and aluminate coupling agent DL-411.
Further, in the step (3), the silane coupling agent is one or more of a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH561, a silane coupling agent KH570 and a silane coupling agent KH 792.
Further, in the step (3), the amount of the modifier is 0.1-1%, preferably 0.3-0.8% of the mass of the dry calcium sulfate.
Further, in the step (3), the rotating speed of the stirring is 1000-2000 r/min, preferably 1300-1800 r/min; during stirring, the temperature of the material is 50-150 ℃, and preferably 80-120 ℃; the stirring time is 5-15 min, preferably 10 min.
The invention has the following beneficial effects: the method has the advantages of wide raw material source and simple operation, fully utilizes the heat energy in the electromagnetic drying, realizes the high-efficiency utilization of the heat energy, reduces the production cost, and obtains the modified calcium sulfate product with high whiteness, good toughness, rigidity and compatibility with other related materials.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1:
(1) crushing the natural gypsum mixed raw ore to reach a particle size of 5500-6500 meshes to obtain natural gypsum mixed raw ore powder;
(2) preparing the natural gypsum mixed raw ore powder obtained in the step (1) into natural gypsum mixed raw ore slurry, adding a composite flotation agent in which the weight ratio of sodium polyoxybutenol dithiophosphate to alkyl sodium dithiocarbonate is 4:1 into the natural gypsum mixed raw ore slurry, wherein the addition amount of the composite flotation agent is 0.05 percent of the weight of the natural gypsum mixed raw ore slurry, and performing flotation to obtain water-containing flotation gypsum powder;
(3) electromagnetically drying the water-containing flotation gypsum powder obtained in the step (2), wherein the drying temperature is 200 ℃, and the drying time is 1 h; and after drying, adding an aluminate coupling agent F-1 which is 0.5 percent of the mass of the dried calcium sulfate while the calcium sulfate is hot, mixing and stirring at the rotating speed of 1500 r/min, and reacting at 100 ℃ for 10min to obtain the modified calcium sulfate.
Through detection, the obtained modified calcium sulfate blue light whiteness 91 is measured according to the method provided by the national standard GB/T17669.3-1999, and has the advantages of flexural strength of 9.8 Mpa, compressive strength of 61.3 Mpa and good compatibility with natural rubber.
Example 2:
(1) crushing natural gypsum mixed raw ore until the particle size is 5500-6500 meshes to obtain natural gypsum mixed raw ore powder;
(2) preparing the natural gypsum mixed raw ore powder obtained in the step (1) into natural gypsum mixed raw ore slurry, adding a composite flotation agent in which the weight ratio of sodium polyoxybutenol dithiophosphate to alkyl sodium dithiocarbonate is 4:1 into the natural gypsum mixed raw ore slurry, wherein the addition amount of the composite flotation agent is 0.05 percent of the weight of the natural gypsum mixed raw ore slurry, and performing flotation to obtain water-containing flotation gypsum powder;
(3) electromagnetically drying the water-containing flotation gypsum powder obtained in the step (2), wherein the drying temperature is 220 ℃, and the drying time is 1.5 h; and after drying, adding a silane coupling agent KH550 which is 0.5 percent of the mass of the dried calcium sulfate while the calcium sulfate is hot, mixing and stirring at the rotating speed of 1500 r/min, and reacting at 100 ℃ for 10min to obtain the modified calcium sulfate.
Through detection, the obtained modified calcium sulfate blue light whiteness 94 is measured according to the method provided by the national standard GB/T17669.3-1999, and has the advantages of flexural strength of 9.5 Mpa, compressive strength of 64.8 Mpa and good compatibility with plastics, rubber and polyester.
Example 3:
(1) crushing natural gypsum mixed raw ore until the particle size is 5500-6500 meshes to obtain natural gypsum mixed raw ore powder;
(2) preparing the natural gypsum mixed raw ore powder obtained in the step (1) into natural gypsum mixed raw ore slurry, adding a composite flotation agent in which the weight ratio of sodium polyoxybutenol dithiophosphate to alkyl sodium dithiocarbonate is 4:1 into the natural gypsum mixed raw ore slurry, wherein the addition amount of the composite flotation agent is 0.05 percent of the weight of the natural gypsum mixed raw ore slurry, and performing flotation to obtain water-containing flotation gypsum powder;
(3) electromagnetically drying the water-containing flotation gypsum powder obtained in the step (2), wherein the drying temperature is 240 ℃, and the drying time is 2 hours; after drying is finished, adding the mesoporous magnesium silicate which is 0.5 percent of the mass of the dried calcium sulfate while the mesoporous magnesium silicate is hot, mixing and stirring the mixture at the rotating speed of 1500 r/min, and reacting the mixture for 10min at the temperature of 100 ℃ to obtain the modified calcium sulfate.
Through detection, the whiteness of the blue light of the obtained modified calcium sulfate is 94, and the flexural strength is 10.3 Mpa, the compressive strength is 60.5 Mpa and the modified calcium sulfate has good biocompatibility by measuring according to the method provided by the national standard GB/T17669.3-1999.
Claims (10)
1. A continuous preparation method of modified calcium sulfate is characterized by comprising the following steps:
(1) crushing the natural gypsum mixed raw ore to obtain natural gypsum mixed raw ore powder;
(2) preparing the natural gypsum mixed raw ore powder obtained in the step (1) into natural gypsum mixed raw ore slurry, adding a composite flotation agent into the natural gypsum mixed raw ore slurry, and performing flotation to obtain water-containing flotation gypsum powder;
(3) drying the water-containing flotation gypsum powder obtained in the step (2), and after the drying is finished,
adding the modifier while the calcium sulfate is hot, mixing and stirring to obtain the modified calcium sulfate.
2. The continuous preparation method of modified calcium sulfate according to claim 1, wherein in the step (2), the composite flotation agent is prepared by mixing polyoxybutenol dithiophosphate and hydrocarbyl dithiocarbonate.
3. The continuous preparation method of the modified calcium sulfate according to claim 2, wherein the weight ratio of the polyoxybutenol dithiophosphate to the alkyl dithiocarbonate in the composite flotation agent is 3-5: 1.
4. The continuous preparation method of modified calcium sulfate according to any one of claims 1 to 3, wherein in the step (2), the addition amount of the composite flotation agent is 0.01 to 0.1%, preferably 0.03 to 0.08% of the weight of the natural gypsum mixed raw ore slurry.
5. The continuous preparation method of modified calcium sulfate according to any one of claims 1 to 4, wherein in the step (3), the drying manner is electromagnetic drying, the drying temperature is 200 to 240 ℃, and the drying time is 1 to 2 hours.
6. The continuous preparation method of modified calcium sulfate according to any one of claims 1 to 5, wherein in the step (3), the modifier is one or more of an aluminate coupling agent, a silane coupling agent and mesoporous magnesium silicate.
7. The continuous preparation method of modified calcium sulfate according to any one of claims 1 to 6, wherein in the step (3), the aluminate coupling agent is one or more of aluminate coupling agent F-1, aluminate coupling agent LS-821, aluminate coupling agent HY-133, aluminate coupling agent HY-988 and aluminate coupling agent DL-411.
8. The continuous production method of modified calcium sulfate according to any one of claims 1 to 7, wherein in the step (3), the silane coupling agent is one or more of a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH561, a silane coupling agent KH570, and a silane coupling agent KH 792.
9. The continuous preparation method of modified calcium sulfate according to any one of claims 1 to 8, wherein in the step (3), the amount of the modifier is 0.1 to 1 percent, preferably 0.3 to 0.8 percent, based on the mass of the dry calcium sulfate.
10. The continuous preparation method of modified calcium sulfate according to any one of claims 1 to 9, wherein in the step (3), the rotation speed of the stirring is 1000 to 2000r/min, preferably 1300 to 1800 r/min; during stirring, the temperature of the material is 50-150 ℃, and preferably 80-120 ℃; the stirring time is 5-15 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920480A (en) * | 2022-07-06 | 2022-08-19 | 云南中洲海绵城市建材有限公司 | Method for producing high-strength high-performance concrete mineral admixture by using solid waste |
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| CN102219930A (en) * | 2011-06-07 | 2011-10-19 | 刘立文 | Calcium sulfate whisker surface modification technology |
| CN102534773A (en) * | 2012-02-02 | 2012-07-04 | 四川万润非金属矿物材料有限公司 | Production method of high-reinforcement modified anhydrous calcium sulfate crystal whiskers |
| CN103523814A (en) * | 2013-09-18 | 2014-01-22 | 西南科技大学 | Gypsum abnormity powder preparation and modification integrated method in normal-pressure open system |
| CN107309079A (en) * | 2016-04-26 | 2017-11-03 | 上海鑫和镍业科技有限公司 | A kind of method and its beneficiation method for handling low-grade laterite nickel ore |
| CN109292809A (en) * | 2018-09-30 | 2019-02-01 | 攀钢集团攀枝花钢铁研究院有限公司 | The application of the method for purification, gypsum and gypsum of titanium gypsum |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219930A (en) * | 2011-06-07 | 2011-10-19 | 刘立文 | Calcium sulfate whisker surface modification technology |
| CN102534773A (en) * | 2012-02-02 | 2012-07-04 | 四川万润非金属矿物材料有限公司 | Production method of high-reinforcement modified anhydrous calcium sulfate crystal whiskers |
| CN103523814A (en) * | 2013-09-18 | 2014-01-22 | 西南科技大学 | Gypsum abnormity powder preparation and modification integrated method in normal-pressure open system |
| CN107309079A (en) * | 2016-04-26 | 2017-11-03 | 上海鑫和镍业科技有限公司 | A kind of method and its beneficiation method for handling low-grade laterite nickel ore |
| CN109292809A (en) * | 2018-09-30 | 2019-02-01 | 攀钢集团攀枝花钢铁研究院有限公司 | The application of the method for purification, gypsum and gypsum of titanium gypsum |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920480A (en) * | 2022-07-06 | 2022-08-19 | 云南中洲海绵城市建材有限公司 | Method for producing high-strength high-performance concrete mineral admixture by using solid waste |
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