CN112299468A - Flaky calcium sulfate crystal and preparation method thereof - Google Patents
Flaky calcium sulfate crystal and preparation method thereof Download PDFInfo
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- CN112299468A CN112299468A CN202011191613.XA CN202011191613A CN112299468A CN 112299468 A CN112299468 A CN 112299468A CN 202011191613 A CN202011191613 A CN 202011191613A CN 112299468 A CN112299468 A CN 112299468A
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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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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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
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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Abstract
The invention relates to a flaky calcium sulfate crystal and a preparation method thereof, belonging to the technical field of reforming catalysts. The flaky calcium sulfate crystal provided by the invention comprises the following raw materials in parts by mass: 30-75 parts of calcium chloride, 30-70 parts of sulfate, 5-50 parts of crystal stabilizer and 800-1500 parts of reaction medium. The flaky calcium sulfate crystal and the preparation method thereof have the advantages of easily available raw materials, simple process, low cost and wide application market.
Description
Technical Field
The invention relates to a flaky calcium sulfate crystal and a preparation method thereof, belonging to the technical field of reforming catalysts.
Background
Calcium sulfate is commonly known as gypsum, plaster of paris or gypsum, anhydrite, stucco, and the like, and is a common laboratory or industrial chemical of the chemical formula CaSO4、CaSO4(1/2)H2O (hemihydrate), CaSO4(2)H2O (dihydrate), colorless orthorhombic or monoclinic crystal or white monoclinic crystal or crystalline inorganic salt powder, no odor and hygroscopicity; soluble in acid, sodium thiosulfate and ammonium salt solutions, poorly soluble in water, less soluble in hot water, very slowly soluble in glycerol, and practically insoluble in ethanol and most organic solvents. The relative density is 2.32, the product is irritant, usually contains 2 crystal waters, and the natural product is usually in the form of gypsum ore. The calcium sulfate has the characteristics of high whiteness, low hardness, high temperature resistance, chemical corrosion resistance, strong affinity with polymers, no toxicity and the like, and the product has wide application.
With the development of industry and science and technology, the living standard of people is improved, and the consumption demand of downstream fields such as building materials, foods, medicines and the like in China for calcium sulfate is increasing day by day. The flaky calcium sulfate as a special crystal material is more and more applied to the filling agent, the reinforcing agent and the flame retardant of rubber and plastics, and the flaky calcium sulfate material also receives wide attention as an improver of smoothness and touch of the extender pigment on skin in the field of cosmetics.
In the existing research on calcium sulfate crystal materials, the main method for obtaining calcium sulfate crystals with ideal crystal forms is a hydrothermal method, namely, the calcium sulfate crystals with ideal forms can be generated only by taking water as a solvent and giving certain growth time to the crystals under certain temperature and pressure in a closed container. This is a very demanding device and the increase in production is also a toggle.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a flaky calcium sulfate crystal and a preparation method thereof, wherein the flaky calcium sulfate crystal has the advantages of easily available raw materials, simple process, low cost, stable product quality and wide application market.
The flaky calcium sulfate crystal provided by the invention comprises the following raw materials in parts by mass:
30-75 parts of calcium chloride
30-70 parts of sulfate
5-50 parts of crystal stabilizer
800-1500 parts of reaction medium.
Preferably, the sulfate is one or more of sodium sulfate, potassium sulfate or magnesium sulfate.
Preferably, the crystal stabilizer is one or more of magnesium chloride, potassium chloride or sodium chloride.
Preferably, the reaction medium is deionized water.
The preparation method of the flaky calcium sulfate crystal comprises the following steps:
(1) dissolving sulfate and part of crystal stabilizer in part of reaction medium, and keeping the temperature at 20-100 ℃ after uniform dissolution to obtain sulfate base solution;
(2) dissolving calcium chloride and the rest of crystal stabilizer in the rest of reaction medium, keeping the temperature at 20-95 ℃ to obtain calcium salt solution, and then dropwise adding the calcium salt solution into the sulfate base solution, wherein the dropwise adding time is controlled to be 1.5-2 h;
(3) keeping the constant temperature for 1-3 h for aging after the dripping is finished;
(4) and (3) carrying out solid-liquid separation on the reaction product through centrifugation and filter pressing, washing the solid product with deionized water to remove chloride ions and soluble salts, and drying at 50-120 ℃ to obtain the flaky calcium sulfate.
The mass ratio of the crystal stabilizer in the step (1) to the crystal stabilizer in the step (2) is 1-6: 1-4.
The mass ratio of the reaction medium in the step (1) to the reaction medium in the step (2) is 4-8: 4-7.
Adding sodium carbonate solution into the filtrate to obtain basic magnesium carbonate and brine solution.
Evaporating, concentrating and crystallizing the saline solution to obtain sodium chloride crystals.
Compared with the prior art, the invention has the following beneficial effects:
(1) the raw materials used in the invention are common and easily available industrial raw materials, and the price is low;
(2) the stable flaky calcium sulfate is produced at a proper temperature through the action of sulfate and a crystal stabilizer (the crystal stabilizer changes the arrangement mode of molecules when a target product is crystallized according to different properties such as electrical property, dipole moment and the like to complete the control of different crystal appearances);
(3) in the preparation method, the reaction is simple and convenient to control, and the reaction control cost is reduced;
(4) the product filtrate can be recycled (used for dissolving sulfate in the first step), and can be subjected to reaction precipitation with a soda ash solution, solid-liquid separation, solid washing and drying, secondary filtrate concentration, crystallization and other steps to completely convert waste liquid into byproducts, so that the environment-friendly industrial production of zero waste is realized.
Drawings
FIG. 1 is a scanning electron micrograph of the platy calcium sulfate and basic magnesium carbonate prepared in example 1;
FIG. 2 is a scanning electron micrograph of the product prepared in example 2;
FIG. 3 is a scanning electron micrograph of the platy calcium sulfate and basic magnesium carbonate prepared in example 3;
in the figure: 1a is flaky calcium sulfate, and 1b is basic magnesium carbonate;
3a is flaky calcium sulfate, and 3b is basic magnesium carbonate.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
Magnesium sulfate, sodium sulfate, crystal stabilizer magnesium chloride and deionized water are mixed according to the following mass ratio: 40: 30:5:800 as a base solution:
calcium chloride, crystal stabilizer magnesium chloride and deionized water are mixed according to the following mass ratio: 60: 5, uniformly dissolving 700 to obtain a dropwise added solution;
slowly dripping the calcium chloride solution into the sulfate solution when the base solution and the dripping solution are constant in temperature to 50 +/-5 ℃, controlling the dripping time to be 2 hours, and reacting for 2 hours at constant temperature after the dripping is finished; and (3) centrifugally separating a reaction product, washing a solid product, and drying the solid product at the temperature of 60 +/-5 ℃ to obtain the flaky calcium sulfate.
After the filtrate reacts with a sodium carbonate solution, the solid-liquid separation is carried out to produce basic magnesium carbonate and sodium chloride.
Example 2
Potassium sulfate, magnesium sulfate, crystal stabilizer sodium chloride and deionized water are mixed according to the following mass ratio: 30: uniformly dissolving the mixture at a ratio of 40:5:600 to obtain a base solution;
calcium chloride, crystal stabilizer sodium chloride and deionized water are mixed according to the following mass ratio: 55: 10: 800 is dissolved uniformly to be used as a dropwise adding solution;
slowly dripping the calcium chloride solution into the sulfate solution when the base solution and the dripping solution are kept at the constant temperature of 70 +/-5 ℃, controlling the dripping time to be 1.5 hours, and reacting at the constant temperature for 1.5 hours after the dripping is finished; and (3) centrifugally separating a reaction product, washing a solid product, and drying the solid product at the temperature of 80 +/-5 ℃ to obtain the flaky calcium sulfate.
The filtrate is recycled, and the dissolved sulfate is used as the base solution for secondary use.
Example 3
Sodium sulfate, potassium sulfate, a crystal stabilizer potassium chloride and deionized water are mixed according to the following mass ratio of 35: uniformly dissolving the mixture at a ratio of 35:10:700 to obtain a base solution;
uniformly dissolving calcium chloride, a crystal stabilizer potassium chloride and deionized water according to the mass ratio of 50:5:700 to obtain a dropwise added solution;
slowly dripping the calcium chloride solution into the sulfate solution when the base solution and the dripping solution are kept at the constant temperature of 80 +/-5 ℃, controlling the dripping time to be 2 hours, and reacting for 1 hour at the constant temperature after the dripping is finished; centrifugally separating the reaction product, washing the solid product, and drying the solid product at 90 +/-5 ℃ to obtain flaky calcium sulfate; the filtrate can dissolve sulfate for recycling.
Comparative example 1
The raw materials and proportions used are the same as in example 3, except that:
sodium sulfate, potassium sulfate, a crystal stabilizer potassium chloride and deionized water are mixed according to the following mass ratio of 35: 35:15:1400, slowly dripping the calcium chloride solution into the mixed solution when the temperature is kept to 80 +/-5 ℃, controlling the dripping time to be 2 hours, and reacting for 1 hour at constant temperature after the dripping is finished; and (3) centrifugally separating a reaction product, washing a solid product, and drying at 90 +/-5 ℃, but the flaky calcium sulfate cannot be obtained.
Claims (9)
1. A flaky calcium sulfate crystal characterized by: the composite material comprises the following raw materials in parts by mass:
2. the flaky calcium sulfate crystal according to claim 1, characterized in that: the sulfate is one or more of sodium sulfate, potassium sulfate or magnesium sulfate.
3. The flaky calcium sulfate crystal according to claim 1, characterized in that: the crystal stabilizer is one or more of magnesium chloride, potassium chloride or sodium chloride.
4. The flaky calcium sulfate crystal according to claim 1, characterized in that: the reaction medium is deionized water.
5. A method for producing the flaky calcium sulfate crystal according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
(1) dissolving sulfate and part of crystal stabilizer in part of reaction medium, and keeping the temperature at 20-100 ℃ after uniform dissolution to obtain sulfate base solution;
(2) dissolving calcium chloride and the rest of crystal stabilizer in the rest of reaction medium, keeping the temperature at 20-95 ℃ to obtain calcium salt solution, and then dropwise adding the calcium salt solution into the sulfate base solution, wherein the dropwise adding time is controlled to be 1.5-2 h;
(3) keeping the constant temperature for 1-3 h for aging after the dripping is finished;
(4) and (3) carrying out solid-liquid separation on the reaction product through centrifugation and filter pressing, washing the solid product with deionized water to remove chloride ions and soluble salts, and drying at 50-120 ℃ to obtain the flaky calcium sulfate.
6. The method for producing flaky calcium sulfate crystals according to claim 5, characterized in that: the mass ratio of the crystal stabilizer in the step (1) to the crystal stabilizer in the step (2) is 1-6: 1-4.
7. The method for producing flaky calcium sulfate crystals according to claim 5, characterized in that: the mass ratio of the reaction medium in the step (1) to the reaction medium in the step (2) is 4-8: 4-7.
8. The method for producing flaky calcium sulfate crystals according to claim 5, characterized in that: adding sodium carbonate solution into the filtrate to obtain basic magnesium carbonate and brine solution.
9. The method for producing flaky calcium sulfate crystals according to claim 8, characterized in that: evaporating, concentrating and crystallizing the saline solution to obtain sodium chloride crystals.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281062A (en) * | 2004-03-30 | 2005-10-13 | Toray Ind Inc | Gypsum composition and manufacturing method therefor |
| CN102965721A (en) * | 2012-11-13 | 2013-03-13 | 沈阳化工大学 | Method for preparing calcium sulfate crystal whisker in low cost |
| CN103553385A (en) * | 2013-10-17 | 2014-02-05 | 天津大学 | Method for preparing high-strength alpha-semi-hydrated gypsum from flue gas desulfurization gypsum |
| CN104532339A (en) * | 2014-12-16 | 2015-04-22 | 青海博川矿业开发有限公司 | Method for preparing calcium sulfate whisker from low-grade natural gypsum or gypsum tailings |
| CN104928758A (en) * | 2015-05-13 | 2015-09-23 | 四川理工学院 | Mixed additives and method for producing anhydrous dead-burned type of calcium sulfate whisker |
| CN106629792A (en) * | 2016-11-28 | 2017-05-10 | 浙江联大化工股份有限公司 | Co-production technology for preparing high-purity magnesium hydrate and preparing calcium sulfate whiskers from magnesium hydrate production byproduct |
| CN110040991A (en) * | 2019-05-07 | 2019-07-23 | 东北大学 | A method of quickly preparing short cylinder sulfate hemihydrate calcium material using calcium sulphate dihydrate |
-
2020
- 2020-10-30 CN CN202011191613.XA patent/CN112299468B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281062A (en) * | 2004-03-30 | 2005-10-13 | Toray Ind Inc | Gypsum composition and manufacturing method therefor |
| CN102965721A (en) * | 2012-11-13 | 2013-03-13 | 沈阳化工大学 | Method for preparing calcium sulfate crystal whisker in low cost |
| CN103553385A (en) * | 2013-10-17 | 2014-02-05 | 天津大学 | Method for preparing high-strength alpha-semi-hydrated gypsum from flue gas desulfurization gypsum |
| CN104532339A (en) * | 2014-12-16 | 2015-04-22 | 青海博川矿业开发有限公司 | Method for preparing calcium sulfate whisker from low-grade natural gypsum or gypsum tailings |
| CN104928758A (en) * | 2015-05-13 | 2015-09-23 | 四川理工学院 | Mixed additives and method for producing anhydrous dead-burned type of calcium sulfate whisker |
| CN106629792A (en) * | 2016-11-28 | 2017-05-10 | 浙江联大化工股份有限公司 | Co-production technology for preparing high-purity magnesium hydrate and preparing calcium sulfate whiskers from magnesium hydrate production byproduct |
| CN110040991A (en) * | 2019-05-07 | 2019-07-23 | 东北大学 | A method of quickly preparing short cylinder sulfate hemihydrate calcium material using calcium sulphate dihydrate |
Non-Patent Citations (1)
| Title |
|---|
| 李强等: "金属离子对硫酸钙晶须形貌影响的试验研究", 《非金属矿》 * |
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