CN111875269A - Calcium sulfate gypsum and preparation method thereof - Google Patents
Calcium sulfate gypsum and preparation method thereof Download PDFInfo
- Publication number
- CN111875269A CN111875269A CN202010810583.XA CN202010810583A CN111875269A CN 111875269 A CN111875269 A CN 111875269A CN 202010810583 A CN202010810583 A CN 202010810583A CN 111875269 A CN111875269 A CN 111875269A
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- CN
- China
- Prior art keywords
- gypsum
- glauberite
- calcium sulfate
- waste residue
- preparation
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
- C04B22/146—Calcium-sulfate other waste Ca-sulfate
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides calcium sulfate gypsum and a preparation method thereof, and belongs to the technical field of waste recycling and cement. The calcium sulfate gypsum provided by the invention is prepared from the following raw materials: glauberite waste residue and dihydrate gypsum. The invention takes the glauberite waste residue and the dihydrate gypsum as the raw materials to prepare the calcium sulfate gypsum used as the raw material of the industrial cement, thereby realizing the resource recycling of the glauberite waste residue. Meanwhile, the invention also provides a preparation method of the glauber salt waste residue, which utilizes a small amount of sodium sulfate in the glauber salt waste residue to greatly save the reaction time of the crystal water and improve the working efficiency, and the temperature is controlled below 60 ℃, so that the crystal water can be effectively controlled and prevented from being converted into external water, and the final sulfur trioxide in the calcium sulfate gypsum is ensured to be more than 35% by mass, the crystal water is more than 8% by mass, and the external water is less than 10% by mass. The invention realizes the resource recycling and brings good economic and social benefits.
Description
Technical Field
The invention relates to the technical field of waste recycling and cement, in particular to calcium sulfate gypsum and a preparation method thereof.
Background
The natural gypsum is an indispensable raw material for cement production and mainly comprises calcium sulfate and crystal water, wherein the main indexes of the natural gypsum are that the mass percentage of sulfur trioxide is about 30 percent, and the mass percentage of the crystal water is about 10 percent. The glauberite waste slag produced by enterprises producing sodium sulfate is formed by mixing 20 mass percent of calcium sulfate and 40 mass percent of sodium sulfate, and the mass percent of the gypsum raw material sodium sulfate used for cement production cannot exceed 2.5 percent, otherwise, the glauberite waste slag causes great loss to the 28-day strength of cement; therefore, glauberite slag cannot be used as a gypsum raw material for cement production. Therefore, the treatment method of the calcium mango nitre slag is open-air stacking, and finally, the loess is used for landfill treatment, so that the resource waste is caused. Therefore, how to improve the utilization rate of the calcium-mango nitrate slag becomes a research hotspot.
Disclosure of Invention
In view of the above, the present invention aims to provide calcium sulfate gypsum and a preparation method thereof. The invention takes the glauberite waste residue and the dihydrate gypsum as the raw materials to prepare the calcium sulfate gypsum used as the raw material of the industrial cement, thereby realizing the resource recycling of the glauberite waste residue.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides calcium sulfate gypsum which is prepared from the following raw materials: glauberite waste residue and dihydrate gypsum.
Preferably, the mass percentage content of sodium sulfate in the glauberite waste residue is less than or equal to 5%.
Preferably, the dihydrate gypsum is fluorgypsum and/or titanium gypsum.
Preferably, in the calcium sulfate gypsum, the mass percentage of crystal water is more than or equal to 8 percent, the mass percentage of external water is less than 10 percent, the mass percentage of sodium sulfate is less than or equal to 2.5 percent, and the mass percentage of sulfur trioxide is more than or equal to 35 percent
Preferably, the particle size of the calcium sulfate gypsum is 20-80 mm.
The invention also provides a preparation method of the calcium sulfate gypsum, which comprises the following steps:
and mixing the glauberite waste residue and the dihydrate gypsum for crystallization reaction, and crushing to obtain the calcium sulfate gypsum.
Preferably, the temperature of the crystallization reaction is less than or equal to 60 ℃ and the time is 3-24 hours.
Preferably, the glauberite slag is prepared by a method comprising the following steps of:
and leaching the glauberite waste residue raw material to obtain the glauberite waste residue.
The invention provides calcium sulfate gypsum which is prepared from the following raw materials: glauberite waste residue and dihydrate gypsum. The invention takes the glauberite waste residue and the dihydrate gypsum as the raw materials to prepare the calcium sulfate gypsum used as the raw material of the industrial cement, thereby realizing the resource recycling of the glauberite waste residue.
The invention also provides a preparation method of the calcium sulfate gypsum, which takes the glauber salt waste residue and the dihydrate gypsum as raw materials, utilizes a small amount of sodium sulfate in the glauber salt waste residue, greatly saves the reaction time of crystal water, improves the working efficiency, controls the temperature below 60 ℃, can effectively control and prevent the crystal water from being converted into external water, and ensures that the final calcium sulfate gypsum contains more than 35 percent of sulfur trioxide by mass, 8 percent of crystal water by mass, less than 10 percent of external water by mass and less than 2.5 percent of sodium sulfate by mass. According to the invention, the glauberite waste residue is applied to the preparation of calcium sulfate gypsum and further applied to cement, so that good economic and social benefits are brought while resource recycling is realized.
Detailed Description
The invention provides calcium sulfate gypsum which is prepared from the following raw materials: glauberite waste residue and dihydrate gypsum.
In the calcium sulfate gypsum, the mass percentage of crystal water is preferably more than or equal to 8%, the mass percentage of external water is preferably less than 10%, the mass percentage of sodium sulfate is preferably less than or equal to 2.5%, and the mass percentage of sulfur trioxide is preferably more than or equal to 35%
In the invention, the particle size of the calcium sulfate gypsum is preferably 20-80 mm.
In the invention, the mass percentage content of sodium sulfate in the glauberite waste residue is preferably less than or equal to 5%.
In the present invention, the dihydrate gypsum is preferably fluorgypsum and/or titanium gypsum; when the dihydrate gypsum is preferably a mixture of the fluorine gypsum and the titanium gypsum, the mass ratio of the fluorine gypsum to the titanium gypsum is preferably (20-30): 30.
In the invention, the mass ratio of the glauberite waste residue to the dihydrate gypsum is preferably (400-500) to (300-700).
The invention also provides a preparation method of the calcium sulfate gypsum, which comprises the following steps:
and mixing the glauberite waste residue and the dihydrate gypsum for crystallization reaction, and crushing to obtain the calcium sulfate gypsum.
In the invention, the glauberite slag is preferably prepared by a method comprising the following steps of:
and leaching the glauberite waste residue raw material to obtain the glauberite waste residue. In the present invention, the specific process of the leaching is preferably as follows: leveling the glauberite waste residue raw material, leaching with water for 2-3 days, and naturally drying to obtain primary leached glauberite waste residue; and after the glauberite waste residues which are leached for the first time are turned flat, leaching for 2-3 days with water, and naturally drying to obtain the glauberite waste residues.
In the invention, the temperature of the crystallization reaction is preferably less than or equal to 60 ℃, and is further preferably 20-30 ℃; the time is preferably 3 to 24 hours.
In the present invention, the chemical formula of the crystallization reaction is:
the crushing mode is not particularly limited, and the calcium sulfate gypsum can have a particle size of 20-80 mm.
According to the invention, the glauberite waste residue and the dihydrate gypsum are mixed to generate the calcium sulfate gypsum, a small amount of sodium sulfate in the glauberite waste residue is utilized, the reaction time of crystal water is greatly saved, the working efficiency is improved, the temperature is controlled below 60 ℃, the crystal water can be effectively controlled and prevented from being converted into external water, the final calcium sulfate gypsum is ensured to contain more than 35% by mass of sulfur trioxide, 8% by mass of crystal water, less than 10% by mass of external water and less than 2.5% by mass of sodium sulfate. According to the invention, the glauberite waste residue is applied to the preparation of calcium sulfate gypsum, and further applied to cement, so that good economic and social benefits are brought while resource recycling is realized.
The calcium sulfate gypsum and the method for preparing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
And (2) uniformly mixing 500kg of glauberite waste residues (the mass percentage of sodium sulfate is 5%) and 500kg of fluorgypsum, stirring, controlling the temperature at 60 ℃ to perform crystallization reaction for 8 hours, and crushing the mixture into granules after the crystallization reaction is finished to obtain the glauberite with the particle size of 20-80 mm.
The preparation method of the glauberite waste residue comprises the following steps:
leveling the glauberite waste residue raw material, leaching for 3 days with water, and naturally drying to obtain primary leached glauberite waste residue;
and after the glauberite waste residue which is leached for the first time is turned flat, leaching for 3 days with water, and naturally drying to obtain the glauberite waste residue.
Example 2
Taking 400kg of glauberite waste residue (the mass content of sodium sulfate is 5%), 300kg of fluorgypsum and 300kg of titanium gypsum, mixing and stirring uniformly, controlling the temperature to perform crystallization reaction at 30 ℃ for 3 hours, and crushing into granules after the crystallization reaction is finished to obtain the calcium sulfate gypsum with the particle size of 20-80 mm.
Example 3
500kg of glauberite waste residue (the mass percentage of sodium sulfate is 5 percent), 300kg of fluorgypsum and 200kg of titanium gypsum are mixed and stirred uniformly, the temperature is controlled at 30 ℃ for crystallization reaction for 8 hours, and after the crystallization reaction is finished, the product is crushed into particles, so that the calcium sulfate gypsum with the particle size of 20-80 mm is obtained.
The calcium sulfate gypsum obtained in examples 1 to 3 was tested for the crystal water content, the external water content, the sulfur trioxide content and the sodium sulfate content, and the results are shown in table 1.
TABLE 1 test results of the crystal water content, external water content, sulfur trioxide content and sodium sulfate content of calcium sulfate gypsum obtained in examples 1 to 3
As can be seen from table 1: the mass percentage of the crystal water in the obtained calcium sulfate gypsum is 8%, the mass percentage of the external water is less than 10%, the mass percentage of the sodium sulfate is less than or equal to 2.5%, and the mass percentage of the sulfur trioxide is more than or equal to 35%, so that the calcium sulfate gypsum can be used as a cement preparation raw material.
According to the invention, redundant sodium sulfate in the glauberite waste residues stacked in the open air is washed away by adopting a water leaching mode, and then the glauberite waste residues are used as raw materials to obtain calcium sulfate gypsum meeting the requirements under the combined action of dihydrate gypsum, so that the glauberite waste residues are applied to the field of cement preparation. The invention realizes the resource recycling and brings good economic and social benefits.
The above description is only a preferred embodiment of the present invention, and is used in cement production. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. Calcium sulfate gypsum is characterized by being prepared from the following raw materials: glauberite waste residue and dihydrate gypsum.
2. The calcium sulfate gypsum according to claim 1, wherein the mass percentage content of sodium sulfate in the glauberite slag is less than or equal to 5%.
3. Calcium sulphate gypsum according to claim 1 wherein the dihydrate gypsum is fluorgypsum and/or titanium gypsum.
4. The calcium sulfate gypsum according to claim 1, wherein the mass percentage of crystal water is not less than 8%, the mass percentage of external water is less than 10%, the mass percentage of sodium sulfate is not more than 2.5%, and the mass percentage of sulfur trioxide is not less than 35%.
5. The calcium sulfate gypsum according to claim 1 or 4, wherein the particle size of the calcium sulfate gypsum is 20-80 mm.
6. A process for the preparation of calcium sulphate gypsum according to any one of claims 1 to 5 comprising the steps of:
and mixing the glauberite waste residue and the dihydrate gypsum for crystallization reaction, and crushing to obtain the calcium sulfate gypsum.
7. The preparation method according to claim 6, wherein the temperature of the crystallization reaction is less than or equal to 60 ℃ and the time is 3-24 hours.
8. The preparation method according to claim 6, wherein the glauberite slag is prepared by a method comprising the steps of:
and leaching the glauberite waste residue raw material to obtain the glauberite waste residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010810583.XA CN111875269A (en) | 2020-08-11 | 2020-08-11 | Calcium sulfate gypsum and preparation method thereof |
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| CN202010810583.XA CN111875269A (en) | 2020-08-11 | 2020-08-11 | Calcium sulfate gypsum and preparation method thereof |
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| CN111875269A true CN111875269A (en) | 2020-11-03 |
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| CN202010810583.XA Pending CN111875269A (en) | 2020-08-11 | 2020-08-11 | Calcium sulfate gypsum and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196896A (en) * | 2022-07-27 | 2022-10-18 | 湖南仁义环保建材科技有限公司 | Improvement method of desulfurized lime sludge |
| CN115872435A (en) * | 2022-09-20 | 2023-03-31 | 四川大学 | Method for preparing high-purity gypsum through crystal phase reconstruction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241316A (en) * | 2005-03-03 | 2006-09-14 | Taiheiyo Material Kk | Grouting material |
| CN107352824A (en) * | 2017-08-22 | 2017-11-17 | 衡阳市仁义环保建材有限公司 | A kind of commercial synthesis sulphur gypsum and preparation method thereof |
| CN108358493A (en) * | 2018-04-28 | 2018-08-03 | 四川同庆南风有限责任公司 | A kind of mirabilite gypsum can be used as cement retarder |
| CN110903045A (en) * | 2019-12-09 | 2020-03-24 | 汪文杰 | Industrial waste residue natural stone imitation paste and preparation method and application thereof |
-
2020
- 2020-08-11 CN CN202010810583.XA patent/CN111875269A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006241316A (en) * | 2005-03-03 | 2006-09-14 | Taiheiyo Material Kk | Grouting material |
| CN107352824A (en) * | 2017-08-22 | 2017-11-17 | 衡阳市仁义环保建材有限公司 | A kind of commercial synthesis sulphur gypsum and preparation method thereof |
| CN108358493A (en) * | 2018-04-28 | 2018-08-03 | 四川同庆南风有限责任公司 | A kind of mirabilite gypsum can be used as cement retarder |
| CN110903045A (en) * | 2019-12-09 | 2020-03-24 | 汪文杰 | Industrial waste residue natural stone imitation paste and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196896A (en) * | 2022-07-27 | 2022-10-18 | 湖南仁义环保建材科技有限公司 | Improvement method of desulfurized lime sludge |
| CN115872435A (en) * | 2022-09-20 | 2023-03-31 | 四川大学 | Method for preparing high-purity gypsum through crystal phase reconstruction |
| CN115872435B (en) * | 2022-09-20 | 2024-05-14 | 四川大学 | Method for preparing high-purity gypsum by crystal phase reconstruction |
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