CN115434013A - Method for regulating and controlling crystal form of desulfurized gypsum - Google Patents
Method for regulating and controlling crystal form of desulfurized gypsum Download PDFInfo
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- CN115434013A CN115434013A CN202210923077.0A CN202210923077A CN115434013A CN 115434013 A CN115434013 A CN 115434013A CN 202210923077 A CN202210923077 A CN 202210923077A CN 115434013 A CN115434013 A CN 115434013A
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- desulfurized gypsum
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Abstract
A method of modulating the crystal morphology of desulfurized gypsum comprising: reacting the slurry containing calcium carbonate with sulfur dioxide and oxygen to obtain desulfurized gypsum; and, controlling the reaction temperature T of the reaction within the following range: t is more than 45 ℃. The method for regulating and controlling the crystal form of the desulfurized gypsum can obtain the crystal form of the desulfurized gypsum with good crystallization, and improve the quality of the desulfurized gypsum leaving the factory.
Description
Technical Field
The application relates to but is not limited to the field of building materials, in particular to a method for regulating and controlling crystal morphology of desulfurized gypsum.
Background
The desulfurized gypsum is a product of flue gas desulfurization in coal-fired power plants. Limestone-gypsum wet desulphurization is a common flue gas desulphurization method for coal-fired power plants. The basic technological route of said method is that limestone slurry is used as absorption slurry, and SO-containing slurry is added 2 Is blown into the absorption slurry with the flue gas and an oxygen-containing gas (e.g., air, oxygen, etc.), the SO in the flue gas 2 With limestone (the main component being CaCO) in the slurry 3 ) And carrying out chemical reaction with oxygen to generate the desulfurized gypsum. The chemical reaction principle is as follows:
2CaCO 3 +H 2 O+2SO 2 →CaSO 3 ·1/2H 2 O+2CO 2
2CaSO 3 ·1/2H 2 O+O 2 +3H 2 O→2CaSO 4 ·2H 2 O
with the continuous improvement of the technology, the desulfurized gypsum can basically replace natural gypsum and is fully and comprehensively applied. However, most of the current concerns of the coal-fired power plant about the content of soluble impurity ions (e.g., chloride ions) and the content of attached water for the desulfurization gypsum leaving the plant are not concerned about the specific crystal morphology of the desulfurization gypsum.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the present application.
The embodiment of the application provides a method for regulating and controlling the crystal form of desulfurized gypsum, which can obtain the crystal form of desulfurized gypsum with good crystallization and improve the quality of the desulfurized gypsum leaving a factory.
The embodiment of the application provides a method for regulating and controlling crystal morphology of desulfurized gypsum, which comprises the following steps:
reacting the slurry containing calcium carbonate with sulfur dioxide and oxygen to obtain desulfurized gypsum;
and controlling the reaction temperature T of the reaction within the following range: t is more than 45 ℃.
In the examples of the present application, the reaction temperature T of the reaction may be controlled within the following range: t is more than 45 ℃ and less than or equal to 85 ℃.
In the practice of the present applicationIn the examples, the reaction temperature T of the reaction may be controlled within the following range: t is more than or equal to 55 DEG C 1 ≤85℃。
In an embodiment of the present application, the size of the grains of the desulfurized gypsum may be D v (50)≥45μm。
In an embodiment of the present application, the shape of the grains of the desulfurized gypsum may include a quadrangular prism shape or a hexagonal prism shape.
In an embodiment of the present application, the shape of the crystal grains of the desulfurized gypsum may further include a plate shape, and a ratio of a thickness to a width of the plate-shaped crystal grains is not less than 10.
In embodiments of the present application, the calcium carbonate-containing slurry may be formed from limestone and water.
In an embodiment of the present application, the sulfur dioxide may be sulfur dioxide in flue gas of a coal fired power plant.
In an embodiment of the present application, the method for regulating crystal morphology of desulfurized gypsum may comprise:
reacting calcium carbonate-containing slurry formed by limestone and water with sulfur dioxide-containing flue gas of a coal-fired power plant and oxygen-containing gas to obtain desulfurized gypsum;
and controlling the temperature of the flue gas of the coal-fired power plant to control the reaction temperature of the reaction.
The method for regulating and controlling the crystal form of the desulfurized gypsum provided by the embodiment of the application can regulate and control technological parameters in the flue gas desulfurization production process, improve the crystallinity of the desulfurized gypsum, obtain the crystal form of the desulfurized gypsum with good crystallization, improve the water permeability of the desulfurized gypsum and reduce the content of the attached water and soluble impurities of the desulfurized gypsum leaving the factory.
Additional features and advantages of the present application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the present application. Other advantages of the present application can be realized and attained by the instrumentalities and combinations particularly pointed out in the specification and the drawings.
Drawings
The accompanying drawings are included to provide an understanding of the present disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the examples serve to explain the principles of the disclosure and not to limit the disclosure.
FIG. 1 is a scanning electron micrograph of a desulfurized gypsum crystal obtained in comparative example 1 of the present application;
FIG. 2 is a scanning electron micrograph of a desulfurized gypsum crystal obtained in comparative example 2 of the present application;
FIG. 3 is a scanning electron micrograph of desulfurized gypsum crystals obtained in example 1 of the present application;
FIG. 4 is a scanning electron micrograph of desulfurized gypsum crystals obtained in example 2 of the present application;
FIG. 5 is a scanning electron micrograph of desulfurized gypsum crystals obtained in example 3 of the present application;
FIG. 6 is a scanning electron micrograph of desulfurization gypsum crystals obtained in example 4 of the present application.
Detailed Description
To make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The inventor of the application finds that the crystal form of the desulfurized gypsum directly influences the water content of the desulfurized gypsum leaving the factory and the content of soluble impurity ions, and because the crystal of the desulfurized gypsum with complete crystal faces and good crystallinity has better water permeability, the desulfurized gypsum is easier to filter when being washed before being discharged, so that the content of attached water and soluble ions is lower.
The embodiment of the application provides a method for regulating and controlling crystal morphology of desulfurized gypsum, which comprises the following steps:
reacting the slurry containing calcium carbonate with sulfur dioxide and oxygen to obtain desulfurized gypsum;
and controlling the reaction temperature T of the reaction within the following range: t is more than 45 ℃.
In the examples herein, the reaction temperature T of the reaction may be controlled within the following range: t is more than 45 ℃ and less than or equal to 85 ℃, for example, the temperature T of the desulfurization gypsum reaction system can be controlled at about 46 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and 55 ℃.
In the examples herein, the reaction temperature T of the reaction may be controlled within the following range: t is more than or equal to 55 DEG C 1 ≤85℃。
In an embodiment of the present application, the size of the grains of the desulfurized gypsum may be D v (50)≥45μm。
In an embodiment of the present application, the shape of the grains of the desulfurized gypsum may include a quadrangular prism shape or a hexagonal prism shape.
In an embodiment of the present application, the shape of the crystal grains of the desulfurized gypsum may further include a plate shape, and a ratio of a thickness to a width of the plate-shaped crystal grains is not less than 10. The plate-like crystal grains have a length, a width and a thickness, and the length is equal to or greater than the width. When the ratio of the thickness to the width of the plate-like crystal grains is not less than 10. In embodiments of the present application, the calcium carbonate-containing slurry may be formed from limestone and water.
In an embodiment of the present application, the sulfur dioxide may be sulfur dioxide in flue gas of a coal fired power plant.
In an embodiment of the present application, the method of regulating the crystal morphology of desulfurized gypsum can comprise:
reacting calcium carbonate-containing slurry formed by limestone and water with sulfur dioxide-containing flue gas of a coal-fired power plant and oxygen-containing gas to obtain desulfurized gypsum;
and controlling the reaction temperature of the reaction by controlling the temperature of the coal fired power plant flue gas (i.e. the temperature of the coal fired power plant flue gas prior to contacting with the calcium carbonate containing slurry).
In the embodiment of the application, the temperature of the flue gas of the coal-fired power plant can be controlled to be a proper problem according to the actual production condition so as to achieve the purpose of controlling the reaction temperature of the reaction.
In embodiments of the present application, the oxygen-containing gas may include any one or more of oxygen and air.
Comparative example and example
100g of limestone powder with the granularity of 320 meshes is taken and added with deionized water to prepare slurry with the concentration of 10 weight percent, sulfur dioxide standard gas with the flow rate of 80mL/min and aeration air with the flow rate of 3.2L/min are simultaneously introduced, the mixture is stirred and reacted for 7 hours at the rotating speed of 400r/min, and the reaction temperature of the comparative example and the example is as follows:
comparative example 1:35 ℃;
comparative example 2:45 ℃;
example 1:55 ℃;
example 2:65 ℃;
example 3:75 ℃;
example 4:85 ℃.
FIGS. 1 to 6 are scanning electron micrographs of the crystals of desulfurized gypsum obtained in comparative examples 1 to 2 and examples 1 to 4 of the present application, respectively.
It can be seen that the crystal morphology of the desulfurized gypsum of comparative example 1 is plate-like with a thickness of about 4 μm, the crystal morphology of the desulfurized gypsum of comparative example 2 is plate-like with a thickness of about 5 μm, and the ratio of the thickness to the width of the plate-like crystal grains of comparative examples 1 and 2 is less than 10; the crystal morphology of the desulfurized gypsum of example 1 is a mixture of plate-like and quadrangular prism-like, but the thickness of the plate-like crystals is significantly increased; the crystal morphology of the desulfurized gypsum of example 2 is a mixture of plate-like, quadrangular prism-like and hexagonal prism-like morphologies, and the ratio of the thickness to the width of the plate-like crystal grains of examples 1 and 2 is greater than 10; the crystal morphology of the desulfurized gypsum of example 3 is hexagonal prism-like; the crystal morphology of the desulfurized gypsum of example 4 is a mixture of quadrangular and hexagonal prisms, with the gypsum crystals being coarser but of relatively shorter length; d of crystal grains of desulfurized Gypsum of examples 1 to 4 v (50) Not less than 45 μm, wherein D is the crystal grain of the desulfurized gypsum of example 4 v (50)＝66.2μm。
Although the embodiments disclosed in the present application are described above, the descriptions are only for the convenience of understanding the present application, and are not intended to limit the present application. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the appended claims.
Claims (9)
1. A method of modulating the crystal morphology of desulfurized gypsum comprising:
reacting the slurry containing calcium carbonate with sulfur dioxide and oxygen to obtain desulfurized gypsum;
it is characterized by also comprising: controlling the reaction temperature T of the reaction within the following range: t is more than 45 ℃.
2. The method for regulating the crystal morphology of desulfurized gypsum according to claim 1, wherein the reaction temperature T of said reaction is controlled within the following range: t is more than 45 ℃ and less than or equal to 85 ℃.
3. The method for regulating the crystal morphology of desulfurized gypsum according to claim 2, wherein the reaction temperature T of said reaction is controlled within the following range: t is more than or equal to 55 DEG C 1 ≤85℃。
4. The method for regulating the crystal morphology of desulfurized gypsum according to any one of claims 1 to 3, wherein the crystal grains of desulfurized gypsum have a size D v (50)≥45μm。
5. The method of modulating the crystal morphology of desulfurized gypsum according to any one of claims 1 to 3, wherein the shape of the crystal grains of desulfurized gypsum comprises a quadrangular prism or a hexagonal prism.
6. The method for regulating and controlling the crystal morphology of desulfurized gypsum according to claim 5, wherein the shape of the crystal grains of desulfurized gypsum further comprises plate-like shape, and the ratio of the thickness to the width of the plate-like crystal grains is not less than 10.
7. The method of modulating the crystal morphology of desulfurized gypsum according to any one of claims 1 to 6, wherein said calcium carbonate-containing slurry is formed from limestone and water.
8. The method for regulating and controlling the crystal morphology of desulfurized gypsum according to any one of claims 1 to 6, wherein the sulfur dioxide is sulfur dioxide in flue gas of coal-fired power plants.
9. The method of modulating the crystal morphology of desulfurized gypsum according to claim 8 comprising:
reacting calcium carbonate-containing slurry formed by limestone and water with sulfur dioxide-containing flue gas of a coal-fired power plant and oxygen-containing gas to obtain desulfurized gypsum;
and controlling the temperature of the flue gas of the coal-fired power plant to control the reaction temperature of the reaction.
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Citations (3)
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| KR20200057396A (en) * | 2018-11-16 | 2020-05-26 | 주식회사 세명케미칼 | Method for manufacturing desulfurization gypsum |
| CN113149055A (en) * | 2021-05-27 | 2021-07-23 | 湖南西林环保材料有限公司 | Method for preparing calcium carbonate and sulfate by using industrial desulfurized gypsum |
| CN113929328A (en) * | 2021-11-15 | 2022-01-14 | 华能沁北发电有限责任公司 | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200057396A (en) * | 2018-11-16 | 2020-05-26 | 주식회사 세명케미칼 | Method for manufacturing desulfurization gypsum |
| CN113149055A (en) * | 2021-05-27 | 2021-07-23 | 湖南西林环保材料有限公司 | Method for preparing calcium carbonate and sulfate by using industrial desulfurized gypsum |
| CN113929328A (en) * | 2021-11-15 | 2022-01-14 | 华能沁北发电有限责任公司 | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer |
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