CN113929328B - Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer - Google Patents
Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer Download PDFInfo
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- CN113929328B CN113929328B CN202111350793.6A CN202111350793A CN113929328B CN 113929328 B CN113929328 B CN 113929328B CN 202111350793 A CN202111350793 A CN 202111350793A CN 113929328 B CN113929328 B CN 113929328B
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- desulfurizer
- carbide slag
- desulfurization
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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
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
- C04B11/264—Gypsum from the desulfurisation of flue gases
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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
Abstract
The invention belongs to the technical field of resource recycling processes, and particularly relates to a method for promoting the crystal growth of desulfurized gypsum by regulating and controlling a carbide slag-based desulfurizer, which comprises the following steps: (1) preparing a desulfurizing agent from carbide slag: pretreating carbide slag to obtain a desulfurizing agent; (2) wet desulphurization process: adding water into the desulfurizer obtained in the step (1) and pulping to prepare desulfurized slurry, feeding the desulfurized slurry into a desulfurization reaction tower, carrying out contact reaction with sulfur-containing flue gas through a spraying system to carry out desulfurization, adding an induced growth agent in the desulfurization process, controlling the particle size morphology of calcium sulfate crystals, and dehydrating to obtain desulfurized gypsum. The method takes solid waste as a raw material, has simple process and short flow, does not discharge secondary solid waste, effectively solves the pollution problem of the carbide slag, and has good economic and social values.
Description
Technical Field
The invention belongs to the technical field of resource recycling processes, and particularly relates to a method for promoting the crystal growth of desulfurized gypsum by regulating and controlling a carbide slag-based desulfurizer.
Background
The carbide slag is a solid waste generated in the process of preparing acetylene by reacting calcium carbide with water, and 1800 ten thousand tons of carbide slag are discharged every year in the polyvinyl chloride (PVC) industry. The energy structure of China is mainly coal, and the flue gas discharged by coal combustion contains a large amount of SO 2 And a large amount of primary limestone resources are consumed for flue gas desulfurization. Calcium carbideThe content of calcium hydroxide in the slag reaches 80-90%, and the calcium hydroxide can be used as a desulfurizer after impurities are removed, so that the pollution problem caused by sulfur dioxide can be greatly reduced, and the utilization efficiency of the carbide slag is improved.
In the process of using the carbide slag as a desulfurizing agent, the reaction process difference is obvious compared with the traditional limestone, and the crystal growth of the desulfurized gypsum is greatly influenced. The Chinese invention patent with the application number of CN107617326A discloses a method for mixed desulfurization of carbide slag-based desulfurizer and magnesium oxide, wherein the desulfurizer composition consists of 40-80 parts by weight of carbide slag and 20-60 parts by weight of magnesium oxide; the Chinese patent with the application number of CN102658007A discloses a method for producing a passivated calcium oxide desulfurizer by using carbide slag, and the method comprises the steps of filtering and screening ferrosilicon particles by using a vibrating screen, then carrying out plate-and-frame filter pressing, adding a passivator and a reinforcing agent, extruding, granulating, drying, roasting at high temperature and the like to prepare the desulfurizer. The Chinese invention patent with the application number of CN109603498A discloses a flue gas desulfurization process by a carbide slag-gypsum method, wherein a mixture of sodium hypochlorite and magnesium hypochlorite is added in the desulfurization process to promote oxidation.
However, the process method in the prior art is complicated, most processes are directed at the process of generating the desulfurized gypsum through the oxidation of calcium sulfite, the quality control of the desulfurized gypsum is still insufficient in the process of using the carbide slag as the desulfurizer, the method does not take corresponding consideration on the crystal growth process of the gypsum, and the crystal structure and the particle size of the gypsum have great influence on the water content and the rear-end use process of the gypsum. In summary, the application process of the carbide slag-based desulfurizer also needs to realize the crystal growth regulation of gypsum according to the properties of carbide slag.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for promoting the crystal growth of desulfurized gypsum by regulating and controlling a carbide slag-based desulfurizer, which is beneficial to the crystal growth and shape regulation of desulfurized gypsum by combining the addition of an induced growth agent in the crystallization process through the existing impurity component characteristics of carbide slag, thereby realizing the large-scale consumption of carbide slag and the quality improvement of desulfurized gypsum.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for regulating and promoting gypsum crystal growth by using a carbide slag-based desulfurizer comprises the following steps:
(1) The process for preparing the desulfurizer from the carbide slag comprises the following steps: pretreating dry/wet carbide slag to obtain a fine-particle desulfurizer product with the particle size smaller than a certain size, wherein the content of impurities such as Mg, si, fe and the like in the desulfurizer is kept in a certain range;
(2) And (3) a wet desulphurization process: adding water into the carbide slag-based desulfurizer obtained in the step (1) and pulping to prepare desulfurized slurry, introducing sulfur-containing flue gas in industries such as energy and metallurgy into a desulfurization reaction tower, carrying out contact reaction with the carbide slag desulfurizer slurry through a spraying system, adding an induced growth agent, controlling the particle size morphology of calcium sulfate crystals while realizing effective removal of sulfur dioxide, and dehydrating to obtain desulfurized gypsum.
Preferably, in the step (1), the contents of impurities such as Mg, si, fe and the like in the desulfurizer are controlled through pretreatment, wherein the content of Mg is 0-0.5%, the content of Si is 0-1.0%, and the content of Fe is 0-0.5%.
Preferably, the carbide slag in the step (1) can be produced by a dry method and a wet method acetylene production process.
Preferably, the particle size of the fine particle desulfurizer product in the step (1) is less than 106 μm, the content of particles is more than 90%, and the content of dry-based calcium oxide is more than or equal to 72%.
Preferably, the growth-inducing agent in step (2) is mainly one or more of sodium polyacrylate, polyethylene glycol and polyvinyl alcohol.
Preferably, the addition amount of the growth-inducing agent in the step (2) is 0.005-3% of the addition amount of the desulfurizing agent.
Preferably, in the step (2), water is added into the carbide slag-based desulfurizer, and the mixture is stirred to prepare the desulfurization slurry, wherein the mass ratio of the carbide slag to the water is 1:1-1.
Preferably, the sulfur content of the flue gas in the desulfurization process in the step (2) is 500-5000ppm, and the sulfur content of the flue gas after desulfurization is 0.5-25ppm.
Preferably, the particle size range of the desulfurized gypsum in the desulfurization process in the step (2) is controlled to be 10-1000 microns, and the main morphology is short rod shape, whisker shape and thick rod shape.
Preferably, the water content of the gypsum in the step (2) is less than 15%.
Advantageous effects
The invention discloses a method for regulating and controlling and promoting the crystal growth of desulfurized gypsum by using a carbide slag-based desulfurizer, and compared with the prior art, the method has the following beneficial effects:
1. the carbide slag-based desulfurizer used by the invention contains impurities such as Fe, si, mg and the like in a certain proportion, and the elements and oxides thereof are beneficial to the growth of gypsum crystals in a certain mass content interval; in the desulfurization process, a certain proportion of polymer dispersant is added as an induced growth agent, so that the number of nucleation particles and small particle agglomeration can be reduced, the induced growth of gypsum crystals in a local area is facilitated, and a gypsum product with a target morphology is formed.
2. After sulfur-containing flue gas in the industries of energy, metallurgy and the like is treated by the method, the desulfurization rate is as high as 99.5%, the water content of the desulfurized gypsum produced by the method is 11% at least, and the desulfurized gypsum can be long rod-shaped, thick rod-shaped, short rod-shaped and whisker-shaped, so that a good foundation is provided for the application of the desulfurized gypsum in the aspects of building gypsum, high-strength gypsum powder, paper-faced gypsum boards, fiber reinforced gypsum boards and the like.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
A method for regulating and promoting gypsum crystal growth by using a carbide slag-based desulfurizer comprises the following steps:
(1) Preparing a desulfurizer from carbide slag:
pretreating the carbide slag to obtain a desulfurizer, wherein the grain diameter of the pretreated carbide slag product is less than 105 mu m, the grain proportion is 94.15%, the content of dry calcium oxide is 72.05%, the content of Mg is 0.3%, and the content of Si is 0.8%;
(2) And (3) wet desulphurization:
preparing desulfurization slurry according to the mass ratio of the desulfurizer to the water of 1:4, and preparing flue gas SO at the inlet of a desulfurization system 2 3500ppm concentration, measured 24 hours of tail gas SO 2 The concentration is always lower than 20ppm, polyethylene glycol with the mass of 0.005% of the desulfurizer is added into the desulfurization slurry, the desulfurization gypsum is in a long rod shape, the particle size range is controlled to be 100-1000 microns, and the water content of the desulfurization gypsum is 13.5%.
Example 2
A method for regulating and promoting gypsum crystal growth by using a carbide slag-based desulfurizer comprises the following steps:
(1) Preparing a desulfurizer from carbide slag:
pretreating the carbide slag to obtain a desulfurizer, wherein the proportion of particles with the particle diameter less than 105 mu m of the carbide slag product after pretreatment is 91.08%, the content of dry calcium oxide is 73.80%, the content of Mg is 0.1%, and the content of Fe is 0.5%;
(2) And (3) wet desulphurization:
preparing desulfurization slurry according to the mass ratio of the desulfurizer to the water of 1:4, and preparing flue gas SO at the inlet of a desulfurization system 2 The concentration is 2600ppm, and the measured tail gas SO is 24 hours 2 The concentration is always lower than 15ppm, polyvinyl alcohol with the mass of 0.5 percent of the desulfurizer is added into the desulfurization slurry, the desulfurization gypsum is in a shape of a thick rod, a short rod, the particle size range is controlled to be 100-670 micrometers, and the water content of the desulfurization gypsum is 12.5 percent.
Example 3
A method for regulating and promoting gypsum crystal growth by carbide slag-based desulfurizer comprises the following steps:
(1) Preparing a desulfurizer from carbide slag:
pretreating the carbide slag to obtain a desulfurizer, wherein the proportion of particles with the particle diameter less than 105 mu m of the carbide slag product after pretreatment is 93.14%, the content of dry calcium oxide is 74.32%, the content of Mg is 0.4%, the content of Si is 0.5%, and the content of Fe is 0.1%;
(2) And (3) wet desulphurization:
preparing desulfurization slurry according to the mass ratio of the desulfurizer to the water of 1:3, and preparing flue gas SO at the inlet of a desulfurization system 2 Concentration of 5000ppm, measured 24 hours of tail gas SO 2 The concentration is always lower than 25ppm, sodium polyacrylate with the mass of 3.0 percent of the desulfurizer is added in the desulfurization process, the desulfurization gypsum is in a whisker shape, the particle size range is controlled to be 200-890 microns, and the water content of the desulfurization gypsum is 14.5 percent.
Example 4
A method for regulating and promoting gypsum crystal growth by using a carbide slag-based desulfurizer comprises the following steps:
(1) Preparing a desulfurizer from carbide slag:
pretreating the carbide slag to obtain a desulfurizer, wherein the proportion of particles with the particle size of less than 105 mu m of the pretreated carbide slag product is 90.13%, the content of dry-based calcium oxide is 72.06%, and the content of Si is 1.0%;
(2) And (3) wet desulphurization:
preparing desulfurization slurry according to the mass ratio of the desulfurizer to the water of 1:3, and preparing flue gas SO at the inlet of a desulfurization system 2 The concentration is 4300ppm, and the measured tail gas SO of 24 hours 2 The concentration is always lower than 25ppm, sodium polyacrylate with the mass of 1.0 percent of desulfurizer and polyethylene glycol with the mass of 0.5 percent are added in the desulfurization process, the shape of the desulfurization gypsum is that whiskers and slender rods coexist, the particle size range is controlled to be 10-730 micrometers, and the water content of the desulfurization gypsum is 15.0 percent.
Example 5
A method for regulating and promoting gypsum crystal growth by using a carbide slag-based desulfurizer comprises the following steps:
(1) Preparing a desulfurizer from carbide slag:
pretreating the carbide slag to obtain a desulfurizer, wherein the proportion of particles with the particle size of less than 105 mu m of the pretreated carbide slag product is 95.01%, the content of dry-based calcium oxide is 74.16%, and the content of Fe is 0.5%;
(2) And (3) wet desulphurization:
preparing desulfurization slurry according to the mass ratio of the desulfurizer to the water of 1:3, and preparing flue gas SO at the inlet of a desulfurization system 2 The concentration is 2200ppm, and the measured 24-hour tail gas SO 2 The concentration is always lower than 5ppm, sodium polyacrylate with the mass of 1.0 percent of desulfurizer, 0.5 percent of polyethylene glycol and 0.8 percent of polyvinyl alcohol are added in the desulfurization process, the desulfurization gypsum is coexisted in the shape of crystal whisker, slender rod and thick and short rod, the particle size range is controlled to be 300-950 microns, and the water content of the desulfurization gypsum is 11.0 percent.
The method takes solid waste as raw material, has simple process and short flow, does not discharge secondary solid waste, effectively solves the pollution problem of the carbide slag, and has good economic and social values.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (5)
1. A method for regulating and promoting the crystal growth of desulfurized gypsum by using a carbide slag-based desulfurizer is characterized by comprising the following steps:
(1) Preparing a desulfurizer from carbide slag: pretreating carbide slag to obtain a desulfurizer, wherein the content of Mg in the desulfurizer is 0-0.5%, the content of Si in the desulfurizer is 0-1.0%, and the content of Fe in the desulfurizer is 0-0.5%; the particle size of the desulfurizer is less than 105 μm, the content of the particles is more than 90%, and the content of dry-based calcium oxide is more than or equal to 72%;
(2) And (3) wet desulphurization: adding water into the desulfurizer obtained in the step (1) and pulping to prepare desulfurized slurry, feeding the desulfurized slurry into a desulfurization reaction tower, carrying out contact reaction on the desulfurized slurry and sulfur-containing flue gas through a spraying system to carry out desulfurization, adding an induction growth agent in the desulfurization process, controlling the particle size morphology of calcium sulfate crystals, and dehydrating to obtain desulfurized gypsum; the induced growth agent comprises one or a combination of more of sodium polyacrylate, polyethylene glycol and polyvinyl alcohol, and the addition amount is 0.005-3% of the mass of the desulfurizer; the mass ratio of the carbide slag to the water in the desulfurization slurry is 1:1-1.
2. The method for regulating and promoting the crystal growth of desulfurized gypsum by using the carbide slag-based desulfurizing agent according to claim 1, wherein the carbide slag in the step (1) is produced by a dry or wet acetylene production process.
3. The method for regulating and promoting the crystal growth of desulfurized gypsum by using the carbide slag-based desulfurizer as claimed in claim 1, wherein in step (2), the sulfur content of flue gas at the inlet of the desulfurization reaction tower is in the range of 500 to 5000ppm, and the sulfur content of flue gas after desulfurization is in the range of 0.5 to 25ppm.
4. The method for regulating and promoting the crystal growth of the desulfurized gypsum according to claim 1, wherein the particle size of the desulfurized gypsum in the step (2) is controlled within the range of 10-1000 μm, and the main morphology comprises a short rod shape, a whisker shape and a thick rod shape.
5. The method for regulating and promoting the crystal growth of desulfurized gypsum according to claim 1, wherein the water content of desulfurized gypsum in step (2) is 11-15%.
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