CN113233920B - Chlorine corrosion resistant refractory material - Google Patents
Chlorine corrosion resistant refractory material Download PDFInfo
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- CN113233920B CN113233920B CN202110739692.1A CN202110739692A CN113233920B CN 113233920 B CN113233920 B CN 113233920B CN 202110739692 A CN202110739692 A CN 202110739692A CN 113233920 B CN113233920 B CN 113233920B
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- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5042—Zirconium oxides or zirconates; Hafnium oxides or hafnates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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Abstract
The invention discloses a modification method for improving chlorine corrosion resistance of a refractory material, which takes the refractory material to be modified and a zirconium nitrate aqueous solution as raw materials, places the refractory material to be modified in the zirconium nitrate aqueous solution, heats, stirs and dries, and finally bakes to obtain the modified refractory material. The refractory material modified by the method has excellent chlorine corrosion resistance, can be applied to a hazardous waste incineration rotary kiln, and solves the problems of insufficient chlorine corrosion resistance and short service life of the conventional hazardous waste incineration rotary kiln refractory material.
Description
Technical Field
The invention relates to improvement of a refractory material, in particular to a modification method for improving chlorine corrosion resistance of the refractory material, and belongs to the technical field of refractory materials.
Background
The high-temperature incineration method can effectively treat dangerous wastes and has the advantages of high harmless degree, good volume reduction effect, high recycling rate, small occupied area and the like. In addition, the method can thoroughly kill harmful microorganisms, viruses and the like in the waste, and optimize the decomposition of the compound into CO 2 And H 2 And O, so that inflammable substances are thoroughly oxidized to reach a stable state. However due to incineration of smokeThe gas contains a certain amount of chloride, and researches show that HCl can change the crystal form of the refractory material to destroy the crystal structure of the mineral, and meanwhile, the inside of the refractory material is loose due to the transformation of the crystal structure, so that the refractory material is more prone to cracking. In addition, HCl can also form hydrochloride with other elements in the refractory material, so that the combination mode among original substances is disturbed, the performance of the refractory material is influenced, the service life of the refractory material is shortened, and the cost is increased. Therefore, the modification of the refractory material to improve the chlorine corrosion resistance thereof is of great importance.
Disclosure of Invention
Aiming at the problem that the refractory material in the existing garbage incineration rotary kiln is seriously corroded by chlorine, the invention aims to provide a modification method for improving the chlorine corrosion resistance of the refractory material, so that the service life of the refractory material is prolonged.
In order to solve the technical problems, the invention adopts the following technical scheme:
a modifying method for improving the chlorine corrosion resistance of refractory material is to take refractory material to be modified and zirconium nitrate aqueous solution as raw materials, put the refractory material to be modified into zirconium nitrate aqueous solution, heat, stir and dry, finally bake to obtain the modified refractory material.
The specific modification steps are as follows,
1) Preparing zirconium nitrate aqueous solution
Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate aqueous solution is 0.1-0.5mol/L;
2) Refractory material impregnation modification
Placing the refractory material to be modified into the zirconium nitrate aqueous solution in the step 1), and heating, stirring and evaporating to dryness to obtain a modified refractory material precursor; the mass ratio of the refractory material to be modified to the zirconium nitrate in the zirconium nitrate aqueous solution is 2.84% -28.4%;
3) Roasting modification of precursor of modified refractory material
Roasting the modified refractory material precursor obtained in the step 2), wherein the roasting temperature is 300-600 ℃, the roasting time is 60-300 min, the heating rate is 5-20 ℃/min, and the modified refractory material is obtained after natural cooling after roasting is finished; wherein the mass fraction of zirconia in the modified refractory material is 1-10wt%.
The heating temperature of the step 2) is 80-120 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the refractory material modified by the method has excellent chlorine corrosion resistance, can be applied to a hazardous waste incineration rotary kiln, and solves the problems of insufficient chlorine corrosion resistance and short service life of the conventional hazardous waste incineration rotary kiln refractory material. The modification method has low requirements on the properties and the forming method of the refractory material, has wide applicability, and has the advantages of simple and feasible process, safety, short production period, energy conservation, environmental protection and easy popularization.
As the hazardous waste contains a large amount of chlorine elements, chlorides are formed by burning the hazardous waste in a rotary kiln, the substances can cause serious corrosion to refractory materials in equipment, the service life of the refractory materials is reduced, and the use cost is increased. ZrO (ZrO) 2 The invention is widely studied and applied because of excellent thermal stability, and proposes that zirconium nitrate aqueous solution is used as raw material, is introduced to the surface of refractory material through impregnation, and is roasted to form compact ZrO 2 The film can effectively protect the refractory material.
Drawings
FIG. 1-photo comparison of the appearance of the refractory material of the present invention after chlorine corrosion resistance test.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
The invention relates to a modification method for improving chlorine corrosion resistance of a refractory material, which takes the refractory material to be modified and a zirconium nitrate aqueous solution as raw materials, places the refractory material to be modified in the zirconium nitrate aqueous solution, heats, stirs and dries, and finally bakes to obtain the modified refractory material.
The specific modification steps are as follows,
1) Preparing zirconium nitrate aqueous solution
Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate aqueous solution is 0.1-0.5mol/L;
2) Refractory material impregnation modification
Placing the refractory material to be modified into the zirconium nitrate aqueous solution in the step 1), and heating, stirring and evaporating to dryness, wherein the heating temperature is 80-120 ℃, so as to obtain a modified refractory material precursor; the mass ratio of the refractory material to be modified and the zirconium nitrate in the zirconium nitrate aqueous solution is 2.84 percent to 28.40 percent
3) Roasting modification of precursor of modified refractory material
Roasting the modified refractory material precursor obtained in the step 2), wherein the roasting temperature is 300-600 ℃, the roasting time is 60-300 min, the heating rate is 5-20 ℃/min, and the modified refractory material is obtained after natural cooling after roasting is finished; wherein the mass fraction of zirconia in the modified refractory material is 1-10wt%.
The following examples are included to further aid in the understanding of the invention.
Example 1
(1) Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate solution is 0.1 mol/L.
(2) And (3) putting the refractory material to be modified into the solution in the step (1), heating, stirring and evaporating to dryness, wherein the heating temperature is 80 ℃ to obtain a modified refractory material precursor. The mass ratio of the refractory material to be modified to the zirconium nitrate in the zirconium nitrate aqueous solution is 2.84 percent
(3) And (3) roasting the modified refractory material precursor obtained in the step (2), roasting at 300 ℃ for 60 min, and naturally cooling at a heating rate of 5 ℃/min to obtain the modified refractory material, wherein the mass fraction of zirconia in the modified refractory material is 1wt%.
Example 2
(1) Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate solution is 0.3 mol/L.
(2) And (3) putting the refractory material to be modified into the solution in the step (1), heating, stirring and evaporating to dryness, wherein the heating temperature is 100 ℃ to obtain a modified refractory material precursor. The mass ratio of the refractory material to be modified to the zirconium nitrate in the zirconium nitrate aqueous solution is 19.84%.
(3) And (3) roasting the modified refractory material precursor obtained in the step (2), roasting at 400 ℃ for 150 min, and naturally cooling at a heating rate of 10 ℃/min to obtain the modified refractory material, wherein the mass fraction of zirconia in the modified refractory material is 7wt%.
Example 3
(1) Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate solution is 0.3 mol/L.
(2) And (3) putting the refractory material to be modified into the solution in the step (1), heating, stirring and evaporating to dryness, wherein the heating temperature is 100 ℃ to obtain a modified refractory material precursor. The mass ratio of the refractory material to be modified to the zirconium nitrate in the zirconium nitrate aqueous solution is 14.20%.
(3) And (3) roasting the modified refractory material precursor obtained in the step (2), and roasting at 450 ℃ for 200 min at a heating rate of 10 ℃/min, and naturally cooling to obtain the modified refractory material, wherein the mass fraction of zirconia in the modified refractory material is 5wt%.
Example 4
(1) Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate solution is 0.4 mol/L.
(3) And (2) putting the refractory material to be modified into the solution in the step (1), and heating, stirring and evaporating to dryness, wherein the heating temperature is 120 ℃ to obtain a modified refractory material precursor. The mass ratio of the refractory material to be modified to the zirconium nitrate in the zirconium nitrate aqueous solution is 22.72%.
(3) And (3) roasting the modified refractory material precursor obtained in the step (2), roasting at 500 ℃ for 300 min, wherein the heating rate is 15 ℃/min, and naturally cooling to obtain the modified refractory material, wherein the mass fraction of zirconia in the modified refractory material is 8wt%.
Example 5
(1) Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate solution is 0.5 mol/L.
(4) And (2) putting the refractory material to be modified into the solution in the step (1), and heating, stirring and evaporating to dryness, wherein the heating temperature is 120 ℃ to obtain a modified refractory material precursor. The mass ratio of the refractory material to be modified to the zirconium nitrate in the zirconium nitrate aqueous solution is 28.40%.
(3) And (3) roasting the modified refractory precursor obtained in the step (2), roasting at 600 ℃ for 300 min, wherein the heating rate is 20 ℃/min, and naturally cooling to obtain the modified refractory, wherein the mass fraction of zirconia in the modified refractory is 10wt%.
Compression molding is carried out on the refractory materials obtained by modification in examples 1-5, the molded sample and the molded sample of the unmodified refractory material are put into a vacuum atmosphere furnace together for chlorine corrosion resistance test, and HCl-N with the flow rate of 4L/min is introduced 2 The mixture was incubated at 1100℃for 72 h at a HCl concentration of 1000 ppm. FIG. 1 shows comparative photographs of the appearance of the products of the chlorine corrosion resistance test conducted according to the present method for the refractory material before modification of the present invention and the modified refractory material according to example 4 (left side refractory material is not modified, right side refractory material is modified according to example 4). The results show that the color and pores of the modified refractory material are better than those of the unmodified refractory material (compared with the unmodified refractory material), the color of the unmodified refractory material is obviously changed, the pores on the surface of the modified refractory material are reduced compared with the modified refractory material, and the surface of the modified refractory material is partially collapsed. The reason is that the chlorine corrosion process of the refractory material is the process of reacting components in the refractory material with chloride, the reaction causes color change, holes are reduced, and collapse occurs. The modified refractory material of the invention forms a layer of compact ZrO on the surface of the refractory material 2 The film can effectively protect the refractory material, greatly reduce contact and reaction with chloride, maximally maintain the original shape and function of the refractory material, and greatly improve the chlorine corrosion resistance.
The modification method for improving the chlorine corrosion resistance of the refractory material has low requirements on the material quality of the refractory material and the preparation method, has wide applicability, and has simple process and short production period.
Finally, it is noted that the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and that although the present invention has been described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein. Obvious changes that are extended by the technical proposal of the invention are still within the scope of the invention.
Claims (2)
1. A chlorine corrosion resistant refractory, characterized by: taking a refractory material to be modified and a zirconium nitrate aqueous solution as raw materials, placing the refractory material to be modified in the zirconium nitrate aqueous solution, heating, stirring and drying, and roasting to obtain the modified refractory material; finally, the modified refractory material is pressed and molded to obtain a refractory material product;
the preparation method of the modified refractory material is as follows,
1) Preparing zirconium nitrate aqueous solution
Uniformly mixing zirconium nitrate pentahydrate with water according to a certain mass fraction, and performing ultrasonic dispersion, wherein the concentration of the zirconium nitrate aqueous solution is 0.1-0.5mol/L;
2) Refractory material impregnation modification
Placing the refractory material to be modified into the zirconium nitrate aqueous solution in the step 1), and heating, stirring and evaporating to dryness to obtain a modified refractory material precursor; the mass ratio of the refractory material to be modified to the zirconium nitrate in the zirconium nitrate aqueous solution is 2.84% -28.4%;
3) Roasting modification of precursor of modified refractory material
Roasting the modified refractory material precursor obtained in the step 2), wherein the roasting temperature is 300-600 ℃, the roasting time is 60-300 min, the heating rate is 5-20 ℃/min, and the modified refractory material is obtained after natural cooling after roasting is finished; wherein the mass fraction of zirconia in the modified refractory material is 1-10wt%.
2. A chlorine corrosion resistant refractory according to claim 1, wherein: the heating temperature of the step 2) is 80-120 ℃.
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| ATA208693A (en) * | 1993-10-18 | 1997-11-15 | Ica Innoconsult Ag | CORROSION PROTECTION METHOD FOR COMBUSTION PLANTS |
| EP1306469A1 (en) * | 2000-07-24 | 2003-05-02 | Nkk Corporation | Steel pipe coated with composite material and method for production thereof |
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| JP4475998B2 (en) * | 2004-03-29 | 2010-06-09 | 九州電力株式会社 | Method for forming corrosion-resistant laminated film and corrosion-resistant laminated film |
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| Songjie Yang等.Study on High-temperature Erosion Resistance of Precursor Ceramic Coatings.《IOP Conference Series: Earth and Environmental Science》.2020,第474卷全文. * |
| 周耀.锆和锆合金在化工设备中的应用.《化工设计》.2003,全文. * |
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