CN107540226B - Acid-resistant enamel glaze with fly ash as raw material and preparation method thereof - Google Patents
Acid-resistant enamel glaze with fly ash as raw material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an acid-resistant enamel glaze taking fly ash as a raw material and a preparation method thereof, wherein the raw material comprises the following components: according to the mass percentage of the whole enamel glaze, 5-35 percent of fly ash and 45-65 percent of SiO2、0‑3％Al2O3、2‑6％B2O3、0‑2％MgO、0‑4％CaO、6‑16％Na2O、0‑5％K2O、0‑2％TiO2、0.5‑1.5％Co2O30.5-1.5% of NiO and 0-1% of additive. The invention mixes the power plant fly ash and the additive according to the formula of the enamel glaze, melts the mixture at high temperature and then quenches the mixture with water, adds a certain proportion of clay, bentonite, borax, surface modifier and water for grinding, and prepares acid-resistant enamel glaze slurry to coat on a metal tube to prepare an acid-resistant enamel product by firing at high temperature. The high acid-resistant alumina and calcium oxide contained in the fly ash of the power plant are utilized, so that the acid-resistant enamel glaze is prepared by combining quartz sand and other raw materials, and the acid-resistant enamel glaze is used for producing an air preheater for a power plant and the like, so that the energy conservation and environmental protection of the whole industrial chain are realized, and the economic benefit is very good. Simple steps, convenient operation and strong practicability.
Description
Technical Field
The invention belongs to the field of acid-resistant enamel glaze manufacture, and particularly relates to an acid-resistant enamel glaze taking fly ash as a raw material and a preparation method thereof.
Background
Along with the adjustment of enamel industry and product structure and the change of market demand, the application range of enamel products in the industrial field is widened. For example, the enamel of the heat transfer elements at the cold end and the hot end of the air preheater in the power generation boiler is required to be acid-resistant, the thickness of the plate is 0.5-0.8 mm, and the industrial acid-resistant glaze is used, so that the product has large deformation and is easy to fall off during installation due to high firing temperature.
The invention patent of the fly ash environment-friendly sound-absorbing board (application number: 201310475274.1) is applied in 2013 of Schqinghua, and the patent is granted in 2016. The patent of the invention of fly ash standard brick (application number: 200610050954.9) is applied in 2006 and 2 months after Zhangxue, and the patent is granted in 2009. The fly ash brick invention patent (application number: 201410848138.7) is filed in 2014 and 12 months. Also relates to a brick formed from fly ash and a method of forming such an article. Zhao Tong et al filed for dry-mixed fly ash mortar (application number: 201010608676.0) in 12 months in 2010, and were granted in 2013. Jiang Guping (Yixing hong Wei science and technology limited company) applied for the invention patent of the fly ash composite grinding aid in 10 months in 2012 (application number: 201210420974.6), xuqinghua et al applied for the invention patent of the fly ash flame-retardant foaming agent in 5 months in 2013 (application number: 201310198238.5), and granted in 12 months 2014. The invention discloses a fly ash flame-retardant foaming agent which is suitable for producing flame-retardant fire-extinguishing, light plates, light walls and noise-reducing products. Liulin application 10 of 2014 filed a fly ash hollow brick invention patent (application number: 201410551770.5). Hu Shuo et al filed an invention patent for fly ash cement in 2016, 8 months. It can be seen that the cyclic utilization of fly ash is a development trend, but the preparation of enamel glaze, especially acid-resistant enamel glaze, by using fly ash is a vacancy at present.
There are also some patents on acid-resistant enamel. For example, Zhang hu 2015, 7.month, applied for an acid-proof enamel glaze slurry and a method for preparing an enamel product by using the glaze slurry (application number: 201510385499.7). The invention discloses a cowden steel enamel base coat and a cowden steel enamel base coat glaze slip invention patent (application number: 200910073081.7) applied in 2009 in Liuguangyang, and the application is granted in 2012. An acid and alkali resistant cast iron antimony overglaze (application number: 201310166328.6) for enamel is applied by Wangzhongsong in 2013 and 5 months, and is authorized in 2015. An enamel glaze (application number: 200710038484.9) for acid-resistant cast iron sanitary ware is applied in cymbidium hybridum spring 2007 and 9 months, and is authorized in 2010. The aspects are improved from the aspects of raw materials of acid-resistant enamel glaze and the like, but the fly ash is not involved.
Disclosure of Invention
In order to overcome the defects, the invention provides an acid-resistant enamel glaze taking fly ash as a raw material and a preparation method thereof. The high acid-resistant alumina and calcium oxide contained in the fly ash of the power plant are utilized, so that the acid-resistant enamel glaze is prepared by combining quartz sand and other raw materials, and the acid-resistant enamel glaze is used for producing an air preheater for a power plant and the like, so that the energy conservation and environmental protection of the whole industrial chain are realized, and the economic benefit is very good.
In order to achieve the purpose, the invention adopts the following technical scheme:
an acid-resistant enamel glaze taking power plant fly ash as a raw material comprises the following raw materials in percentage by weight: 5-35% of fly ash and 45-65% of SiO2、0-3％Al2O3、2-6％B2O3、0-2％MgO、0-4％CaO、6-16％Na2O、0-5％K2O、0-2％TiO2、0.5-1.5％Co2O30.5-1.5 percent of NiO and the balance of additive.
Preferably, the material composition comprises the following raw materials in percentage by weight: 5-20% of fly ash and 45-55% of SiO2、0-1.5％Al2O3、2-4％B2O3、0-1％MgO、0-2％CaO、6-11％Na2O、0-2.5％K2O、0-1％TiO2、0.5-1.0％Co2O30.5-1.0% of NiO and the balance of additives.
Preferably, for example, prepared fromThe raw materials with the following weight percentages are as follows: 20-35% of fly ash and 55-65% of SiO2、1.5-3％Al2O3、4-6％B2O3、1-2％MgO、2-4％CaO、11-16％Na2O、2.5-5％K2O、1-2％TiO2、1.0-1.5％Co2O31.0-1.5 percent of NiO and the balance of additive.
Preferably, the additive is zirconium oxide, or a zirconium-containing salt.
Preferably, the fly ash is used for various power plants, and the power plant is at least one of a pulverized coal power plant, a coal slime power plant and a biomass power plant.
The invention also provides a preparation method of the acid-resistant enamel glaze by taking the fly ash of the power plant as the raw material, which comprises the following steps:
the first procedure, weighing raw materials, grinding and uniformly mixing to obtain a mixture;
the second procedure, melting the mixture for 3-4h at 1400-1480 ℃ to obtain flawless high-temperature glass liquid, and then carrying out water quenching treatment to obtain glass lining glaze clinker;
and a third step, cleaning, selecting and decontaminating the glass enamel clinker, adding clay, bentonite, borax and a surface modifier, and grinding to obtain the acid-resistant enamel glaze.
Preferably, the surface modifier is at least one of sodium polyphosphate, sodium lignosulfonate and sodium nitrate.
Preferably, in the third step, the addition amounts of the clay, the bentonite, the borax and the surface modifier are respectively 0-5%, 0-5% and 0-1% of the weight of the glass lining glaze clinker.
Preferably, the particle size of the acid-resistant enamel glaze is 5-100 micrometers.
The invention also provides application of any one of the acid-resistant enamel glaze in producing an air preheater or a hot-end heat transfer element for a power plant.
The invention has the advantages of
(1) The acid-resistant enamel glaze prepared by taking the fly ash of the power plant as the raw material is compared with the conventional acid-resistant enamel glaze in terms of various properties, and the result shows that the acid resistance of the acid-resistant enamel glaze is good and is higher than the relative industrial standard.
(2) The fly ash acid-resistant enamel glaze developed by the invention has great economic benefit, environmental benefit and social benefit.
(3) The preparation method is simple, high in detection efficiency, strong in practicability and easy to popularize.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is an SEM of acid resistant enamel glaze powder;
FIG. 2 is a particle size distribution diagram of the acid-resistant enamel glaze powder.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
An acid-resistant enamel glaze taking power plant fly ash as a raw material comprises the following raw material components: according to the mass percentage of the whole enamel glaze, 5-35 percent of fly ash and 45-65 percent of SiO2、0-3％Al2O3、2-6％B2O3、0-2％MgO、0-4％CaO、6-16％Na2O、0-5％K2O、0-2％TiO2、0.5-1.5％Co2O30.5-1.5% of NiO and 0-1% of additive.
The additive is zirconium oxide or zirconium-containing salts.
The invention relates to an acid-resistant enamel glaze taking fly ash as a raw material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) weighing raw materials, grinding and uniformly mixing to obtain a mixture, adding the mixture into a crucible, and placing the crucible in a melting furnace;
(2) melting for 3-4h at 1400-1480 ℃ to obtain defect-free high-temperature glass liquid, and then performing water quenching treatment;
(3) after washing, selecting and decontaminating water-quenched enamel glass glaze clinker, adding 0-5% of clay, 0-5% of bentonite, 0-5% of borax and 0-1% of surface modifier, and carrying out dry grinding or wet grinding by using a grinding device until the particle size is about 5-100 microns, thus obtaining the acid-resistant enamel glaze.
The surface modifier in the step (3) is one or more of sodium polyphosphate, sodium lignosulfonate and sodium nitrate.
Example 1
The mass fraction of the fly ash component of a certain coal slime power plant is 45.30 percent of SiO2，0.76％Na2O，1.46％K2O，11.48％CaO，27.95％Al2O3，1.27％MgO，1.51％TiO2，6.99％Fe2O33.32 percent of C, and adding 20 percent of fly ash to prepare the acid-resistant enamel glaze according to actual needs, wherein the specific mixture ratio is as follows:
(1) the raw materials are weighed as follows: SiO 22、Na2O、B2O3、TiO2The mass percentages of NiO, CoO, BaO, CaO and MgO are respectively 55.00%, 14.50%, 3.00%, 1.00%, 1.50%, 2.00%, 1.50% and 0.50%. The mass percentage of the coal slurry power plant fly ash is 20%.
(2) According to the formula, the raw materials are weighed according to the proportion, and SiO in the raw materials2、Na2O、B2O3、TiO2NiO, CoO, BaO, CaO, MgO, etc. in the form of quartz sand, sodium carbonate, borax or boric acid, titanium white, NiO, CoO, BaCO, etc3Calcite or dolomite, and the purity of the introduced substances is higher than the industrial purity.
(3) Weighing raw materials, grinding and uniformly mixing to obtain a mixture, adding the mixture into a crucible, and placing the crucible in a melting furnace;
(4) melting for 4h at 1460 ℃ to obtain defect-free high-temperature glass liquid, and then performing water quenching treatment;
(5) after water quenching treatment of enamel glass glaze clinker, washing, selecting and decontaminating, adding 2% of clay, 3% of bentonite, 0.3% of borax and 0.5% of sodium polyphosphate, and dry grinding or wet grinding by using a grinding device until the average particle size is about 18 microns, thus obtaining the acid-resistant enamel glaze.
According to the standard in ISO 28706-2/GB/T7989-2013, the weight loss rate in concentrated sulfuric acid with the mass fraction of 30% is only 6.3 g/square meter, which is higher than the requirement of NB/T47049-2016 tubular air preheater in the industrial standard on the acid resistance of the air preheater to be not higher than 10 g/square meter.
Example 2
The mass fraction of the fly ash component of a certain coal slime power plant is 45.30 percent of SiO2，0.76％Na2O，1.46％K2O，11.48％CaO，27.95％Al2O3，1.27％MgO，1.51％TiO2，6.99％Fe2O33.32 percent of C, and adding 10 percent of fly ash to prepare the acid-resistant enamel glaze according to actual needs, wherein the specific mixture ratio is as follows:
(1) the raw materials are weighed as follows: SiO 22、Na2O、B2O3、TiO2The mass percentages of NiO, CoO, BaO, CaO and MgO are 63.00%, 12.50%, 4.00%, 1.00%, 1.20%, 1.80%, 3.00%, 2.50% and 1.00%, respectively. The mass percentage of the coal slurry power plant fly ash is 10%.
(2) According to the formula, the raw materials are weighed according to the proportion, and SiO in the raw materials2、Na2O、B2O3、TiO2NiO, CoO, BaO, CaO, MgO, etc. in the form of quartz sand, sodium carbonate, borax or boric acid, titanium white, NiO, CoO, BaCO, etc3Calcite or dolomite, and the purity of the introduced substances is higher than the industrial purity.
(3) Weighing raw materials, grinding and uniformly mixing to obtain a mixture, adding the mixture into a crucible, and placing the crucible in a melting furnace;
(4) melting for 4h at 1460 ℃ to obtain defect-free high-temperature glass liquid, and then performing water quenching treatment;
(5) after water quenching treatment of enamel glass glaze clinker, cleaning, selecting and decontaminating, adding 4% of clay, 0.5% of bentonite, 0.4% of borax and 0.3% of sodium polyphosphate, and dry-grinding or wet-grinding by using a grinding device until the average particle size is about 25 microns, thus obtaining the acid-resistant enamel glaze.
According to the standard in ISO 28706-2/GB/T7989-2013, the weight loss rate in concentrated sulfuric acid with the mass fraction of 30% is only 8.2 g/square meter, which is higher than the requirement of NB/T47049-2016 tubular air preheater in the industrial standard on the acid resistance of the air preheater to be not higher than 10 g/square meter.
Example 3
The mass fraction of the fly ash component of a certain biomass power plant is 39.04 percent SiO2，15.70％Al2O3，5.51％Fe2O3，17.65％CaO，2.62％MgO，2.73％Na2O，7.2％K2O，1.07％TiO23.43 percent of C, and adding 30 percent of fly ash according to actual needs to prepare the acid-resistant enamel glaze, wherein the specific mixture ratio is as follows:
(1) the raw materials are weighed as follows: SiO 22、Na2O、B2O3、TiO2NiO, CoO, BaO, CaO and MgO are respectively 52.00%, 9.50%, 2.50%, 1.00%, 1.50%, 2.00%, 0.30% and 0.20% in percentage by mass. The mass percentage of the coal slurry power plant fly ash is 30%.
(2) According to the formula, the raw materials are weighed according to the proportion, and SiO in the raw materials2、Na2O、B2O3、TiO2NiO, CoO, BaO, CaO, MgO, etc. in the form of quartz sand, sodium carbonate, borax or boric acid, titanium white, NiO, CoO, BaCO, etc3Calcite or dolomite, and the purity of the introduced substances is higher than the industrial purity.
(3) Weighing raw materials, grinding and uniformly mixing to obtain a mixture, adding the mixture into a crucible, and placing the crucible in a melting furnace;
(4) melting for 4h at 1460 ℃ to obtain defect-free high-temperature glass liquid, and then performing water quenching treatment;
(5) after water quenching treatment of enamel glass glaze clinker, cleaning, selecting and decontaminating, adding 1% of clay, 4% of bentonite, 0.2% of borax and 0.6% of sodium polyphosphate, and dry grinding or wet grinding by using a grinding device until the average particle size is about 28 microns, thus obtaining the acid-resistant enamel glaze.
According to the standard in ISO 28706-2/GB/T7989-2013, the weight loss rate in concentrated sulfuric acid with the mass fraction of 30% is only 9.2 g/square meter, which is higher than the requirement of NB/T47049-2016 tubular air preheater in the industrial standard on the acid resistance of the air preheater to be not higher than 10 g/square meter.
Example 4
The mass fraction of the fly ash component of a certain biomass power plant is 39.04 percent SiO2，15.70％Al2O3，5.51％Fe2O3，17.65％CaO，2.62％MgO，2.73％Na2O，7.2％K2O，1.07％TiO23.43 percent of C, adding 15 percent of fly ash according to actual needs to prepare the acid-resistant enamel glaze, wherein the specific mixture ratio is as follows:
(1) the raw materials are weighed as follows: SiO 22、Na2O、B2O3、TiO2The mass percentages of NiO, CoO, BaO, CaO and MgO are respectively 61.00%, 12.50%, 3.00%, 2.00%, 1.20%, 1.80%, 2.00%, 0.50% and 1.00%. The mass percentage of the coal slurry power plant fly ash is 15%.
(2) According to the formula, the raw materials are weighed according to the proportion, and SiO in the raw materials2、Na2O、B2O3、TiO2NiO, CoO, BaO, CaO, MgO, etc. in the form of quartz sand, sodium carbonate, borax or boric acid, titanium white, NiO, CoO, BaCO, etc3Calcite or dolomite, and the purity of the introduced substances is higher than the industrial purity.
(3) Weighing raw materials, grinding and uniformly mixing to obtain a mixture, adding the mixture into a crucible, and placing the crucible in a melting furnace;
(4) melting for 3.5h at 1440 ℃ to obtain defect-free high-temperature glass liquid, and then carrying out water quenching treatment;
(5) after water quenching treatment of enamel glass glaze clinker, washing, selecting and decontaminating, adding 2% of clay, 3% of bentonite, 0.3% of borax and 0.4% of sodium polyphosphate, and dry grinding or wet grinding by using a grinding device until the average particle size is about 15 microns, thus obtaining the acid-resistant enamel glaze.
According to the standard in ISO 28706-2/GB/T7989-2013, the weight loss rate in concentrated sulfuric acid with the mass fraction of 30% is only 8.9 g/square meter, which is higher than the requirement of NB/T47049-2016 tubular air preheater in the industrial standard on the acid resistance of the air preheater to be not higher than 10 g/square meter.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. An acid-resistant enamel glaze taking power plant fly ash as a raw material is characterized in that: the composite material consists of the following raw materials in percentage by weight: 5-35% of fly ash and 45-65% of SiO2、0-3％Al2O3、2-6％B2O3、0-2％MgO、0-4％CaO、6-16％Na2O、0-5％K2O、0-2％TiO2、0.5-1.5％Co2O30.5-1.5% of NiO, and the balance of additive;
the coal ash is used for various power plants, and the power plant is at least one of a coal powder power plant, a coal slime power plant and a biomass power plant;
the additive is zirconium oxide or zirconium-containing salts.
2. The acid-resistant enamel glaze according to claim 1, which is prepared from the following raw materials in percentage by weight: 5-20% of fly ash and 45-55% of SiO2、0-1.5％Al2O3、2-4％B2O3、0-1％MgO、0-2％CaO、6-11％Na2O、0-2.5％K2O、0-1％TiO2、0.5-1.0％Co2O30.5-1.0% of NiO and the balance of additives.
3. The acid-resistant enamel glaze according to claim 1, which is prepared from the following raw materials in percentage by weight: 20-35% of fly ash and 55-65% of SiO2、1.5-3％Al2O3、4-6％B2O3、1-2％MgO、2-4％CaO、11-16％Na2O、2.5-5％K2O、1-2％TiO2、1.0-1.5％Co2O31.0-1.5 percent of NiO and the balance of additive.
4. A method for preparing acid-resistant enamel glaze by using power plant fly ash as a raw material, wherein the acid-resistant enamel glaze of claim 1 is prepared by the following steps:
the first procedure, weighing raw materials, grinding and uniformly mixing to obtain a mixture;
the second procedure, melting the mixture for 3-4h at 1400-1480 ℃ to obtain flawless high-temperature glass liquid, and then carrying out water quenching treatment to obtain glass lining glaze clinker;
and a third step, cleaning, selecting and decontaminating the glass enamel clinker, adding clay, bentonite, borax and a surface modifier, and grinding to obtain the acid-resistant enamel glaze.
5. The method of claim 4, wherein: the surface modifier is at least one of sodium polyphosphate, sodium lignosulfonate and sodium nitrate.
6. The method according to claim 4, wherein in the third step, the clay, bentonite, borax and surface modifier are added in amounts of 0-5%, 0-5% and 0-1% by weight of the glass enamel clinker.
7. The acid-resistant enamel glaze prepared by the method of claim 4, wherein the particle size of the acid-resistant enamel glaze is 5 to 100 μm.
8. Use of the acid-resistant enamel of any one of claims 1 to 3 in the production of an air preheater or a hot-end heat transfer element for power plants.
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| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
| CN105254279A (en) * | 2015-09-30 | 2016-01-20 | 鄂尔多斯市兴辉陶瓷有限公司 | Method for manufacturing ceramic tiles by utilizing desert sand and pulverized fuel ash |
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| CN101921063A (en) * | 2010-08-05 | 2010-12-22 | 奇瑞汽车股份有限公司 | Enamel and preparation method thereof |
| CN105254279A (en) * | 2015-09-30 | 2016-01-20 | 鄂尔多斯市兴辉陶瓷有限公司 | Method for manufacturing ceramic tiles by utilizing desert sand and pulverized fuel ash |
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