CN108218396B - Low-thermal-expansion high-strength antibacterial ceramic prepared from silver ore tailings and preparation method thereof - Google Patents
Low-thermal-expansion high-strength antibacterial ceramic prepared from silver ore tailings and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a formula and a method for preparing antibacterial ceramic with high and low thermal expansion strength by utilizing silver ore tailings. The ceramic has the characteristics of high strength, small thermal expansion coefficient and high antibacterial rate, and heavy metal ions in the silver tailings are completely solidified. Compared with silver tailings used as building sand, concrete filler, ceramsite and foam glass, the silver tailings have superior performance, and the application field is widened; the silver mine tailings are used as main raw materials, so that the cost is reduced, and the additional value is improved. The method can bring great economic benefits while solving the problem of environmental pollution of the silver tailings.
Description
Technical Field
The invention relates to a preparation method of ceramic with high compressive strength, low coefficient of thermal expansion ceramics and high antibacterial rate by using silver tailings as main material ores.
Background
Silver mine tailings are solid wastes generated in the mineral separation process of silver ores, a large amount of silver mine tailings are produced every year, the silver mine tailings are mainly placed in a tailing pond or backfilled into a mine in the prior treatment method, the silver mine tailings are accumulated in a large amount by the treatment method, waste of space resources and dust pollution are caused, meanwhile, the tailings contain a certain amount of heavy metals, and the heavy metals can permeate into surrounding soil and underground water after long-term accumulation, so that the health of human beings is threatened, and therefore, the silver mine tailings are treated at will. At present, the comprehensive utilization of the silver mine tailings is mainly used for building materials such as building sand, concrete filler, ceramsite and the like. The preparation of ceramics with high strength, low thermal expansion and high antibacterial property by utilizing the silver mine tailings has not been reported.
Novel building materials, 2010, 9: 17-18 Liudan pill, Lexuan, Linnao and Yangxicang in the 'research and application of silver mine tailings to building mortar', research feasibility of silver mine tailings replacing lime to be used for building mortar; construction techniques, 2013, 11: 91-92 Zhuhuilong and Ruanzhen in the experimental study of silver-tail foam concrete, namely, the foam concrete is prepared by utilizing silver mine tailings, ordinary cement, a foaming agent, a water reducing agent and waste polystyrene foam particles; guangdong building materials 2013, (8) 21-24, Chenwei in the article "exploration on silver mine tailing sand high-strength ceramsite production process": the high-strength ceramsite is produced by utilizing the silver ore tailing sand, and the performance of the ceramsite product obtained by production meets the requirements of the national standard; 2018.1.9, judian discloses a patent of invention "a method for producing foam glass using silver tailings". 2015.12, the subject group discloses an invention patent of 'antibacterial ceramic prepared by taking silver tailings as main materials'.
In the above researches, the first 2 items only use the silver tailings as building sand and concrete filler for research, and the additional value is low. If not, 2, the ceramsite and the foam glass prepared by the silver tailings are used for obtaining the ceramsite meeting the national standard requirements and the foam glass with good performance, but the action of residual Ag in the silver tailings is not considered, and the curing effect of other heavy metal ions in the tailings is not discussed. The antibacterial ceramic prepared by taking silver tailings as a main material disclosed by the subject group is prepared by adding clay, quartz and a fluxing agent into raw materials except the silver tailings. Except silver tailings, the raw materials are conventional ceramic raw materials, and the obtained ceramic has other performances except antibacterial property and only meets the national standard requirements. Silver contained in tailings is used as an antibacterial agent, and the content of the silver is low (ppm level) and is mostly natural silver, so the activity is low. If the ceramic cannot be effectively activated and enriched in the ceramic making process, the prepared ceramic has low antibacterial rate. How to enrich and activate natural silver with lower content in silver tailings in the ceramic preparation process is the technical key for preparing antibacterial ceramic by using the silver tailings, and the antibacterial ceramic prepared by using the silver tailings as a main material is not disclosed. Meanwhile, whether toxic heavy metal ions in tailings can be effectively cured in the process of making the ceramic is also the key for determining whether the ceramic can be applied, and the 'antibacterial ceramic prepared by taking silver tailings as a main material' does not show the curing effect of the heavy metal.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides an antibacterial ceramic with low thermal expansion and high strength prepared by using silver ore tailings as a raw material, which comprises the following formula:
the material composition according to the mass percentage is as follows: 50-85% of silver ore tailings, 15-5% of wollastonite, 20-5% of kaolin, 15-5% of talc, 1-2% of fluorite and 1-2% of activating agent.
The activator is a high valence variable valence metal compound K2MnO4、As2O5Or Sb2O5。
The preparation method for preparing the low-thermal-expansion high-strength antibacterial ceramic by utilizing the silver ore tailings comprises the following steps:
(1) preparing raw materials:
crushing, grinding and ball milling various raw materials respectively to obtain various raw material powder of 2000-3000 meshes;
(2) preparing a green body:
uniformly mixing the raw materials according to the proportion, and then placing the mixture into a mold for molding, wherein the molding pressure is 30MPa-50 MPa;
(3) firing the ceramic:
drying the formed blank, putting the blank into a kiln, heating to 500-600 ℃ by adopting gradient heating for 25-40 minutes, and heating the blank in the kiln
Keeping the temperature for 20-35 minutes at the temperature, then heating to 1100-1300 ℃ after 50-70 minutes, keeping the temperature for 60-120 minutes, and then rapidly cooling.
The ceramic obtained by the formula and the process has the main properties that the thermal expansion coefficient is less than 4 × 10-6/DEG C, high bending strength
The antibacterial rate is 100% under 85 MPa; the solidification rate of heavy metal in the silver tailings is 100 percent.
Advantageous effects
The silver mine tailings are used as raw materials, and wollastonite, talcum, kaolin, fluorite and calcium are addedThe activating agent is matched according to a certain mass percentage, and the porcelain is manufactured under reasonable process conditions. During the sintering process of the ceramic, wollastonite and silver tailings react to form diopside so as to increase the strength of the ceramic; the talc, the kaolin and the silver tailings are subjected to solid-phase reaction to form cordierite so as to reduce the thermal expansion coefficient of the ceramic; finally obtaining the diopside-cordierite-cristobalite complex phase ceramic with high strength and low thermal expansion performance. Meanwhile, fluorite with a certain proportion is introduced into the ceramic formula, and the fluorite has the functions of destroying Si-O bonds in the silver tailings, increasing liquid phase quantity and reducing liquid phase viscosity, so that heavy metal ions in the silver tailings are easy to enter a liquid phase to be solidified; the function of the activator is to convert natural silver into silver ions during the sintering process of the ceramic to improve the activity of the ceramic. The activator is a high valence variable valence metal element compound, such as: k2MnO4、As2O5、Sb2O5And the like. The action mechanism is that high valence variable valence metal elements can be reduced in the ceramic sintering process, so that natural silver is oxidized to form silver ions. Silver ions and fluorine ions generated by fluorite decomposition are subjected to complexation and migrate and enrichment to the surface of the ceramic, so that the surface of the ceramic has good antibacterial performance.
Compared with the silver ore tailings used as building materials such as sand, concrete filler, ceramsite, foam glass and the like, the antibacterial ceramic prepared by using the silver ore tailings has the following advantages:
1. the application range of the ceramic is expanded, and the ceramic not only can be used as building ceramics, but also can be used as functional ceramics such as daily-use ceramics, sanitary ceramics, catalytic carrier ceramics and the like.
2. The method for preparing the ceramic by using the silver tailings as the raw material realizes the recycling of solid wastes, reduces the cost of the ceramic and improves the economic benefit.
3. The silver tailings are used for preparing the porcelain, so that the environmental problem caused by the silver tailings is solved.
Detailed Description
The purpose of the invention is realized by the following technical scheme:
example 1
a. The silver mine tailings, wollastonite, kaolin, talc, fluorite and an activating agent are respectively ground by using a jaw crusher, a disc type pulverizer and a planetary ball mill to respectively obtain various raw material powders with 2000-3000 meshes.
b. According to the total mass 100 of the ceramic raw materials: respectively weighing 50g of silver mine tailings, 19g of kaolin, 14g of wollastonite, 15g of talcum, 1g of fluorite and K2MnO41g, and uniformly mixing the raw materials by using a mixer.
c. Placing the mixed batch into a porcelain blank mold for molding, wherein the molding pressure is 30 MPa;
d. drying the formed blank, putting the blank into a kiln, heating to 600 ℃ by adopting gradient heating within 40 minutes, preserving the heat at the temperature for 30 minutes, and heating to 1200 ℃ within 70 minutes.
e. Keeping the temperature at the roasting temperature for 60min, and then quickly cooling.
f. The obtained ceramic has flexural strength of 97MPa and thermal expansion coefficient of 3.0 × 10-6The antibacterial rate is 100 percent and the heavy metal curing rate is 100 percent.
Example 2
a. The silver mine tailings, wollastonite, kaolin, talc, fluorite and an activating agent are respectively ground by using a jaw crusher, a disc type pulverizer and a planetary ball mill to respectively obtain various raw material powders with 2000-3000 meshes.
b. According to the total mass 100 of the ceramic raw materials: respectively weighing 70g of silver mine tailings, 13g of kaolin, 7g of wollastonite, 7g of talcum, 2g of fluorite and As2O51g, and uniformly mixing the raw materials by using a mixer.
c. Placing the mixed batch into a porcelain blank mold for molding, wherein the molding pressure is 35 MPa;
d. drying the formed blank, putting the blank into a kiln, heating to 550 ℃ by adopting gradient heating for 35 minutes, preserving the heat for 35 minutes at the temperature, and heating to 1200 ℃ by 70 minutes.
e. Keeping the temperature at the roasting temperature for 90min, and then quickly cooling.
f. The obtained ceramic has flexural strength of 92MPa and thermal expansion coefficient of 3.5 × 10-6The antibacterial rate is 100 percent and the heavy metal curing rate is 100 percent.
Example 3
a. The silver mine tailings, wollastonite, kaolin, talc, fluorite and an activating agent are respectively ground by using a jaw crusher, a disc type pulverizer and a planetary ball mill to respectively obtain various raw material powders with 2000-3000 meshes.
b. According to the total mass 100 of the ceramic raw materials: respectively weighing 80g of silver ore tailings, 6g of kaolin, 5g of wollastonite, 5g of talcum, 1g of fluorite and Sb2O52g, and uniformly mixing the raw materials by using a mixer.
c. Placing the mixed batch into a porcelain blank mold for molding, wherein the molding pressure is 40 MPa;
d. drying the formed blank, putting the blank into a kiln, heating to 500 ℃ by adopting gradient heating within 25 minutes, preserving the heat at the temperature for 30 minutes, and heating to 1200 ℃ within 70 minutes.
e. Keeping the temperature at the roasting temperature for 120min, and rapidly cooling to obtain the ceramic with the rupture strength of 86Mpa and the thermal expansion coefficient of 4.0 × 10-6The antibacterial rate at/DEG C is 100%, and the heavy metal curing rate is 100%.
Claims (3)
1. The low-thermal-expansion high-strength antibacterial ceramic prepared from the silver ore tailings is characterized by comprising the following raw materials in percentage by mass: 50-85% of silver ore tailings, 15-5% of wollastonite, 20-5% of kaolin, 15-5% of talc, 1-2% of fluorite and 1-2% of activating agent; the sum of the percentages of the raw material components is one hundred percent; the activator is a high valence variable valence metal compound K2MnO4、As2O5Or Sb2O5。
2. The preparation method for preparing the low-thermal-expansion high-strength antibacterial ceramic by using the silver ore tailings according to claim 1, wherein the preparation process comprises the following steps:
preparing raw materials:
crushing, grinding and ball milling various raw materials respectively to obtain various raw material powder of 2000-3000 meshes;
preparing a green body:
uniformly mixing the raw materials according to the proportion, and then placing the mixture into a mold for molding, wherein the molding pressure is 30MPa-50 MPa;
firing the ceramic:
drying the formed blank, putting the blank into a kiln, heating to 500-600 ℃ by adopting gradient heating for 25-40 minutes, and heating the blank in the kiln
Keeping the temperature for 20-35 minutes at the temperature, then heating to 1100-1300 ℃ after 50-70 minutes, keeping the temperature for 60-120 minutes, and then rapidly cooling.
3. The method for preparing the antibacterial ceramic with low thermal expansion and high strength by using the silver mine tailings according to claim 2, wherein the ceramic obtained by the formula and the process has the main properties that the thermal expansion coefficient is less than 4 × 10-6/° C, the bending strength is more than 85MPa, and the antibacterial rate is 100%; the solidification rate of heavy metal in the silver tailings is 100 percent.
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| CN113307603A (en) * | 2021-06-22 | 2021-08-27 | 隆昌华恒玻陶科技有限公司 | Nano titanium dioxide antibacterial ceramic mold and manufacturing method thereof |
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| CN105272162A (en) * | 2015-11-24 | 2016-01-27 | 吉林大学 | Antibiotic porcelain prepared with silver ore tailings as main material |
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| JP2720398B2 (en) * | 1988-11-12 | 1998-03-04 | 日本製箔株式会社 | Antibacterial cement |
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| CN105272162A (en) * | 2015-11-24 | 2016-01-27 | 吉林大学 | Antibiotic porcelain prepared with silver ore tailings as main material |
| CN105970220A (en) * | 2016-03-23 | 2016-09-28 | 马鞍山金晟工业设计有限公司 | Antibacterial anticorrosion coating material |
| CN107555947A (en) * | 2017-09-02 | 2018-01-09 | 福建省德化业美陶瓷有限公司 | An a kind of low temperature fast firing light ceramics product and its manufacturing process |
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