KR101309713B1 - the ceramic to manufacture using waste of Masato and method for the same - Google Patents

Abstract

Ceramic manufactured using Masato waste, which has the absorption rate and strength that can be generally utilized by forming the secondary phase (Anorthite) by separating the necessary ingredients from the waste of minato Masato waste and molybdenum and adding the remaining molybdenum tailings. And a method of manufacturing the same. The present invention is characterized in that 10-30% by weight of molybdenum tailings is added to the remaining by-products after collecting sand from Masato, and subjected to a calcination process at a temperature of less than 1000 ℃ after grinding and molding, by-products of mining waste through the present invention Can be effectively recycled, and a strong ceramic can be obtained at low temperatures.

Description

The ceramic to manufacture using waste of Masato and method for the same}

The present invention relates to a ceramic manufactured using Masato waste, and a method of manufacturing the same, and in particular, to form a secondary phase (Anorthite) by adding the remaining molybdenum tailings after separating necessary components from the waste of Masato, which is a mining waste, and molybdenum. The present invention relates to a ceramic manufactured using Masato waste having an absorption rate and strength that can be generally utilized by firing, and a method of manufacturing the same.

In general, it is widely known that ceramics are manufactured by a method of drying and calcining by adding clay (clay, kaolin, pottery stone), silica sand and feldspar. That is, the main method is to produce 60 to 90% by weight of the clay composition and 10 to 40% by weight of the additives excluding the clay, followed by drying and calcining. Ceramic products manufactured using clay are generally manufactured by firing at a high temperature of 1,200 ° C. or higher.

Since clay bricks and ceramics manufactured by such conventional methods generally have to be hot baked (over 1200 ° C.), they cause a cost increase such as fuel cost required for high temperature firing and eventually a high production cost due to the cost increase. It was. Therefore, attempts have been made to lower the firing temperature using various additives in the ceramic production method.

However, the ceramic manufacturing method for lowering the firing temperature by using various additives is complicated manufacturing process, there are many kinds of raw materials used, and the use of additives such as chemicals is likely to cause harmful substances during the firing process, There are still problems such as rising costs.

On the other hand, mine waste refers to the material remaining after separating the necessary components from the ore, which is called tailings.In order to treat the tailings scattered around the waste mines, the tailings are solidified / stabilized with cement and then shielded facility which is a block type concrete reclamation facility. Safe landfill is a stable treatment method.

If the tailings are placed in the tailings dam, environmental problems such as fugitive dust and heavy metal leaching may occur in the long term, but if they can be recycled as recycling resources, they can conserve the environment and extend the life of the mineral resources. Have.

The recycling of ore wastes (tailings) is currently being conducted by researchers in many fields as an alternative to prevent pollution of the soil and water environment by such mine wastes, but the application is only in very narrow fields. This is being tried.

The present invention has been invented to solve the above problems, by using a waste of Masato and molybdenum to manufacture a ceramic, a building material that reduces the manufacturing cost by lowering the firing temperature, causing environmental pollution and recycling waste minerals In addition, the object of the present invention is to provide a ceramic and a method for producing the same, which are manufactured using Masato waste, which has improved compressive strength and has low water absorption as compared with ceramic prepared by a conventional high temperature firing method.

The present invention for performing such an object,

The present invention 20 to 30% of the water content of the pulverized mixture obtained by crushing a mixture of 70 ~ 90% by weight of Masato waste and 10 to 30% by weight of molybdenum tailings, which are the byproducts of the sand (mass), with 40 to 100 mesh particles. Mixing and forming steps of removing water to make a molded body;

Drying the molded product produced in the mixing and molding step at room temperature for 10 to 30 hours, and then drying at a temperature of 140 ° C. to 180 ° C. for 1 to 3 days;

After the drying step is a method of manufacturing a ceramic produced using the Masato waste comprising the firing step of producing a ceramic product by firing the dried molded body at 800 ℃ ~ 1000 ℃ temperature for 2 to 6 hours.

According to a preferred embodiment of the present invention, a frit coating step of applying a glaze containing a frit having a softening point of about 600 ° C to 800 ° C as a main component before the firing step is 0.5 to 5.0 µm in thickness.

In the present invention, in the mixing and forming step, the press-molding method for press molding at a molding pressure of 15MPa ~ 30MPa and the extrusion molding method for extrusion molding under vacuum is used for the production of the molded body.

  In addition, the ceramic product according to the invention is characterized in that the product of any one of brick, ondol, tile, panel, tile and ceramics.

The present invention manufactures high value-added ceramics by recycling the waste of Masato, a mining waste which is a by-product left after collecting sand (mass), and molybdenum tailings. By controlling the mixing ratio of masato by-product and molybdenum tailings properly, it can be fired at about 300 ℃ lower than the conventional clay ceramic temperature, reducing the manufacturing cost of ceramics and the compressive strength during firing corresponds to more than one type of plastic clay brick. As a ceramic with energy saving effects, it is possible to confirm the possibility of recycling resources.

1 is a photograph showing a microstructure of a ceramic manufactured according to Example 4 of the present invention.
2 is a photograph showing a microstructure of a ceramic baked by applying a frit glaze according to Example 5 of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Masato by-products used in the present invention are to collect sand from Masato and use the generated by-products (waste). Masato is a feldspar mineral, which is dug, crushed, and sorted to collect grains of a certain size in the form of sand. Particularly, when the sieves are filtered through a wet sieve to remove soils, Sort by by-product. Selected by-products, unlike general mining by-products, are subjected to wet sieving and are removed from the soil by a filter press to remove moisture by a filter press. Selected by-products are left unused or used for landfill, but if left untreated, they contaminate surface water and groundwater, and are viscous particulates for landfilling.

Molybdenum ore is produced as ore mineral, but most of its grade is less than 1%, so most of the mined ore is discarded as tailings even if it is enhanced by increasing the quality of the concentrate and increasing the error rate by more than 95%. In addition, the tailings are discarded because most of the tailings are pulverized and separated for the separation of ore minerals and gangue minerals.

Masato by-product is <Table 1> SiO ₂ 61.02 wt%, Al ₂ O ₃ 20.32% by weight of the chemical composition as shown in, Fe ₂ O ₃ 4.96 is composed of by weight%, CaO 7.74% by weight, such as, SiO ₂ and Al ₂ Rich in O ₃ clay minerals, molybdenum tailings contain 68.4% by weight SiO ₂ , 3.55% by weight Fe ₂ O ₃ , 13.5% by weight Al ₂ O ₃ , 3.17% by weight CaO, 3.61% by weight MgO, It contains a large amount of feldspar minerals, such as 3.28 wt% Na ₂ O and 2.74 wt% K ₂ O.

In addition, Masato by-products contain SiO ₂ and Al ₂ O ₃ , which have a composition ratio capable of liquid-melting molten glass, and because they are plastic, they can be molded by themselves. Since molybdenum tailings have a CaO, k ₂ 0 and Na ₂ O total of 10 wt% or more, the molten glass liquid phase is advantageously formed at low temperature, and the molten glass liquid phase promotes fluidity or sintering between particles, resulting in Masato. Specimens from by-products and molybdenum tailings can be shaped by plasticity, sintered at low temperatures and sintered into ceramics.

Percentage of Masanto By-Products and Molybdenum Tailings
Sample

SiO ₂
Al ₂ O ₃
Fe ₂ O ₃
MgO
CaO
K ₂ O
Na ₂ O
Etc

Masato byproduct
61.02
20.32
4.96
2.09
7.74
2.22
0.25
1.4

Molybdenum tailings

68.4
13.5
3.55
1.75
3.17
3.28
3.61
2.74

Therefore, in the present invention, a ceramic product can be manufactured by adding molybdenum tailings in which molten glass liquid phase is advantageously formed in the Masato by-product having excellent plasticity in a range of 10 to 30% by weight and firing. When the added amount of molybdenum tailings is less than the above range, the object desired in the present invention cannot be achieved, and when it exceeds the above range, plasticity becomes insufficient and molding becomes difficult. Masato by-products and molybdenum tailings are mixed and pulverized into 40-100 mesh particles by a wet ball mill.

The molding method is not particularly limited and may be a press molding method by a press or an extrusion molding method that is molded by extruding under vacuum. The molded product is subjected to natural drying at room temperature for 1 day to suppress cracks and deformation, and dried for 48 hours at a temperature of 120 to 160 ° C., and calcined in an oxidizing atmosphere, but firing is performed at 900 ° C. The holding time at the highest temperature may be appropriately determined depending on the thickness and shape of the molded body, but generally, about 1 hour may be maintained.

The ceramic thus manufactured has a water absorption of about 1 to 3%, similar to that of conventional ceramics, and shows low values for clay bricks of 8 to 10%. According to the present invention, by adding molybdenum tailings to the masato by-products, the filling properties of the masato by-products are increased, thereby improving moldability, exhibiting plastic bonding strength even at low temperatures, and by controlling the mixing ratio, it is possible to obtain a low-temperature fired ceramic product.

It is calcined according to the weight% of by-products added, and it promotes the formation of a molten liquid phase between particles, thereby causing plastic shrinkage, and sintering at a low temperature is possible by the liquid phase sintering. The product has characteristics of product quality, such as compactness and low water absorption, and high compressive strength, which is much higher than that of clay bricks.

1 and 2, by adding molybdenum tailings to the Masato by-product, the present invention produces a secondary phase Anorthite (CaAl ₂ Si ₂ O ₈ ), thereby filling up pores and facilitating densification, thereby lowering the absorption rate and compressive strength. It rises sharply. Such secondary phases are believed to have been produced by the reaction of CaO, NaO, K ₂ O and aluminosilicates present in large quantities in the by-products.

In addition, in order to utilize as a general ceramic is to apply a frit glaze having a softening point of 700 ℃ or less so that the thickness of the molded body after the molding is 0.5 ~ 5.0㎛. Due to the characteristics of the product, it is possible to treat the surface of the ceramic and to reduce the absorbency and at the same time to increase the durability by improving the durability, it is possible to reduce the maintenance cost.

In the ceramic manufacturing method of the present invention, after adding a certain amount of molybdenum tailings to the masato by-products and grinding them through a wet grinding process, the water is removed so that the water content of the mixture is 20-23%, and then the mixed clay is press-molded. It is uniaxially press-molded and dried and fired.

According to another aspect of the present invention, a method of manufacturing ceramics is performed by adding a predetermined amount of molybdenum tailings to masato by-products and grinding the mixed soil through a wet grinding process to dry and adjust the water content to 25 to 30%, followed by a vacuum drill machine. By extrusion molding, and the molded product is cut into a desired size, dried and fired.

Embodiments of the present invention are as follows, and the following embodiments are related to ceramics, but the manufacturing method of the present invention does not specifically define ceramics, and in particular, may be applied to bricks, ondols, tiles, panels, tiles, ceramics, and the like. .

(Example 1)

10 parts by weight of molybdenum tailings having the composition of Table 1 was mixed with masato by-products, followed by wet grinding by a ball mill, and after the moisture was removed to make the water content of the mixture 20 to 30%, the mixture was 240 × 115 mm square mold. It was filled in to the compression molding machine using a pressure molding machine to compression molding to a molding pressure of 20MPa to prepare a molded body.

The molded product was naturally dried at room temperature for 1 day, then dried at 160 ° C. for 48 hours, calcined at 900 ° C. for 4 hours, and then cooled to prepare a ceramic.

(Example 2)

20 minutes by weight of molybdenum tailings was mixed with the masato by-product, and the wet grinding was performed. The water was removed so that the water content of the mixture was 20-30%, and a ceramic was manufactured through the same manufacturing process as in Example 1.

(Example 3)

30 minutes by weight of molybdenum tailings was mixed with the masato by-product, and the wet grinding was performed. The water was removed so that the water content of the mixture was 20-30%, and a ceramic was manufactured through the same manufacturing process as in Example 1.

(Example 4)

After mixing and pulverizing the raw materials under the same mixing conditions as in Example 2, the mixture was molded by vacuum extrusion through a vacuum boring machine and cut to a size of 240 × 115 × 60 mm to prepare a molded body. The manufactured molded article was manufactured in the same drying and firing conditions as in Example 1.

(Example 5)

The molded article obtained in Example 4 was naturally dried at room temperature for 1 day, and then dried at 160 ° C. for 48 hours, and then coated with a frit having a softening point of about 700 ° C. so as to have a thickness of 0.5 to 5.0 μm, followed by 900 ° C. After firing in an electric furnace at a temperature for 4 hours, the mixture was cooled to prepare a ceramic.

(Example 6)

The molded article obtained in Example 4 was naturally dried at room temperature for 1 day, then dried at 160 ° C. for 48 hours and calcined for 4 hours in an electric furnace at 800 ° C., followed by cooling to prepare a ceramic.

(Example 7)

The molded article obtained in Example 4 was naturally dried at room temperature for 1 day, then dried at 160 ° C. for 48 hours and calcined for 4 hours in an electric furnace at 1,000 ° C., followed by cooling to prepare a ceramic.

(Comparative Example 1)

Only Masato by-products were wet milled, and ceramics were prepared through the same manufacturing process as in Example 1.

(Comparative Example 2)

40 wt% molybdenum tailings were mixed with the masato by-product to wet grind, and the water was removed so that the water content of the mixture was 20 to 30%. Then, a ceramic was manufactured through the same manufacturing process as in Example 1.

According to the method of Korean Industrial Standard KSL 4201, the ceramic obtained by the above example was measured for absorption and compressive strength by physical properties. The test results are shown in Table 2 below.

Absorption rate and compressive strength of Examples and Comparative Examples according to the present invention
division

Absorption rate (%) Compressive strength (Mpa)
Example 1

2.1
38.17
Example 2

1.8
45.36
Example 3

1.1
43.22
Example 4

1.5
47.05
Example 5

0.8
52.65
Example 6

10.7
15.22
Example 7

0.4
38.25
Comparative Example 1

15.2
16.34
Comparative Example 2

Molding due to lack of viscosity and plasticity

Absorption rate and compressive strength of ceramics mixed with molybdenum tailings 10-30% in Masato by-products of Examples 1 to 5 are higher than 20.6 MPa of the first type compressive strength of plastic clay brick (KS L 4201). Seems to be.

However, the ceramic prepared in Comparative Example 1 is not completely sintered at 900 ° C., and has a low compressive strength as the superplasticity of general ceramics. Molded products made only of the Masato by-products are fully sintered until 1200 ° C to become ceramics. When the molybdenum tailings is 40% or more as in Comparative Example 2, there is a problem in that molding is not possible due to lack of viscosity and plasticity. Therefore, the molybdenum tailings should be mixed in the range of 10% -30%. In addition, as the molybdenum tailings increases, the sintering is better, but when it is 30% or more, it becomes vitrified and the compressive strength is lowered. The difference in compressive strength between the press-molded condition of Example 2 and the vacuum-treated condition of Example 4 is that the conditions of molding using a vacuum drill machine rather than the press-molding condition make it easier to extract pores existing in the molded body by vacuum. It is considered to express more compact and high compressive strength.

In Examples 1 to 5, the compressive strength is increased by 300% or more compared with Comparative Example 1 fired by Masato byproduct alone. In addition, ceramics fired by applying pleated glaze to 20% mixture of Masato by-product and molybdenum tailings have a water absorption of less than 1.0% and have almost no water absorption, and have a compressive strength of 52.62Mpa, which is the strongest in the test body. Therefore, Example 5 can be manufactured from a commercially available ceramic. In particular, the added amount of molybdenum tailings showed the highest compressive strength performance at 20% by weight. When the sintering temperature of the condition is 800 ℃ or less than 900 ℃ as in Example 6, the sintering reaction does not occur, the strength is lowered. When the temperature is more than 1000 ℃ as in Example 7, it is completely vitrified, the absorption rate is low, but the strength is lowered.

Therefore, according to the experimental example, 20% molybdenum tailings of Example 5 was coated with frit glaze under conditions of molding using a vacuum grinder, and then fired at 900 ° C., thereby making a ceramic having a low absorption rate and a high compressive strength. In addition, it can be seen that the addition effect of molybdenum tailings to the masato byproduct has an effect of lowering the firing temperature by about 300 ° C.

 Although the preferred embodiment of the present invention has been described in detail above, the present invention is not limited thereto and may be improved or modified by those skilled in the art within the scope of the technical idea of the present invention.

Claims (4)

After removing the water so that the water content of the pulverized mixture pulverized the mixture of 70 to 90% by weight of the Masato waste by-product of Masa and 10 to 30% by weight of molybdenum tailings into 40 to 100 mesh particles, the molded body was removed. Mixing and forming steps;
A drying step of naturally drying the molded product produced in the mixing and molding step at room temperature for 10 to 30 hours, and then drying at a temperature of 140 ° C. to 180 ° C. for 1 to 3 days;
A frit coating step of applying a glaze containing a frit having a softening point of about 600 ° C. to 800 ° C. as a main component so as to have a thickness of 0.5 to 5.0 μm; And
And a firing step of firing the molded body dried after the drying step at a temperature of 800 ° C. to 1000 ° C. for 2 to 6 hours to produce a ceramic product. According to claim 1, Masato waste, characterized in that the production of the molded body in the mixing and molding step of any one of the pressure molding method of pressing molding at a molding pressure of 15MPa ~ 30MPa and the extrusion molding method of extrusion molding under vacuum is used. Method for producing a ceramic produced using.
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