KR101579429B1 - Composition for Artificial Stone and Manufacturing Method of the same - Google Patents

Abstract

The present invention relates to a composition for producing high strength artificial stone and a method for producing the same. More particularly, the present invention relates to a composition for manufacturing high strength artificial stone including slag and boron oxide based on zinc oxide (ZnO), which is generated in copper and copper alloy scrap extraction processes, and a method for producing the same.

Description

TECHNICAL FIELD The present invention relates to a composition for producing high strength artificial stone and a method for producing the same.

The present invention relates to a composition for producing high strength artificial stone and a method for producing the same. More particularly, the present invention relates to a composition for manufacturing high strength artificial stone including slag and boron oxide based on zinc oxide (ZnO), which is generated in copper and copper alloy scrap extraction processes, and a method for producing the same.

Artificial stones have been developed to replace natural stones, which have been used mainly as interior and exterior materials for buildings. Recently, various artificial stones have been developed and are being usefully used.

Currently, studies on artificial stones using slag have been actively conducted, but there have been no reports on the manufacture of artificial stones using copper and copper alloy slag mainly composed of ZnO.

Copper and copper alloy slag refers to dross and dust generated during the recycling of copper and copper alloy scrap. At present, copper and copper alloy smelting slag generation amounts to 160,000 tons and 544 billion won, respectively.

Recently, in order to recover useful resources of copper and copper alloy slag, various attempts have been made to recover valuable metals. However, there are few companies that currently have economical recycling technology, and most of them are landfilled or leaking out to foreign countries .

Slag generated in the smelting process of scrap has difficulty in recycling as a resource because it contains oxide, ceramic, carbide, and other foreign materials as an unmelted raw material which is difficult to melt by a general melting method. Examples of manufacturing artificial stones using such slag are a manufacturing method of artificial stone using blast furnace slag and deoxidized steel slag mainly composed of SiO ₂ , Al ₂ O ₃ , CaO as main components, Korean Patent Laid-Open Publication No. 2001-0017578, Publication No. 1993-0017830, there has been no report on the production of artificial stone using copper and copper alloy slag containing ZnO as a main component.

Accordingly, the present applicant intends to provide a technique for manufacturing a high strength artificial stone by adding a boron oxide-based compound for utilization as a resource of copper and copper alloy slag mentioned above.

Korean Patent Laid-Open Publication No. 2001-0017578 (March 23, 2001) Korean Patent Publication No. 1993-0017830 (July 20, 1995)

The present invention was invented for the recycling of copper and copper alloy slag as a resource, and a zinc borate having a low melting point is formed by adding a boron oxide-based compound to the copper and copper alloy smelting slag, which is a main component of zinc oxide having a high melting point, The purpose of the present invention is to manufacture a high strength artificial stone through melting.

An object of the present invention is to provide a composition for manufacturing high-strength artificial stone having high density and hardness and high compressive strength by adding a boron oxide-based compound to copper and copper alloy smelting slag, and a method of manufacturing the same.

The present invention relates to a high-strength artificial stone making composition comprising slag and a boron oxide-based compound.

Further, the present invention relates to a method for producing a high-strength artificial stone including mixing a slag and a boron oxide-based compound to prepare a mixture, and heating the mixture.

Hereinafter, the composition for producing a high strength artificial stone of the present invention will be described in more detail.

The present invention relates to a slag and a boron oxide-based compound, and the slag is a copper and copper alloy smelting slag.

The high-strength artificial stone making composition of the present invention includes slag and a boron oxide-based compound, thereby forming zinc borate having a low melting point.

The slag is preferably zinc oxide as a main component in order to form zinc borate having a low melting point. For example, the slag may contain zinc oxide 53 to 65 wt%, copper oxide 20 to 25 wt%, carbon 1 to 5 wt% 0.1 to 1 wt% of lead, 0.1 to 1 wt% of iron, 0.01 to 0.1 wt% of tin, 1 to 10 wt% of aluminum, 0.01 to 1 wt% of nickel, 0.01 to 0.05 wt% of antimony, And 0.1 to 0.3% by weight of manganese may be used, but the present invention is not limited thereto.

The slag preferably has a particle size of 1 to 1,000 mu m. When the particle size of the slag is less than 1 mu m, the volume of the slag becomes too large, and the weight of the slag that can be reacted at one time decreases. When the particle size exceeds 1,000 mu m, It is preferable to use the above range in the particle size of the slag since the process takes a long time to form zinc borate through the reaction and may cause a problem that the melting of the alina and the slag does not occur.

The boron oxide-based compound may be used as long as it can react with zinc oxide to form zinc borate. Specific examples thereof include boron trioxide (B ₂ O ₃ ) and sodium borate (Na ₂ B ₄ O ₇ ) And mixtures thereof. However, the present invention is not limited thereto. The content thereof is preferably 25 to 30 parts by weight based on 100 parts by weight of the slag in order to produce a high strength artificial stone. When the amount of the boron oxide-based compound is less than 25 parts by weight, melting of the slag does not occur and it may be difficult to produce artificial stone. When the amount exceeds 30 parts by weight, zinc borate may boil over, .

Hereinafter, a method of manufacturing a high strength artificial stone of the present invention will be described in more detail.

A method of manufacturing a high strength artificial stone of the present invention comprises:

Mixing the slag and the boron oxide-based compound to prepare a mixture, and heating the mixture.

The present invention is characterized in that a boron oxide-based compound is added to slag to form zinc borate, whereby zinc oxide, which is a high melting point oxide, can be melted to produce a high strength artificial stone.

In addition, the present invention is characterized in that a high strength artificial stone produced by the method of manufacturing a mixture as described above and heating the mixture has high density and hardness and high compressive strength.

As an example of the present invention, it is possible to carry out an experiment in a box-type electric furnace by placing carbon on the bottom of an alumina crucible, charging a mixture of slag and a boron oxide-based compound thereon, covering the alumina crucible cover, But is not limited to.

The carbon can be separated from the slag by using the gas generated through the combustion reaction of carbon as shown in the following reaction formula 1 as a reducing gas.

[Reaction Scheme 1]

2C + O ₂ = 2CO

The reducing gas for separating the slag and the copper is not particularly limited, but specifically, a reducing gas such as carbon monoxide, hydrogen, or methane is preferable, and the reducing gas is also usable in the air.

The slag is preferably composed mainly of zinc oxide in order to form a zinc borate having a low melting point. The slag may contain, for example, 53 to 65% by weight of zinc oxide, 20 to 25% by weight of copper oxide, 1 to 5% 0.1 to 1 wt% of lead, 0.1 to 1 wt% of iron, 0.01 to 0.1 wt% of tin, 1 to 10 wt% of aluminum, 0.01 to 1 wt% of nickel, 0.01 to 0.05 wt% of antimony, %, And manganese 0.1 to 0.3% by weight.

The heating can proceed in a reducing atmosphere at a high temperature to form zinc borate. More specifically, the slag can be reacted in a reducing atmosphere at a temperature of 1,000 to 1,800 ° C to produce a high-strength artificial stone through melting of the slag.

The boron oxide-based compound may be used as long as it can react with zinc oxide to form zinc borate. Specific examples thereof include boron trioxide (B ₂ O ₃ ) and sodium borate (Na ₂ B ₄ O ₇ ) And mixtures thereof. However, the present invention is not limited thereto. The content thereof is preferably 25 to 30 parts by weight based on 100 parts by weight of the slag in order to produce a high strength artificial stone. When the amount of the boron oxide-based compound is less than 25 parts by weight, melting of the slag does not occur and it may be difficult to produce artificial stone. When the amount exceeds 30 parts by weight, zinc borate may boil over, .

In the present invention, when the high-strength artificial stone is manufactured by the above-described method, the high-strength artificial stone has a density of 2 to 5 g / cm 3, a Vickers hardness of 450 to 600 Hv, and a compressive strength of 80 to 150 MPa.

The present invention can produce a high strength artificial stone by adding a boron oxide compound to the slag to form a zinc borate having a low melting point, thereby enabling the copper and copper alloy smelting slag to be discarded or to be flown abroad to be reused.

In addition, the produced high strength artificial stone of the present invention has excellent density and hardness, and at the same time has a high compressive strength.

In addition, high-strength artificial stones made from slag and boron oxide-based compounds have better density, hardness and compressive strength than conventional stones.

1 shows the results of XRD analysis of copper and copper alloy smelting slag.
2 is an experimental schematic diagram for the production of artificial stone through addition of a boron oxide-based compound.
FIG. 3 is a photograph showing the result of formation of artificial stone according to the addition amount of boron trioxide (B ₂ O ₃ ).
4 is an artificial stone manufactured by the method of Embodiment 5 of the present invention.
FIG. 5 is a SEM photograph of the surface of the high strength artificial stone before and after the chemical chemical experiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments of the present invention may be modified into various forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. Therefore, the present invention may be exaggerated in order to clarify the spirit of the present invention. Also, throughout the specification, like reference numerals designate like elements.

Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

In order to achieve the above object, the present invention has been carried out by collecting copper and copper alloy slag in copper and copper alloy scrap processing companies.

The following physical properties were measured by the following methods.

1) Automatic element analysis

The carbon analysis was performed using an automatic element analyzer (manufactured by Thermo Fisher Scientific, model: Flash EA 1112 series). The analytical method is to burn 20 mg sample at 1800 ℃, and the burned sample is detected by the TCD detector while passing through the GC column after being reduced in the reaction tube.

2) ICP-AES

The composition of the slag was analyzed using ICP-AES (Perkin-Elmer, model: OPTIMA 73000DV). The ICP-AES solution was analyzed by dissolving the slag in a solution of HCl: HNO ₃ : HF = 1: 3: 1.

3) XRD

Phase analysis of the slag was carried out using an XRD analyzer (manufacturer: Siemens, model name: D-5000). The analytical range was measured as 2θ = 20 to 80 °.

4) Chemical resistance experiment

The chemical resistance of the artificial stone according to the present invention was measured by immersing in water at room temperature, boiling water at 100 ° C, ethanol, pH 5.6 solution, acetone and 35% brine for 14 days, Respectively.

- Results of chemical resistance test

◎: Excellent

○: Good

△: Normal

X: Bad

Respectively.

[Example 1]

As shown in Fig. 2, 50 g of carbon (neat carbon) was laid on the bottom of an alumina crucible (diameter 140 mm, height 120 mm).

A mixture of 100 parts by weight of copper and copper alloy slag having the chemical composition ratios shown in Table 1 and 5 parts by weight of boron trioxide (Sejung Chemical Co., Ltd.) was charged into an alumina crucible (diameter 42 mm, height 80 mm).

[Table 1] Chemical Composition Ratio

After the alumina crucible cover was covered, the experiment was carried out in the box type electric furnace. The heating rate of the electric furnace was 5 ° C / min and maintained at 1,200 ° C for two hours for sufficient slag melting and zinc borate formation. After the experiment, the furnace was cooled in an electric furnace to prepare an artificial stone, and the measured physical properties are shown in Table 2.

[Example 2]

An artificial stone was prepared in the same manner as in Example 1, except that boron trioxide was used in an amount of 10 parts by weight in Example 1. The physical properties of the artificial stone were shown in Table 2.

[Example 3]

An artificial stone was prepared in the same manner as in Example 1, except that 15 parts by weight of boron trioxide was used in Example 1. The measured values of physical properties are shown in Table 2.

[Example 4]

An artificial stone was prepared in the same manner as in Example 1 except that 20 parts by weight of boron trioxide was used in Example 1, and the measured physical properties are shown in Table 2.

[Example 5]

An artificial stone was prepared in the same manner as in Example 1, except that 25 parts by weight of boron trioxide was used in Example 1. The measured values of physical properties are shown in Table 2.

[Example 6]

An artificial stone was prepared in the same manner as in Example 1, except that 30 parts by weight of boron trioxide was used in Example 1. The measured values of physical properties are shown in Table 2.

[Example 7]

An artificial stone was prepared in the same manner as in Example 1, except that boron trioxide was used in an amount of 50 parts by weight in Example 1, and the measured physical properties are shown in Table 2.

[Comparative Example 1]

As shown in Fig. 2, 50 g of carbon (neat carbon) was laid on the bottom of an alumina crucible (diameter 140 mm, height 120 mm).

100 parts by weight of copper and copper alloy slag having the chemical composition ratios shown in Table 1 were charged into an alumina crucible (diameter 42 mm, height 80 mm).

[Table 1] Chemical Composition Ratio

After the alumina crucible cover was covered, the experiment was carried out in the box type electric furnace. The heating rate of the electric furnace was 5 ° C./minute and maintained at 1,200 ° C. for two hours. After the experiment, the furnace was cooled in an electric furnace to prepare an artificial stone, and the measured physical properties are shown in Table 2.

[Table 2]

In Table 2, the chemical resistance of the artificial stones prepared in the present invention showed excellent chemical resistance to water at room temperature, boiling water at 100 ° C, ethanol, pH 5.6 solution, acetone and 35% Although the largest weight change was observed in the boiling water at 100 ° C through the reaction experiment, the weight loss was only 0.1 wt%, confirming that the high-strength artificial stone of the present invention exhibits excellent chemical resistance.

FIG. 3 of the present invention shows the result of the formation of artificial stones depending on the amount of boron trioxide added. a) of Comparative Example 1 in which boron trioxide was not added was confirmed that the slag did not completely melt. b) to e) show the results obtained by adding boron trioxide in an amount of 5 to 20 parts by weight, indicating that no complete melting of the slag occurred and no artificial stones were formed. On the other hand, f) in Example 5 in which 25 parts by weight of boron trioxide was added, g) in Example 6 in which 30 parts by weight of boron trioxide was added, and zinc borate was formed by the reaction of slag and boron trioxide, And it was confirmed that the reduced copper and slag can be separated due to the difference in density between artificial stone and copper.

5 of the present invention, SEM analysis of the surface of artificial stone before and after the chemical chemical experiment showed no significant change except boiling water at 100 캜. (a) is a photograph of the surface of the manufactured high strength artificial stone, (b) is a photograph of the reaction in water at room temperature, (c) is a photograph of the reaction in boiling water at 100 ° C., F) is the photograph after the reaction in acetone, g) is the photograph after the reaction in the 35% salt water, and the artificial stone before and after the chemical experiment is bigger than the boiling water at 100 ℃ And confirmed that there was no change.

The density, hardness and compressive strength of the high-strength artificial stone prepared from Example 5 of the present invention are 3.267 g / cm3, 524.4 Hv and 111.9 ㎫, respectively, and the density, hardness and compressive strength of the conventional marble are 2.37 g / 320 Hv, and 68.9 MPa, respectively. It was confirmed that the high-strength artificial stone produced from the present invention had better physical properties than the conventional marble.

Claims (9)

Wherein the slag and the boron oxide based compound are contained in an amount of 25 to 30 parts by weight based on 100 parts by weight of the slag, and the slag is copper and copper alloy smelting slag. delete The method according to claim 1,
Wherein the slag is composed of 53 to 65 wt% of zinc oxide, 20 to 25 wt% of copper oxide, 1 to 5 wt% of carbon, 0.1 to 1 wt% of lead, 0.1 to 1 wt% of iron, 0.01 to 0.1 wt% of tin, Wherein the composition contains 10 to 10 wt% of nickel, 0.01 to 1 wt% of nickel, 0.01 to 0.05 wt% of antimony, 1 to 10 wt% of silicon, and 0.1 to 0.3 wt% of manganese. The method according to claim 1,
Wherein the slag has a particle size of 1 to 1,000 占 퐉. The method according to claim 1,
Wherein the boron oxide-based compound is any one selected from the group of boron trioxide and sodium borate. Mixing 25 to 30 parts by weight of a boron oxide-based compound with 100 parts by weight of the slag to prepare a mixture, and
Heating the mixture,
And the slag is copper and copper alloy smelting slag. The method according to claim 6,
Wherein the heating temperature is 1,000 to 1,800 ° C. delete A high strength artificial stone produced according to any one of claims 6 to 7 having a density of 2 to 5 g / cm 3, a Vickers hardness of 450 to 600 Hv and a compressive strength of 80 to 150 MPa.

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