KR101575673B1 - Method for reproducing carbonizing metalic materials - Google Patents

Abstract

The present invention relates to carbide metal recycling a waste shell. The present invention comprises the steps of: preparing the waste shell (200) (S310); impregnating the waste shell (200) in a separator (S320); withdrawing the waste shell (200) to be dried in the room temperature (S330); impregnating the waste shell (200) in a primary acid treatment agent (S340); withdrawing the waste shell (200) to be dried in the room temperature (S350); impregnating the waste shell (200) in a secondary acid treatment agent (S360); withdrawing the waste shell (200) to be dried in the room temperature (S370); coating the surface of the waste shell (200) (S380); and withdrawing the waste shell (200) to be dried in the room temperature (S390).

Description

METHOD FOR REPRODUCING CARBONIZING METALIC MATERIALS [0002]

The present invention relates to a method for recovering metal carbide, and more particularly, to a method for recovering metal carbide from a metal (brass) carbide used in a large diameter canvas having a diameter of 105 mm or more (hereinafter referred to as " Soot and enamel formed due to the deterioration due to the ignition of the waste, and the soot and the molten resin which have not been removed through the releasing agent are treated again through the primary acid treating agent, and the secondary acid treating agent It prevents the change of gloss and coat the surface of the waste shell with a finishing agent (coating agent) to strengthen the mechanical strength such as tensile strength, rupture strength and impact strength, and prevent corrosion, And a method for regenerating water.

The shell used in the conventional canvas is a metal shell, and it has been considered necessary to prevent the high pressure inside the chamber from leaking toward the chamber located at the rear of the shell when the shell is fired. Brass used in metal casings is expensive and is a valuable strategic material in the world's main industries, so it was necessary to reclaim and reclaim the waste casings during the war.

As shown in FIGS. 1A and 1B, a conventional waste cartridge is fused with a molten resin such as soot and enamel on the inside of the waste cartridge and the surface of the waste cartridge by the deterioration phenomenon necessarily occurring when the warhead is fired. The molten resin such as soot and enamel melts and the attached waste cartridge is melted and recycled, resulting in a human and economic burden.

To solve these problems, Korean Patent Publication No. 1993-0022257 has been proposed.

The above-mentioned prior patent discloses a method for producing a wet-felt having a slurry solid content containing continuous-promoting fibers, structural fibers, and nitrocellulose stabilizers, drying and molding the same to thereby produce a combustible article, For 1 to 5 minutes, preliminarily cured at 40 to 90 DEG C for 10 to 50 minutes, and then continuously cured at 90 to 130 DEG C for 0.2 to 1.5 hour to produce a combustible casing.

However, there is a problem in that the combustible shell fabricated by the prior patent is insufficient to prevent damage due to external environment factors due to lack of mechanical strength such as tensile strength, burst strength and impact strength.

1. Korean Patent Publication No. 1993-0022257 "Combustible casings and methods for producing the same" (Published date: November 23, 1993)

Accordingly, an object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a method for removing a non-chlorine-based releasing agent having excellent effects on a coating film such as a fluorine resin, a polyurethane resin, an epoxy resin, a polyester resin, a melamine resin, Which is capable of producing a recycled waste cartridge having excellent mechanical strength such as tensile strength, rupture strength and impact strength by a primary process, a secondary acid treatment process, and a finish treatment (coating) process comprising a silicone- Reproducing method.

The method for recovering metal carbide according to the present invention comprises the steps of: preparing a waste cartridge; Immersing the waste cartridge in a stripping agent; Removing the waste cartridge dipped in the releasing agent, washing first with water, and drying at room temperature; Immersing the primary washed and dried waste casings in a primary acid treating agent; A second step of taking out the waste liquor immersed in the primary acid treatment agent and then drying it at room temperature; Immersing the secondary washed and dried waste casings in a secondary acid treatment agent; Removing the waste cartridge slipped in the secondary acid treatment agent, washing it with water for three times, and drying at room temperature; Immersing the third washed and dried waste casings in a finishing agent to coat the surface of the felt jacket; And a step of taking out the waste cartridge immersed in the finishing agent and drying at a room temperature, wherein the finishing agent comprises 40 to 50% by weight of an organosiloxane-based alkoxysilane, 10 to 20% by weight of a silicone acrylic resin, By weight, and 30 to 40% by weight of isoprofum alcohol are mixed.

As described above, the carbonated-metal-material recycling method according to the present invention has an advantage that the waste cartridge can be recycled by regenerating the waste cartridge with enhanced mechanical strength such as tensile strength, burst strength and impact strength.

In addition, there is an advantage that resource recycling and environment protection can be achieved by recycling the waste cartridge.

FIGS. 1A and 1B are a perspective view and a cross-sectional view of a conventional waste cartridge.
FIGS. 2A and 2B are a perspective view and a cross-sectional view of a waste cartridge flask reproduced by the method of regenerating the carbonated metal water according to the present invention. FIG.
3 is a flow chart of a method for regenerating a metal carbide water according to the present invention.

Hereinafter, a method for regenerating a carbonated metal material according to the present invention will be described in detail with reference to the detailed description of embodiments with reference to the drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. The following terms are defined in consideration of the functions of the present invention, and they may vary depending on the intentions or customs of the client, the operator, the user, and the like. Therefore, the definition should be based on the contents throughout this specification.

Like numbers refer to like elements throughout the drawings.

FIGS. 2A and 2B are a perspective view and a sectional view, respectively, of a waste carbon film reproduced by the method of recovering a carbonated metal material according to the present invention, and FIG. 3 is a flowchart of a method of recovering a carbonated metal material according to the present invention.

As shown in FIGS. 2A and 2B, the waste cartridge 200 regenerated by the method of regenerating the carbonated-metal water according to the present invention includes a fluororesin, a polyurethane resin, an epoxy resin, a polyester resin, a melamine resin, A peeling step of peeling the molten resin such as soot and enamel adhering to the inside of the waste cartridge 200 and the waste cartridge surface 210 by a non-chlorine releasing agent having an excellent effect on the coating film; A secondary acid treatment step for recovering the gloss of the waste cartridge surface 210 from which the molten resin such as soot and enamel is peeled off, Treated by a finishing treatment process comprising a silicone-based coating composition for enhancing mechanical strength such as tensile strength, rupture strength and impact strength of the waste cartridge surface 210, The mechanical strength of the waste cartridge surface 210 was enhanced, and the surface gloss was restored.

Hereinafter, the release agent, the primary acid treatment agent, the secondary acid treatment agent and the finishing agent (coating agent) used in the peeling step, the primary acid treatment step, the secondary acid treatment step and the finishing treatment step will be described in more detail.

<Remover>

"Hakurisuto-01" of Japan "RYOKO" Chemical Co., Ltd., which is a non-chlorine-based releasing agent, is composed of an alkali-based solvent, rust inhibitor and water and can be used for metals and non-ferrous metals. And the weight change are shown in Table 1 below.

material Appearance change Weight change iron ○ ○ aluminum ○ ○ SUS430 ○ ○ Brass △ ○ Copper △ ○ Stone △ △

In Table 1, the symbol "o" in the appearance change indicates the case where there is no occurrence of rust and discoloration, "Δ" means that there is little rusting and no discoloration, "o" in weight change means a case where the weight change rate is less than ± 1% Is not less than ± 1% and less than ± 5%. As can be seen from the above Table 1, iron, aluminum, SUS430, brass, copper, and iron are immersed in Hakurisuto-01 of Japan RYOKO Chemical Co., Ltd., a non-chlorine remover, There is no change in weight, and brass and copper are slightly rusted but there is no weight change, and the rust is slightly rusted and has a weight change of more than ± 1% to less than ± 5%.

Hakurisuto-01 ", a non-chlorine-based releasing agent of Japan" RYOKO "Chemical Co., Ltd., can be used for rubber and resin. When used for the above metals and non-ferrous metals, As shown in Table 2.

material Appearance change Weight change Natural rubber △ △ Chloroprene △ △ PP ○ ○ Soft vinyl chloride △ X Acrylic resin X X PVC △ △ silicon ○ △

In Table 2, O in appearance changes when there is no expansion, dissolution, or whitening; A is when expansion, dissolution, or whitening occurs a little; and X is a case where many expansion, dissolution, and whitening occur. The symbol? Represents the case where the weight change rate is less than 占 1%,? Represents the case where the weight change rate is not less than 1% and less than 5%, and X is the case where the weight change rate is not less than 5%. As can be seen from Table 2, when natural rubber, chloroprene, PP, soft vinyl chloride, acrylic resin, PVC and silicone are immersed in 'Hakurisuto-01' of Japan "RYOKO" Chloroprene and PVC have little swelling, melting and whitening, and have a weight change of more than ± 1% to less than ± 5%. PP has no appearance change and weight change, and soft vinyl chloride has little swelling, dissolution, whitening There is a weight change of more than ± 5%. Acrylic resin has many swelling, dissolution, whitening and weight change of more than ± 5%. Silicone has no change in appearance but has a weight change of more than ± 1% to less than ± 5% have.

<Primary Acid Treatment>

1 liter of water is prepared by mixing 2 to 30 ml of sulfuric acid, 1 to 20 ml of nitric acid, and 0.1 to 5 ml of hydrochloric acid. Here, sulfuric acid has a function of rapidly removing phosphorus (cyan) on the surface of copper or brass, and when added to a mixture of silver nitrate with hydrochloric acid and sulfuric acid, it functions to provide uniform gloss, and hydrochloric acid acts as copper or brass When the surface is removed with a small amount of cyan (rust), it functions to reduce the gas generated during the acid treatment. If the amount of the sulfuric acid is less than 2 ml, the acid treatment reaction does not occur. If the amount of the sulfuric acid exceeds 30 ml, the acid treatment reaction becomes so fast that it becomes very difficult to catch the acid treatment time. If the amount of the nitric acid is less than 1 ml, the acid treatment reaction does not occur. If the amount of the nitric acid exceeds 20 ml, the gloss disappears or the gloss is treated in an abnormal color. If the amount of the hydrochloric acid is less than 0.1 ml, the acid treatment reaction does not occur and the rust can not be removed. If the amount of the hydrochloric acid exceeds 5 ml, the gas generated during the acid treatment can not be reduced.

&Lt; Second acid treatment agent >

And mixing 10 to 500 ml of chromic acid with 1 liter of water. Here, chromic acid forms a Cr thin film on the surface of brass to prevent the surface of brass from being oxidized due to the atmosphere. If the chromic acid is less than 10 ml, the acid treatment reaction does not occur. If the chromic acid exceeds 500 ml, the acid treatment reaction becomes too fast, and it becomes very difficult to catch the acid treatment time.

<Finishing agent>

The finishing agent is used for top coating for the prevention of corrosion and weatherability, and the finishing agent contains 40 to 50% by weight of an organosiloxane-based alkoxysilane, 10 to 20% by weight of a silicone acrylic resin, And 30 to 40% by weight of furoful alcohol. The alkoxysilane is a simple and basic silicone monomer having an organic functional group that binds to an organic material in the same molecule and a hydrolyzable group that reacts with an inorganic material to improve the modification of a material composed of organic and inorganic complex systems, It is widely used for improvement of water resistance and improvement of electric characteristics after immersion. If the amount of the alkoxysilane is less than 40% by weight, corrosion resistance and weather resistance are reduced. If the amount of the alkoxysilane exceeds 50% by weight, the production cost is increased. If the amount of the silicone acrylic resin is less than 10% by weight, the adhesive force is decreased. When the amount of the silicone acrylic resin exceeds 20% by weight, the viscosity is high and the smoothness is lowered. When the isoflavone alcohol is less than 30% by weight, the volatilization proceeds slowly during natural drying to prevent film formation. When the isoflavone alcohol is more than 40% by weight, the volatilization proceeds excessively during natural drying, .

Now, referring to FIG. 3, a description will be made of a flow of a method for regenerating a metal carbide according to the present invention.

First, the waste cartridge 200 is prepared (S310).

Thereafter, the waste cartridge 200 is immersed in a stripping agent (S320). As the releasing agent, Hakurisuto-01 manufactured by Japan RYOKO Chemical Co., Ltd. as described above is used. At this time, the molten resin such as soot and attached enamel formed due to deterioration due to ignition or explosion of the charge is removed from the waste cartridge surface 210 of the waste cartridge 200. When the waste cartridge 200 is immersed in the releasing agent for less than 3 seconds, the soot formed on the waste cartridge surface 210 and the attached enamel 200 are immersed in the releasing agent for 3 to 7 seconds. If the waste cartridge 200 is immersed in the releasing agent for more than 7 seconds, the waste cartridge surface 210 from which the soot and enamel resin are removed may be damaged.

Thereafter, the waste cartridge 200 immersed in the releasing agent is taken out, washed first with water, and dried at room temperature (S330).

Then, in step S330, the first dried and dried waste shell 200 is immersed in the first acid treatment agent (S340). At this time, the soot and the molten resin of the waste cartridge surface 210 not removed through the exfoliating agent are removed again. The primary acid treatment agent is prepared by mixing 2 to 30 ml of sulfuric acid, 1 to 20 ml of nitric acid, and 0.1 to 5 ml of hydrochloric acid in 1 liter of water. When the waste cartridge 200 is immersed in the primary acid treatment agent for less than 3 seconds, the waste cartridge 200 is immersed in the primary acid treatment agent for 3 to 7 seconds. When the waste cartridge 200 is immersed in the primary acid treatment agent for less than 3 seconds, The remaining molten resin such as soot and enamel is not completely removed. If the waste article 200 is immersed in the primary acid treatment agent for more than 7 seconds, the waste article surface 210 itself may be damaged.

Thereafter, the waste cartridge 200 immersed in the primary acid treatment agent is taken out, washed with water and dried at room temperature (S350).

Then, in step S360, the secondarily cleaned and dried waste shell 200 is immersed in the second acid treatment agent (S360). At this time, the gloss of the waste cartridge surface 210 is restored. The secondary acid treatment agent is prepared by mixing 10 to 500 ml of chromic acid in 1 liter of water. When the waste article 200 is immersed in the secondary acid treatment agent for less than 3 seconds, the waste article 200 is immersed in the secondary acid treatment agent for 3 to 7 seconds. When the waste article 200 is immersed in the secondary acid treatment agent for less than 3 seconds, Gloss is not restored, and even if the waste cartridge 200 is immersed in the secondary acid treatment agent for more than 7 seconds, there is no difference in gloss of the waste cartridge surface 210.

Thereafter, the waste cartridge 200 immersed in the secondary acid treatment agent is taken out, washed with water three times, and dried at room temperature (S370).

Thereafter, in step S370, the waste cartridge 200, which is thirdly washed and dried, is immersed in the finishing agent (S380). At this time, the finishing agent coats the surface of the waste cartridge surface 210 to strengthen mechanical strength such as tensile strength, rupture strength and impact strength of the waste cartridge surface 210, and to prevent corrosion. When the waste cartridge 200 is immersed in the finishing agent for less than 3 seconds, the mechanical strength of the waste cartridge surface 210 is strengthened. In other words, the waste cartridge 200 is immersed in the finishing agent for 3 to 7 seconds. And the mechanical strength of the waste cartridge surface 210 is not different even if the waste cartridge 200 is immersed in the finishing agent for more than 7 seconds.

Thereafter, the waste cartridge 200 immersed in the finishing agent is taken out and dried at room temperature (S390).

By this process, the waste cartridge is regenerated and recycled.

Now, the method of regenerating the metal carbide of the present invention will be described in more detail through the following examples.

A first acid treatment agent is prepared by mixing 10 ml of sulfuric acid, 15 ml of nitric acid and 1 ml of hydrochloric acid, and 300 ml of chromic acid is mixed with 1 liter of water to prepare a second acid treatment agent. Organic siloxane system is mixed with 46.25 weight By weight, 18.25% by weight of silicone acrylic resin, and 36.25% by weight of isoprofum alcohol were mixed to prepare a finishing agent. Thereafter, the manufactured primary acid treatment agent is immersed in a waste cartridge for 5 seconds, taken out, and then packed with water, dried at room temperature, and subjected to primary acid treatment. Thereafter, the primary acid-treated waste casings are immersed in the secondary acid treatment agent for 5 seconds, taken out, and packed in water, followed by drying at room temperature to carry out secondary acid treatment. Thereafter, the secondary acid-treated waste casings are dipped in a finishing agent for 5 seconds, taken out, and dried at room temperature to regenerate the waste casings.

Test results for the corrosion resistance, water resistance, stain resistance and weather resistance of the waste shell recovered in the manner of the above examples are shown in Tables 3 and 4 below.

Test Items result Test Methods Touch dry (minute) 20 KSM 5000-03 Drying (curing) time 3 KSM 5000-03 Gloss (60 ℃) 120 KSM ISO 2813-02 Pencil Strength 3H KSD 3520-65 Attachment 100/100 KSD 3520-65 Bond strength (N / mm2) (steel plate) 3.8 KSF 4715-01 Water resistance (20 ± 1 ℃, 168 hours immersion) clear KSM ISO 2812-2-02 Sea water, etc. (boiling water, immersion for 4 hours) clear KSM ISO 2812-2-02 Alkali resistance (20 ± 1 ° C, saturated Na ₂ CO ₃ , 168 hours) clear KSM ISO 2812-1-02 Acid resistance (20 ± 1 ° C, 5% H ₂ SO ₄ , 168 hours) clear KSM ISO 2812-1-02 Saltwater (20 ± 1 ° C, 5% Nacl ₂ , 168 hours) clear KSM ISO 2812-1-02 Salt spray (720 hours) clear JIS Z-2371 Water temperature resistance (40 ± 1 ℃, immersed for 279 hours) clear KSM ISO 2812-2-02 Moisture resistance (50 ± 1 ° C, 98 ± 2% RH, 240 hours) clear KSM ISO 6270-1-02 Cold repeat test clear 80 ± 1 ° C × 2 hr, 2 cycles Gloss remains 96% Stain resistance (4 hours with contaminants at 20 ± 3 ℃) clear

Test Items

Test Methods

unit
Test result
Criteria
One 2 3 Mass reduction rate KS F ISO 1182: 2004 % 0.0 0.1 0.0 30 or less Nonflammability test Maximum temperature and final
Difference in flat temperature ℃ 1.3 1.6 2.0 Should not exceed 20 Gas hazard test Downtime
KS F 2271-2006 min: s 14:58 14.58 - 9:00 or more
Accelerated weathering
(Xenon, 168 hours)

ASTM G 155: 2005

-

clear
-

As can be seen from Tables 3 and 4, it can be seen that the finishing agent conforms to the Ministry of Land, Transport and Maritime Affairs Notice No. 2011-39, Noncombustible Material Standards.

As described above, the carbonized metal water regeneration method according to the present invention can recycle the waste cartridge by regenerating the waste cartridge with enhanced mechanical strength such as tensile strength, burst strength and impact strength. In addition, environmental protection and resource conservation are possible by recycling waste casings.

Although, in the embodiment of the present invention, the waste shell is mainly mentioned, it is needless to say that the present invention can be applied to all places where the metal carbide is regenerated.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, Various changes, modifications or adjustments to the example will be possible. Therefore, the scope of protection of the present invention should be construed as including all changes, modifications, and adjustments that fall within the spirit of the technical idea of the present invention.

200: Waste cartridge shell 210: Waste cartridge shell surface

Claims (5)

Preparing a waste cartridge 200 (S310);
(S320) of immersing the waste cartridge 200 in a stripping agent;
Removing the waste cartridge 200 immersed in the exfoliating agent, washing it first with water and drying it at room temperature (S330);
(S340) of immersing the first dried and dried waste shell 200 in the first acid treatment agent in step S330;
Removing the waste cartridge 200 immersed in the primary acid treatment agent, washing it with water for a second time and drying it at room temperature (S350);
(S360) of immersing the waste cartridge 200, which is secondarily cleaned and dried in step S350, in a second acid treatment agent;
Removing the waste cartridge 200 immersed in the secondary acid treatment agent, washing it with water for a third time and drying it at room temperature (S370);
(S380) of coating the surface of the wicket 200 by dipping the waste jacket 200, which has been thirdly washed and dried in step S370, into a finish agent; And
A step (S390) of taking out the waste cartridge 200 immersed in the finishing agent and drying at a room temperature,
The finishing agent of step S380 is prepared by mixing 40 to 50% by weight of organosiloxane-based alkoxysilane, 10 to 20% by weight of silicone acryl resin, and 30 to 40% by weight of isoprofum alcohol with respect to the total weight of the finishing agent Wherein the carbonized water is recycled.
The method according to claim 1,
The molten resin including the soot and the enamel formed due to deterioration due to ignition or explosion of the charge is removed from the waste cartridge surface 210 of the waste cartridge 200 in step S320 .
The method according to claim 1,
The soot and the molten resin of the waste cartridge surface 210 that have not been removed through the exfoliating agent are removed again in step S340;
Wherein the primary acid treatment agent is prepared by mixing 2 to 30 ml of sulfuric acid, 1 to 20 ml of nitric acid, and 0.1 to 5 ml of hydrochloric acid in 1 liter of water.
The method according to claim 1,
The gloss of the waste cartridge surface 210 is restored in step S360;
Wherein the secondary acid treatment agent is prepared by mixing 10 to 500 ml of chromic acid with 1 liter of water. delete

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