KR101887113B1 - Liquid binder for metal by-product briquettes - Google Patents

Abstract

The present invention relates to a liquid binder for a metal by-product briquette for manufacturing a metal by-product briquette used when special steel is manufactured. The liquid binder can comprise: polyvinylalcohol; a solution of carageenin; and other additives. When a metal by-product briquette is manufactured by using the liquid binder for a briquette, molding strength such as compressive strength and falling strength can be improved. Moreover, such improvement in molding strength prevents damage to the metal by-product briquette even under external impacts so that a yielding percentage and a molding percentage can be increased, thereby increasing productivity.

Description

[0001] LIQUID BINDER FOR METAL BY-PRODUCT BRIQUETTES [

The present invention relates to a liquid binder for metal by-product briquettes, and more particularly to a liquid binder used in the production of metal by-product briquettes, wherein the briquettes produced by using the liquid binder are used in the production of a special steel, To a liquid binder for briquettes capable of producing metal by-product briquettes having excellent strength and moldability.

Generally, special steels such as X-ray tube, resistance wire for electric furnace, stainless steel and SCM steel are manufactured by adding molybdenum which has high hardness and corrosion resistance and can withstand a considerable high temperature in order to improve the strength of steel .

As described above, molybdenum is an alloy element added to carbon steel or stainless steel in order to improve the physical properties of steel. Since the melting point thereof is significantly higher than the molten steel temperature that is processed in the ordinary steelmaking process, molybdenum dissolves molybdenum And it takes a lot of time and cost to uniformize the components. In order to solve this problem, ferromolybdenum (Fe-Mo alloy) having a lower melting point than metal molybdenum is used. However, since ferromolybdenum is expensive, when it is applied to steelmaking, It can be a problem in terms of economy.

In order to solve this problem, recently, molybdenum oxide has been used, but since molybdenum oxide is mostly in the form of powder, when the molybdenum oxide is directly introduced into the furnace, molybdenum oxide in powder form is scattered The molybdenum oxide to be added is used in the form of a briquette because it can not control the composition ratio of the special steel to be produced at the time of steelmaking in the furnace.

In the prior art related to the above-mentioned molybdenum oxide briquettes, for example, in Korean Patent Registration No. 10-0248108, a metal sludge briquette used as an alloy additive for steel by mixing sodium hydroxide with molybdenum oxide powder However, in the prior art, there has been known a method in which a molybdenum oxide is partially converted into molybdenum sodium by adding alkali such as sodium silicate, potassium silicate, sodium carbonate, sodium hydroxide, etc. to molybdenum oxide and melts it to briquetize It is not out of the category of technology.

As described above, when an alkaline compound is used to produce the molybdenum oxide briquettes, the refractory of the furnace is eroded by the alkaline compound and the service life thereof is lowered. The content of molybdenum, which is an additive contained in the produced special steel, The yield is low as compared with the theoretical amount, and an excessive amount of molybdenum oxide must be added to the furnace, which causes a problem that the manufacturing cost is excessively increased.

In addition, Korean Patent Publication No. 10-0338998 discloses a technique for mixing and molding molybdenum oxide and starch in water in a manufacturing apparatus for a molded briquette, and Korean Patent Publication No. 10-0751776 discloses a technique for mixing molybdenum oxide Bentonite, starch, and water glass are disclosed. However, the inorganic binder such as bentonite or water glass, which is a viscous component, becomes weak due to the poor reduction of molybdenum oxide depending on its composition ratio There is a problem that the quality is poor. In the case of using starch as the binder, in order to have the degree of cohesion, the starch is separately processed in the raw material mixing portion, that is, , Which complicates the molding process and increases the cost.

In order to remove impurities such as phosphorus (P) and sulfur (S) from the metal blast furnace during steelmaking and to improve the fluidity of the slag, calcium oxide (CaO) or fluorite (CaF2) Respectively.

In addition, metal additives for alloys were often added to achieve mechanical performance depending on the use of special steels. However, these methods fail to remove impurities in the molten steel in the steelmaking process. In the case of alloy metal additives, the specific gravity of the metal is different from the specific gravity of the steel which is the matrix, It is difficult to obtain a steel product of an alloy material satisfactory because the components are oxidized and an ideal alloy is difficult. In addition, impurities can not be removed during the steelmaking process, so that expensive high-purity metal additives have to be used, resulting in increased production costs.

In addition to molybdenum oxide, it is necessary to develop a metal by-product briquette which has excellent molding strength by using a metal by-product, is not easily broken by an external impact, and is excellent in productivity. It is urgently required to develop a liquid binder for a briquette.

It is an object of the present invention to provide a liquid binder for a metal byproduct briquette having excellent strength.

Another object of the present invention is to provide a briquetting liquid binder for producing a metal by-product briquettes having high productivity and excellent productivity because of high molding strength such as compressive strength and falling strength, .

It is another object of the present invention to provide a liquid binder for briquettes capable of producing the above-mentioned metal by-product briquette with high productivity by a simple and inexpensive process.

According to an embodiment of the present invention, a liquid binder for a metal by-product briquette according to the present invention is a liquid binder used for manufacturing a metal by-product briquette having excellent strength, the liquid binder includes polyvinyl alcohol Polyvinyl alcohol, an aqueous solution of carrageenin, and other additives.

The metal by-product may be selected from the group consisting of molybdenum oxide (MoO ₃ ), mill scale, aluminum sludge, stainless sludge, and mixtures thereof.

The concentration of the carrageenan aqueous solution is 1 to 50% by weight.

The liquid binder includes polyvinyl alcohol, and may contain 2 to 30 parts by weight of an aqueous solution of carrageenan and 0.1 to 30 parts by weight of other additives relative to 100 parts by weight of the polyvinyl alcohol.

The other additives may be contained in the carrageenan solution in a weight ratio of 0.1: 1 to 1: 1.

The other additives may be selected from the group consisting of surfactants, polyhydric alcohols, and mixtures thereof.

The surfactant may be selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and mixtures thereof.

The polyhydric alcohol may be selected from the group consisting of glycerin, ethylene glycol, polyethylene glycol, propylene glycol, and mixtures thereof.

Said metal-product briquettes teuyong liquid binders include borax _{(Na 2 B 4 O 7)} , boric acid (H ₃ BO _3), metaboric acid sodium (NaBO _2), further comprising a silica and a base metal oxide selected from the group consisting of a mixture thereof can do.

The aqueous solution of carrageenin may be selected from the group consisting of lambda-carrageenin, kappa-carrageenin, iota-carrageenin, and mixtures thereof.

The aqueous solution of the carrageenan may include lambda-carrageenin, kappa-carrageenin and iota-carrageenin in a weight ratio of 1: 0.1: 0.1 to 1: 0.5: 0.5.

The liquid binder for the metal by-product briquettes may further comprise a natural mixture.

The present invention relates to a liquid binder for a metal by-product briquette, which is excellent in molding strength such as compression strength and dropping strength when producing a metal by-product briquette using the liquid binder for briquettes, It is possible to provide a metal by-product briquette which is not damaged even in an external impact, has a high rate of realization, and is excellent in the rate of molding and high in productivity.

Hereinafter, the present invention will be described in more detail with reference to Examples. It will be apparent to those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

The present invention relates to a liquid binder for a briquette used in the production of a metal by-product briquette used for improving the physical properties of steel during the production of a special steel. The present invention improves the problem of a binder which has conventionally used polyvinyl alcohol as a main component, The briquettes of the present invention are excellent in molding strength such as compressive strength and falling strength, and are not easily broken even by external impacts, and are excellent in moldability when producing the metal by-product briquette using the liquid binder of the invention.

The present invention relates to a liquid binder for a metal by-product briquette, which comprises an aqueous solution of polyvinyl alcohol, carrageenin and other additives, so that when used in the production of briquettes, the molding strength and the forming rate Can be significantly improved.

The briquettes are used in the manufacture of specialty steels and the metal by-products used in the manufacture of the briquettes are selected from the group consisting of molybdenum oxide (MoO ₃ ), mill scale, aluminum sludge, stainless sludge, .

Most of the above-mentioned metal byproducts are industrial wastes, and they are manufactured as separate products for waste recycling. In addition, the metal by-product is generally a by-product generated in a rolling process or a submerged furnace, and has a problem that it can not be recycled solely as a sludge containing powder or a large amount of water. Accordingly, the liquid binder of the present invention can be made into briquettes regardless of the kind of the metal byproduct.

As an example of the metal by-product, molybdenum oxide acts as a source of molybdenum, the mill scale serves as an iron source, the aluminum sludge serves as an aluminum source, and the stainless steel sludge serves as a stainless source. The molybdenum oxide may be contained in the form of a powder. The mean particle size of the powder is not particularly limited, but may be 10 mm or less, for example.

Conventionally, a binder used in the production of a briquette has been made of a polymer binder containing polyvinyl alcohol as a main component. However, such a binder has drawbacks in that when the briquettes are produced using metal by-products, There was a concern that the product was easily broken.

Accordingly, the present invention can solve the problems of the binder used in the conventional briquette production by including the carrageenan aqueous solution and other additives in polyvinyl alcohol. Since the liquid binder of the present invention includes polyvinyl alcohol, carrageenan aqueous solution and other additives, the molding strength such as the compressive strength and the falling strength of the briquette is remarkably improved, , And the molding rate can also be improved, so that it can be produced with high productivity at the time of production.

The term " carrageenin " used in the present invention is also referred to as " carrageenan ", and is a kind of galactan having a sulfate group. D-galactose and sulfuric acid, or D-galactose, 3,6-anhydro-D-galactose, and sulfuric acid. Extraction of hot water from red algae, or repetition of alcohol precipitation. It is similar to agar, but the gelation zone is weak. Hot water is available, but some are available with cold water. It is used as a flammatory agent, and the inflammation that occurs when an aqueous solution is injected subcutaneously into an animal is sometimes used as a model of a hemp. It is well-digested by macrophages. There is no example of using the carrageenan as a binder for a metal by-product briquette.

In the present invention, by using the above-mentioned karagenin aqueous solution, the molding strength such as the compressive strength and drop strength of the metal by-product briquette is remarkably improved, so that it is not damaged even by external impact, .

In the present invention, it is preferable that the liquid binder is contained in an amount of 2 to 30 parts by weight of an aqueous solution of carrageenan based on 100 parts by weight of polyvinyl alcohol. When the content of the carrageenan aqueous solution is less than 2 parts by weight, the strength of the briquettes may be weak and may be easily broken. When the content exceeds 30 parts by weight, it is difficult to expect a further increase in strength. Which results in a reduction in the content, which may be an economic problem.

In the present invention, the aqueous solution of carrageenan is used at a concentration of 1 to 50% by weight, more specifically, at a concentration of 5 to 30% by weight. When the concentration of carrageenan in the carrageenan aqueous solution is less than 1% by weight, the effect of addition is insignificant and the forming rate of the raw material mixture is lowered, and the compression strength of the metal sludge briquettes finally obtained is low, It is possible to break down to cause loss of metal by-product briquettes, and also to deteriorate the handling property, thereby failing to provide desired high-quality metal by-product briquettes. Further, when the concentration of carrageenan in the carrageenan aqueous solution exceeds 50 wt%, it is difficult to expect the effect of improving the compressive strength of the metal by-product briquettes further, which is problematic from the economical point of view.

The aqueous carrageenan solution may further comprise kappa-carrageenin and iota-carraenin. The above-mentioned carrageenan aqueous solution contains rhamma-carrageenin, which is the most common form, and can be used by mixing kappa-carrageenin and iota-carrageenin in the aqueous solution of lambda-carrageenan. The lambda-carrageenin, kappa-carrageenin and iota-carrageenin differ slightly in their degree of structure and sulphatation. Iota-carrageenin is a soft gel-forming sulfated galactan extracted mainly from red seaweed Gigartina stellata and Chondrus crispus. On the other hand, kappa-carrageenin is a strong and hard gel-forming sulfated galactan extracted from Kappaphycus cottonii.

The carrageenan aqueous solution is contained in the production of the metal by-product briquette to improve the molding rate and the productivity, and it is preferable that the carrageenan solution contains lambda-carrageenin, kappa-carrageenin and iota- When a carrageenan aqueous solution is used, the molding strength such as compressive strength and drop strength can be remarkably improved.

Preferably, the carrageenan in the aqueous solution of carrageenan comprises a mixture of lambda-carrageenin, kappa-carrageenin and iota-carrageenin as described above, and the lambda-carrageenin, kappa-carraenin And iota-carrageenin may be mixed in a weight ratio of 1: 0.1: 0.1 to 1: 0.5: 0.5. Within this weight range, kappa-carrageenin and iota-carrageenin are mixed in small amounts with lambda-carrageenin, which can significantly improve the molding strength, such as compressive strength and drop strength, in the production of metal byproduct briquettes with carrageenan aqueous solution .

The present invention relates to a liquid binder for use in the production of briquettes, which is characterized in that when the polyvinyl alcohol and the aqueous solution of carrageenin are mixed, the components of the aqueous carrageenan solution are uniformly blended with the polyvinyl alcohol, At least one other additive selected from the group consisting of surfactants and polyhydric alcohols.

The liquid binder includes polyvinyl alcohol, and may contain 2 to 30 parts by weight of an aqueous solution of carrageenan and 0.1 to 30 parts by weight of other additives relative to 100 parts by weight of the polyvinyl alcohol. In the above range, a synergistic effect with a critical significance is expressed by a synergistic effect due to the interaction of the respective components. When the above range is exceeded, the synergistic effect is remarkably reduced or hardly obtained. That is, when the aqueous solution of carrageenan is contained in an amount of less than 2 parts by weight, too little of the active ingredient of carrageenan is contained, resulting in a problem that the moldability of the produced briquettes is lowered and the molding strength is lowered. In addition, when the aqueous solution of carrageenan is contained in an amount exceeding 30 parts by weight, the aqueous solution of carrageenan is excessively higher than that of polyvinyl alcohol, which may result in a problem of poor productivity in the production of briquettes.

When the amount of other additives is less than 0.1 parts by weight, the aqueous solution of polyvinyl alcohol and carrageenin is not uniformly mixed. When the amount of the additive is more than 30 parts by weight, There arises a problem that moldability and molding strength of the briquette are lowered.

In the present invention, it is preferable to include the aqueous solution of carrageenan, other additives including at least one of surfactant and polyhydric alcohol in a weight ratio of 1: 0.1 to 1: 1, and if it exceeds the above range, The manufacturing cost may increase, which may be an economic problem.

In addition, in the present invention, the kind of the surfactant is not particularly limited, but at least one selected from the group consisting of an anionic surfactant, a cationic surfactant and a nonionic surfactant can be used.

The anionic surfactant may be a salt of a sulfonic acid, a sulfonic acid derivative, a sulfonic acid or a sulfonic acid derivative. Examples of the cationic surfactant include cocamido propyl betaine, lauryl betaine, betaine, lauramidopropyl betaine, sodium lauroamphoacetate and disodium cocoamphodiacetate, and the nonionic (nonionic) surfactant may be selected from the group consisting of betaine, betaine, lauramidopropyl betaine, sodium lauroamphoacetate and disodium cocoamphodiacetate. The surfactant may be at least one selected from the group consisting of Polysorbate 80, Tween 80, Decyl glucoside, and C _8-14 alkyl polyglucoside.

In the present invention, the polyhydric alcohol is used as a moisturizing agent. Although the kind of the polyhydric alcohol is not particularly limited, for example, at least one selected from the group consisting of glycerin, ethylene glycol, polyethylene glycol and propylene glycol can be used, Glycerin. However, the polyhydric alcohol which can be used as a moisturizing agent is not limited to the above-mentioned examples.

The liquid binder of the present invention can be produced by mixing borax (Na ₂ B ₄ O ₇ ), boric acid (H ₃ BO ₃ ), sodium metaborate (sodium borate) NaBO < ₂ >), silica, and mixtures thereof. Preferably a mixture of borax, boric acid and sodium metaborate.

The liquid binder for the metal by-product briquettes of the present invention may further comprise a natural extract. As the natural extract is contained in a small amount in the liquid binder, the synergistic action between the components in the liquid binder is induced, and the molding strength such as the compressive strength and drop strength of the produced briquette can be remarkably improved.

Preferably, the natural extract is a mixture of Locust bean gum, Glycine soja Siebold & Zucc. Extract and hydroxyethylcellulose.

More preferably, the liquid binder for the metal byproduct briquette of the present invention comprises polyvinyl alcohol, wherein 2 to 30 parts by weight of an aqueous solution of carrageenin and 0.1 to 30 parts by weight of other additives are added to 100 parts by weight of the polyvinyl alcohol And 1 to 5 parts by weight of a natural mixture of Locust bean gum, Glycine soja Siebold & Zucc. Extract and hydroxyethylcellulose.

The natural mixture may contain Locust bean gum, Glycine soja Siebold & Zucc. Extract, and hydroxyethylcellulose in a weight ratio of 1: 0.5: 1 to 1: 1: 1 . In the above range, a synergistic effect with a critical significance is expressed by a synergistic effect due to the interaction of the respective components. When the above range is exceeded, the synergistic effect is remarkably reduced or hardly obtained.

The dolphin is a vine growing perennial plant with a length of 2m and brown hairs pointing downward. Leaves are alive and have three lobules and short hairs. The lobules are oval lanceolate, obtuse, and have original or dull. The flowers are light purple and bloom in July and August. The fruit is slightly bent with the cone and the seed is a little flat and a little bean. After drying and pulverizing the bean curd, distilled water having a weight of 5 to 10 times is added to the pulverized dolomite powder and extracted under reflux, and then filtered and concentrated using a lyophilizer to produce a hot water extract of dolomoe.

In addition to the hot-water extract, the extract may be used as an extraction solvent with an alcohol having 1 to 4 carbon atoms, but the present invention is not limited thereto.

More preferably, the liquid binder for the metal byproduct briquette of the present invention comprises polyvinyl alcohol, wherein 2 to 30 parts by weight of an aqueous solution of carrageenin is added to 100 parts by weight of the polyvinyl alcohol; 1 to 5 parts by weight of a natural mixture of Locust bean gum, Glycine soja Siebold & Zucc. Extract and hydroxyethylcellulose, borax (Na ₂ B ₄ O ₇ ), boric acid (H ₃ BO ₃ ), Sodium metaborate (NaBO ₂ ), silica, and mixtures thereof, and 0.1 to 30 parts by weight of other additives. When mixing the raw material mixture and the carrageenan aqueous solution within the above weight range, further mixing of the nonmetal oxides can remarkably improve the molding strength such as compressive strength and drop strength during the production of the metal by-product briquette.

On the other hand, according to the present invention, by using the carrageenan aqueous solution, the molding strength such as the compressive strength and drop strength of the produced metal sludge briquette is remarkably improved, so that it is not damaged even in an external impact, And can be produced with high productivity during manufacture.

According to another embodiment of the present invention, there is provided a process for preparing a liquid binder for a metal by-product briquette comprising the steps of: 1) preparing a first mixture by mixing an aqueous solution of polyvinylalcohol, carrageenin and a surfactant; 2) first heating the first mixture in step 1) to 60-80 占 폚; 3) primary stirring the heated first mixture of step 2); 4) after the 3) primary agitation step, cooling the first mixture to 20 to 25 ° C; 5) adding a polyhydric alcohol to the first mixture of step 4) and heating the mixture at 40 to 60 ° C; And 6) adding the nonmetal oxide and then stirring the mixture after the second heating step of step 5).

The step 1) is a step of preparing a first mixture by mixing an aqueous solution of polyvinyl alcohol, carrageenin and a surfactant, and is a step of mixing a polyvinyl alcohol, an aqueous solution of carrageenin and a surfactant To prepare a mixture. Thereafter, the primary heating step is carried out at 60 to 80 ° C, and the primary stirring step is carried out so that the aqueous solution of caragenin can be uniformly mixed in polyvinyl alcohol.

When the first mixture is stirred at room temperature and then stirred, the mixture is heated to an appropriate temperature of 60 to 80 占 폚 and stirred, and then the aqueous solution of caragenin is evenly mixed in polyvinyl alcohol, In the production of the briquette, the molding strength and the like of the briquette can be improved.

In addition, the primary stirring step is carried out by using a stirrer and stirring is carried out at a stirring speed of 200 to 300 RPM for 30 to 60 minutes. Upon completion of the primary heating and primary agitation process, the cooling step is carried out under an environment of 25 캜, and the first mixture is cooled to a temperature of 20 to 25 캜. That is, the process of cooling the primary mixture is carried out at room temperature. Through the primary heating and primary agitation process, the uniformly mixed first mixture is cooled at room temperature to produce a uniform first mixture.

Thereafter, the polyhydric alcohol is mixed with the first mixture and the second heating step is carried out at 40 to 60 캜. More specifically, the polyhydric alcohol is slowly poured into the first mixture and the mixture is heated to 40 to 60 캜 for a second time. It is possible to mix the polyhydric alcohol with the first mixture and then to carry out the second heating step so as to be uniformly mixed. However, when the polyhydric alcohol is injected and the second heating step is performed as in the present invention, A composition can be prepared. Preferably, the step 5) mixes the polyhydric alcohol and the natural mixture, and proceeds with the second heating step. The secondary heating process proceeds with the heating process to a temperature lower than that of the primary heating process, and by supplying the heat to the second mixture through the heating process, the components in the second mixture can be uniformly mixed.

Then, in the step 6), the non-metallic oxide is added to the second mixture and the second stirring process is performed. The second stirring step is carried out using a stirrer at a stirring speed of 100 to 150 RPM for 1 to 3 hours. Considering that the non-metal oxide is a fine particle, the stirring process is performed at a slower rate for a longer period of time than that of the primary stirring step, so that the non-metallic oxide can be uniformly mixed in the liquid binder.

Preferably, the method for preparing a liquid binder for a metal byproduct briquette of the present invention comprises the steps of: 1) preparing a first mixture by mixing an aqueous solution of polyvinyl alcohol, carrageenin and a surfactant; 2) first heating the first mixture in step 1) to 60-80 占 폚; 3) first stirring the heated first mixture of step 2) at a rate of 200 to 300 RPM for 30 to 60 minutes; 4) after the 3) primary agitation step, cooling the first mixture to 20 to 25 ° C; 5) adding the polyhydric alcohol and the natural mixture to the first mixture in step 4) and heating the mixture at 40 to 60 캜; And 6) adding the non-metal oxide after the second heating step in the step 5), and then performing second stirring at a speed of 100 to 150 RPM for 1 to 3 hours.

Preferably, the viscosity of the liquid binder of the present invention is from 100 to 200 cP at 25 DEG C, and when the viscosity is less than 100 cP, the viscosity of the liquid binder is too low to cause the binder to flow down during the manufacturing process of the briquette, The molding strength of the steel sheet is lowered, and the productivity is lowered. In addition, even if the viscosity exceeds 200 cP, the binder is not uniformly distributed in the manufacturing process of the briquette, and the molding strength is lowered, resulting in a problem that the productivity is lowered.

In the manufacturing method of the present invention, the composition of the raw material mixture, the content of the carrageenan aqueous solution and the composition of the additives are the same as those described in the metal sludge briquettes provided in the present invention, do.

Example

Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[Preparation Example 1: Preparation of liquid binder]

A first mixture was prepared by mixing an aqueous solution of polyvinylalcohol, carrageenin and a surfactant. Thereafter, the first mixture was first heated to 60 to 80 占 폚, and stirred at a rate of 200 to 300 RPM for 30 to 60 minutes. After the completion of the primary stirring step, the mixture was cooled to 20 to 25 DEG C at room temperature. The cooled mixture was mixed with glycerin, Locust bean gum, Glycine soja Siebold & Zucc. Extract and hydroxyethylcellulose, followed by secondary heating at 40 to 60 占 폚. After the second heating step, borax, boric acid and sodium metaborate were added and the mixture was stirred at a rate of 100 to 150 RPM for 1 to 3 hours to prepare a liquid binder.

The specific content of the liquid binder is shown in Table 1 below.

PPC1 PPC2 PPC3 PPC4 PPC5 PPC6 PPC7 PPC8 PPC9 PPC10 PPC11 PVA 100 100 100 100 100 100 100 100 100 100 100 An aqueous solution of caragenin One 2 10 20 30 40 20 20 20 20 20 Surfactants 0.01 0.1 5 10 15 20 10 10 10 10 10 glycerin 0.01 0.1 5 10 15 20 10 10 10 10 10 Natural mixture 0.5 One 2 4 5 5 10 5 4 4 4 Non-metallic oxide One 3 3.5 4 5 5 5 10 4 4 4

(Unit weight parts) The aqueous solution of carrageenin in Table 1 is a mixture of lambda-carrageenin, kappa-carrageenin and iota-carrageenin at a ratio of 1: 0.1: 0.1. Experimental number PC9 was an aqueous solution of carrageenin in which 1: 0.5: 0.5 of lambda-carrageenin, kappa-carrageenin and iota-carrageenin was mixed. Natural mixture of gum, locust bean gum, Glycine soja Siebold & Zucc. Extract and hydroxyethylcellulose, in a weight ratio of 1: 0.5: 1. Experiment No. PC10 used a natural mixture of Locust bean gum, Glycine soja Siebold & Zucc. Extract and hydroxyethylcellulose in a weight ratio of 1: 1: 1.

The nonmetal oxides in Table 1 were mixed in a weight ratio of 1: 1: 1 with a mixture of borax, boric acid and sodium metaborate. Experiment No. PC11 produced a liquid binder using only borax as a non-metallic oxide.

[Preparation Example 2: Preparation of metal by-product briquette]

[Example 1]

A raw material mixture was prepared by mixing 70 wt% of molybdenum oxide powder, 20 wt% of blast furnace slag containing 45 wt% of calcium oxide (CaO) as an evaporation inhibitor, and 10 wt% of aluminum powder as a reducing agent, 10 parts by weight of the liquid binder of Experiment No. PC1 was weighed and mixed uniformly with respect to the weight portion and then compression molded to prepare a metal by-product briquette (sample) of 5 cm in diameter and 32 ± 1 g.

[Example 2]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC2 was used as the liquid binder.

[Example 3]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC3 was used as the liquid binder.

[Example 4]

By-product briquettes were produced in the same manner as in Example 1, except that Experiment No. PC4 was used as a liquid binder.

[Example 5]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC5 was used as a liquid binder.

[Example 6]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC6 was used as a liquid binder.

[Example 7]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC7 was used as the liquid binder.

[Example 8]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC8 was used as a liquid binder.

[Example 9]

By-product briquettes were produced in the same manner as in Example 1, except that Experiment No. PC9 was used as a liquid binder.

[Example 10]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC10 was used as a liquid binder.

[Example 11]

By-product briquettes were prepared in the same manner as in Example 1, except that Experiment No. PC11 was used as a liquid binder.

[Example 12]

By-product briquettes were produced in the same manner as in Example 4 except that wheat scale was used instead of molybdenum oxide.

[Example 13]

By-product briquettes were produced in the same manner as in Example 4 except that aluminum sludge was used instead of molybdenum oxide.

[Comparative Example 1]

By-product briquettes were produced in the same manner as in Example 1, except that sodium silicate was added instead of the liquid binder.

[Comparative Example 2]

A metal by-product briquette was prepared in the same manner as in Example 1, except that molasses was put in place of the liquid binder.

[Comparative Example 3]

By-product briquettes were prepared in the same manner as in Example 1 except that starch was added instead of the liquid binder.

[Comparative Example 4]

By-product briquettes were prepared in the same manner as in Example 1, except that polyvinyl alcohol aqueous solution was used instead of the liquid binder.

[Experimental Example 1: Viscosity Measurement of Liquid Binder]

The viscosities of the liquid binders of Experiment Nos. PC 1 to 11 were measured. The viscosity was measured at 25 캜 using a Brookfield viscometer.

PPC1 PPC2 PPC3 PPC4 PPC5 PPC6 PPC7 PPC8 PPC9 PPC10 PPC11 Viscosity 86 102 120 155 198 240 152 154 156 155 153

(Unit: cP) [Experimental Example 2: Evaluation of compressive strength and differentiation rate]

Ten compression strengths and differentiation ratios of ten metal by-product briquettes prepared in Examples 1 to 13 and Comparative Examples 1 to 4 were tested five times, and the test results (the compressive strength and the differentiation rate were tested successively Are shown in Table 2 below. ≪ tb > < TABLE >

However, the differentiation rate is for measuring the falling strength of the molded carbon. In this experiment, the molding weight of 90g is dropped from the ground at a height of 5 m, As shown in Equation 1, the total weight of the differentiated pieces having a size of 3 mm or less with respect to the weight of the initial-shaped carbon was expressed as a percentage.

[Formula 1]

Differentiation rate (%) = (total weight of differentiated pieces of 3 mm or less / weight of the initial molded) X100

division Compressive strength (kgf / cm ² ) Differentiation rate (%) Example 1 28.6 5.21 Example 2 31.2 4.13 Example 3 32.9 4.24 Example 4 38.2 3.89 Example 5 36.5 3.88 Example 6 29.7 3.99 Example 7 28.4 4.10 Example 8 30.2 4.06 Example 9 43.2 3.34 Example 10 42.8 3.21 Example 11 33.6 4.02 Example 12 38.6 3.42 Example 13 39.1 3.31 Comparative Example 1 7.63 14.76 Comparative Example 2 8.57 20.9 Comparative Example 3 11.2 33.15 Comparative Example 4 15.1 9.35

As shown in Table 1, the metal byproduct briquettes of Examples 1 to 13 belonging to the scope of the present invention had a very high compressive strength of 28.6 to 43.2 kgf / cm ² , while sodium silicate, molasses, starch Or the polyvinyl alcohol aqueous solution, the compressive strength of the metal sludge briquettes of Comparative Examples 1 to 4 is very low, which is a level of 7.63 to 15.1 kgf / cm ² . In addition, the metal by-product briquettes of Examples 1 to 13 falling within the scope of the present invention have very low specificity of 3.21 to 5.21%, while the use of sodium silicate, molasses, starch or polyvinyl alcohol aqueous solution as a binder It can be seen that the metal byproduct briquettes of Comparative Examples 1 to 4 have a very high differentiation rate of 9.35 to 33.15%.

As described above, when the aqueous solution of carrageenan is used in the production of metal by-product briquettes, the compression strength and the drop strength of the natural mixture and the nonmetal oxide are remarkably improved. As a result, it was confirmed that the metal by-product briquettes of the experimental examples of the present invention exhibited excellent physical properties and moldability.

[Experimental Example 3: Evaluation of Molding Rate]

The briquettes of Examples 1 to 13 and Comparative Examples 1 to 4 were weighed and the forming rate was calculated by the following formula 2. The results are shown in Table 2 below.

[Formula 2]

Molding rate (%) = (weight of molded briquette / total weight of sample (mixture) used in molding) X100

division Molding rate (%) Example 1 85 Example 2 88 Example 3 88 Example 4 92 Example 5 87 Example 6 86 Example 7 86 Example 8 85 Example 9 98 Example 10 99 Example 11 86 Example 12 94 Example 13 93 Comparative Example 1 72 Comparative Example 2 68 Comparative Example 3 77 Comparative Example 4 74

As shown in Table 2, the metal by-product briquettes of Examples 1 to 13 falling within the scope of the present invention had an excellent molding rate of 85% or more, and in particular, the metal by-product briquettes of Example 10 had a molding rate of 99% You can see it reaching. However, the metal sludge briquettes of Comparative Examples 1 to 4 produced using sodium silicate, molasses, starch or polyvinyl alcohol aqueous solution as an additive have a molding rate of only 68 to 74%. 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, It will be obvious to those of ordinary skill in the art.

Claims (5)

As a liquid binder used for the production of metal by-product briquettes having excellent strength,
Wherein the liquid binder comprises polyvinyl alcohol,
2 to 30 parts by weight of an aqueous solution of carrageenin relative to 100 parts by weight of the polyvinyl alcohol; 1 to 5 parts by weight of a natural mixture of Locust bean gum, Glycine soja Siebold & Zucc extract and hydroxyethylcellulose, borax (Na ₂ B ₄ O ₇₎ , boric acid (H ₃ BO ₃ to 5 parts by weight of a nonmetal oxide mixed with sodium metabisulphite (NaBO ₂ ) and 0.1 to 30 parts by weight of other additives,
Wherein the locust bean gum, barley extract and hydroxyethyl cellulose are contained in a weight ratio of 1: 0.5: 1 to 1: 1: 1,
The liquid binder exhibits a viscosity of 100 to 200 cP at 25 캜.
Liquid binders for metal by - product briquettes. delete delete The method according to claim 1,
Wherein the aqueous solution of carrageenin is selected from the group consisting of lambda-carrageenin, kappa-carrageenin, iota-carrageenin, and mixtures thereof
Liquid binders for metal by - product briquettes. delete