KR20200134081A - Batch composition for mineral wool and mineral wool manufactured therefrom - Google Patents

Abstract

The present invention relates to a mineral wool batch composition having high economical efficiency and excellent meltability and to a mineral wool manufactured from the mineral wool batch composition. The mineral wool batch composition comprises: 5 to 35 parts by weight of chamotte; 10 to 25 parts by weight of anorthite; 10 to 25 parts by weight of light burned dolomite; 10 to 30 parts by weight of iron slag; and 10 to 25 parts by weight of cullet.

Description

Mineral wool badge composition and mineral wool manufactured therefrom {BATCH COMPOSITION FOR MINERAL WOOL AND MINERAL WOOL MANUFACTURED THEREFROM}

The present invention relates to a mineral wool badge composition comprising industrial by-products and a biodegradable mineral wool prepared therefrom.

Mineral wool is generally produced using stone material and thermal energy based on electric melting. At this time, as a raw material, inorganic oxide-based rocks such as SiO ₂ and Al ₂ O ₃ having excellent heat resistance are generally used. However, the crushing process that occurs during the rock extraction process damages nature and causes air pollution such as fine dust. For this reason, the higher the rate of use of rock raw materials in the production of mineral wool is, the less environmentally friendly and economical are. As an alternative to this, in the late 1990s, a method of recycling slag, an industrial by-product, was proposed to use it as a raw material for mineral wool. In addition, when the use rate of industrial by-products increases during the production of mineral wool, there is an effect of preserving the natural environment as well as economic benefits due to the reduction in disposal costs of industrial by-products.

In this regard, in Korea Patent Registration No. 1,382,377 (Patent Document 1), the fiber body is manufactured by mixing slag generated during the manufacturing process of steel and waste refractory, and the fiber body is 40 to 50% by weight of silicon dioxide (SiO ₂ ), 7 to 15% by weight of iron oxide (Fe ₂ O ₃ ), 7 to 15% by weight of aluminum oxide (Al ₂ O ₃ ), 7 to 15% by weight of calcium oxide (CaO) and 7 to 15% by weight Fibers containing magnesium oxide (MgO) are disclosed. However, Patent Document 1 has a problem in that the content of aluminum oxide and calcium oxide is low and the heat resistance of the fiber is insufficient.

On the other hand, mineral wool has been applied to various industrial fields such as industrial, plant, and marine, and in particular, it is widely used as an indoor ceiling material for construction as an insulating material. In order to improve the convenience of construction and harmlessness to the human body, mineral wool, which is applied to various fields, must have a chemical composition that dissolves in the body when inhaled. In addition, studies on chemical reactions and compositional suitability between the melting furnace and raw materials are required when using by-products of the rock substitute industry as described above. That is, the mineral wool badge composition minimizes the use of by-products that generate harmful gases and requires a study on a chemical composition having biodegradability.

For example, iron slag, a by-product from the steel making process, can be used as a raw material for producing mineral wool. While iron slag is price-competitive, sulfur-containing gases such as sulfur dioxide and sulfur trioxide are generated in the high-temperature melting process because the mixture of sulfur contained in the raw material is higher than that of other raw materials. For this reason, when mineral wool is produced from a badge composition having a high iron slag content, problems such as reduction in durability of process equipment and deterioration of worker health may occur due to an increase in the temperature of the melt and an increase in the amount of harmful gas generated.

In addition, in the case of aluminum slag, an ammonia reaction occurs when the aluminum-nitride component in the slag comes into contact with water. Therefore, when aluminum slag is used as a raw material, ventilation facilities are required due to the occurrence of odor, and some countries in Europe are classified as dangerous substances, making it difficult to supply and supply raw materials.

Therefore, it is necessary to research and develop a mineral wool badge composition that is economical by using industrial by-products, is eco-friendly by minimizing the use of rocks, and has biodegradability in which the manufactured fibers are dissolved in the body when inhaled. .

Korean Patent Registration No. 1,382,377 (published on February 21, 2014)

Accordingly, the present invention is to provide an eco-friendly mineral wool badge composition by using industrial by-products and minimizing the use of rocks, and mineral wool having excellent biodegradability.

The present invention provides a mineral wool badge composition comprising 5 to 35 parts by weight of chamotte, 10 to 25 parts by weight of ileum, 10 to 25 parts by weight of light dolomite, 10 to 30 parts by weight of iron slag, and 10 to 25 parts by weight of cullet. to provide.

In addition, the present invention provides a mineral wool prepared from the mineral wool badge composition.

The mineral wool badge composition according to the present invention is eco-friendly by using industrial by-products, having high economic efficiency, excellent melting properties, and minimizing the use of rocks. In addition, the mineral wool prepared from the badge composition has excellent biodegradability that dissolves in the body when inhaled by the human body.

1 and 2 are photographs for evaluating the meltability of mineral wool according to the present invention evaluated in Test Examples.

Hereinafter, the present invention will be described in detail.

Mineral Wool Badge Composition

The mineral wool badge composition according to the present invention comprises 5 to 35 parts by weight of chamotte, 10 to 25 parts by weight of ileum, 10 to 25 parts by weight of light dolomite, 10 to 30 parts by weight of iron slag and 10 to 25 parts by weight of cullet do.

Chamotte

Chamotte is a refractory brick used in industrial fields such as the steel industry, and is a refractory material that requires periodic replacement because of its non-permanent fire resistance. The chamotte of the present invention refers to a waste chamotte produced by periodic replacement as described above.

In this case, the chamotte may include refractory clay. For example, the chamotte may include SiO _2, Al ₂ O ₃ and Fe ₂ O ₃ . Specifically, the chamotte may include 35 to 45 parts by weight of SiO ₂ , 45 to 55 parts by weight of Al ₂ O ₃ and 1 to 10 parts by weight of Fe ₂ O ₃ .

The chamotte may have a particle size of 1 to 10 mm. When the particle size of the chamotte is within the above range, the melting surface area increases due to the decrease in the particle size, thereby improving the meltability when mixing the raw material.

In addition, the chamotte may be included in the badge composition in an amount of 5 to 35 parts by weight based on 10 to 25 parts by weight of ileum. Specifically, the chamotte may be included in the badge composition in an amount of 10 to 30 parts by weight based on 10 to 25 parts by weight of ileum. When the content of chamotte is out of the above range, there is a problem in that biodegradability and melting properties are deteriorated.

Chairman seat

The chemical composition of ileum can be represented by CaAl ₂ Si ₂ O ₈ . For example, the ileite may include Al ₂ O ₃ , SiO ₂ and CaO. Specifically, the ileite may include 20 to 30 parts by weight of Al ₂ O ₃ , 40 to 60 parts by weight of SiO ₂ and 10 to 30 parts by weight of CaO.

The ileal stone may be included in the badge composition in an amount of 10 to 25 parts by weight based on 5 to 35 parts by weight of chamotte. Specifically, the ileite may be included in the badge composition in an amount of 13 to 24 parts by weight based on 5 to 35 parts by weight of chamotte. When the content of ileum is out of the above range, there is a problem in that heat resistance and fiber tensile strength are deteriorated.

Gyeongso Dolomite

The light dolomite is obtained by sintering dolomite, and may include, for example, CaO and MgO. Specifically, the light dolomite may include 40 to 70 parts by weight of CaO and 30 to 60 parts by weight of MgO.

The light dolomite may be included in the badge composition in an amount of 10 to 25 parts by weight based on 5 to 35 parts by weight of chamotte. Specifically, the light dolomite may be included in the badge composition in an amount of 16 to 23 parts by weight based on 5 to 35 parts by weight of chamotte. When the content of light dolomite is out of the above range, there is a problem in that melting and heat resistance are deteriorated.

Iron slag

Iron slag is a by-product remaining after separating iron from iron ore, and may include, for example, CaO and Al ₂ O ₃ . Specifically, the iron slag may include 30 to 90 parts by weight of CaO and 10 to 70 parts by weight of Al ₂ O ₃ .

The iron slag may be included in the badge composition in an amount of 10 to 30 parts by weight based on 5 to 35 parts by weight of chamotte. Specifically, the iron slag may be included in the badge composition in an amount of 13 to 27 parts by weight based on 5 to 35 parts by weight of chamotte. When the content of the iron slag is out of the above range, there is a problem in that heat resistance and fiber tensile strength are deteriorated.

Cullet

Cullet means crushed glass, and may include, for example, SiO ₂ , CaO, MgO and Na ₂ O. Specifically, the cullet may include 65 to 75 parts by weight of SiO ₂ , 5 to 15 parts by weight of CaO, 1 to 5 parts by weight of MgO, and 10 to 15 parts by weight of Na ₂ O.

In addition, the cullet may be included in the badge composition in an amount of 10 to 25 parts by weight based on 5 to 35 parts by weight of chamotte. Specifically, the cullet may be included in the badge composition in an amount of 12 to 22 parts by weight based on 5 to 35 parts by weight of chamotte. When the content of cullet is out of the above range, there is a problem in that heat resistance is lowered compared to an increase in meltability.

Chemical composition

The mineral wool badge composition contains 37 to 46 parts by weight of SiO ₂ , 16 to 24 parts by weight of Al ₂ O ₃ , 0.5 to 3 parts by weight of iron oxide, 16 to 40 parts by weight of alkaline earth metal oxide, and 0.3 to 5 parts by weight of alkali metal oxide. can do.

SiO ₂ is a network former oxide that serves to form the basic skeleton of glass. Specifically, the SiO ₂ may be included in the composition in an amount of 37 to 42 parts by weight. When the content of SiO ₂ is within the above range, the problem that the diameter of the fiber prepared from the composition containing the same is too large is prevented, and the heat resistance of the fiber is improved.

Al ₂ O ₃ is an intermediate oxide that serves to improve the biodegradability and thermal properties of the composition containing the same and the elasticity of the fibers produced therefrom. In addition, depending on the coordination number of Al ³⁺ , some may replace the role of SiO ₂ or serve as a modifier oxide, which may vary depending on the content of other modified oxides. In addition, the Al ₂ O ₃ may be included in the composition in an amount of 16 to 24 parts by weight. When the content of Al ₂ O ₃ is within the above range, there is an effect of improving the elasticity and thermal properties of the fiber prepared from a composition containing the same.

Iron oxide serves to improve the heat resistance of the mineral wool prepared from the composition containing the same. At this time, the iron oxide may include at least one selected from the group consisting of FeO and Fe ₂ O ₃ . Specifically, the iron oxide may include Fe ₂ O ₃ .

When the content of the iron oxide is increased, the heat resistance of the produced fiber is improved, the meltability is lowered, and the roughness of the fiber is roughened, so it is necessary to adjust it to an appropriate content. Specifically, the iron oxide may be included in the composition in an amount of 0.5 to 2 parts by weight. When the content of iron oxide is within the above range, there is an effect of improving the heat resistance of the fiber prepared from the composition containing the same.

Alkaline earth metal oxide serves as a fluxing agent as a modifier oxide, and serves to improve durability such as brittleness of fibers manufactured from a composition containing the same, and elasticity of fibers. For example, the alkaline earth metal oxide may include at least one selected from the group consisting of CaO and MgO. Specifically, the alkaline earth metal oxide may include CaO and MgO.

Specifically, the alkaline earth metal oxide may be included in the composition in an amount of 28 to 40 parts by weight. Specifically, the mineral wool badge composition may include 20 to 35 parts by weight, or 22 to 30 parts by weight of CaO and 1 to 20 parts by weight, or 5 to 11 parts by weight of MgO. When the content of the alkaline earth metal oxide is within the above range, biodegradability in the human body is possible. Further, when the content of CaO is within the above range, it is possible to prevent the problem of deteriorating elasticity due to excessively improved brittleness of the fiber prepared from the composition containing the same, a problem of lowering heat resistance, and a problem of insufficient melt viscosity. In addition, when the content of MgO is within the above range, the elasticity of the manufactured fiber is increased, so that the fiber resilience is excellent, and a problem of insufficient melt viscosity can be prevented.

Alkali metal oxides are modified oxides that generate non-crosslinked oxygen in the glass so that melting is smoothly performed during melting, and serves to improve the biodegradability of fibers. In this case, the alkali metal oxide may include at least one selected from the group consisting of Na ₂ O and K ₂ O. Specifically, the alkali metal oxide may include Na ₂ O and K ₂ O.

As the content of the alkali metal oxide increases, the meltability of the manufactured fiber improves, but it is necessary to appropriately control it in consideration of the biodegradability-based resilience of the manufactured fiber. Specifically, the alkali metal oxide may be included in the composition in an amount of 1 to 5 parts by weight. When the content of the alkali metal oxide is within the above range, melting of the composition containing the same is difficult, so that a large amount of melting energy is consumed, and the melt viscosity is increased, resulting in a decrease in the flexibility of the fabricated fiber and a high possibility of occurrence of unfibrillated particles, And it is possible to prevent the problem of insufficient water resistance and high temperature stability of the produced fiber.

On the other hand, the mineral wool badge composition may contain components such as TiO ₂ , SO ₂ , P ₂ O ₅ as impurities, depending on the raw materials included, and the content is 3 parts by weight or less, or 1 part by weight based on 100 parts by weight of the composition. If it is kept below parts by weight, it is preferable because it does not affect the physical properties of the manufactured fiber.

In addition, the mineral wool badge composition according to the present invention is economical, including chamotte, which is an industrial by-product, and is eco-friendly by minimizing the use of rocks.

Mineral wool

In addition, the mineral wool according to the present invention is prepared from the mineral wool badge composition as described above. The mineral wool has excellent biodegradability that dissolves in the body when inhaled.

The mineral wool may have a dissolution rate constant of 300 ng/cm 2·hr or more for an artificial body fluid. When the dissolution rate constant of the mineral wool in the artificial body fluid is 300 ng/cm 2·hr or more, there is an effect of having excellent biodegradability.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Example]

Examples 1 to 7 and Comparative Examples 1 to 3. Preparation of mineral wool

A mineral wool badge composition was prepared by mixing the components so as to have the compositions shown in Tables 1 and 2 below by a melting method of an electric current method using an electric furnace equipped with a three-phase graphite electrode. Thereafter, the mineral wool badge composition was introduced into the conventional spinning process for mineral wool manufacturing (a method of stretching the fibers by dropping the melt on the surface of a spinner in the form of a disk that rotates centrifugally, and simultaneously spraying high-pressure air from the rear to turn the fibers into fibers). Thus, mineral wool was prepared.

The prepared mineral wool badge composition and the physical properties of the mineral wool prepared by the above method were measured by the following method, and the results are shown in Tables 1 and 2.

Classification Raw material name Example 1 Example 2 Example 3 Example 4 Example 5 input
Raw material
(Part by weight) rock Chairman seat 22 20 23 24 13 Gyeongso Dolomite 21 18 18 16 23 Industrial by-products Iron slag 25 27 19 23 13 Chamotte-1
(Particle size 1 to 5㎛) 10 - 20 - 30 Chamotte-2
(Particle size 6-10㎛) - 15 - 25 - Chamotte-3
(Particle size exceeds 10㎛) - - - - - Cullet 22 20 20 12 21 Chemical composition (Part by weight) SiO ₂ 39.9 39.8 40.6 41.5 37.5 Al ₂ O ₃ 16.7 19.2 21.7 23.6 23.7 Fe ₂ O ₃ 0.7 0.7 0.7 0.8 1.1 CaO 27.6 26.5 23.3 22.8 22.4 MgO 9.9 8.8 8.5 6.6 10.3 Na ₂ O 4.1 3.8 3.9 3.5 3.6 K ₂ O 0.6 0.6 0.6 0.6 0.6 Impurities (TiO ₂ +SO ₂ +P ₂ O ₅ ) 0.5 0.6 0.7 0.6 0.8 Total amount 100 100 100 100 100

Classification Raw material name Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 input
Raw material
(Part by weight) rock Chairman seat 10 18 20 10 20 Gyeongso Dolomite 23 22 15 25 25 Industrial by-products Iron slag 12 30 17 5 30 Chamotte-1
(Particle size 1 to 5㎛) - - 38 - 3 Chamotte-2
(Particle size 6-10㎛) - - - 40 - Chamotte-3
(Particle size exceeds 10㎛) 30 10 - - - Cullet 25 20 10 20 22 Chemical composition (Part by weight) SiO ₂ 39.0 38.0 38.4 37.0 37.8 Al ₂ O ₃ 22.7 16.8 29.8 27.2 13.0 Fe ₂ O ₃ 0.6 0.7 0.7 0.6 0.7 CaO 21.9 29.2 20.1 19.6 31.9 MgO 10.4 10.4 7.0 10.8 11.6 Na ₂ O 4.1 3.7 2.5 3.4 4.0 K ₂ O 0.6 0.6 0.6 0.6 0.5 Impurities (TiO ₂ +SO ₂ +P ₂ O ₅ ) 0.7 0.6 0.9 0.8 0.5 Total amount 100 100 100 100 100

Test Example 1: Meltability

The mineral wools of Examples 1 to 7 and Comparative Examples 1 to 3 were heat-treated at 1450° C. for 30 minutes, and then fiber meltability was evaluated, and the results are shown in FIGS. 1 and 2.

As shown in Figs. 1 and 2, the mineral wool of Examples 1 to 7 had all of the raw materials melted without unmelted materials on the top and the side, so that the whole appeared black, and it was found that the melting property was remarkably excellent. On the other hand, it was found that the mineral wool of Comparative Examples 1 to 3 had insufficient melting properties due to the remaining white unmelted material in the upper and/or lower portions.

Test Example 2: Dissolution rate constant (K _dis )

In order to evaluate the biodegradability of the manufactured fiber, the solubility of the artificial body fluid was calculated as follows.

Specifically, the biodegradability of mineral wool (fiber) in the body is evaluated based on the solubility of the fiber in the artificial body fluid. After comparing the residence time in the body based on the solubility, the dissolution rate constant ( K _dis ) was calculated.

In Equation 1, d ₀ is the initial average fiber diameter (µm), ρ is the initial density (g/cm 3) of the fiber, M ₀ is the initial fiber mass (mg), and M is the mass of the remaining fiber after being dissolved. (Mg), and t is the experiment time (hr).

At this time, the dissolution rate was determined by placing the mineral wool prepared in Examples and Comparative Examples between a thin layer between 0.2 μm polycarbonate membrane filters fixed with a plastic filter support and filtering the artificial bodily fluid through these filters. Was measured. During the experiment, the temperature of the artificial body fluid was continuously adjusted to 37° C., the flow rate was adjusted to 135 mL/day, and the pH was maintained at 4.5 using hydrochloric acid (HCl, 35.0-37.0%).

)를 계산하였으며, 그 결과를 표 2 및 3에 나타내었다.In order to accurately measure the solubility of the fiber that occurs over a long period of time, the fiber is leached for 21 days, while inducing the filtered artificial body fluid at specific intervals (1 day, 4 days, 7 days, 11 days, 14 days, or 21 days) After analyzing the dissolved ions using an Inductively Coupled Plasma Spectrometer (ICP), the dissolution rate constant (

) Was calculated, and the results are shown in Tables 2 and 3.

In addition, the content (g) of the component contained in 1L of the artificial body fluid used to measure the dissolution rate of the fiber is shown in Table 3, and the results are shown in Table 4.

Components of artificial body fluids Content (g/L) NaCl 7.120 MgCl ₂ 6H ₂ O 0.212 CaCl ₂ 2H ₂ O 0.029 Na ₂ SO ₄ 0.079 Na ₂ HPO ₄ 0.148 NaHCO ₃ 1.950 Na ₂ Tartrate 2H ₂ O 0.180 Na ₃ Citrate 2H ₂ O 0.152 90% Lactic Acid 0.156 C ₂ H ₃ NO ₂ Glycine 0.118 Na-Pyruvate 0.172 HCl (for pH adjustment) 0.750

Dissolution rate constant (K _dis )(ng/㎠·hr) Example 1 308 Example 2 315 Example 3 350 Example 4 339 Example 5 322 Example 6 319 Example 7 303 Comparative Example 1 294 Comparative Example 2 289 Comparative Example 3 276

As shown in Table 4, the mineral wool of Examples 1 to 7 had an excellent biodegradability effect with a dissolution rate constant of 300 ng/cm 2·hr or more for an artificial body fluid.

Claims (6)

A mineral wool badge composition comprising 5 to 35 parts by weight of chamotte, 10 to 25 parts by weight of ileum, 10 to 25 parts by weight of light dolomite, 10 to 30 parts by weight of iron slag and 10 to 25 parts by weight of cullet. The method according to claim 1,
The chamotte has a particle size of 1 to 10 mm, mineral wool badge composition. The method according to claim 1,
The chamotte is 35 to 45 parts by weight of SiO ₂ , 45 to 55 parts by weight of Al ₂ O ₃ and 1 to 10 parts by weight of Fe ₂ O ₃ containing, mineral wool badge composition. The method according to claim 1,
The mineral wool badge composition comprises 10 to 30 parts by weight of chamotte, 13 to 24 parts by weight of ileum, 16 to 23 parts by weight of light dolomite, 13 to 27 parts by weight of iron slag and 12 to 22 parts by weight of cullet, mineral Wool badge composition. The method according to claim 1,
The mineral wool badge composition contains 37 to 46 parts by weight of SiO ₂ , 16 to 24 parts by weight of Al ₂ O ₃ , 0.5 to 3 parts by weight of iron oxide, 16 to 40 parts by weight of alkaline earth metal oxide, and 0.3 to 5 parts by weight of alkali metal oxide. That, mineral wool badge composition. Mineral wool prepared from the mineral wool badge composition of any one of claims 1 to 5.

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