KR101748486B1 - Composition for preparing saline soluble mineral wool fiber with improved brightness and mineral wool fiber prepared therefrom - Google Patents
Composition for preparing saline soluble mineral wool fiber with improved brightness and mineral wool fiber prepared therefrom Download PDFInfo
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- KR101748486B1 KR101748486B1 KR1020150096944A KR20150096944A KR101748486B1 KR 101748486 B1 KR101748486 B1 KR 101748486B1 KR 1020150096944 A KR1020150096944 A KR 1020150096944A KR 20150096944 A KR20150096944 A KR 20150096944A KR 101748486 B1 KR101748486 B1 KR 101748486B1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
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Abstract
The present invention relates to a composition for preparing a salt-soluble soluble mineral wool fiber having improved whiteness including SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , CaO, MgO, an alkali metal oxide and a reducing agent, Soluble mineral wool fiber which can improve whiteness and salt solubility by controlling the content of each component, particularly iron oxide, and a mineral wool fiber produced from the salt-soluble mineral wool fiber.
Description
The present invention relates to a method for producing a salt-soluble mineral wool fiber composition having improved whiteness and a mineral wool fiber produced therefrom.
The mineral wool (bale wool), which is mainly used for the ceiling board, is mainly made of iron slag, which is a by-product of the steel industry. Iron slag is a by-product after iron is separated from iron ore. It is characterized in that CaO content is higher than about 40% and iron content is lower than 1%. In addition, since the steel slags contain essentially of about 11%, the Al 2 O 3 content, the mineral wool being iron slag is used as a main raw material is difficult that Al 2 O 3 composition design. Therefore, in the conventional low-alumina method, there is a limit to improve the solubility of mineral wool in the melting process, which is a condition difficult to be practically achieved.
For the production of mineral wool fibers with improved salt solubility, melting and fiberization are generally carried out using a cupola or an electric furnace. In the case of the cupola, the coke is injected as a heat source, which causes melting of the reducing atmosphere inside the cupola, so that most of the iron oxide is present in the iron oxide (FeO) state in the fibrous composition. The mineral wool fiber produced through the cupola in which the melting of the reducing atmosphere occurs has a whiteness of not less than 40 and is suitable for use as a raw material for a sound-absorbing ceiling panel. However, cupola has the disadvantage of generating a large amount of greenhouse gases such as CO 2 during melting.
On the other hand, when the electric furnace is melted using an electric resistance type electric furnace, such greenhouse gas emission can be greatly reduced, temperature control in the furnace is easy, and the quality of the melt can be stabilized by improving the homogeneity of the melt. . However, since the electric furnace is melted in an oxidizing atmosphere, there is a problem that whiteness of the fiber is lowered.
Korean Patent Laid-Open Publication No. 2012-0116235 discloses a biodegradable mineral wool fiber composition having improved bioavailability and greatly reducing the harmfulness to the human body. However, when manufacturing mineral wool fibers using an electric furnace, There was a problem that could not be done.
Korean Patent Laid-Open Publication No. 2013-0113129 discloses a mineral wool composition which is excellent in solubility in body fluids, heat resistance and water resistance. However, there is a problem that the whiteness of mineral wool is not improved due to a large amount of iron oxide.
Therefore, it is possible to produce mineral wool fibers with high whiteness even in electric furnace even if they are directly exposed to users when they are applied to general building materials such as building insulation materials and ceiling boards by securing improved salt solubility including Al 2 O 3 . Development of wool fiber compositions and manufacturing methods is required.
The present invention relates to a composition for preparing a salt-soluble soluble mineral wool fiber having improved whiteness including SiO 2 , Al 2 O 3 , FeO, Fe 2 O 3 , CaO, MgO, an alkali metal oxide and a reducing agent, And a mineral wool fiber produced therefrom, which is capable of securing an improved degree of whiteness and salt solubility by controlling the content of each component, in particular, the iron oxide content, and a mineral wool fiber produced from the salt-soluble mineral wool fiber.
Soluble salts of mineral wool fibers for manufacture of compositions of the present invention, SiO 2, relative to the total 100 wt. 33 to 45 wt% Al 2 O 3, 16 to 24 wt% Al 2 O 3 , 0.2 to 1.5 wt% FeO, 0.1 to 1.0 wt% Fe 2 O 3 , 25 to 35 wt% CaO, 2 to 7 wt% 1 to 4% by weight of a base composition; And 0.5 to 5% by weight based on 100% by weight of the base composition.
The process for preparing salt-soluble mineral wool fibers of the present invention comprises melting the composition using an electric furnace.
The salt-soluble mineral wool fiber of the present invention is prepared by the above-mentioned method of producing a salt-soluble mineral wool fiber.
According to the present invention, since salt-soluble mineral wool fibers having improved whiteness can be produced, it is possible to manufacture a building material having a beautiful appearance without using an excessive amount of white paint, thereby reducing manufacturing costs and manufacturing using an electric furnace It is possible to provide a fiber having stable quality while significantly reducing greenhouse gas emissions.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a mineral wool fiber prepared using a conventional cupola furnace.
2 is a photograph of a mineral wool fiber produced by using an ordinary electric furnace.
3 is a photograph of the mineral wool fiber produced in Comparative Example 5 of the present invention.
Figure 4 is a photograph of mineral wool fibers made in an embodiment of the present invention.
5 is a photograph of a pellet for measuring whiteness of mineral wool fibers manufactured according to an embodiment of the present invention.
Hereinafter, the present invention will be described in more detail.
Soluble salts of mineral wool fibers for manufacture of compositions of the present invention, SiO 2, relative to the total 100 wt. 33 to 45 wt% Al 2 O 3, 16 to 24 wt% Al 2 O 3 , 0.2 to 1.5 wt% FeO, 0.1 to 1.0 wt% Fe 2 O 3 , 25 to 35 wt% CaO, 2 to 7 wt% 1 to 4% by weight of a base composition; And 0.5 to 5% by weight based on 100% by weight of the base composition.
The composition for preparing a salt-soluble mineral wool fiber of the present invention may contain a reducing agent as described above. The composition may be prepared by melting the composition in an electric furnace, and the whiteness and salt solubility can be improved by controlling the content of each component. In the electric furnace, the whiteness of the fiber is lowered due to the occurrence of melting in the oxidizing atmosphere (see FIG. 2). However, if the content of iron oxide is lowered and the reducing agent is added, Can have a degree of whiteness equivalent to that of fiber produced through a cupola (see FIG. 1).
Therefore, by using the mineral wool fiber of the present invention, it is possible to provide a building material having a beautiful appearance even if the white paint is not excessively used, and it is possible to provide, for example, a sound absorbing ceiling material, a heat insulating material,
The composition for preparing a salt-soluble mineral wool fiber of the present invention may contain 0.5 to 5% by weight of a reducing agent based on 100% by weight of the base composition, and is not particularly limited, but iron slag may be used as a raw material, , Anthracite, and mixtures thereof.
In the cupola, the Fe 2 O 3 is reduced to FeO or Fe because it is melted in a reducing atmosphere. Accordingly, when iron oxide exists in the entire iron oxide as FeO or Fe 2 O 3 , the absorption wavelength of light is different and the color changes. Therefore, in order to improve the whiteness in an electric furnace, it is necessary to forcibly convert iron oxide present as Fe 2 O 3 into FeO by adding a reducing agent in a certain amount.
When the composition for making fibers of the present invention is melted in an electric furnace, the reducing agent preferably has an average particle size of 1 to 20 mm, for example, 1 to 12 mm, for example, 1 to 10 mm, and most preferably 1 to 20 mm, 5 mm. When the fine powder is used in the range below the above range, there is a problem that the fine powder flows into the upper part due to the gas generated in the electric furnace.
The SiO 2 (silicon dioxide) used in the composition of the present invention is a network-forming oxide forming a basic structure of mineral wool fibers, and may contain 33 to 45% by weight based on 100% by weight of the base composition. If the content of SiO 2 is too small, the strength of the fiber of the mineral wool fibers may be lowered. On the other hand, if the content of SiO 2 is too large, the viscosity of the melt may be increased and the whiteness and biodegradability may be lowered.
Al 2 O 3 used in the composition of the present invention is an intermediate oxide which improves the heat resistance and water resistance of mineral wool fibers, and may contain 16 to 24 wt% based on 100 wt% of the base composition. If the content of Al 2 O 3 is too small, the dissolution rate constant may decrease. If the content of Al 2 O 3 is too large, there is a difficulty in melting during fiberization, and a large amount of molten raw material is contained.
The iron oxide used in the composition of the present invention affects the whiteness degree, heat resistance and linear shrinkage ratio of mineral wool fibers as FeO and Fe 2 O 3 , and is in the range of 0.2 to 1.5 wt% of FeO, for example, 0.5 to 0.9 wt% % And Fe 2 O 3 0.1 to 1.0% by weight, for example, 0.2 to 0.8% by weight. If the content of each of FeO and Fe 2 O 3 in the composition is less than the above-mentioned level, it is necessary to use an expensive raw material having a very high purity of the raw material to be used, and if it exceeds this value, the whiteness of the fiber is lowered, When the total content of iron oxide (FeO + Fe 2 O 3 ) is more than about 3.0 wt% with respect to 100 wt%, the whiteness may be lowered even if the Redox value described later is satisfied. The composition of the present invention can produce mineral wool having improved whiteness by lowering the total content of iron oxide.
The Redox value of the iron in the composition [FeO wt% / (FeO wt% + Fe 2 O 3 wt%)] represents the ratio of the FeO content in the total iron content. Therefore, when the redox value is increased, the content of FeO is relatively increased, which means that the ratio of Fe 2 + in the whole iron in the fiber is higher than Fe 3 + . In one preferred embodiment of the present invention, the redox value of the iron in the composition is 0.4 or higher, for example 0.4 to 1.0, such as 0.4 to 0.8, in which case the mineral wool fibers with a whiteness of 40 or higher can be obtained.
CaO and MgO used in the composition of the present invention are modified oxides which improve the salt solubility of mineral wool fibers, decrease the viscosity of the glass melt, and improve the chemical durability. The oxides include CaO 25 to 35 weight% % And MgO 2 to 7% by weight. If the content of each of CaO and MgO is too small, the disintegration rate of mineral wool fibers may increase. Conversely, if the content is too large, the difference between the crystallization temperature and the fiberization temperature decreases, Which causes deterioration of the fiber quality such as an increase in the content.
The alkali metal oxide used in the composition of the present invention is a further modified oxide which functions as a non-crosslinking agent for the glass to smoothly melt when melted and to improve salt solubility, The oxide may be sodium oxide (Na 2 O), potassium oxide (K 2 O), or a mixture thereof. The content of the alkali metal oxide may be from 1 to 4% by weight based on 100% by weight of the base composition. When the content is too small, the melting is difficult and the melting energy is consumed and the melt viscosity is increased, If the content is too large, the water resistance may deteriorate and the high temperature stability may also be lowered.
Meanwhile, the composition for preparing mineral wool fibers according to the present invention may contain components such as TiO 2 , SO 2 , P 2 O 5 and the like as impurities, and the amount thereof may be 3 wt% Or less maintains the physical properties of the fiber.
There is no particular limitation on the method for fiberizing the composition for producing mineral wool fibers of the present invention, and a conventional fibrous method such as a blowing method or a spinning method can be applied, and a commonly used fibrous device can be applied . In applying such a fibrosis method, the viscosity range required for the composition for making fibers can be from 20 to 100 poise. The viscosity of the melt is a function of the temperature and the composition, and the viscosity of the melt with the same composition depends on the temperature. When the temperature of the melt is high, the viscosity is low. On the contrary, when the temperature of the melt is low, the viscosity is high, which affects the fiberization. If the viscosity of the fiber composition is too low at the fiberization temperature, the length of the resulting fiber is short and not only fine but also a lot of fine microfibrillated shots are produced, resulting in a low yield of fiberization, and even if the viscosity is too high, There arises a problem that the large fibers are formed and the thick microfibrillated particles (shot) increase.
The mineral wool fibers of the present invention are prepared from the composition for preparing the salt-soluble mineral wool fibers, and the composition can be prepared by melting using the electric furnace. In the electric furnace, the whiteness of the fiber is lowered due to the occurrence of melting in the oxidizing atmosphere. However, the present invention can control the redox value by forming the electric furnace inside the reducing atmosphere owing to the reducing agent contained in the composition, Can have the same degree of whiteness as fibers made through conventional cupola.
The mineral wool fiber of the present invention is a salt-soluble mineral wool fiber having improved whiteness and is not particularly limited. However, the dissolution rate constant for a physiological saline solution of pH 4.5 is not less than 300 ng / cm 2 · hr, for example, not less than 310 ng / It may be 315 ng / cm < 2 > hr or more. Further, since the whiteness is 40 or more, a building material having a beautiful appearance can be manufactured without using excessive white paint, thereby reducing the manufacturing cost.
The building material of the present invention includes the mineral wool fibers of the present invention as described above. For example, the building material may be a building material in which an organic binder is injected between the fibers and cured to reinforce the bonding strength between the fibers. The type of the building material is not particularly limited, and may be, for example, an insulation material, a ceiling material, an exterior material, or other building materials. According to one embodiment of the present invention, the building material may be a sound absorbing ceiling material.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited to these examples.
[Examples 1 to 5]
The composition for the preparation of the salt-soluble mineral wool fibers of Examples 1 to 5 having the composition shown in the following Table 1 was prepared by a conventional spinning process for producing mineral wool (the melt was centrifugally rotated A method of dropping the fiber on the disk-shaped spinner surface to stretch the fibers, and simultaneously spraying high-pressure air from the back surface to make the fibers into fine fibers). The weight of the reducing agent (coke, average particle size 3 mm) charged into the electric furnace with respect to 100 wt% of the base composition is as shown in Table 1.
The content of each component was measured by an inductively coupled plasma (ICP) method. The physical properties of each component were measured by the following methods and shown in Table 1.
Redox value
Approximately 300 ml of water was added to a 500 ml beaker, which was boiled, then CO 2 was evacuated and then cooled. 10 ml of sulfuric acid (1: 1) and 10 ml of a saturated solution of boric acid were added thereto and used as a test solution. 0.2 to 0.5 g of a powder sample finely ground to a particle size of about 50 μm or less by coagulating the mineral wool melts is placed in a sealable plastic beaker and wetted with the above test solution (10 ml), and the same amount of sulfuric acid (1: 1) 10 ml) was added thereto, followed by stirring. After the powder sample was completely decomposed, a solution in which saturated boric acid was excessively added was used as an analytical sample. 10 ml of Reinhard Zimmermann solution was added to this analytical sample and titrated with 1/50-N KMnO 4 solution. The end point was defined as the point at which the pale pink did not disappear for 30 seconds. After performing the blank test in parallel, the Redox value was calculated from the following equation. At this time, the total iron content as a total of FeO and Fe 2 O 3 was determined by ICP analysis.
SW: Sample weight (g)
F: 1/50-N Amount of KMnO 4 (ml)
Vt: amount of 1/50-N KMnO 4 consumed in the FeO titration (ml)
Vb: Amount of 1/50-N KMnO 4 consumed in blank test (ml)
Artificial body fluid dissolution rate constant (Kdis)
In order to evaluate the salt solubility of the prepared fibers, the solubility in the artificial body fluid was determined as follows. The biodegradability of the ceramic fiber was evaluated on the basis of the solubility of the fibers in the artificial body fluid. The dissolution rate constant (K dis ) was calculated using the following equation after comparing the residence time based on the solubility.
Wherein, d 0 is the initial average fiber particle size (㎛), ρ the initial density of the fiber (g / cm 3), M 0 is the mass of the initial fiber (mg), M is the mass (mg) of the dissolved and the remaining fibers, And t represents the experiment time (hr).
The measured fibers were placed between thin layers between 0.2 μm polycarbonate membrane filters fixed with a plastic filter support, and the dissolution rate was measured by filtering the artificial body fluid between the filters. During the experiment, the temperature of the artificial body fluid was adjusted to 37 ° C and the flow rate to 135 mL / day, and the pH was maintained at 4.5 using hydrochloric acid (HCl, 35.0 to 37.0%).
In order to accurately measure the solubility of fibers occurring over a long period of time, artificial body fluids filtered at specific intervals (1, 4, 7, 11, 14, 21 days) were subjected to inductively coupled plasma analysis (ICP, And the dissolution rate constant (K dis ) was calculated from the above results using the above equation.
The content (g) of the composition component contained in 1 L of the artificial body fluid used for measuring the dissolution rate of the fiber was as follows.
Whiteness
The prepared fibers were pulverized as fine powders by using a ring mill, and the powders were pressed with a press to produce pellets. The pellet surface was measured for whiteness using a colorimeter (see Fig. 5).
[Comparative Examples 1 to 5]
Mineral wool fibers were prepared in the same manner as in Example 1 using the compositions for preparing salt-soluble mineral wool fibers of Comparative Examples 1 to 5 having the compositions shown in Table 2 below. The physical properties of the produced mineral wool fibers were measured and are shown in Table 2.
As can be seen from Table 1, the mineral wool fibers produced by the method of the present invention have a whiteness degree of 40 or more, and thus excessive use of the coating material is not required when the building material is manufactured. When the dissolution rate constant value is 300 ng / hr. < / RTI >
On the other hand, as can be seen from Table 2, in Comparative Example 1 in which the Al 2 O 3 content was too small, the low solubility rate constant value was poor and the salt solubility was poor. In Comparative Example 1 in which the content of Al 2 O 3 , the reducing agent, 2, the values of the dissolution rate constant and the degree of whiteness were inferior, indicating that the properties required in the present invention were not satisfied. Comparative Example 3 in which the content of SiO 2 was exceeded and the content of the reducing agent and CaO was less, showed a low redox value and the dissolution rate constant and whiteness were poor. In Comparative Examples 4 and 5 in which the amount of the reducing agent added during the raw material melting process was small, the whiteness was poor due to the low Redox value (see FIG. 3), and the content of the iron oxide exceeded 3% by weight and the content of the reducing agent was small In Example 6, whiteness was found to be poor.
Accordingly, the mineral wool fiber of the present invention is improved in whiteness degree and salt solubility. Thus, it is possible to manufacture a building material having a beautiful appearance without using an excessive amount of white paint, and it is possible to reduce the manufacturing cost and manufacture by using an electric furnace It was confirmed that it is possible to provide fibers with stable quality while significantly reducing GHG emissions.
Claims (7)
SiO 2 33 to 45% by weight to the total 100% by weight, Al 2 O 3 16 to 24 wt.%, FeO 0.2 to 1.5 wt%, Fe 2 O 3 0.1 to 1.0% by weight, CaO 25 to 35 wt%, MgO 2 To 7% by weight of an alkali metal oxide and 1 to 4% by weight of an alkali metal oxide; And
0.5 to 5% by weight based on 100% by weight of the base composition,
The total content of iron oxide (FeO + Fe 2 O 3 ) is 3% by weight or less based on 100% by weight of the base composition,
(FeO / (FeO + Fe 2 O 3 )) of iron in the base composition is 0.4 to 1.0,
Showing a whiteness of 40 or more,
Compositions for the manufacture of salt-soluble mineral wool fibers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102097293B1 (en) | 2019-07-05 | 2020-04-06 | 해원엠에스씨(주) | Manufacturing method of ceramic panel comprising slag and stone powder |
| KR102097289B1 (en) | 2019-07-05 | 2020-04-10 | 해원엠에스씨(주) | Ceramic panel comprising slag and stone powder |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102322353B1 (en) | 2018-11-26 | 2021-11-09 | 주식회사 벽산 | Inorganic fiber composition using recycled material, inorganic fiber formed of the same, inorganic thermal insulator including the inorganic fiber and method for manufacturing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001279534A (en) * | 2000-03-28 | 2001-10-10 | Taiheiyo Cement Corp | Fiber composition produced by using coal ash as main material and method for producing the composition |
| KR101438366B1 (en) * | 2013-07-17 | 2014-09-05 | 한국세라믹기술원 | A manufacturing method for E-glass fibers using the coal Waste and manufacturing for E-glass fibers |
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- 2015-07-08 KR KR1020150096944A patent/KR101748486B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001279534A (en) * | 2000-03-28 | 2001-10-10 | Taiheiyo Cement Corp | Fiber composition produced by using coal ash as main material and method for producing the composition |
| KR101438366B1 (en) * | 2013-07-17 | 2014-09-05 | 한국세라믹기술원 | A manufacturing method for E-glass fibers using the coal Waste and manufacturing for E-glass fibers |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102097293B1 (en) | 2019-07-05 | 2020-04-06 | 해원엠에스씨(주) | Manufacturing method of ceramic panel comprising slag and stone powder |
| KR102097289B1 (en) | 2019-07-05 | 2020-04-10 | 해원엠에스씨(주) | Ceramic panel comprising slag and stone powder |
| US11230498B2 (en) | 2019-07-05 | 2022-01-25 | Haewonmsc Co., Ltd | Ceramic panel including slag and stone dust |
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