KR20100055157A - Porous ceramic structures, preparation methods thereof, humidifiers and air-purifiers comprising the same - Google Patents

Abstract

PURPOSE: A porous ceramic structure, a preparation method thereof, a humidifier and an air-purifier comprising the same are provided, which can suppress elution of phosphorus. CONSTITUTION: A porous ceramic structure(110) satisfies the condition of the general equation 1, 1 P <= 15 ppm. In the general equation 1, P represents that amount of the phosphorus contents eluted from structure to the water when the porous ceramic structure is immersed in water. The porous ceramic structure is formed on the porous ceramic paper and comprises a first coating layer containing one or more selected from silicon and aluminum and zirconium.

Description

Porous ceramic structures, preparation methods thereof, humidification apparatus and air purifying apparatus including the above {Porous ceramic structures, preparation methods, humidifiers and air-purifiers comprising the same}

The present invention provides a porous ceramic structure which is excellent in light weight, mechanical strength and pore characteristics, and does not emit harmful components such as phosphorus component to the outside when exposed to moisture, etc., a method of manufacturing the same, a humidifier including the above, and air purification Relates to a device.

Porous materials generally refer to materials composed of pores of 15% to 95% of the volume, for example, hazardous material removal filters, waste smoke removal devices, catalyst carriers for chemical reactions, cores of secondary batteries It is applied in various fields such as components, heat insulating materials, sound absorbing materials or sound insulating materials.

Ceramic porous structures, which are representative examples of such porous materials, are generally formed by extrusion molding by mixing ceramic particles such as cordierite, silicon carbide (SiC), or aluminum nitride with an organic binder, followed by sintering at high temperature. The ceramic fiber is bonded by the interparticle bonding force by heat treatment after coating the ceramic particle slurry having low clay or melting temperature on the molded body composed of the ceramic fiber or forming the porous by the sintering effect between particles. Prepared in such a way.

Among the above methods, the method using the sintering effect between particles requires a heat treatment at high temperature for bonding between the particles due to the high melting temperature of the ceramic material, and particle size and mixing to control pore properties (ex. Pore size, porosity, etc.). Since uniform control of the state is required, there is a disadvantage in that productivity is lowered.

On the other hand, the method using the ceramic fiber has the advantage of high productivity, mass production, and easy control of pore characteristics. However, there is a disadvantage that the type of the inorganic binder that can impart a strong bonding force to the ceramic fiber is limited. That is, in this system, clay or low melting temperature ceramic particles are generally dispersed in the form of a slurry, and then the slurry is applied to a ceramic fiber molded body and sintered. By the way, in order to prepare a slurry uniformly dispersed in the above, the solid content concentration of the particles included is limited, and thus several repeated applications are required. In addition, the bonding between the inorganic binders applied during firing occurs easily, whereas the bonding between the inorganic binder particles and the surface of the ceramic fiber does not occur easily, resulting in a decrease in the strength of the entire ceramic structure.

In addition, the inorganic binders used in the preparation of the above-mentioned conventional porous structures may be harmful components. Accordingly, when the structures are directly exposed to moisture or exposed to humid conditions, the harmful components used in the manufacturing process may be used. Since it has a disadvantage that is emitted to the external environment, there is also a problem that the range of application to household goods and the like is limited.

The present invention has been made in consideration of the above-described problems of the prior art, and is light in weight but excellent in mechanical strength, excellent in pore properties such as pore size and porosity, and when exposed to moisture, the harmful components are not released to the outside. A ceramic structure, a manufacturing method thereof, a humidifier and an air purifier including the same.

The present invention provides a porous ceramic structure that satisfies the conditions of the following general formula (1) as a means for solving the above problems.

[Formula 1]

P ≤ 10 ppm

In Formula 1, P represents the amount of phosphorus component eluted from the structure when the porous ceramic structure is immersed in water having a weight of 10 times the weight of the structure for 24 hours at room temperature.

As another means for solving the above problems, the present invention comprises a first step of coating the porous ceramic green paper with a primary coating liquid containing at least one selected from the group consisting of silicon, aluminum and zirconium; And

Provided is a method of manufacturing a porous ceramic structure comprising a second step of firing a paper subjected to a first step at a temperature of 930 ° C. or higher.

The present invention is another means for solving the above problems, the porous ceramic structure according to the present invention described above; And

It provides a humidifying device comprising a storage tank capable of supplying water to the structure.

The present invention is another means for solving the above problems, the porous ceramic structure according to the present invention described above; And

It provides an air purifying device comprising a device capable of sucking or blowing air via the structure.

In the present invention, it is possible to provide a porous ceramic structure having improved mechanical strength and pore characteristics while maintaining the advantages of the porous structure using the existing ceramic fibers. In addition, the porous ceramic structure of the present invention is suppressed in the content of the phosphorus component eluted to the external environment when exposed to wet and humid conditions. Thus, for example, the structure of the present invention has the advantage that it can be effectively applied to well-being products, such as a humidifier or an air purifier.

The present invention relates to a porous ceramic structure satisfying the conditions of the following general formula (1).

[Formula 1]

P ≤ 15 ppm

In Formula 1, P represents the amount of the phosphorus component eluted from the structure when the porous ceramic structure is immersed in water having a weight 10 times the weight of the structure for 24 hours at room temperature.

Hereinafter, the porous ceramic structure of the present invention will be described in detail.

The porous ceramic structure of the present invention is characterized in that, under specific conditions, the amount of phosphorus (P) component (ex. Phosphorus (P) ions) eluted from the structure is controlled to be below a specific range. That is, when the porous ceramic structure of the present invention is immersed in a predetermined weight of water at a predetermined temperature for a certain time, the amount of phosphorus component eluted from the structure into water can be suppressed to 15 ppm or less. The amount of the phosphorus component eluted above is more preferably 5 ppm or less, still more preferably 3 ppm or less, and most preferably 2 ppm or less. When the content of the eluted phosphorus component exceeds 15 ppm, for example, when the porous ceramic structure is applied to a product such as a humidification module or an air purifier, the content of the phosphorus component released into the surrounding environment is increased, thereby limiting its application. There is a concern.

As long as the porous ceramic structure of the present invention has the above properties, the specific structure thereof is not particularly limited. For example, the porous ceramic structure may include porous ceramic paper; And a coating layer formed on the porous ceramic paper and containing one or more selected from the group consisting of silicon, aluminum, and zirconium (hereinafter referred to as "primary coating layer").

In the present invention, the porous ceramic paper may have a honeycomb structure including ceramic corrugated paper and ceramic plate-shaped paper attached to the corrugated paper. As such, when the porous structure is formed using the ceramic paper, mass production is possible, and the pore characteristics (eg, pore size and porosity, etc.) of the final structure can be effectively controlled.

The ceramic plate-like and corrugated paper (hereinafter sometimes referred to as "ceramic paper") may be produced using ceramic fibers. Ceramic fibers that can be used in the manufacture of ceramic paper generally have a diameter of 1 micron to 20 microns, the average length of which is preferably 0.1 mm to 10 mm, more preferably 0.1 mm to 5 mm, and more preferably 0.1 More preferably, it is mm to 1 mm. If the length is less than 0.1 mm, the strength of the ceramic paper may be lowered. If the length is more than 10 mm, it is difficult to uniformly disperse the fibers in the slurry, which is a raw material, causing unevenness of the paper.

The ceramic fiber used in the present invention is also preferably a material that can withstand high temperatures of about 1,200 ° C. or more. Examples of such materials include aluminum and / or silicon, and specifically, one or more selected from the group consisting of silica, alumina, silica-alumina, aluminosilicate, alumino borosilicate and mullite, It is not limited to this.

The ceramic paper of the present invention may further include 5 parts by weight to 30 parts by weight of organic fibers, based on 100 parts by weight of the ceramic fiber. Examples of the organic fibers that can be used in the present invention include natural fibers such as conifer pulp, wood fibers or hemps; And synthetic fibers such as nylon, rayon, polyester, polypropylene, polyethylene, aramid or acrylic, and one or more of the above may be used. Such organic fibers are preferably included in an amount of 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the ceramic fiber. If the content is less than 5 parts by weight, it is difficult to maintain the tensile strength of the ceramic green paper, making it difficult to corrugate during the manufacturing process. If the content is more than 30 parts by weight, the porosity of the ceramic structure is excessively increased to reduce the strength. There is.

The ceramic paper of the present invention may also further comprise 5 parts by weight to 20 parts by weight of the binder together with the aforementioned ceramic fibers and organic fibers. In the present invention, it is preferable to use an organic binder. For example, an epoxy binder, sodium carboxymethyl cellulose (CMC), polyacrylamide (PAM), polyethylene oxide (PEO), methyl cellulose, hydroxyethyl cellulose, tablets Starch, dextrin, polyvinyl alcohol, polyvinyl butyral, polymethyl (meth) acrylate, polyethylene glycol, paraffin, wax emulsion, and a mixture of one or more kinds of microcrystalline wax. Such a binder is preferably included in the ceramic paper in an amount of 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the ceramic fiber. If the content is less than 5 parts by weight, there is a fear that the bonding strength between the fibers is lowered, if it exceeds 20 parts by weight, the flowability and adhesion of the ceramic green paper is increased, there is a fear that the workability.

In the present invention, the porous ceramic paper has an average peak load of 300 g or more and a gas permeability of 12 cc / sec / cm ² or more, but is not limited thereto.

The structure of the present invention is formed on the ceramic paper as described above, and may include a coating layer (hereinafter sometimes referred to as "primary coating layer") containing at least one selected from the group consisting of silicon, aluminum and zirconium. . At this time, the material constituting the primary coating layer is not particularly limited as long as it is a material capable of hardening by a sol-gel process or the like to enhance the wet strength of the ceramic paper. In the present invention, for example, a compound containing at least one selected from the group consisting of silicon, aluminum and zirconium may be used as a material forming the primary coating layer, and more specifically, silica, silane, siloxane, alumina, One or more selected from the group consisting of zirconia and aluminum silicates can be used. Although not particularly limited, in the present invention, when the secondary coating layer described below is formed on the primary coating layer, the primary coating layer may be made of aluminum silicate in view of the affinity between the coating layers.

The ceramic structure of the present invention is further formed on the coating layer (primary coating layer), and may further include a coating layer (hereinafter sometimes referred to as a "secondary coating layer") containing an aluminum component and a phosphorus component. have. That is, the ceramic structure of the present invention may be applied to a product in the state in which the above-described primary coating layer is formed, but by further forming a coating layer containing a specific component on the primary coating layer, it is possible to further improve the physical properties of the structure Can be. When the secondary coating layer is additionally formed, the coating layer (primary coating layer) formed directly on the ceramic paper may serve as a buffer layer or a primer layer between the ceramic paper and the secondary coating layer, and more specifically, the ceramic layer. The role of protecting the paper and strengthening the adhesion with the secondary coating layer can be performed at the same time.

The secondary coating layer may include an aluminum component and a phosphorus component, wherein the atomic ratio (P / Al) of phosphorus and aluminum included in the secondary coating layer is preferably 3 to 50. When the said atomic ratio is less than 3, there exists a possibility that a coating layer may not be formed smoothly, and when it exceeds 50, a fiber surface may be damaged and a strength may fall. Although not particularly limited, the secondary coating layer preferably includes aluminum phosphate, and more preferably, two phases of Al (PO ₃ ) ₃ (aluminum metaphosphate) and AlPO ₄ (aluminum orthophosphate) are present in a mixed state. Do.

The primary and / or secondary coating layer may also further comprise one or more kinds of magnesium, calcium and boron containing compounds in view of further improvement of interfiber bonding strength. The component partially replaces aluminum ions and the like included in the coating layer, thereby increasing the bonding strength of the inorganic binder and improving thermal stability at high temperature. The specific kind of the compound which can be used in the present invention is not particularly limited, and examples thereof include one kind or two or more kinds of boric acid, magnesium oxide and calcium chloride. Such components are preferably included in an amount of 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the components constituting the primary or secondary coating layer, but is not limited thereto.

The coating layer may also contain an additional amount of additional oxide ceramics such as silica, zirconia and / or titania in view of further improvement in the mechanical strength of the ceramic structure.

The ceramic structure of the present invention may further comprise a clay component-containing outer wall formed integrally with the ceramic paper. By forming such an outer wall, it is possible to obtain effects such as thermal insulation effect due to the clay component and further improvement of structural mechanical strength. Specific examples of the clay component that may be included in the outer wall include bentonite, kaolin, feldspar and talc, or a mixture of two or more kinds, among which bentonite is more preferable. Bentonite is a mineral containing montmorillonite as a main component, and its kind is largely divided into Ca-based bentonite and Na-based bentonite. Among these, Na-based bentonite has fine particles, high swelling properties, and excellent gel-forming ability upon water absorption. In the present invention, it is particularly preferable to use bentonite having a high content of montmorillonite and Na-based, and specifically, bentonite having a Ca content of less than 1% and a Na content of 1% or more. . The clay component-containing outer wall as described above may be formed by impregnating the ceramic paper into the clay component-containing slurry, and then attaching it to the porous ceramic structure, or applying the slurry to the structure. In addition, the clay component-containing outer wall may further include an appropriate amount of one or more kinds of ceramic fibers, oxide particles, ceramic powder, and the like from the viewpoint of preventing cracking and separation phenomenon in the drying process. Specific types of ceramic fibers are as described above, but when the outer wall is formed, it is preferable that the average length of the fibers is 0.1 mm to 0.5 mm. In addition, examples of the oxide particles include silica and the like, and examples of the ceramic powder include silicon carbide and the like. The content in the outer wall of the components such as the ceramic fiber is 0.5 parts by weight to 2 parts by weight, more preferably 0.5 parts by weight to 1.5 parts by weight. If the content is less than 0.5 parts by weight, there is a fear that cracks occur in the outer wall, and if it exceeds 2 parts by weight, separation of the clay outer wall and the structure may occur.

The ceramic structure of the present invention may further include a zirconia layer formed between the primary coating layer and the secondary coating layer, and this additional layer may further improve the strength of the structure. Such a zirconia layer may be formed by a method of additionally applying a precursor such as zirconium acetate or the like after the first coating solution in the structure manufacturing process.

The present invention also includes a first step of coating the porous ceramic green paper with a coating liquid containing at least one component selected from the group consisting of silicon, aluminum and zirconium; And

It relates to a method for producing a porous ceramic structure comprising a second step of firing the paper subjected to the first step at a temperature of 930 ℃ or more.

The coating liquid used in the production method of the present invention is an inorganic binder precursor solution, hereinafter "coating liquid" and "inorganic binder precursor solution" may be used in the same sense.

As described above, in the present invention, by using the inorganic binder precursor solution at the time of forming the coating layer, uniform coating using the capillary effect of the porous ceramic formed body (ceramic green paper) is possible. Therefore, in the present invention, it is possible to solve the difficulty of pore control due to the non-uniform formation of the coating layer, and also improve the bonding strength between the fibers by chemically bonding the binder precursor with excellent reactivity with the ceramic fibers, thereby providing excellent mechanical strength to the structure. have.

The first step of the present invention is a step of coating the ceramic green paper with the primary coating liquid that will constitute the primary coating layer. At this time, since the coating solution is in solution, it may be uniformly applied to the surface of the paper through the capillary effect of the ceramic green paper. In addition, since the inorganic binder precursor included in the coating solution has high reactivity, the bonding force between the ceramic fibers may be improved through the second step firing process, thereby significantly improving the mechanical strength of the entire structure. In addition, the coating of the primary coating liquid may serve to prevent a decrease in the wet strength during the manufacture of the ceramic structure, thereby maintaining the structure of the green fiber molded body.

The ceramic green paper used in the first step of the present invention may have a honeycomb structure, and more specifically, (1) preparing a ceramic corrugated paper by corrugating the ceramic green paper; And

(2) The corrugated paper can be manufactured by attaching the corrugated paper with a ceramic plate-shaped paper.

The ceramic green paper used above may be manufactured using a slurry including ceramic fibers, organic fibers, and a binder, and the manufacturing method is not particularly limited, and a general papermaking method may be used. Specific kinds and contents of each component constituting the slurry are as described above. The slurry may be prepared by dissolving the aforementioned components in a general solvent such as water, wherein the content of the ceramic piper in the slurry may be 50 wt% to 80 wt% based on solids, and 70 wt% to 80 wt% It is more preferable that is. However, the content of the ceramic fiber is not particularly limited as long as the concentration of the slurry is maintained to such an extent that the entire process can be smoothly maintained.

In the process of manufacturing ceramic green paper, a vacuum pump is connected to a paper making device to smoothly remove water during the process, to remove excess water through the pump, and to remove excess water through an additional means such as a press. You can also remove it.

The slurry used for the ceramic green paper may also further comprise a pH adjuster, in view of further improvement of the adhesion of the binder component and the fiber component. The specific kind of the pH adjuster is not particularly limited, and a general means such as ammonium aluminum sulfate (alum) can be used. The content of the pH adjuster is not particularly limited and may be added, for example, in an amount capable of maintaining the pH of the slurry in the range of 5.5 to 6.5.

The method of performing the waveform of the step (1) using the ceramic paper produced in the present invention is not particularly limited, and can be performed using, for example, a general waveform device. The corrugating apparatus used in the present invention has a depth of the valley of the drum of about 1.5 mm to 3.5 mm, a pitch of each of about 1.5 mm to 4.5 mm, the surface temperature and the feed rate of the paper is adjustable It is preferred, but not limited to.

In addition, in the step (2), the plate and corrugated paper may be attached, for example, by placing the ceramic plate paper on the lower portion of the ceramic corrugated paper, applying an adhesive to the contact surface, and then attaching the plate. In this case, the adhesive may use an adhesive generally used in the art, which is not particularly limited.

The ceramic green paper manufactured by attaching the plate and corrugated paper as described above may be wound and molded into a shape such as a cochlear shape or a cylindrical shape to enter the first step.

However, this is only one aspect of the present invention, and in the present invention, the molded article of ceramic green paper may be applied to the coating process as described above, or the honeycomb structured body may be formed using the ceramic green paper after the coating process is completed. After the preparation, the firing process may be performed.

The first step of the present invention is to apply the ceramic green paper (ex. Ceramic green paper molded body) manufactured through the above steps to the primary coating process. The primary coating liquid used in the first step is not particularly limited as long as it contains one kind or more than one kind of silicon, aluminum and zirconium, and can maintain the wet strength of the ceramic paper. Specific examples of such a primary coating solution may be a mixture of one or more kinds of zirconium acetate, zirconia sol, silica sol, alumina sol and aluminum silicate solution. In particular, the aluminum silicate solution has an advantage in that aluminum is present in an ionic form, and the adhesion to the surface of the ceramic paper, which is generally positively charged during the coating process, is generally neutral because the solution is generally neutral. Such aluminum silicate solution preferably comprises an alcohol, an aluminum precursor, tetraalkyl orthosilicate and an acid. At this time, by properly adjusting the concentration of the acid included, the tetraalkyl orthosilicate contained in the solution can be applied to the coating process in the step before the hydrolysis and before the formation of the particles and gelation, the coating efficiency is improved have. Specific examples of the alcohol may include lower alcohols having 1 to 6 carbon atoms such as methanol or ethanol, and examples of the aluminum precursor may include aluminum nitrate, aluminum acetate, aluminum halide (ex. Aluminum chloride) or aluminum hydroxide ( aluminum hydroxide), and among these, aluminum nitrate is more preferable, and examples of tetraalkyl orthosilicate include tetraethyl orthosilicate (TEOS), and examples of acids include hydrochloric acid, but are not limited thereto. It doesn't happen.

The composition of the aluminum silicate solution is not particularly limited, but based on 1 mol of tetraalkyl orthosilicate, 0.2 mol to 0.5 mol of alcohol, 0.01 mol to 0.02 mol of aluminum precursor and 0.1 × 10 ^-3 mol to 0.2 × acid It is preferably included in an amount of 10 ^-3 moles. If the amount of the alcohol is less than 0.2 mole, the aluminum precursor may not be sufficiently dissolved. If the amount of the alcohol is more than 0.5 mole, the concentration of the aluminum precursor may be lowered to make it difficult to form a coating layer having an appropriate thickness. In addition, when the content of the aluminum precursor is less than 0.01 mol, there is a risk that the formation of aluminum silicate becomes difficult, and when it exceeds 0.02 mol, there is a fear that the solubility in alcohol is lowered. In addition, if the amount of the hydrochloric acid is less than 0.1 × 10 ^-3 moles, there is a fear that the hydrolysis reaction may not be performed smoothly, if the amount of more than 0.2 × 10 ^-3 moles, the hydrolysis rate is excessively increased, the particle form Gel formation may occur rapidly, resulting in a decrease in dispersion and pore blocking.

The method of coating the primary coating solution as described above is not particularly limited, and may be performed by a conventional method such as, for example, impregnation or spraying.

In the first step of the present invention, from the viewpoint of improving the mechanical strength of the structure, the above-described coating and drying process of the primary coating solution may be repeated several times.

In addition, in the first step, a process of forming a zirconia layer after application and drying of the first coating solution may be further performed. At this time, the method is not particularly limited, and for example, a method in which zirconia is formed in a subsequent firing step by applying a precursor solution such as a zirconium acetate solution.

The first step of the method of the present invention may also further perform the step of coating the paper prepared by the first step following the above-described process with a secondary coating liquid containing aluminum and phosphorus.

As such, the additional secondary coating process may be performed after the ceramic green paper is dried under appropriate conditions after the primary coating process. At this time, the drying temperature may be in the range of room temperature to 200 ° C, but is not particularly limited as long as it is controlled to allow sufficient drying.

The secondary coating solution may be prepared by mixing a solution containing an aluminum component and a solution containing a phosphorus component, or by simultaneously or sequentially dissolving an aluminum component or a phosphorus component in a suitable solvent. Examples of the solvent that can be used at this time may include an organic solvent such as water, an acidic solution or alcohol, but is not limited thereto. Examples of the aluminum component may include aluminum nitrate, aluminum acetate, aluminum halide (ex. Aluminum chloride) or one or more kinds of aluminum hydroxide, among which aluminum nitrate is more preferable, and examples of phosphorus component The phosphate compound or the phosphate may be mentioned, but is not limited thereto.

At this time, the atomic ratio (P / Al) of phosphorus and aluminum contained in the secondary coating solution is preferably 3 to 50. If the atomic ratio is less than 3, the formation of an inorganic binder (ex. Aluminum phosphate) may not be smooth. If the atomic ratio exceeds 50, the coating property may be degraded due to the excess phosphorus component or damage may occur on the surface of the piper. There is a possibility that the strength of the resin may be lowered.

In addition, the concentration of the inorganic binder (ex. Aluminum phosphate) precursor material in the solution is preferably 1% to 80% by weight based on solids. If the concentration is less than 1% by weight, the coating process may need to be repeated several times in order to form an appropriate amount of coating layer, and if it exceeds 80% by weight, pore blocking of the structure may occur.

The secondary coating solution may also further comprise a mixed solvent of water and a penetrating solvent. At this time, examples of the penetrating solvent include ethanol and / or isopropyl alcohol. In addition, the content of the penetrating solvent is preferably 1 part by weight to 30 parts by weight based on 100 parts by weight of water. If the content is less than 1 part by weight, the process efficiency may decrease, and if it exceeds 30 parts by weight, the inorganic binder may be precipitated before firing. In addition, the mixed solvent as described above is preferably included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the secondary coating solution, but is not limited thereto.

In addition, the secondary coating solution may suitably include a kind or mixture of two or more kinds of components such as alumina, silica, zirconia and titania from the viewpoint of further improving the mechanical strength of the structure.

The coating method of the secondary coating solution may be performed in the same manner as the above-described coating of the primary coating solution. In addition, the drying step after the application of the secondary coating solution is also not particularly limited as long as the coating solution applied in the same manner as described above can be sufficiently dried.

The coating liquid used in the first step and the second step of the present invention may appropriately contain a mixture of one or more kinds of magnesium ions, calcium ions and boron-containing compounds in view of improving the binding properties of the inorganic binder and the thermal stability of the structure. It may be.

Each coating step as described above may be performed only once, and each coating step may be performed two or more times in view of improving the mechanical strength of the structure.

In the first step of the present invention, it is also possible to further perform a process of forming the clay component-containing outer wall after the application of the primary or secondary coating solution. At this time, the method of forming the outer wall is not particularly limited, and may be formed by, for example, treating the ceramic paper as described above with a clay fiber-containing slurry (eg, impregnating or applying) and then attaching the ceramic paper to the ceramic paper. have. The kind of the clay component containing slurry used at this time is not specifically limited. For example, the slurry may include bentonite, silica sol, solids (ex. Ceramic powder), and the like. At this time, the content of each component is preferably 1 part by weight to 10 parts by weight, 1 part by weight to 10 parts by weight and 5 to 30 parts by weight of solid sol based on 100 parts by weight of the slurry, but is not limited thereto.

According to another aspect of the present invention, the clay component-containing slurry may be water (eg distilled water) in which clay and ceramic fibers are dispersed. Specific types of clays and fibers used above are as described above, the content of which is 12 to 25 parts by weight of clay, 0.5 to 2 parts by weight of ceramic fiber, and 100 parts by weight of water. Preferably, the amount may be 0.5 parts by weight to 1.5 parts by weight, but is not limited thereto.

The second step of the present invention is a process of firing the ceramic green paper subjected to the coating treatment as described above, in which the inorganic binder precursor solution uniformly applied to the paper forms strong bonds between the fibers, thereby improving the mechanical strength of the structure. Can be improved. At this time, the conditions of the firing process are carried out in a temperature range of 930 ° C. or higher in, for example, vacuum, inert gas or air. As for the said baking temperature, it is more preferable that it is 950 degreeC or more, and it is more preferable that it is 1,000 degreeC or more. If the firing temperature is less than 930 ° C, the removal of the organic component may be insufficient, or the control of the amount of elution of the phosphorus component of the final product may be difficult. In the present invention, the upper limit of the firing temperature is not particularly limited to be determined according to the structure to be fired, and may be, for example, 2,000 ° C. or less, preferably 1,500 ° C. or less, and more preferably 1,200 ° C. or less. When the firing temperature exceeds 2,000 ° C., there is a fear that the strength is lowered by the deformation of the components included in the coating layer.

In addition, the time for which the firing process of the second step of the present invention is performed is not particularly limited to be appropriately selected according to the firing temperature, for example, about 10 to 100 minutes, about 15 to 90 minutes, or about It may be carried out for 15 to 60 minutes.

In the present invention, the above-described firing process may be repeated two or more times, or in some cases, the above-described coating, drying and firing processes may be repeatedly performed several times in sequence.

The present invention also provides a porous ceramic structure according to the present invention described above; And

It relates to a humidifying device comprising a storage tank capable of supplying water to the structure.

By using the porous ceramic structure characteristic of the present invention, the humidifier can be driven with a significantly lower electricity consumption than the conventional humidifier which used evaporation means such as an ultrasonic vibrator. In addition, the humidifier according to the present invention can generate finer and more uniform moisture particles by using the capillary effect of the porous ceramic structure, and thus, maintains uniform humidity even in a large space even when configured in a small size. Has the advantage.

Hereinafter, a humidifying apparatus of the present invention will be described in detail with reference to the accompanying drawings. 1 is a schematic diagram showing a humidifying apparatus according to an aspect of the present invention.

As shown in FIG. 1, the humidifying apparatus 100 according to an aspect of the present invention includes a case 120 in which a discharge port 121 is formed, a water storage tank 130 disposed in the case 120, and the storage tank. The water may be supplied from the 130, and may include the porous ceramic structure 110 according to the present invention capable of storing a large amount of moisture therein.

At this time, the storage tank 130 may be used as a conventional water tank, the structure 110 is submerged in the storage tank 130 a portion of the storage tank 130 so as to receive and store the water. May be disposed in the case 120. At this time, since the structure 110 has a high porosity, a large amount of water may be stored therein by capillary action. In addition, the structure 110 of the present invention can keep the water sucked into the clean state because the amount of harmful components eluted into the water under such conditions is suppressed.

In addition, the humidifier device 100 according to an aspect of the present invention is mounted to the case 120, the device capable of sucking the outside air into the case 120 to blow toward the porous ceramic structure 110 ( ex. pan) 140 may be further included.

In the present invention, it is also possible to further install a normal heating means and / or cooling means (not shown) on the suction side of the device 140 such as the fan to increase or decrease the temperature of the sucked air. .

In the present invention, an additional air purification filter may be installed in the humidification device, or an air purification catalyst or the like may be added to the structure itself to simultaneously purify and humidify the outside air.

The present invention also provides a porous ceramic structure according to the present invention described above; And

It relates to an air purifying device including a device capable of blowing or sucking air via the structure.

That is, in the present invention, by using the structure itself as a filter for air purification, the air purification apparatus can be configured by allowing the polluted outside air to be blown or sucked through the structure.

In this case, the porous ceramic structure of the present invention may perform a role of dust removal, harmful gas adsorption and / or antibacterial filter, etc. In order to perform such a function more efficiently, the conventional harmful gas removal on the structure is performed. A catalyst or an antimicrobial agent may be added (ex. Supported) and used.

The type of the device capable of sucking or blowing air in the air purifier is not particularly limited, and for example, a general fan or the like can be used.

Hereinafter, the present invention will be described in more detail through examples according to the present invention, but the scope of the present invention is not limited to the examples given below.

Preparation Example 1.

(1) Preparation of corrugated ceramic green paper

3 g of alumina-silica fiber having an average length of 300 μm was added to 2000 ml of water, followed by vigorous stirring to disperse the fibers. Subsequently, coniferous pulp was added as an organic fiber at 25% by weight based on the ceramic fiber content, and an acrylic binder was added in an amount of 10% by weight based on the fiber. Thereafter, 1 ml of an aqueous 1% ammonium aluminum sulfate solution of pH 3 was added to adjust the pH of the entire slurry solution to about 5.5. Thereafter, the mixture was continuously stirred gently so that the solids in the slurry were evenly mixed, and a ceramic green paper having a thickness of 800 μm was prepared using a papermaking apparatus. Thereafter, the ceramic green paper prepared above was naturally dried at room temperature for 30 minutes, and then the remaining moisture was dried in a drying oven at 100 ° C. The prepared green paper was corrugated at a feed rate of 2-10 m / min at a surface temperature of 150 ° C. using a corrugating apparatus (model name: KIER, goal: 2 mm, pitch: 3 mm, and a chemical device). , Ceramic corrugated paper was prepared.

(2) Manufacture of Ceramic Plate Paper

A ceramic green paper was prepared in the same manner as in (1) except that the corrugation process was not performed, and this was used as the ceramic plate-shaped paper.

Example 1.

A ceramic sheet was prepared by attaching the ceramic plate-shaped paper and corrugated paper prepared in Preparation Example 1, and the sheet was manufactured in a cylindrical shape having a diameter of 3.5 cm and a height of 5 cm. Subsequently, the prepared cylindrical green compact was supported on silica sol (solid content concentration: 20%), and then taken out and dried in an oven at 120 ° C. Meanwhile, 32 g of aluminum acetate was added to 100 g of water, and 230 g of phosphoric acid was gradually added while stirring to prepare a secondary coating solution as a precursor of the inorganic binder. The dried cylindrical green molded body was impregnated into the prepared secondary coating solution, and then taken out to remove the remaining solution between the bones. Thereafter, the mixture was naturally dried at room temperature for 1 hour, then calcined at a temperature of 950 ° C. for 60 minutes, and cooled in a furnace to prepare a ceramic structure.

Example 2

The ceramic plate-shaped paper was placed under the ceramic corrugated paper prepared in Preparation Example 1 and bonded with an adhesive. At this time, in order to enhance the adhesive force after high temperature heat processing, the thing which added silica powder to the starch powder was used as an adhesive agent. The bonded ceramic green molded body was wound in a cochlear shape, heated and dried at about 100 ° C. to prepare a honeycomb structure. Further, 40 g of aluminum nitrate and 4 g of boric acid were added to 100 ml of ethanol, and then 100 ml of TEOS was added while stirring to prepare a primary coating solution. The honeycomb structured body was immersed in the prepared primary coating solution for 5 seconds, taken out, and dried at about 120 ° C. Next, after dissolving 75 g of aluminum nitrate and 5 g of boric acid in 200 ml of distilled water, the primary coating honeycomb structure was immersed in a secondary coating solution prepared by adding 100 ml of 85% phosphoric acid solution for 5 seconds, and taken out at 120 ° C. After drying, the substrate was calcined at a temperature of 1,000 ° C. for 15 minutes to prepare a ceramic structure.

Example 3

The ceramic plate-shaped paper was placed under the ceramic corrugated paper prepared in Preparation Example 1 and bonded with an adhesive. At this time, in order to enhance the adhesive force after high temperature heat processing, the thing which added silica powder to the starch powder was used as an adhesive agent. The bonded ceramic green molded body was wound in a cochlear shape, heated and dried at about 100 ° C. to prepare a honeycomb structure. In addition, a primary coating solution was prepared by adding and stirring a 30% solution of silica sol to 100 ml of ethanol. The honeycomb structured body was immersed in the prepared primary coating solution for 5 seconds, taken out, and dried at about 170 ° C. The dried honeycomb structure was calcined at a temperature of 900 ° C. under atmospheric conditions to prepare a structure capable of immersing a secondary coating solution while removing organic fibers and organic compounds contained in green paper. Subsequently, 230 g of 85% phosphoric acid solution was added to 260 g of distilled water, followed by stirring to dissolve 38 g of aluminum acetate powder. After drying, the substrate was calcined at a temperature of 1,000 ° C. for 60 minutes to prepare a ceramic structure.

Comparative Example 1

After the immersion and drying process in the secondary coating solution, a ceramic structure was prepared in the same manner as in Example 3 except that it was baked for 15 minutes at a temperature of 900 ℃.

Comparative Example 2

After the immersion and drying process in the secondary coating solution, a ceramic structure was prepared in the same manner as in Example 3 except that it was calcined for 60 minutes at a temperature of 900 ℃.

The elution amount of the phosphorus component was measured under the following conditions with respect to the ceramic structures of Examples and Comparative Examples prepared above.

Test Example 1.

10 g of each of the structures prepared in Examples and Comparative Examples was immersed in a polypropylene (PP) container containing 100 g of water, and then maintained at room temperature for 24 hours. Thereafter, the content of P ions released into the water from the structure was quantitatively analyzed using ICP-OES (Perkin Elmer Optima 5300DV).

The analysis results are summarized in Table 1 below.

TABLE 1

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Phosphorus ion
Emission amount (ppm) 4.4 3.7 1.8 37 21

As can be seen from the results of Table 1, in Examples 1 to 3 according to the present invention, the content of the phosphorus component eluted to the outside when immersed in water is suppressed, so that the life of a humidifier or air purifier, etc. It was found that it can be applied directly to the article and used effectively. However, in the case of the comparative example, it was found that a large amount of phosphorus component is eluted to the external environment, making it difficult to apply to well-being products such as humidifiers.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the humidification apparatus which concerns on one aspect of this invention.

&Lt; Description of reference numerals &

100: humidification device

110: porous ceramic structure

120: case

121: discharge port

130: water storage tank

140: fan

150: inlet port

Claims (15)

Porous ceramic structure meeting the conditions of the following general formula 1: [Formula 1] P ≤ 15 ppm In Formula 1, P represents the amount of the phosphorus component eluted from the structure when the porous ceramic structure is immersed in water having a weight 10 times the weight of the structure for 24 hours at room temperature. The method of claim 1, further comprising: porous ceramic paper; And a primary coating layer formed on the porous ceramic paper and containing at least one selected from the group consisting of silicon, aluminum and zirconium. 3. The method of claim 2, wherein the porous ceramic paper comprises: ceramic corrugated paper; And a honeycomb structure comprising ceramic plate-shaped paper attached to the corrugated paper. The porous ceramic structure of claim 2, wherein the primary coating layer comprises at least one selected from the group consisting of silica, silane, siloxane, alumina, zirconia, and aluminum silicate. The porous ceramic structure according to claim 2, wherein a secondary coating layer containing an aluminum component and a phosphorus component is further formed on the primary coating layer. The porous ceramic structure according to claim 5, wherein the atomic ratio (P / Al) of phosphorus and aluminum contained in the secondary coating layer is 3 to 50. 6. The porous ceramic structure of claim 5 wherein the secondary coating layer comprises aluminum phosphate. 3. The porous ceramic structure according to claim 2, further comprising a clay component-containing outer wall integrally formed with the ceramic paper. 6. The porous ceramic structure according to claim 5, further comprising a zirconia layer formed between the primary coating layer and the secondary coating layer. A first step of coating the porous ceramic green paper with a primary coating liquid containing at least one component selected from the group consisting of silicon, aluminum and zirconium; And A method of manufacturing a porous ceramic structure comprising a second step of firing a paper produced through a first step at a temperature of 930 ° C. or higher. The method of claim 10, wherein the primary coating solution is at least one selected from the group consisting of zirconium acetate, zirconia sol, silica sol, alumina sol and aluminum silicate solution. The method of claim 11, wherein the aluminum silicate solution comprises an alcohol, an aluminum precursor, tetraalkyl orthosilicate and an acid. The method of claim 10, further comprising coating the paper prepared by the first step with a secondary coating liquid comprising aluminum and phosphorus. A porous ceramic structure according to any one of claims 1 to 9; And And a storage tank capable of supplying water to the structure. A porous ceramic structure according to any one of claims 1 to 9; And And a device capable of sucking or blowing air via the structure.

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