WO2013118940A1 - Porous composite, preparation method thereof, and cement composition containing porous composite - Google Patents

Porous composite, preparation method thereof, and cement composition containing porous composite Download PDF

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Publication number
WO2013118940A1
WO2013118940A1 PCT/KR2012/002462 KR2012002462W WO2013118940A1 WO 2013118940 A1 WO2013118940 A1 WO 2013118940A1 KR 2012002462 W KR2012002462 W KR 2012002462W WO 2013118940 A1 WO2013118940 A1 WO 2013118940A1
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WIPO (PCT)
Prior art keywords
porous composite
metal oxide
porous
cement composition
present
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Application number
PCT/KR2012/002462
Other languages
French (fr)
Inventor
Jong Ho Kim
Jong Beom Kim
Se Min Park
Ki Won Lee
Soo Jeam PARK
Tae Kyoon Kim
Original Assignee
Photo & Environmental Technology Co.
Hwaseung T&C Co., Ltd.
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Application filed by Photo & Environmental Technology Co., Hwaseung T&C Co., Ltd. filed Critical Photo & Environmental Technology Co.
Publication of WO2013118940A1 publication Critical patent/WO2013118940A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1066—Oxides, Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3285—Coating or impregnation layers comprising different type of functional groups or interactions, e.g. different ligands in various parts of the sorbent, mixed mode, dual zone, bimodal, multimodal, ionic or hydrophobic, cationic or anionic, hydrophilic or hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
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    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/30—Silica
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    • B01D—SEPARATION
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/40—Nitrogen compounds
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • C04B2111/00827—Photocatalysts

Definitions

  • the present invention relates to a porous composite, and more particularly, to a composite and its preparation method where the composite has a porous silica coating as a three-dimensional net structure surrounding metal oxides and thus can be widely applied in various fields, such as insulating materials, energy and chemical applications, and so forth, through control of specific surface area and dispersibi 1 ity.
  • a photocatalyst refers to a substance that is used to accelerate chemical reactions using a light.
  • the conventional techniques using titanium dioxide(Ti02) or the like as a photocatalyst involve using a photocatalyst powder alone or in combination with a binder and then applying the powder on a support or a carrier; or coating a support with titanium oxides such as titanium tetrachloride or titanium alkoxide and then forming a thin film of anatase type titanium dioxide on the surface of the support using the sol-gel technique.
  • titanium dioxide powder As a photocatalyst, it is required to synthesize titanium dioxide powder in anatase crystal form or anatase-rut i le mixed crystal form through the sulfuric acid or chlorine method.
  • the titanium dioxide powder thus obtained is used in the slurry form or as a coating on the surface of a support.
  • metal oxides such as titanium dioxide
  • other substances can lead to excess consistency, surface whitening, or coagulation.
  • metal oxides are ready not only to change other organic substances due to their photocatalyt ic activity to oxidize almost all organic substances and degrade them into carbon dioxide and water but also to undergo deformation of crystalline structure at high temperature.
  • the method of using a thin film of titanium dioxide formed by sol-gel technique ends up with a small specific surface area and deterioration of photocatalytic activity due to the coating, consequently with a limitation in use for industrial materials.
  • the present invention is to provide a preparation method for a porous composite and a porous composite prepared by the method, where the porous composite has excellences in dispersibi 1 ity and stability with no deterioration of photocatalytic activity caused by a coating and hence can be widely applied in various industrial fields.
  • the present invention provides a method for preparing a porous composite that includes: (a) mixing a metal oxide with at least one of water glass(Na 2 Si0 3 ) , potassium silicate, calcium silicate, and silica sol to prepare a sol type mixture of the metal oxide; (b) gelating the mixture of the metal oxide to form a metal oxide gel; (c) surface-modifying the metal oxide gel; (d) drying the metal oxide gel to form a porous composite having a coating of silica aerogel around the metal oxide; and (e) conducting a plastic working on the porous composite.
  • the porous composite is mixed with water glass for gelation to form a porous silica coating having a three- dimensional net structure in which metal oxides are coated with silica aerogel .
  • the present invention also provides the porous composite formed by the preparation method. Furthermore, the porous composite is ready to control in hydrophi 1 ici ty and hydrophobic ity through plastic working. Using the porous composite in a cement composition can provide a structure having a hydrophobic surface. [Advantageous Effects]
  • the porous composite formed by the preparation method of the present invention consists of such a high porosity to provide a superior insulation performance.
  • a composite formed from a porous silica coating with high photocatalyt ic activity, dispersibi 1 ity, and stabi 1 ity.
  • a porous composite and a cement composition containing the same that have an excellent effect of removing harmful substances. Due to the coating of silica aerogel, the porous composite of the present invention is miscible with other materials by avoiding degradation or coagulation of other organic compositions. Accordingly, the use of the porous composite can provide a cement composition uniformly miscible and excellent in stability. Using the cement composition in concrete, interlocking blocks, pipes, slates, or the like can provide eco-friendly building materials harmless to the humane body. [Description of Drawings]
  • FIG. 1 is a mimetic diagram showing a porous composite according to one example of the present invention.
  • FIG. 2 shows microscopic pictures (SEM (Scanning Electron Microscope
  • FIG. 3 is a graph showing the X-ray diffraction patterns of the porous composite according to one example of the present invention and the crystal phase of a comparative example.
  • FIG. 4 is a graph plotting the adsorbed amount of nitrogen as a function of atmospheric pressure for the porous composite according to one example of the present invention.
  • FIG. 5 is a graph showing the photocatalyt ic activity for acetaldehyde degradation for the porous composite according to one example of the present invention and a comparative example.
  • FIG. 6 presents pictures showing the change of temperature when heating an insulating material containing the porous composite according to one example of the present invention.
  • FIG. 7 is a schematic diagram showing a device for NOx removal testing.
  • FIG. 8 shows the results when the porous composite according to one example of the present invention removes NOx.
  • FIG. 9 shows the results when the comparative example removes NOx.
  • FIG. 10 shows the evaluation results when a concrete according to one example of the present invention removes NOx.
  • the present invention is directed to a method for preparing a porous composite that includes: (a) mixing a metal oxide with at least one of water glass (Na 2 Si0 3 ), potassium silicate, calcium silicate, and silica sol to prepare a sol type mixture of the metal oxide! (b) gelating the mixture of the metal oxide to form a metal oxide gel; (c) surface-modifying the metal oxide gel; (d) drying the metal oxide gel to form a porous composite having a coating of silica aerogel around the metal oxide; and (e) conducting a plastic working on the porous composite.
  • the porous composite is mixed with water glass for gelation to form a porous silica coating having a three- dimensional net structure that metal oxides are coated with silica aerogel.
  • the silica aerogel surrounding the metal oxides consists of 2 ⁇ 5nm- diameter spherical silica particles that form a three-dimensional net-like cluster to provide a porous structure with nano-sized pores.
  • the present invention forms a coating of silica aerogel low in thermal conductivity around metal oxides to enhance porosity and hence provide high thermal stability.
  • FIG. 1 shows a mimetic diagram of the porous composite formed by the preparation method of the present invention.
  • a coating of silica aerogel (Si0 2 ) surrounds metal oxides such as titanium dioxide(Ti0 2 ) .
  • the porous composite formed by the preparation method of the present invention contains more silicon(Si) due to the coating of silica aerogel and, compared to the existing commercial composites having photocatalyt ic activity, uses a much lower quantity of an expensive component such as titanium(Ti) , thus reducing the production cost.
  • the porous composite formed by the preparation method may have a three- dimensional net structure.
  • the metal oxide used in the step (a) of the preparation method is preferably an oxide having photocatalyt ic activity, such as, for example, Ti0 2 , Zn02, ZnO, SrTi0 3 , CdS, GaP, InP, GaAs, BaTi0 3 ,
  • titanium dioxide(Ti0 2 ) may be directly used alone, or doped with anions, such as of nitrogen, sulfur, boron, carbon, etc. to form a visible responsive photocatalyst. Titanium dioxide(Ti0 2 ) is a cheap substance harmless to the human body and excellent in photocatalyt ic activity and resistant to light-induced corrosion.
  • the metal oxide may be used in combination with a metaKe.g.,
  • Ti(0H) 4 or TiO(OH) 2 may also be used.
  • the metal oxide is preferably mixed with any one of water glass, potassium silicate, calcium silicate, and silica sol preferably at such a mixing ratio that the weight ratio of the metal oxide to silica contained in any one of water glass, potassium silicate, calcium silicate, and silica sol is in the range of 0.01— 10 : 1.
  • the preparation method may further include a step of treating the metal oxide with a modifier in order to enhance the -OH bonding strength between silica and the metal oxide.
  • the modifier for the metal oxide may be hydrogen peroxide water or a solution of an acid(e.g., hydrochloric acid, nitric acid, sulfuric acid, acetic acid, polycarboxyl ic acid, etc.) or a base(e.g. , sodium hydroxide, ammonia water, etc.) with water.
  • the modifier is preferably used in an amount of 0.01 to 1.00 wt.%.
  • the mixed solution of metal oxide and water glass is subjected to vigorous agitation to form a mixed sol.
  • the metal oxide gel in the step (b) is formed by adding an acid solution at pH 1— 10 to the metal oxide mixture for gelation.
  • the acid may be prepared by diluting hydrochloric acid, sulfuric acid, nitric acid, etc. with a solvent.
  • the solvent may be methanol, ethanol, but nol , isopropanol, etc. as used in combination with water.
  • the temperature or the agitation rate can be regulated in order to control the gelation rate and uniformity.
  • the surface modification in the step (c) may be conducted by adding an organo-funct ional si lane to the metal oxide gel in an organic solvent.
  • the organic solvent may be ethanol, butanol, hexanol , or the like.
  • the organofunct ional si lane may be any one selected from the group consisting of trimethyl chlorosi lane(TMCS) , hexamethyl disi lazane(HMDS) , methyl trimethoxy si lane, and trimethyl ethoxy si lane.
  • the wet metal oxide gel obtained from the steps (a) and (b) is added to an organic solvent and mixed with a defined amount of an organo-funct ional si lane for surface modification.
  • the added amount of the organic solvent or the organo ⁇ funct ional si lane can be regulated in order to control the modification rate and the hydrophobicity of the surface.
  • the metal oxide gel of the step (d) is preferably subjected to ambient drying in an oven at 60 to 200 ° C for 1 to 24 hours. Drying the metal oxide gel under the above-defined temperature and time conditions can achieve a desired pore size of the metal oxide. Drying at an abruptly increased temperature higher than the above-defined temperature range or for a longer time than the above-defined time range may end up with a loss of porosity.
  • the drying process can be conducted as supercritical drying, which leaves almost no surface tension and hence no damage on the product.
  • the preparation method for the porous composite may further include a step (e) of conducting a plastic working for the porous composite after the step (d).
  • the plastic working is to control the hydrophi 1 icity and hydrophobicity of the porous composite.
  • the plastic working on the porous composite in the step (e) may be conducted at 400 to 800 ° C for 1 to 24 hours.
  • This step is to eliminate organic substances endowing hydrophobicity from the surface of the silica gel to make the surface hydrophi lie while maintaining porosity and structure.
  • the temperature below the range cannot remove organic substances effectively, whereas the temperature above the range can cause the structural frame shrunken to damage the product .
  • the present invention is also directed to a porous composite formed by the above-described preparation method.
  • the porous composite may be a porous silica coating having a three- dimensional net structure in which metal oxides are coated with silica aerogel.
  • the porous composite preferably has a porosity of 80 to 99 %.
  • the crystal phase may be anatase with a particle size of 10 to 30 nm.
  • the porous composite of the present invention has a specific surface
  • the porous composite of the present invention can be controlled in hydrophi 1 icity or hydrophobicity through a plastic working, where the pore size and density are determined depending on the chemical conditions, such as the used amount of the solvent, the type of the modifier, or the mixing ratio of titanium dioxide and water glass, or drying conditions.
  • the present invention is also directed to a cement composition containing the porous composite.
  • the porous composite is preferably used in an amount of 0.1 to 10 wt. with respect to the total weight of the cement compos i t i on .
  • the porous composite of the present invention not only maintains the high photocatalyt ic activity of the metal oxide but also keeps the metal oxide from a direct contact with an organic support or a binder due to a three-dimensional porous structure of the silica aerogel coating surrounding the metal oxide, thereby preventing degradation of the organic support or the binder, which has been the problem with the conventional photocatalysts .
  • the porous composite of the present invention which forms a three-dimensional net structure with a coating silica aerogel surrounding the metal oxide, can have a large specific surface area and thus remove harmful substances more effectively than the conventional photocatalyst powder.
  • the porous composite is useful to effectively degrade air pollutants such as nitrogen oxides(N0 x ) or sulfur oxides(S0 x ), or other chemicals such as TVOC, formaldehyde, ammonia, etc.
  • the use of the cement composition containing the porous composite in fabrication of building materials for medical facility, housing, water/sewer treatment facility, or the like can provide eco-friendly buildings or facilities that are harmless to the human body and effective in degradation of environmental contaminants, air purification, and deodor izat ion.
  • the porous composite of the present invention which is controllable in hydrophi 1 icity and hydrophobici ty through plastic working, can also be used in a cement composition to provide a structure having a hydrophobic surface. Therefore, the hydrophi 1 ici ty and hydrophobicity of the porous composition can be controlled depending on the uses and functions of the resultant structure. It is thus possible to provide a hydrophobic, water- repellent cement composition simply by controlling the plastic working temperature.
  • n-hexane at weight ratio of 4 with respect to the wet gel
  • ethanoKat weight ratio of 1 with respect to the wet gel
  • TMCS trimethyl chlorosi lane
  • porous composite having a weight ratio(titanium dioxide to silica) of 0.8, excepting that 48 g of titanium dioxide(Ti0 2 ) powder treated with hydrogen peroxide water was added to 200 g of water glassCcontaining 30 wt.% of S1O 2 ) commercially available.
  • the comparative example was P-25 powder supplied by EV0NIK Industries, which is a titanium dioxide(Ti0 2 ) powder not coated with silica aerogel.
  • Table 1 shows a comparison in composition between Example 1 of the present invention and Comparative Example. The content of each ingredient was analyzed with an EDX (Energy Dispersive X-ray Spectroscope(EX-250 supplied by Horiba).
  • EDX Energy Dispersive X-ray Spectroscope
  • FIGS. 2a and 2b present pictures of Example 1 of the present invention as taken with SEM( Scanning Electron Microscope, Hitachi S-4700) and TEM (Transmission Electron Microscope, JEM 2000 FXII, JE0L).
  • the porous photocatalyst powder consists of 10 ⁇ 30nm-diameter particles combining together, as shown in (a); and when magnified 1,500,000 times, the particles look like gather together to form pores about 10 to 50 nm in diameter, which form a large pore, as shown in (b).
  • Comparative Example 1 were analyzed using X-ray diffraction pattern(XRD) .
  • the analytical results are presented in FIG. 3.
  • a heat treatment in the oxygen atmosphere at 200 to 1,000 ° C was also conducted to analyze the thermal stabi 1 ity.
  • Examples 1 to 4 of the present invention had a specific surface area about 3 to 8 times as large as Comparative Example 1. Further, the specific surface area decreased as the added amount of titanium dioxide increased in the order from Example 1 to Example 4. As for average pore size, it is well known that Comparative Example 1 has no pores in the particles but 8 nm-diameter gaps between the particles. But, Examples 1 to 4 of the present invention had a constant pore size of 4 nm regardless of the change in the added amount of titanium dioxide.
  • Comparative Example 1 and Example 1 of the present invention were measured in regard to the adsorbed amount of nitrogen based on the atmospheric pressure.
  • the results are presented in FIG. 4.
  • Comparative Example 1 had an adsorbed amount of nitrogen abruptly increasing with an increase in the atmospheric pressure from the point, of P/Po about 0.8 or above and showed a maximum absorbed amount
  • Example 1 of the present invention had an absorbed amount of nitrogen increasing with an increase in
  • Comparative Example 1 was added as a catalyst in a 2 L reactor, and 2,000 ppm of acetaldehyde was then added for equilibrium adsorption. After 2-hour irradiation with UV lamps(10W x 3 eaXSankyodenki ) , a comparative analysis was conducted using a gas chromatograph system(HP 6890) and an FI detector. The results are presented in FIG. 5.
  • Comparative Example 1 had an acetaldehyde degrading activity initially low and increased with an elapse of time to achieve a degrading performance of about 98 % after two hours.
  • Example 4 had an initial activity considerably high as about 70%, and all had an increase in the activity with an elapse of 2 hours up to 96%, 92%, 88% and 85% respectively in the order of Example 1, Example 2, Example 3, and Example 4.
  • Comparative Example 1 contained 32.0 wt.% of Ti with respect to the total weight of the composition, considerably high in Ti content relative to Examples 1 to 4 of the present invention.
  • FIG. 6 shows that Example 1 had a higher initial activity and an average photocatalyt ic activity about 5 times higher than that of Comparative Example 1.
  • a general industrial insulating material was coated with the porous composite prepared in Example 1 of the present invention to fabricate a novel insulating material.
  • the novel insulating material and the general insulating material were heated with a hot air gun at 300 ° C for one minute, and the change of temperature in the back side was measure for each insulating material .
  • the insulating material using the porous composite powder of the present invention as a photocatalyst had a surface temperature of 36 ° C with almost no change of temperature, whereas the general insulating material had a surface temperature of 237 ° C , showing a considerably poor thermal insulation relative to the present invention.
  • the reason of this result is that the porous composite of the present invention had titanium dioxide coated with silica aerogel to form a porous silica coating which provided high thermal stability.
  • FIG. 7 An evaluation system(FIG. 7) for nitrogen oxide removal testing according to S L ISO 22197-1 was used to measure the performance of the porous composite according to one embodiment of the present invention in removing nitrogen oxides(N0 x ) considered as harmful substances.
  • Example 1 and Comparative Example 1 The measurement results for Example 1 and Comparative Example 1 in regard to the performance of removing nitrogen oxides are presented in FIGS. 8 and 9.
  • the powder of Comparative Example 1 which was a general compound with a photocatalyt ic activity showed a decrease in NO concentration by no more than 40% and a decrease in N0 X concentration by about 10% upon UV irradiation.
  • the powder of Example 1 which was a porous composite with a photocatalyt ic activity had a dramatic decrease in NO concentration by 50% or below and a decrease in N0 X concentration by about 20% upon UV irradiation.
  • the porous composite according to one example of the present invention had a three-dimensional net structure of a silica aerogel coating to secure a large specific surface area and a high photocatalyt ic activity. Accordingly, the porous composite of the present invention was excellent in the effect of removing nitrogen oxides.
  • the cement composition was cured for more 28 days to form a final cement composition containing the porous composite according to one example of the present invention.
  • FIG. 7 An evaluation system(FIG. 7) for nitrogen oxide removal testing according to KS L ISO 22197-1 was used to measure the performance of the cement composition according to one embodiment of the present invention in removing nitrogen oxides(N0 x ) considered as harmful substances.
  • the cement composition containing, with respect to the total weight of the composition, 3 wt.% of the porous composite which includes titanium dioxide and silica at a weight ratio of 0.2 according to one example of the present invention was prepared in accordance with the above-described preparation process. Then, the change of nitrogen oxide concentration was measured by blocking light for 0.5 hour, UV-irradiat ing for 2 hours, blocking light for 2 hours, UV-irradiat ing for 2 hours, and then blocking light for 0.5 hour.

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Abstract

The present invention is directed to a method for preparing a porous composite that contains metal oxides coated with silica aerogel to form a porous silica coating having a three-dimensional net structure. The preparation method for porous composite enables the porous composite useful in a wide range of applications of various fields, such as insulating materials, energy and chemical applications, and so forth, through control of specific surface area and dispersibility. The present invention is also directed to a porous composite formed by the preparation method, and a cement composition containing the porous composite.

Description

[DESCRIPTION]
[Invention Title]
POROUS COMPOSITE, PREPARATION METHOD THEREOF, AND CEMENT COMPOSITION CONTAINING POROUS COMPOSITE
[Technical Field]
<i> The present invention relates to a porous composite, and more particularly, to a composite and its preparation method where the composite has a porous silica coating as a three-dimensional net structure surrounding metal oxides and thus can be widely applied in various fields, such as insulating materials, energy and chemical applications, and so forth, through control of specific surface area and dispersibi 1 ity.
[Background Art]
<2> A photocatalyst refers to a substance that is used to accelerate chemical reactions using a light. For example, the conventional techniques using titanium dioxide(Ti02) or the like as a photocatalyst involve using a photocatalyst powder alone or in combination with a binder and then applying the powder on a support or a carrier; or coating a support with titanium oxides such as titanium tetrachloride or titanium alkoxide and then forming a thin film of anatase type titanium dioxide on the surface of the support using the sol-gel technique. To use the titanium dioxide powder as a photocatalyst, it is required to synthesize titanium dioxide powder in anatase crystal form or anatase-rut i le mixed crystal form through the sulfuric acid or chlorine method. The titanium dioxide powder thus obtained is used in the slurry form or as a coating on the surface of a support.
<3> However, blending metal oxides such as titanium dioxide with other substances can lead to excess consistency, surface whitening, or coagulation. Further, such metal oxides are ready not only to change other organic substances due to their photocatalyt ic activity to oxidize almost all organic substances and degrade them into carbon dioxide and water but also to undergo deformation of crystalline structure at high temperature. These problems limit the uses of metal oxides in industrial applications.
<4> Further, the method of using a thin film of titanium dioxide formed by sol-gel technique ends up with a small specific surface area and deterioration of photocatalytic activity due to the coating, consequently with a limitation in use for industrial materials.
<5> Hence, there is a demand for developing photocatalysts that maintain a high photocatalytic activity and have good resistance to coagulation, that is, high dispersibi 1 ity and stability for use purpose in various fields.
[Disclosure]
[Technical Problem]
<6> Accordingly, in an effort to solve the above-mentioned problems with the conventional photocatalysts, the present invention is to provide a preparation method for a porous composite and a porous composite prepared by the method, where the porous composite has excellences in dispersibi 1 ity and stability with no deterioration of photocatalytic activity caused by a coating and hence can be widely applied in various industrial fields.
[Technical Solution]
<7> To achieve the above object, the present invention provides a method for preparing a porous composite that includes: (a) mixing a metal oxide with at least one of water glass(Na2Si03) , potassium silicate, calcium silicate, and silica sol to prepare a sol type mixture of the metal oxide; (b) gelating the mixture of the metal oxide to form a metal oxide gel; (c) surface-modifying the metal oxide gel; (d) drying the metal oxide gel to form a porous composite having a coating of silica aerogel around the metal oxide; and (e) conducting a plastic working on the porous composite.
<8> According to the preparation method, the porous composite is mixed with water glass for gelation to form a porous silica coating having a three- dimensional net structure in which metal oxides are coated with silica aerogel .
<9> To achieve the object of the present invention, the present invention also provides the porous composite formed by the preparation method. Furthermore, the porous composite is ready to control in hydrophi 1 ici ty and hydrophobic ity through plastic working. Using the porous composite in a cement composition can provide a structure having a hydrophobic surface. [Advantageous Effects]
<u> In accordance with the present invention, there is provided a method for preparing a porous composite in which metal oxides are coated with silica aerogel to form a porous silica coating having a three-dimensional net structure, to secure a large specific surface area and hence high photocatalyt ic activity and high dispersibi 1 ity . Further, the porous composite formed by the preparation method of the present invention consists of such a high porosity to provide a superior insulation performance.
<12> In accordance with the present invention, there is also provided a composite formed from a porous silica coating with high photocatalyt ic activity, dispersibi 1 ity, and stabi 1 ity.
<i3> In accordance with the present invention, there are also provided a porous composite and a cement composition containing the same that have an excellent effect of removing harmful substances. Due to the coating of silica aerogel, the porous composite of the present invention is miscible with other materials by avoiding degradation or coagulation of other organic compositions. Accordingly, the use of the porous composite can provide a cement composition uniformly miscible and excellent in stability. Using the cement composition in concrete, interlocking blocks, pipes, slates, or the like can provide eco-friendly building materials harmless to the humane body. [Description of Drawings]
<14> FIG. 1 is a mimetic diagram showing a porous composite according to one example of the present invention.
<15> FIG. 2 shows microscopic pictures (SEM (Scanning Electron Microscope,
Hitachi S-4700) and TEM (Transmission Electron Microscope, JEM 2000 FXII, JE0O) of the porous composite according to one .example of the present i nvent i on .
<i6> FIG. 3 is a graph showing the X-ray diffraction patterns of the porous composite according to one example of the present invention and the crystal phase of a comparative example.
<17> FIG. 4 is a graph plotting the adsorbed amount of nitrogen as a function of atmospheric pressure for the porous composite according to one example of the present invention.
<18> FIG. 5 is a graph showing the photocatalyt ic activity for acetaldehyde degradation for the porous composite according to one example of the present invention and a comparative example.
<19> FIG. 6 presents pictures showing the change of temperature when heating an insulating material containing the porous composite according to one example of the present invention.
<20> FIG. 7 is a schematic diagram showing a device for NOx removal testing.
<2i> FIG. 8 shows the results when the porous composite according to one example of the present invention removes NOx.
<22> FIG. 9 shows the results when the comparative example removes NOx.
<23> FIG. 10 shows the evaluation results when a concrete according to one example of the present invention removes NOx.
[Best Mode]
<24> The present invention is directed to a method for preparing a porous composite that includes: (a) mixing a metal oxide with at least one of water glass (Na2Si03), potassium silicate, calcium silicate, and silica sol to prepare a sol type mixture of the metal oxide! (b) gelating the mixture of the metal oxide to form a metal oxide gel; (c) surface-modifying the metal oxide gel; (d) drying the metal oxide gel to form a porous composite having a coating of silica aerogel around the metal oxide; and (e) conducting a plastic working on the porous composite.
<25> According to the preparation method, the porous composite is mixed with water glass for gelation to form a porous silica coating having a three- dimensional net structure that metal oxides are coated with silica aerogel.
<26> The silica aerogel surrounding the metal oxides consists of 2~5nm- diameter spherical silica particles that form a three-dimensional net-like cluster to provide a porous structure with nano-sized pores. In this manner, the present invention forms a coating of silica aerogel low in thermal conductivity around metal oxides to enhance porosity and hence provide high thermal stability.
<27> Besides, such a three-dimensional net structure is useful for light contact to the photocatalyst inside without being blocked by silica, which contributes to maintaining the photocatalyt ic activity without deterioration! increases the specific surface area of the porous composite to enhance adsorption performance and photocatalyt ic activity; and prevents coagulation of photocatalyst particles to enhance dispersibi 1 i ty . The three-dimensional porous coating of silica gel formed to surround the photocatalyst can keep the photocatalyst from getting in direct contact with an organic support or a binder, thereby overcoming the problem with the conventional photocatalysts that the organic support or the binder undergoes degradation. FIG. 1 shows a mimetic diagram of the porous composite formed by the preparation method of the present invention. As shown in FIG. 1, a coating of silica aerogel (Si02) surrounds metal oxides such as titanium dioxide(Ti02) .
<28> Further, the porous composite formed by the preparation method of the present invention contains more silicon(Si) due to the coating of silica aerogel and, compared to the existing commercial composites having photocatalyt ic activity, uses a much lower quantity of an expensive component such as titanium(Ti) , thus reducing the production cost.
<29> The porous composite formed by the preparation method may have a three- dimensional net structure. The metal oxide used in the step (a) of the preparation method is preferably an oxide having photocatalyt ic activity, such as, for example, Ti02, Zn02, ZnO, SrTi03, CdS, GaP, InP, GaAs, BaTi03,
KNbOs, Fe203, Ta205, W03, Sn02, Bi203, NiO, Cu20, SiO, Si02, MoS2, InPb, Ru02,
Ce02, etc. Among these oxides, titanium dioxide(Ti02) may be directly used alone, or doped with anions, such as of nitrogen, sulfur, boron, carbon, etc. to form a visible responsive photocatalyst. Titanium dioxide(Ti02) is a cheap substance harmless to the human body and excellent in photocatalyt ic activity and resistant to light-induced corrosion.
<30> Further, the metal oxide may be used in combination with a metaKe.g.,
Pt , Rh, Ag, Cu, Sn, Ni , Fe, etc.) or another metal oxide to form a composite metal oxide. A titanium intermediate such as Ti(0H)4 or TiO(OH)2 may also be used.
<3i> In the step (a), the metal oxide is preferably mixed with any one of water glass, potassium silicate, calcium silicate, and silica sol preferably at such a mixing ratio that the weight ratio of the metal oxide to silica contained in any one of water glass, potassium silicate, calcium silicate, and silica sol is in the range of 0.01— 10 : 1. The preparation method may further include a step of treating the metal oxide with a modifier in order to enhance the -OH bonding strength between silica and the metal oxide. The modifier for the metal oxide may be hydrogen peroxide water or a solution of an acid(e.g., hydrochloric acid, nitric acid, sulfuric acid, acetic acid, polycarboxyl ic acid, etc.) or a base(e.g. , sodium hydroxide, ammonia water, etc.) with water. The modifier is preferably used in an amount of 0.01 to 1.00 wt.%. The mixed solution of metal oxide and water glass is subjected to vigorous agitation to form a mixed sol.
<32> The metal oxide gel in the step (b) is formed by adding an acid solution at pH 1— 10 to the metal oxide mixture for gelation. Here, the acid may be prepared by diluting hydrochloric acid, sulfuric acid, nitric acid, etc. with a solvent. The solvent may be methanol, ethanol, but nol , isopropanol, etc. as used in combination with water. Further, the temperature or the agitation rate can be regulated in order to control the gelation rate and uniformity.
<33> The surface modification in the step (c) may be conducted by adding an organo-funct ional si lane to the metal oxide gel in an organic solvent. Here, the organic solvent may be ethanol, butanol, hexanol , or the like. The organofunct ional si lane may be any one selected from the group consisting of trimethyl chlorosi lane(TMCS) , hexamethyl disi lazane(HMDS) , methyl trimethoxy si lane, and trimethyl ethoxy si lane. Preferably, the wet metal oxide gel obtained from the steps (a) and (b) is added to an organic solvent and mixed with a defined amount of an organo-funct ional si lane for surface modification. The added amount of the organic solvent or the organo¬ funct ional si lane can be regulated in order to control the modification rate and the hydrophobicity of the surface.
<34> The metal oxide gel of the step (d) is preferably subjected to ambient drying in an oven at 60 to 200 °C for 1 to 24 hours. Drying the metal oxide gel under the above-defined temperature and time conditions can achieve a desired pore size of the metal oxide. Drying at an abruptly increased temperature higher than the above-defined temperature range or for a longer time than the above-defined time range may end up with a loss of porosity.
<35> The drying process can be conducted as supercritical drying, which leaves almost no surface tension and hence no damage on the product.
<36> The preparation method for the porous composite may further include a step (e) of conducting a plastic working for the porous composite after the step (d). The plastic working is to control the hydrophi 1 icity and hydrophobicity of the porous composite. Preferably, the plastic working on the porous composite in the step (e) may be conducted at 400 to 800 °C for 1 to 24 hours. This step is to eliminate organic substances endowing hydrophobicity from the surface of the silica gel to make the surface hydrophi lie while maintaining porosity and structure. The temperature below the range cannot remove organic substances effectively, whereas the temperature above the range can cause the structural frame shrunken to damage the product .
<37> The present invention is also directed to a porous composite formed by the above-described preparation method.
<38> The porous composite may be a porous silica coating having a three- dimensional net structure in which metal oxides are coated with silica aerogel. For sufficient thermal insulation in air, the porous composite preferably has a porosity of 80 to 99 %. The crystal phase may be anatase with a particle size of 10 to 30 nm.
<39> The porous composite of the present invention has a specific surface
2 2
area in the range of 300— 1000 m/g, more preferably 400— 800 m /g.
<40> Further, the porous composite of the present invention can be controlled in hydrophi 1 icity or hydrophobicity through a plastic working, where the pore size and density are determined depending on the chemical conditions, such as the used amount of the solvent, the type of the modifier, or the mixing ratio of titanium dioxide and water glass, or drying conditions. <4i> The present invention is also directed to a cement composition containing the porous composite. The porous composite is preferably used in an amount of 0.1 to 10 wt. with respect to the total weight of the cement compos i t i on .
<42> The porous composite of the present invention not only maintains the high photocatalyt ic activity of the metal oxide but also keeps the metal oxide from a direct contact with an organic support or a binder due to a three-dimensional porous structure of the silica aerogel coating surrounding the metal oxide, thereby preventing degradation of the organic support or the binder, which has been the problem with the conventional photocatalysts .
<43> Therefore, using the porous composite in a cement composition renders the cement composition miscible without causing deformation or coagulation of the composition. Due to high stability of the cement composition, the use of the composition in fabrication of concrete structures, interlocking blocks, pipes, slates, or the like can secure high structural stability.
<44> Further, the porous composite of the present invention, which forms a three-dimensional net structure with a coating silica aerogel surrounding the metal oxide, can have a large specific surface area and thus remove harmful substances more effectively than the conventional photocatalyst powder. In particular, the porous composite is useful to effectively degrade air pollutants such as nitrogen oxides(N0x) or sulfur oxides(S0x), or other chemicals such as TVOC, formaldehyde, ammonia, etc. Hence, the use of the cement composition containing the porous composite in fabrication of building materials for medical facility, housing, water/sewer treatment facility, or the like can provide eco-friendly buildings or facilities that are harmless to the human body and effective in degradation of environmental contaminants, air purification, and deodor izat ion.
<45> Further, the porous composite of the present invention, which is controllable in hydrophi 1 icity and hydrophobici ty through plastic working, can also be used in a cement composition to provide a structure having a hydrophobic surface. Therefore, the hydrophi 1 ici ty and hydrophobicity of the porous composition can be controlled depending on the uses and functions of the resultant structure. It is thus possible to provide a hydrophobic, water- repellent cement composition simply by controlling the plastic working temperature.
[Mode for Invention]
<46> Hereinafter, the present invention will be described with the following examples, which are only for illustrative purposes and are not intended to limit the present invention.
<47> It is also to be understood that modifications and variations of the present invention may be resorted without departing from the technical idea and scope of the present invention as those skilled in the art readily understand.
<48> Example 1
<49> The procedures to prepare a porous composite according to one example of the present invention are described as follows.
<50> 12 g of titanium dioxideCTiCy powder treated with hydrogen peroxide water was added to 200 g of water glass(containing 30 wt.% of S1O2) commercially available, and the mixture was stirred to form a mixed sol of titanium dioxide. An aqueous solution of sulfuric acid was gradually added to the mixed sol to adjust the acidity at pH 7. To eliminate sodium residue, the resultant wet gel was washed with hot water twice and then subjected to dehydration and isolation. To the wet gel were added n-hexane(at weight ratio of 4 with respect to the wet gel), ethanoKat weight ratio of 1 with respect to the wet gel), and trimethyl chlorosi lane(TMCS) (at weight ratio of 2 with respect to the wet gel) to conduct a surface modification at the room temperature for 5 hours. After a subsequent isolation step, the wet gel was dried in an oven under atmospheric pressure at 60 °C for 12 hours and 200 °C at 12 hours to yield a porous composite having a weight ratio (titanium dioxide to silica) of 0.2.
<5i> Example 2
<52> The preparation of a porous composite according to another example of the present invention will be described as follows. The same contents as given in Example 1 are omitted in the description. <53> The procedures were conducted in the same manner as described in Example
1 to yield a porous composite having a weight rat io(t itanium dioxide to silica) of 0.4, excepting that 24 g of titanium dioxide(Ti02) powder treated with hydrogen peroxide water was added to 200 g of water glassCcontaining 30 wt. of S1O2) commercially available.
<54> Example 3
<55> The preparation of a porous composite according to still another example of the present invention will be described as follows. The same contents as given in Example 1 are omitted in the description.
<56> The procedures were conducted in the same manner as described in Example
1 to yield a porous composite having a weight ratio(titanium dioxide to silica) of 0.8, excepting that 48 g of titanium dioxide(Ti02) powder treated with hydrogen peroxide water was added to 200 g of water glassCcontaining 30 wt.% of S1O2) commercially available.
<57> Example 4
<58> The preparation of a porous composite according to another example of the present invention will be described as follows. The same contents as given in Example 1 are omitted in the description.
<59> The procedures were conducted in the same manner as described in Example
1 to yield a porous composite having a weight rat io(t itanium dioxide to silica) of 1.2, excepting that 72 g of titanium dioxide(Ti02) powder treated with hydrogen peroxide water was added to 200 g of water glassCcontaining 30 wt.% of S1O2) commercially available.
<60> Comparative Exam le 1
<6 i> For more definite description on the characteristics of the examples of the present invention, a conventional photocatalyst is used as a comparative example in comparison to the examples of the present invention.
<62> The comparative example was P-25 powder supplied by EV0NIK Industries, which is a titanium dioxide(Ti02) powder not coated with silica aerogel.
<63> <64> Table 1 shows a comparison in composition between Example 1 of the present invention and Comparative Example. The content of each ingredient was analyzed with an EDX (Energy Dispersive X-ray Spectroscope(EX-250 supplied by Horiba).
<65> [Table 1]
Figure imgf000012_0001
<67> FIGS. 2a and 2b present pictures of Example 1 of the present invention as taken with SEM( Scanning Electron Microscope, Hitachi S-4700) and TEM (Transmission Electron Microscope, JEM 2000 FXII, JE0L). Referring to FIG. 2a, the porous photocatalyst powder consists of 10~30nm-diameter particles combining together, as shown in (a); and when magnified 1,500,000 times, the particles look like gather together to form pores about 10 to 50 nm in diameter, which form a large pore, as shown in (b).
<68>
<69> Analysis of Crystal Phase and Thermal Stability
<70> For comparison of crystal phase, the composites of Example 4 and
Comparative Example 1 were analyzed using X-ray diffraction pattern(XRD) . The analytical results are presented in FIG. 3. A heat treatment in the oxygen atmosphere at 200 to 1,000 °C was also conducted to analyze the thermal stabi 1 ity.
<7i> The XRD pattern for Comparative Example 1 had large and narrow peaks of anatase, whereas the XRD pattern for Example 4 exhibited small and broad peaks of anatase. This showed that the titanium dioxide particles of the present invention were smaller than those of Comparative Example 1. It is well known that the conventional titanium dioxide upon a plastic working at 800 °C converts its crystalline structure from anatase to rutile. However, the present invention exhibited only peaks of anatase even after heat treatment up to 800 °C , showing that the present invention consisting of titanium dioxide coated with silica aerogel had a high porosity and hence good thermal stability.
<72>
<73> Photocatalytic Activity 1
<74> Prior to measurement of photocatalytic activity, Examples 1 to 4 of the present invention and Comparative Example 1 were measured in regard to
2
specific surface area(m /g) and average pore size(nm). The results are presented in Table 2.
<75> [Table 2]
Figure imgf000013_0001
<77> As can bee seen from Table 2, Comparative Example 1 had a considerably
2
small specific surface area of 55 m /g, whereas Examples 1 to 4 of the present invention had a specific surface area about 3 to 8 times as large as Comparative Example 1. Further, the specific surface area decreased as the added amount of titanium dioxide increased in the order from Example 1 to Example 4. As for average pore size, it is well known that Comparative Example 1 has no pores in the particles but 8 nm-diameter gaps between the particles. But, Examples 1 to 4 of the present invention had a constant pore size of 4 nm regardless of the change in the added amount of titanium dioxide.
<78> For a comparison in the effect pertaining to specific surface area and pore size, Comparative Example 1 and Example 1 of the present invention were measured in regard to the adsorbed amount of nitrogen based on the atmospheric pressure. The results are presented in FIG. 4. As can be seen from the graph of FIG. 4, Comparative Example 1 had an adsorbed amount of nitrogen abruptly increasing with an increase in the atmospheric pressure from the point, of P/Po about 0.8 or above and showed a maximum absorbed amount
3
of nitrogen no more than about 300 m /g. In contrast, Example 1 of the present invention had an absorbed amount of nitrogen increasing with an increase in
3
the atmospheric pressure and approaching to about 600 m /g in maximum. The reason of this result is that the present invention in which titanium dioxide was coated with silica aerogel to form a porous silica coating had a higher photocatalyt ic activity and adsorbed more nitrogen because it was 6 times as large as Comparative Example 1 in specific surface area and only a half in average pore diameter.
<79>
<80> Photocatalyt ic Activity 2
<8 i> An experiment was conducted to measure the acetaldehyde degrading activity of the composites as a photocatalyt ic activity.
<82> 0.5 g of each composite of Examples 1 to 4 of the present invention and
Comparative Example 1 was added as a catalyst in a 2 L reactor, and 2,000 ppm of acetaldehyde was then added for equilibrium adsorption. After 2-hour irradiation with UV lamps(10W x 3 eaXSankyodenki ) , a comparative analysis was conducted using a gas chromatograph system(HP 6890) and an FI detector. The results are presented in FIG. 5.
<83> As can be seen from FIG. 5, Comparative Example 1 had an acetaldehyde degrading activity initially low and increased with an elapse of time to achieve a degrading performance of about 98 % after two hours. As for the present invention, all the examples of the present invention but Example 4 had an initial activity considerably high as about 70%, and all had an increase in the activity with an elapse of 2 hours up to 96%, 92%, 88% and 85% respectively in the order of Example 1, Example 2, Example 3, and Example 4.
<84> According to Table 1, Comparative Example 1 contained 32.0 wt.% of Ti with respect to the total weight of the composition, considerably high in Ti content relative to Examples 1 to 4 of the present invention. Thus, as indicated in terms of the content of titanium dioxide per unit weight(g) of the composition, FIG. 6 shows that Example 1 had a higher initial activity and an average photocatalyt ic activity about 5 times higher than that of Comparative Example 1.
<85>
<86> Thermal Insulation Performance
<87> A general industrial insulating material was coated with the porous composite prepared in Example 1 of the present invention to fabricate a novel insulating material. The novel insulating material and the general insulating material were heated with a hot air gun at 300 °C for one minute, and the change of temperature in the back side was measure for each insulating material .
<88> As shown in FIG. 6, the insulating material using the porous composite powder of the present invention as a photocatalyst had a surface temperature of 36 °C with almost no change of temperature, whereas the general insulating material had a surface temperature of 237 °C , showing a considerably poor thermal insulation relative to the present invention. The reason of this result is that the porous composite of the present invention had titanium dioxide coated with silica aerogel to form a porous silica coating which provided high thermal stability.
<89>
<90> Evaluation of Porous Composite in Effect of Removing Harmful Substance
<9i> An evaluation system(FIG. 7) for nitrogen oxide removal testing according to S L ISO 22197-1 was used to measure the performance of the porous composite according to one embodiment of the present invention in removing nitrogen oxides(N0x) considered as harmful substances.
<92> For the porous compos ite(Example 1) according to one example of the present invention and Comparative Example 1, the change of nitrogen oxide concentration was measured by blocking light for 0.5 hour, UV-irradiating for 6 hours and then blocking light for 0.5 hour. The experimental results are presented in Table
[Table 3]
Figure imgf000016_0001
<96> The measurement results for Example 1 and Comparative Example 1 in regard to the performance of removing nitrogen oxides are presented in FIGS. 8 and 9. As can be seen from Table 3 and FIG. 8, the powder of Comparative Example 1 which was a general compound with a photocatalyt ic activity showed a decrease in NO concentration by no more than 40% and a decrease in N0X concentration by about 10% upon UV irradiation. Contrarily, the powder of Example 1 which was a porous composite with a photocatalyt ic activity had a dramatic decrease in NO concentration by 50% or below and a decrease in N0X concentration by about 20% upon UV irradiation. The reason of this result is that the porous composite according to one example of the present invention had a three-dimensional net structure of a silica aerogel coating to secure a large specific surface area and a high photocatalyt ic activity. Accordingly, the porous composite of the present invention was excellent in the effect of removing nitrogen oxides.
<97>
<98> Cement composition Containing Porous Composite
<99> Hereinafter, a description will be given as to a process for preparing a cement composition containing the porous composite according to one example of the present invention.
<ioo> According to KS L ISO 679(testing method for strength of cement), 3 wt. of the porous composite with respect to the total weight of the cement composition was mixed with a standard mortar to prepare a cement composition having a photocatalyt ic activity. The cement composition was poured in a
3
mold(50 x 100 x 10 mm ) and cured in a constant temperature and humidity chamber under conditions of 20 °C and 65% in relative humidity for one day.
After released from the mold, the cement composition was cured for more 28 days to form a final cement composition containing the porous composite according to one example of the present invention.
<101>
<i02> Evaluation of Cement Composition in Effect of Removing Harmful Substance
<i03> An evaluation system(FIG. 7) for nitrogen oxide removal testing according to KS L ISO 22197-1 was used to measure the performance of the cement composition according to one embodiment of the present invention in removing nitrogen oxides(N0x) considered as harmful substances.
<104> For the testing, the cement composition containing, with respect to the total weight of the composition, 3 wt.% of the porous composite which includes titanium dioxide and silica at a weight ratio of 0.2 according to one example of the present invention was prepared in accordance with the above-described preparation process. Then, the change of nitrogen oxide concentration was measured by blocking light for 0.5 hour, UV-irradiat ing for 2 hours, blocking light for 2 hours, UV-irradiat ing for 2 hours, and then blocking light for 0.5 hour.
<i05> The experimental results are presented in Table 4.
<i06> [Table 4]
Figure imgf000017_0001
<108> The measurement results for the cement composition containing the porous composite in regard to the performance of removing nitrogen oxides are presented in FIG. 10. As can be seen from Table 4 and FIG. 10, the use of the porous composite in the cement composition could reduce the NO concentration by about 12% and the N0X concentration by about 3% upon UV irradiation. In conclusion, using a smallest amount of the porous composite which had a high photocatalytic activity due to a coating of silica aerogel in a cement composition provided a high efficiency of removing harmful substances.

Claims

[CLAIMS]
[Claim 1]
<iio> A method for preparing a porous composite comprising:
<iii> (a) mixing a metal oxide with at least one of water lass(Na2Si03) , potassium silicate, calcium silicate, and silica sol to prepare a sol type mixture of the metal oxide!
<ii2> (b) gelating the mixture of the metal oxide to form a metal oxide gel;
<ii3> (c) surface-modifying the metal oxide gel;
<ii4> (d) drying the metal oxide gel to form a porous composite having a coating of silica aerogel around the metal oxide! and
<ii5> (e) conducting a plastic working on the porous composite.
[Claim 2]
<ii6> The method as claimed in claim 1, wherein the porous composite formed in the step (d) has a three-dimensional net structure.
[Claim 3]
<ii7> The method as claimed in claim 1, wherein the metal oxide is an oxide compound having a photocatalyt ic activity.
[Claim 4]
<ii8> The method as claimed in claim 3, wherein the metal oxide is titanium dioxide (Ti02).
[Claim 5]
<ii9> The method as claimed in claim 1, wherein in the step (a), the metal oxide is mixed with any one of water glass, potassium silicate, calcium silicate, and silica sol to have a weight ratio of the metal oxide to the silica contained in any one of water glass, potassium silicate, calcium silicate, and silica sol in the range of 0.01— 10 : 1.
[Claim 6]
<120> The method as claimed in claim 1, further comprising:
<i2i> treating the metal oxide of the step (a) with a modifier.
[Claim 7]
<i22> The method as claimed in claim 1, wherein in the step (b), the metal oxide gel is formed by adding an acid solution having an acidity of pH 1— 10 to the mixture of the metal oxide for gelation.
[Claim 8]
<123> The method as claimed in claim 1, wherein the surface modification of the step (c) is conducted by adding an organo-functional si lane to the metal oxide gel in an organic solvent.
[Claim 9]
<124> The method as claimed in claim 8, wherein the organo-functional si lane is selected from the group consisting of trimethyl chlorosi lane, hexamethyl disilazane, methyl trimethoxy si lane, and trimethyl ethoxy si lane.
[Claim 10]
<125> The method as claimed in claim 1, wherein the step (d) of drying the metal oxide gel is conducted at 60— 200 °C .
[Claim 11]
<126> The method as claimed in claim 1, further comprising:
<i27> in the step (e), controlling the temperature of the plastic working to adjust the hydrophi 1 icity and hydrophobicity of the porous composite.
[Claim 12]
<128> The method as claimed in claim 11, wherein the porous composition has hydrophobicity.
[Claim 13]
<i29> A porous composite prepared by the method as claimed in any one of the claims 1 to 12.
[Claim 14]
<130> The porous composite as claimed in claim 13, wherein the porous composite has a porosity of 80— 99 .
[Claim 15]
<i3i> The porous composite as claimed in claim 13, wherein the porous
2
composite has a specific surface area of 300— 1,000 m /g.
[Claim 16]
<132> A cement composition, which contains a porous composite, wherein the porous composite is the porous composite as claimed in claim 13.
[Claim 17] <133> The cement composition as claimed in claim 16, wherein the porous composite is contained in an amount of 0.1 to 10 wt.% with respect to the total weight of the cement composition.
[Claim 18]
<i34> The cement composition as claimed in claim 16, wherein the porous composite has surface hydrophobicity.
[Claim 19]
<i35> A cement structure, which is fabricated using a cement composition containing a porous composite, wherein the porous composite is the porous composite as claimed in claim 13.
[Claim 20]
<136> An interlocking block, which is fabricated using a cement composition containing a porous composite, wherein the porous composite is the porous composite as claimed in claim 13.
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