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US20020175118A1 - Water purification filter - Google Patents

Water purification filter Download PDF

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Publication number
US20020175118A1
US20020175118A1 US10/154,771 US15477102A US2002175118A1 US 20020175118 A1 US20020175118 A1 US 20020175118A1 US 15477102 A US15477102 A US 15477102A US 2002175118 A1 US2002175118 A1 US 2002175118A1
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United States
Prior art keywords
ceramics
water purification
purification filter
fine powder
crb
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US10/154,771
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Kazuo Hokkirigawa
Motoharu Akiyama
Noriyuki Yoshimura
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Minebea Co Ltd
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Individual
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Assigned to MINEBEA CO., LTD. reassignment MINEBEA CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YOSHIMURA, NORIYUKI, AKIYAMA, MOTOHARU, HOKKIRIGAWA, KAZUO
Publication of US20020175118A1 publication Critical patent/US20020175118A1/en
Priority to US10/793,258 priority Critical patent/US6821433B2/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid 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 form
    • B01J20/28042Shaped bodies; Monolithic structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/16Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/20Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2055Carbonaceous material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/20Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2055Carbonaceous material
    • B01D39/2058Carbonaceous material the material being particulate
    • B01D39/2062Bonded, e.g. activated carbon blocks
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/20Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068Other inorganic materials, e.g. ceramics
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • B01J20/18Synthetic zeolitic molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/28026Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
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    • B01J20/28014Solid 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 form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid 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 form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28035Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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
    • B01J20/28069Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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
    • B01J20/28069Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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
    • B01J20/28069Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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
    • B01J20/28078Pore diameter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/0241Types of fibres, filaments or particles, self-supporting or supported materials comprising electrically conductive fibres or particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0407Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604Arrangement of the fibres in the filtering material
    • B01D2239/0618Non-woven
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/065More than one layer present in the filtering material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D2239/12Special parameters characterising the filtering material
    • B01D2239/1208Porosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/286Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/288Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered

Definitions

  • This invention relates to a water purification filter used for filtering water, especially for filtering tap water, industrial water, river water, waste
  • Conventional water purification filters comprise polyolefin or polyester fabric or felt, or dry or wet non-woven fabric or felt, span-bond non-woven fabric or felt, equivalents. and active carbon materials or zeolite supported between such fabric or non-woven fabric or felt.
  • Japanese Patent Nos.A-H07-26,460, A-H0 8-24,535 and A-H07-207,566 describe a filter material which is relatively cheap and makes it possible to reduce the critical particle diameter of filtration by laminating and gluing melt-blow non-woven fabric or felt and span-bond non-woven fabric or felt.
  • a water purification filter itself can be formed by simply applying RB ceramics and/or CRB ceramics as a moldable carbon material, thereby the present invention being developed.
  • Further object of the present invention is to provide a water purification filter in which a fine powder of RB ceramics and/or CRB ceramics is supported on non-woven fabric or felt.
  • RB ceramics and/or CRB ceramics of 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm 3 /g in pore volume is used as a filter material of water purification filter.
  • FIG. 1 a is an illustration of a relatively large pore of CRB ceramics
  • FIG. 1 b is an illustration of pores of CRB ceramics caused by rice bran
  • FIG. 1 c is an illustration of pores of CRB ceramics caused by polymer chain
  • FIG. 2 is a perspective view of a disk-form water purification filter of the present invention
  • FIG. 3 is a perspective view of a cylindrical water purification filter of the present invention.
  • FIG. 4 is a sectional view of a cylindrical water purification filter of the present invention in which non-woven fabric or felt is used.
  • a RB ceramics and/or CRB ceramics material applied to a water purification filter of the present invention is prepared from a defatted product of rice bran as a main raw material and a thermosetting resin.
  • the above mentioned literature describes a carbon material or so-called RB ceramics by mixing and kneading a defatted product of rice bran and a thermosetting resin, press-molding the mixture to form a molded material, followed by drying and then baking the dried material in an atmosphere of inert gas.
  • Defatted rice bran used in the present invention is not limited to a specific species of rice and may either be a product of Japan or foreign countries.
  • thermosetting resin used herein may also be any resin which can be thermally set and typically includes phenol-, diarylphthalate-, unsaturated polyester-, epoxy-, polyimide- and triazine resins, although a phenol resin is preferably used.
  • thermoplastic resin such as polyamide may also be used together without departing from a scope of the present invention.
  • a mixing ratio of the defatted rice bran to the thermosetting resin is in the range of 50 to 90:50 to 10 and preferably 70 to 80:30 to 20 in by weight.
  • CRB ceramics used in the present invention is an improved material of RB ceramics obtained from defatted rice bran and a thermosetting resin and is prepared by mixing and kneading both of these materials and primarily baking the mixture in an inert gas at 700 to 1,000° C., followed by grinding to form a carbonated powder of about 60 mesh or less, which is then mixed and kneaded with the thermosetting resin to yield a mixture (hereinafter referred to as a CRB precursor), press-molded at a pressure of 20 to 30 Mpa and further heat-treated the thus molded material in an atmosphere of inert gas at 500 to 1,100° C. to form a molded product.
  • a CRB precursor press-molded at a pressure of 20 to 30 Mpa
  • CRB ceramics is a porous material having innumerable pores. These pores formed in CRB ceramics can be classified into three kinds of types depending on a formation process thereof.
  • a pore shown in FIG. 1( a ) is relatively large one having a pore diameter of 5 ⁇ m or more, which is formed as a space between CRB fine particles when they overlap each other.
  • a peak pore value of this type is about 15 ⁇ m.
  • FIG. 1( b ) What is shown in FIG. 1( b ) is a pore having a pore diameter of less than 5 ⁇ m which is formed by fiber structure caused by rice bran. A peak pore value of this type is about 1.8 ⁇ m.
  • a pore shown in FIG. 1( c ) is a small one having a pore diameter of 0.2 ⁇ m or less which is formed as a space between molecular chains of high molecular polymer such as a phenol resin when the polymer is carbonated at high temperatures.
  • a peak pore value of this type is about 0.05 ⁇ m.
  • the thus formed three kinds of pores of CRB ceramics function as a filter for fine particles of various size corresponding to each pore diameter, respectively.
  • RB ceramics should not be excluded from embodiments of the present invention, because it is possible to mold RB ceramics by means of a little bit larger mold, which is then reduced to a desired size through secondary processing.
  • Porosity of RB ceramics and/or CRB ceramics can be controlled by changing baking conditions, which is one of characteristic features of these materials.
  • the molded material desirably has a pore diameter of 10 to 2,000 angstrom and a pore volume of 0.1 to 1.1 cm 3 /g.
  • Porosity is an important factor of RB ceramics and/or CRB ceramics used in the present invention, which is influenced by the primary baking temperature of RB ceramics and by both of the primary baking temperature and the secondary heat-treating temperature of CRB ceramics.
  • RB ceramics or CRB ceramics of optimum porosity can be yielded by primary baking or secondary heat treatment thereof at a temperature of 800 to 1,000° C.
  • non-woven fabric or felt is a suitable material to support the powder.
  • a well-known carbon fine powder may be used together with the ceramics powder.
  • a ratio of the fine powder of RB ceramics and/or CRB ceramics to the carbon powder is desirably 50 to 90:50 to 10 by weight.
  • the fine powder of RB ceramics or CRB ceramics is hard, while its surface is quite rough, which characteristically increases maintaining properties thereof as a powdery material on a support and allows the powder to be hardly flown away by a fluid flow.
  • inorganic materials such as glass wool and asbestos, synthetic polymers such as polyester and polyamide and natural materials such as cellulose, hemp and cotton as a fibrous material in the present invention.
  • non-woven fabric or felt used in the present invention It is required for non-woven fabric or felt used in the present invention to have properties of average 1 to 30 ⁇ m and the maximum 80 ⁇ m or less in pore diameter and pure water filtration discharge of 3 l/m 2 ⁇ min. or more at differential pressure of 1 cm-H 2 O.
  • Non-woven fabric or felt having such properties is well-known and commercially available.
  • a water purification filter in which RB ceramics and/or CRB ceramics of 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm 3 /g in pore volume is used as an absorption and filtration material.
  • a water purification filter in which a RB ceramics fine powder and/or CRB ceramics fine powder of 1 to 500 ⁇ m in an average particle diameter, 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm 3 /g in pore volume is supported on non-woven fabric.
  • a water purification filter of the present invention can be molded into free shapes while keeping predetermined properties due to the use of RB ceramics and CRB ceramics. It has been also found a fine powder of RB ceramics and CRB ceramics exhibits suitable properties as a water purification filter.
  • a defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture.
  • the mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes.
  • the carbonated material thus baked was screened through a 300-mesh screen to form a carbonated powder of 50 to 80 ⁇ m in particle diameter.
  • the thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and then at 950° C. for about 120 minutes.
  • the molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C. to yield a molded product of CRB ceramics 1 as shown in FIG. 2.
  • the molded product of CRB ceramics 1 showed an average pore diameter of 350 angstrom and a pore volume of 0.65 cm 3 /g.
  • a defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture.
  • the mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes.
  • the carbonated material thus baked was screened through a 200-mesh screen to form a carbonated powder of 50 to 120 ⁇ m in particle diameter.
  • the thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and then at 1,000° C. for about 150 minutes.
  • the molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C. to yield a molded product of CRB ceramics 2 as shown in FIG. 2.
  • the molded product of CRB ceramics 1 showed an average pore diameter of 450 angstrom and a pore volume of 0.52 cm 3 /g.
  • a defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture.
  • the thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 800° C. for 120 minutes. The molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C.
  • the molded product of CRB ceramics 1 showed an average pore diameter of 500 angstrom and a pore volume of 0.51 cm 3 /g, although it shrank slightly.
  • a defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture.
  • the mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes.
  • the carbonated material thus baked was screened through a 100-mesh screen to form a carbonated powder of 50 to 250 ⁇ m in particle diameter.
  • the thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and then at 1,000° C. for about 120 minutes.
  • the molded product of CRB ceramics 1 showed an average pore diameter of 550 angstrom and a pore volume of 0.50 cm 3 /g.
  • a defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture.
  • the mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes.
  • the carbonated material thus baked was ground by means of a grinder and screened through a 100-mesh screen to form a carbonated powder of 50 to 250 ⁇ m in particle diameter.
  • the plastic mixture was then press-molded at a pressure of 20 Mpa to form a spherical body of 3 cm in diameter.
  • the mold temperature was 150° C.
  • the thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and sintering at 950° C. for about 120 minutes.
  • the molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C.
  • the sintered spherical body of 3 cm in diameter was ground by means of a grinder and further finely ground by means of a ball mill to form CRB ceramics fine particles of 5 to 10 ⁇ m in average particle diameter.
  • CRB ceramics fine particles 3 of 7 ⁇ m in average particle diameter were kept between nylon 6 non-woven fabric 4 having properties of 5 ⁇ m in average particle diameter, 18 ⁇ m in maximum particle diameter, 6 cm 3 /cm 2 -second of gas permeability and 31 l/cm 2 -minute-cm-H 2 O of filtration discharge rate and sealed top and bottom ends thereof with an adhesive 5.
  • the CRB ceramics fine particles 3 showed an average particle diameter of 7 ⁇ m and a pore volume of 0.58 cm 3 /g.

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Abstract

There is provided a water purification filter capable of molding into free shapes in which RB ceramics and/or CRB ceramics of 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm3/g in pore volume is used as an absorption and filtration material.

Description

    FIELD OF THE INVENTION
  • This invention relates to a water purification filter used for filtering water, especially for filtering tap water, industrial water, river water, waste [0001]
  • BACKGROUND OF THE INVENTION
  • Conventional water purification filters comprise polyolefin or polyester fabric or felt, or dry or wet non-woven fabric or felt, span-bond non-woven fabric or felt, equivalents. and active carbon materials or zeolite supported between such fabric or non-woven fabric or felt. [0002]
  • For example, Japanese Patent Nos.A-H07-26,460, A-H0 8-24,535 and A-H07-207,566 describe a filter material which is relatively cheap and makes it possible to reduce the critical particle diameter of filtration by laminating and gluing melt-blow non-woven fabric or felt and span-bond non-woven fabric or felt. [0003]
  • In any case of conventional water purification filters, it is necessary to form non-woven fabric or felt into a specific shape and support zeolite or active carbon thereon. [0004]
  • The inventors have found that a water purification filter itself can be formed by simply applying RB ceramics and/or CRB ceramics as a moldable carbon material, thereby the present invention being developed. [0005]
  • SUMMARY OF THE INVENTION
  • Accordingly, it is an object of the present invention to provide a water purification filter which is directly molded from RB ceramics and/or CRB ceramics. [0006]
  • Further object of the present invention is to provide a water purification filter in which a fine powder of RB ceramics and/or CRB ceramics is supported on non-woven fabric or felt. [0007]
  • According to the present invention, RB ceramics and/or CRB ceramics of 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm[0008] 3/g in pore volume is used as a filter material of water purification filter.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1[0009] a is an illustration of a relatively large pore of CRB ceramics;
  • FIG. 1[0010] b is an illustration of pores of CRB ceramics caused by rice bran;
  • FIG. 1[0011] c is an illustration of pores of CRB ceramics caused by polymer chain;
  • FIG. 2 is a perspective view of a disk-form water purification filter of the present invention; [0012]
  • FIG. 3 is a perspective view of a cylindrical water purification filter of the present invention; and [0013]
  • FIG. 4 is a sectional view of a cylindrical water purification filter of the present invention in which non-woven fabric or felt is used.[0014]
  • PREFERRED EMBODIMENTS OF THE INVENTION
  • A RB ceramics and/or CRB ceramics material applied to a water purification filter of the present invention is prepared from a defatted product of rice bran as a main raw material and a thermosetting resin. [0015]
  • As is known that Dr. Kazuo Hokkirigawa, the first inventor of the present invention, proposed an idea to obtain a porous carbon material by the use of rice bran which is by-produced 0.9 million ton/year in Japan or 3.3 million ton/year in the world (see, Kinou Zairyou, Vol. 17, No. 5, pp. 24 to 28, May 1997). [0016]
  • The above mentioned literature describes a carbon material or so-called RB ceramics by mixing and kneading a defatted product of rice bran and a thermosetting resin, press-molding the mixture to form a molded material, followed by drying and then baking the dried material in an atmosphere of inert gas. [0017]
  • Defatted rice bran used in the present invention is not limited to a specific species of rice and may either be a product of Japan or foreign countries. [0018]
  • A thermosetting resin used herein may also be any resin which can be thermally set and typically includes phenol-, diarylphthalate-, unsaturated polyester-, epoxy-, polyimide- and triazine resins, although a phenol resin is preferably used. [0019]
  • A thermoplastic resin such as polyamide may also be used together without departing from a scope of the present invention. [0020]
  • A mixing ratio of the defatted rice bran to the thermosetting resin is in the range of 50 to 90:50 to 10 and preferably 70 to 80:30 to 20 in by weight. [0021]
  • According to the above mentioned method, difference in ratio of shrinkage between the press-molded material and the finally molded material which is baked in an atmosphere of inert gas reached almost 25%. Such a difference made it substantially difficult to form a precisely molded material, but has been finally improved as a result of development of CRB ceramics. [0022]
  • CRB ceramics used in the present invention is an improved material of RB ceramics obtained from defatted rice bran and a thermosetting resin and is prepared by mixing and kneading both of these materials and primarily baking the mixture in an inert gas at 700 to 1,000° C., followed by grinding to form a carbonated powder of about 60 mesh or less, which is then mixed and kneaded with the thermosetting resin to yield a mixture (hereinafter referred to as a CRB precursor), press-molded at a pressure of 20 to 30 Mpa and further heat-treated the thus molded material in an atmosphere of inert gas at 500 to 1,100° C. to form a molded product. [0023]
  • CRB ceramics is a porous material having innumerable pores. These pores formed in CRB ceramics can be classified into three kinds of types depending on a formation process thereof. [0024]
  • A pore shown in FIG. 1([0025] a) is relatively large one having a pore diameter of 5 μm or more, which is formed as a space between CRB fine particles when they overlap each other. A peak pore value of this type is about 15 μm.
  • What is shown in FIG. 1([0026] b) is a pore having a pore diameter of less than 5 μm which is formed by fiber structure caused by rice bran. A peak pore value of this type is about 1.8 μm.
  • A pore shown in FIG. 1([0027] c) is a small one having a pore diameter of 0.2 μm or less which is formed as a space between molecular chains of high molecular polymer such as a phenol resin when the polymer is carbonated at high temperatures. A peak pore value of this type is about 0.05 μm.
  • The thus formed three kinds of pores of CRB ceramics function as a filter for fine particles of various size corresponding to each pore diameter, respectively. [0028]
  • The most typical distinction of RB ceramics and CRB ceramics is that a difference in ratio of shrinkage between molded RB ceramics and a final product thereof is almost 25%, while that of CRB ceramics is so low as 3% or less, which makes the latter material much useful. [0029]
  • General properties of RB ceramics and CRB ceramics are as in the following: [0030]
  • extremely high hardness; [0031]
  • extremely small heat expansion coefficient; [0032]
  • porous structure; [0033]
  • electrical conductivity; [0034]
  • low specific gravity, light weighted; [0035]
  • improved abrasion resistance; [0036]
  • easiness of molding and mold making; [0037]
  • capable of being powdered; and [0038]
  • less negative effect to global environment and more resource conservation due to rice bran to be used as a starting material. [0039]
  • When a water purification filter is prepared directly from RB ceramics and/or CRB ceramics as a molded material, it is desirable to use CRB ceramics because of its precise moldability. However, even in the above mentioned case, RB ceramics should not be excluded from embodiments of the present invention, because it is possible to mold RB ceramics by means of a little bit larger mold, which is then reduced to a desired size through secondary processing. [0040]
  • Porosity of RB ceramics and/or CRB ceramics can be controlled by changing baking conditions, which is one of characteristic features of these materials. [0041]
  • It is generally confirmed that such porosity is increased with an increase in heat-treating temperature. [0042]
  • When a water purification filter is prepared as a molded material directly from RB ceramics and/or CRB ceramics according to the present invention, the molded material desirably has a pore diameter of 10 to 2,000 angstrom and a pore volume of 0.1 to 1.1 cm[0043] 3/g.
  • When powdery RB ceramics is used in the present invention, it is not necessary to consider a difference in shrinkage between RB ceramics and CRB ceramics so that basically either of these materials may be used on an equal footing. Particle size of RB ceramics or CRB ceramics powder varies depending on the purpose to be used, although an average particle diameter of 1 to 500 μm is generally used. [0044]
  • Porosity is an important factor of RB ceramics and/or CRB ceramics used in the present invention, which is influenced by the primary baking temperature of RB ceramics and by both of the primary baking temperature and the secondary heat-treating temperature of CRB ceramics. [0045]
  • RB ceramics or CRB ceramics of optimum porosity can be yielded by primary baking or secondary heat treatment thereof at a temperature of 800 to 1,000° C. [0046]
  • When RB ceramics and/or CRB ceramics is used as a fine powder, non-woven fabric or felt is a suitable material to support the powder. A well-known carbon fine powder may be used together with the ceramics powder. [0047]
  • A ratio of the fine powder of RB ceramics and/or CRB ceramics to the carbon powder is desirably 50 to 90:50 to 10 by weight. [0048]
  • The fine powder of RB ceramics or CRB ceramics is hard, while its surface is quite rough, which characteristically increases maintaining properties thereof as a powdery material on a support and allows the powder to be hardly flown away by a fluid flow. [0049]
  • Further, there may be used inorganic materials such as glass wool and asbestos, synthetic polymers such as polyester and polyamide and natural materials such as cellulose, hemp and cotton as a fibrous material in the present invention. [0050]
  • It is required for non-woven fabric or felt used in the present invention to have properties of average 1 to 30 μm and the maximum 80 μm or less in pore diameter and pure water filtration discharge of 3 l/m[0051] 2·min. or more at differential pressure of 1 cm-H2O. Non-woven fabric or felt having such properties is well-known and commercially available.
  • Embodiments of the present invention will be summarised as in the following. [0052]
  • 1. A water purification filter in which RB ceramics and/or CRB ceramics of 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm[0053] 3/g in pore volume is used as an absorption and filtration material.
  • 2. A water purification filter described in the above item 1 in which RB ceramics and/or CRB ceramics is a filter molded into a cylindrical form. A water purification filter described in the [0054] above item 2 in which plural thin cylindrical filters are fitted in order while altering a diameter of each cylinder.
  • 3. A water purification filter described in the [0055] above item 3 in which a zeolite fine powder or active carbon fine powder is filled between cylinders.
  • 4. A water purification filter described in the above item 1 in which RB ceramics and/or CRB ceramics is a filter molded into a solid cylinder form. [0056]
  • 5. A water purification filter in which a RB ceramics fine powder and/or CRB ceramics fine powder of 1 to 500 μm in an average particle diameter, 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm[0057] 3/g in pore volume is supported on non-woven fabric.
  • 6. A water purification filter described in the above item 6 in which an active carbon fine powder is supported on non-woven fabric in addition to RB ceramics fine powder and/or CRB fine powder. [0058]
  • 8. A water purification filter described in the above item 6 in which a ratio of a RB ceramics fine powder and/or CRB ceramics fine powder to a well-known active carbon fine powder is 50 to 90:50 to 10 by weight. [0059]
  • 9. A water purification filter described in either one of the aboveitems 6 to 8 in which non-woven fabric has properties of average 1 to 30 μm and the maximum 80 μm or less in pore diameter and pure water filtration discharge of 3 l/m[0060] 2·min.or more at differential pressure of 1 cm-H2O.
  • It has been found that a water purification filter of the present invention can be molded into free shapes while keeping predetermined properties due to the use of RB ceramics and CRB ceramics. It has been also found a fine powder of RB ceramics and CRB ceramics exhibits suitable properties as a water purification filter. [0061]
  • This invention will be further described in the following examples. [0062]
  • EXAMPLE 1
  • Preparation of CRB Ceramics Precursor [0063]
  • A defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture. [0064]
  • The mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes. The carbonated material thus baked was screened through a 300-mesh screen to form a carbonated powder of 50 to 80 μm in particle diameter. [0065]
  • The carbonated powder thus obtained in an amount of 75 kg and a solid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 100 to 150° C. to form a plastic and homogeneous mixture as a plastic CRB ceramics precursor. [0066]
  • Molding of a Water Purification Filter [0067]
  • Then, there was made a mold for molding a disk [0068] 1 of 20.0 cm in diameter and 1.5 cm in thickness as shown in FIG. 2, to which the plastic CRB ceramics precursor was pored and press-molded at a pressure of 22 Mpa. The mold temperature was 150° C.
  • The thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and then at 950° C. for about 120 minutes. [0069]
  • The molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C. to yield a molded product of CRB ceramics 1 as shown in FIG. 2. [0070]
  • Properties of the Water Purification Filter [0071]
  • The molded product of CRB ceramics [0072] 1 showed an average pore diameter of 350 angstrom and a pore volume of 0.65 cm3/g.
  • EXAMPLE 2
  • Preparation of CRB Ceramics Precursor [0073]
  • A defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture. [0074]
  • The mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes. The carbonated material thus baked was screened through a 200-mesh screen to form a carbonated powder of 50 to 120 μm in particle diameter. [0075]
  • The carbonated powder thus obtained in an amount of 75 kg and a solid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 100 to 150° C. to form a plastic and homogeneous mixture as a plastic CRB ceramics precursor. [0076]
  • Molding of a Water Purification Filter [0077]
  • Then, there was made a mold for molding a disk [0078] 1 of 20.0 cm in diameter and 1.5 cm in thickness as shown in FIG. 2, to which the plastic CRB ceramics precursor was pored and press-molded at a pressure of 25 Mpa. The mold temperature was 150° C.
  • The thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and then at 1,000° C. for about 150 minutes. [0079]
  • The molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C. to yield a molded product of [0080] CRB ceramics 2 as shown in FIG. 2.
  • Properties of the Water Purification Filter [0081]
  • The molded product of CRB ceramics [0082] 1 showed an average pore diameter of 450 angstrom and a pore volume of 0.52 cm3/g.
  • EXAMPLE 3
  • Preparation of RB Ceramics Precursor [0083]
  • A defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture. [0084]
  • Molding of a Water Purification Filter [0085]
  • Then, there was made a mold for molding a disk [0086] 1 of 20.0 cm in diameter and 1.5 cm in thickness as shown in FIG. 2 similarly as Example 1, to which the plastic CRB ceramics precursor was pored and press-molded at a pressure of 22 Mpa. The mold temperature was 170° C.
  • The thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 800° C. for 120 minutes. The molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C. [0087]
  • Properties of the Water Purification Filter [0088]
  • The molded product of CRB ceramics [0089] 1 showed an average pore diameter of 500 angstrom and a pore volume of 0.51 cm3/g, although it shrank slightly.
  • EXAMPLE 4
  • Preparation of CRB Ceramics Precursor [0090]
  • A defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture. [0091]
  • The mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes. The carbonated material thus baked was screened through a 100-mesh screen to form a carbonated powder of 50 to 250 μm in particle diameter. [0092]
  • The carbonated powder thus obtained in an amount of 78 kg and a solid phenol resin (resol) in an amount of 22 kg were mixed and kneaded by heating at 100 to 150° C. to form a plastic and homogeneous mixture as a plastic CRB ceramics precursor. [0093]
  • Molding of a Water Purification Filter [0094]
  • Then, there was made a mold for molding a [0095] cylinder 3 of 15 cm in outer diameter, 14.0 cm in inner diameter and 30 cm in length as shown in FIG. 3, to which the plastic CRB ceramics precursor was pored and press-molded at a pressure of 22 Mpa. The mold temperature was 150° C.
  • The thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and then at 1,000° C. for about 120 minutes. [0096]
  • The molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C. to yield a molded product of [0097] CRB ceramics 2 as shown in FIG. 3.
  • Properties of the Water Purification Filter [0098]
  • The molded product of CRB ceramics 1 showed an average pore diameter of 550 angstrom and a pore volume of 0.50 cm[0099] 3/g.
  • EXAMPLE 5
  • Preparation of CRB Ceramics Precursor [0100]
  • A defatted product of rice bran in an amount of 75 kg and a liquid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 50 to 60° C. to form a plastic and homogeneous mixture. [0101]
  • The mixture was primarily baked by means of a rotary kiln in a nitrogen atmosphere at 900° C. for 60 minutes. The carbonated material thus baked was ground by means of a grinder and screened through a 100-mesh screen to form a carbonated powder of 50 to 250 μm in particle diameter. [0102]
  • The carbonated powder thus obtained in an amount of 75 kg and a solid phenol resin (resol) in an amount of 25 kg were mixed and kneaded by heating at 100 to 150° C. to form a plastic and homogeneous mixture. [0103]
  • Preparation of a Fine Powder [0104]
  • The plastic mixture was then press-molded at a pressure of 20 Mpa to form a spherical body of 3 cm in diameter. The mold temperature was 150° C. [0105]
  • The thus molded body was taken out of the mold die and subjected to a heat treatment by heating-up to 500° C. in a nitrogen atmosphere at a heat rising rate of 1° C. per minute and keeping at 500° C. for 60 minutes and sintering at 950° C. for about 120 minutes. [0106]
  • The molded body was then cooled at a cool down rate of 2 to 3° C. per minute down to 500° C., followed by natural heat dissipation under 500° C. [0107]
  • The sintered spherical body of 3 cm in diameter was ground by means of a grinder and further finely ground by means of a ball mill to form CRB ceramics fine particles of 5 to 10 μm in average particle diameter. [0108]
  • Preparation of a Water Purification Filter [0109]
  • As shown in FIG. 4, CRB ceramics [0110] fine particles 3 of 7 μm in average particle diameter were kept between nylon 6 non-woven fabric 4 having properties of 5 μm in average particle diameter, 18 μm in maximum particle diameter, 6 cm3/cm2-second of gas permeability and 31 l/cm2-minute-cm-H2O of filtration discharge rate and sealed top and bottom ends thereof with an adhesive 5.
  • Properties of the Water Purification Filter [0111]
  • The CRB ceramics [0112] fine particles 3 showed an average particle diameter of 7 μm and a pore volume of 0.58 cm3/g.

Claims (9)

What is claimed is:
1. A water purification filter in which RB ceramics and/or CRB ceramics of 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm3/g in pore volume is used as an absorption and filtration material.
2. A water purification filter claimed in claim 1 in which RB ceramics and/or CRB ceramics is a filter molded into a cylindrical form.
3. A water purification filter claimed in claim 2 in which plural thin cylindrical filters are fitted in order while altering a diameter of each cylinder.
4. A water purification filter claimed in claim 3 in which a zeolite fine powder or active carbon fine powder is filled between cylinders.
5. A water purification filter claimed in claim 1 in which RB ceramics and/or CRB ceramics is a filter molded into a solid cylinder form.
6. A water purification filter in which a RB ceramics fine powder and/or CRB ceramics fine powder of 1 to 500 μm in an average particle diameter, 10 to 2,000 angstrom in pore diameter and 0.1 to 1.1 cm3/g in pore volume is supported on non-woven fabric or felt.
7. A water purification filter claimed in claim 6 in which an active carbon fine powder is supported on non-woven fabric or felt in addition to RB ceramics fine powder and/or CRB fine powder.
8. A water purification filter claimed in claim 7 in which a ratio of a RB ceramics fine powder and/or CRB ceramics fine powder to a well-known active carbon fine powder is 50 to 90:50 to 10 by weight.
9. A water purification filter described in either one of claims 6 to 8 in which non-woven fabric or felt has properties of average 1 to 30 μm and the maximum 80 μm or less in pore diameter and pure water filtration discharge of 3 l/m2·min. or more at differential pressure of 1 cm-H2O.
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US7140778B2 (en) 2002-03-01 2006-11-28 Minebea Co., Ltd. Synthetic resin composites and bearings formed therefrom and method
US20030220421A1 (en) * 2002-03-01 2003-11-27 Minebea, Co., Ltd. Low noise synthetic resin composition and method
US20030229161A1 (en) * 2002-03-01 2003-12-11 Minebea, Co., Ltd. Low-friction, high-dispersion synthetic resin compositon containing fine particles of RB ceramic or CRB ceramic and a method for its preparation
US20030179963A1 (en) * 2002-03-01 2003-09-25 Minebea Co., Ltd. Low friction sleeve bearing
US7144932B2 (en) * 2002-03-01 2006-12-05 Minebea Co., Ltd. Low-friction, high-dispersion synthetic resin composition containing fine particles of RB ceramic or CRB ceramic and a method for its preparation
US20030210995A1 (en) * 2002-03-13 2003-11-13 Minebea Co., Ltd. Electrically motorized pump for use in water
US20040031642A1 (en) * 2002-06-05 2004-02-19 Kazuo Hokkirigawa Air purifying sound insulating wall and its applications
US6887288B2 (en) 2002-06-05 2005-05-03 Minebea Co., Ltd. Superfinishing grindstone
US20040132881A1 (en) * 2003-01-07 2004-07-08 Minebea Co., Ltd. Oil repelling agent
US7160622B2 (en) 2003-01-07 2007-01-09 Minebea Co., Ltd. Oil repelling agent
US20040258334A1 (en) * 2003-02-28 2004-12-23 Minebea Co., Ltd. Underwater sleeve bearing and application thereof
US7008196B2 (en) 2003-03-11 2006-03-07 Minebea Co. Ltd. Electrically motorized pump having a submersible sleeve bearing
CN101947050A (en) * 2010-08-03 2011-01-19 黄志发 Ceramic water purifying water fountain

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JP2002346321A (en) 2002-12-03
US20040168984A1 (en) 2004-09-02
AU4437902A (en) 2002-11-28
US6821433B2 (en) 2004-11-23

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