WO2019027047A1 - Élément d'adsorption et procédé de fabrication - Google Patents

Élément d'adsorption et procédé de fabrication Download PDF

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Publication number
WO2019027047A1
WO2019027047A1 PCT/JP2018/029284 JP2018029284W WO2019027047A1 WO 2019027047 A1 WO2019027047 A1 WO 2019027047A1 JP 2018029284 W JP2018029284 W JP 2018029284W WO 2019027047 A1 WO2019027047 A1 WO 2019027047A1
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Prior art keywords
adsorption member
alumina
pore diameter
volume
metal oxide
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PCT/JP2018/029284
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English (en)
Japanese (ja)
Inventor
石澤　俊崇
佐伯　智則
未映子 菓子
敬子 中野
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日立金属株式会社
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Priority to JP2018562146A priority Critical patent/JP6579281B2/ja
Publication of WO2019027047A1 publication Critical patent/WO2019027047A1/fr

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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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
    • 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

Definitions

  • the present invention relates to a water treatment adsorptive member used to adsorb and remove contaminants.
  • Solution processing systems which remove unnecessary components from the solution to make the solution more suitable for the purpose.
  • a water treatment system that treats water in particular is widely used.
  • the water treatment system uses a separation membrane (reverse osmosis membrane etc.) for removing the substance to be separated from the raw water (water to be treated), but if fouling (clogging) occurs in the separation membrane, the substance to be separated is The separation performance to remove water from raw water is reduced.
  • a separation membrane reverse osmosis membrane etc.
  • a membrane clogging substance (foreign substance) causing deterioration of the performance of the separation membrane is adsorbed beforehand to the adsorption member provided in the previous stage of the separation membrane to selectively select from raw water
  • Methods for removal are known.
  • the main membrane clogging substances include dissolved organic matter.
  • polysaccharides are particularly viscous and easily clog the separation membrane, and therefore, are required to be removed in advance.
  • Unexamined-Japanese-Patent No. 2012-91151 is provided with the outer wall, the several flow path provided inside the said outer wall, and the partition which separates the said several flow path, The said partition connects the communication which connects the said adjacent flow path.
  • An adsorption structure having pores and adsorbing an organic substance in the water to be treated is disclosed, wherein the partition wall is made of alumina or a composite oxide containing alumina, and the surface of the partition wall or the communication hole surface within the partition wall Disclosed is a configuration in which a coating containing alumina is formed.
  • Japanese Patent Laid-Open No. 2012-91151 describes that dissolved organic matter in treated water can be adsorbed and removed by forming a part of the partition with alumina.
  • JP-A-2016-198742 includes an outer wall, a plurality of flow channels provided inside the outer wall, and a partition separating each of the plurality of flow channels from each other, and the partition is disposed between adjacent flow channels.
  • suction structure which has several communicating holes to make it connect and which consists of a porous ceramic honeycomb structure by which the at least surface of the said partition was formed with the alumina is disclosed. According to JP-A-2016-198742, even if alumina is formed on a partition made of ceramic such as cordierite as the adsorption structure, the entire partition is formed of alumina. Also stated that it is good.
  • JP-A-2016-198742 sucks and supplies a slurry containing alumina into the inside of the ceramic porous body made of cordierite and then dries it.
  • the method of baking is described.
  • an adsorption structure in which alumina is formed on a ceramic such as cordierite described in JP-A-2012-91151 and JP-A-2016-19872 is an alumina particle when alumina is coated on cordierite by firing.
  • fine pores may not be easily formed, or the specific surface area may be significantly reduced by firing, so that the function as an adsorbent may not work sufficiently.
  • fine pores can not be easily formed, and therefore the adsorption capacity can not be sufficiently enhanced.
  • WO 2015/199017 is an adsorptive member having an outer wall and a flow path provided inside the outer wall, into which treated water containing a hydrophilic substance and a hydrophobic substance is introduced,
  • the flow path has an adsorbing portion having a member that adsorbs the hydrophilic substance and a member that adsorbs the hydrophobic substance, and the member that adsorbs the hydrophilic substance or a member that adsorbs the hydrophobic substance
  • the surface of hydrophilic and hydrophobic particles is coated with a binder so that the adsorption ability of the particles is not sufficiently exhibited. Therefore, it is described that it is desirable to remove the binder covering the surface beforehand, and extra work is required for use. In addition to that, by removing the binder, a part of the fine particles may be exfoliated, and the adsorption capacity of the adsorption member may be reduced.
  • the metal oxide B having the same polarity as the surface charge of the fouling substance on the particle surface of the filtration membrane layer the filtration membrane layer surface of the filter and the fouling-causing substance electrically repel each other. As a result, it has the advantage of being less likely to cause clogging and of being easily removable once it is generated.
  • an object of the present invention is to provide an adsorption member comprising a porous ceramic honeycomb structure excellent in the adsorption ability of dissolved organic matter such as polysaccharides.
  • the present inventors are composed of a base material made of porous ceramic and particles of a metal oxide fixed on at least a part of the surface of the base material and the inner surface of communicating holes.
  • the present invention was conceived based on the finding that the ability to adsorb dissolved organic matter (polysaccharides and the like) in water to be treated was extremely excellent.
  • the adsorption member according to the present invention includes a plurality of axially extending flow paths partitioned by porous partition walls, and the water to be treated is allowed to pass through the plurality of flow paths to adsorb foreign substances in the water to be treated It consists of a porous ceramic honeycomb structure to be removed, The flow path is alternately plugged on the treated water inflow side or the treated water outflow side,
  • the partition wall is It has a communicating hole which connects between the flow paths, A substrate made of porous ceramic, It is comprised by the particle
  • the total pore volume having a pore diameter of 10 to 200 nm is preferably 1.0% or more per apparent volume of the partition walls, and preferably 8% or less.
  • the volume-based median pore diameter measured by mercury porosimetry (however, the volume-based median pore diameter is a total pore volume in a curve showing the relationship between the pore diameter of the partition wall and the cumulative pore volume) Is the pore diameter at a pore volume corresponding to 50% of), the median pore diameter on a surface area basis (however, the median pore diameter on a surface area basis, the relationship between the pore diameter of the partition and the cumulative pore surface area
  • the pore size at the pore surface area corresponding to 50% of the total pore surface area is preferably 50 to 5000 times).
  • the partition wall is The porosity is 25 to 70%, and the volume-based median pore diameter measured by mercury porosimetry (however, the volume-based median pore diameter is a curve showing the relationship between the pore diameter of the partition wall and the cumulative pore volume,
  • the pore diameter at a pore volume corresponding to 50% of the total pore volume is preferably 1 to 50 ⁇ m, and 0.005 to 0.15 times the thickness d of the partition wall.
  • the metal oxide particles are preferably made of a material whose surface is positively charged when in contact with the water to be treated.
  • the metal oxide particles are preferably made of a material having an isoelectric point of pH 8-10.
  • the metal oxide is preferably alumina.
  • the partition wall is A substrate made of porous cordierite, It is preferable to be made of alumina particles coated on at least a part of the surface of the substrate and the inner surface of the communication hole.
  • the alumina is preferably ⁇ -alumina or ⁇ -alumina.
  • the alumina is preferably ⁇ -alumina.
  • the manufacturing method of the adsorption member according to the present invention includes a plurality of axially extending flow paths partitioned by porous partition walls, and the water to be treated is allowed to pass through the plurality of flow paths to remove foreign substances in the water to be treated.
  • a method of manufacturing a suction member to remove by suction A clay containing a ceramic raw material is extruded into a predetermined molded body, and the molded body is dried and fired to form a ceramic honeycomb structure having a plurality of axially extending flow paths partitioned by porous partition walls.
  • the partition wall has communicating holes connecting between the flow channels, and all of the pores have a pore diameter of 10 to 200 nm measured by mercury intrusion method. It is characterized in that the pore volume is 0.1% or more per apparent volume of the partition wall.
  • the ceramic material is preferably a cordierite-forming material.
  • the metal oxide is preferably alumina.
  • an alumina sol as an inorganic binder for coating the particles of the metal oxide.
  • the firing temperature of the metal oxide particles is preferably 900 ° C. or less.
  • the adsorption member of the present invention is excellent in adsorption capacity of foreign matter such as dissolved organic matter, it is suitable as a pretreatment of the treatment process by the separation membrane (reverse osmosis membrane etc.) in the water treatment system.
  • the separation membrane reverse osmosis membrane etc.
  • Adsorption member 1 of the present invention comprises a plurality of axially extending flow channels 3 partitioned by porous partition walls 2;
  • the porous ceramic honeycomb structure 4 is configured to allow the water to be treated to pass through the flow path 3 and to adsorb and remove foreign matter (dissolved organic matter etc.) in the water to be treated.
  • the partition wall 2 has a communicating hole 5 connecting adjacent flow paths 3 and is fixed to at least a part of the base 6 made of porous ceramic, the surface 6 a of the base 6 and the inner surface 6 b of the communicating hole. Characterized in that the total pore volume of the metal oxide particles 7 having a pore diameter of 10 to 200 nm measured by mercury porosimetry is 0.1% or more per apparent volume of the partition wall. Do.
  • the porous ceramic honeycomb structure 4 comprises an outer peripheral wall 8, a plurality of axially extending channels 3 provided inside the outer peripheral wall 8, and a partition wall 2 separating the plurality of channels 3.
  • the partition 2 has a communication hole 5 for connecting the adjacent flow paths 3 to each other.
  • the plurality of flow channels 3 extending in the axial direction (longitudinal direction) of the porous ceramic honeycomb structure 4 are formed in a honeycomb shape, and one end of the porous ceramic honeycomb structure 4 (inflow side of water to be treated ) Or the other end (outgoing side of treated water) by alternately having plugged portions 9a, 9b, the end face 10a on the inflow side of the to-be-treated water opens, and the opposite side of the treated water
  • the first flow path 3a in which the end face 10b on the outflow side is plugged by the plugging portion 9a and the end face 10b on the outflow side of the treated water are opened, and the end face 10a on the inflow side on the other side is plugged And a second flow path 3b plugged by 9b.
  • the first flow path 3a and the second flow path 3b are alternately arranged in the vertical and horizontal directions in the axial direction.
  • the flow of the water to be treated when the water to be treated flows into the porous ceramic honeycomb structure 4 constituting the adsorption member 1 will be described using FIGS. 2 and 3.
  • the water to be treated that has flowed into the first flow path 3a opened to the end face 10a on the inflow side flows into the second flow path 3b through the fine communication holes 5 in the partition 2, and the end face 10b on the outflow side Are discharged to the outside of the adsorption member 1 as treated water.
  • the surface 6a of the base 6 of the partition 2 and the inner surface 6b of the communication hole Removing particles from the water to be treated by contacting the particles 7 of the metal oxide fixed on the metal particles, and the particles 7 of the metal oxide adsorbing foreign matter (dissolved organic matter such as polysaccharides) in the water to be treated it can.
  • the partition wall 2 is composed of the base material 6 made of porous ceramic, and the metal oxide particles 7 fixed to at least a part of the surface 6a of the base material 6 and the inner surface 6b of the communication hole. .
  • the metal oxide particle 7 may be fixed to at least a part of the surface 6a of the base 6 and the inner surface 6b of the communication hole, and is preferably mainly fixed to the inside of the communication hole 6b.
  • the water to be treated passes through the adsorption member, the water to be treated is made of the metal oxide particles 7 fixed to the inner surface 6b of the communication hole rather than the metal oxide particles 7 fixed to the surface 6a of the substrate 6 Since the contact time is longer, by fixing a large number of metal oxide particles 7 on the inner surface 6b of the communication hole, foreign matter such as dissolved organic matter can be efficiently adsorbed and removed.
  • the metal oxide particles 7 are laminated and fixed to the surface 6 a of the base 6 and the inner surface 6 b of the communication hole, as shown in FIG. 4.
  • a large number of fine pores of 1 ⁇ m or less can be formed, and an adsorption member having a high specific surface area can be formed. Therefore, foreign matter such as dissolved organic matter in the water to be treated can be efficiently adsorbed and removed.
  • the partition wall 2 has a structure including relatively large pores forming the communication holes 5 and fine pores of 1 ⁇ m or less formed by the particles 7 of the metal oxide.
  • the partition 2 has a total pore volume with a pore diameter of 10 to 200 nm measured by mercury porosimetry at 0.1% or more per apparent volume of the partition. This value is the ratio of "total pore volume having a pore diameter of 10 to 200 nm" in "per apparent volume of partition wall", and the pore volume of 10 to 200 nm per apparent volume of partition wall It is also called the percentage of Pores having a pore diameter of 10 to 200 nm are mainly formed by the metal oxide particles 7 and largely contribute to the adsorption of foreign substances (dissolved organic matter etc.) in the water to be treated.
  • the total pore volume with a pore size of 10 to 200 nm measured by mercury porosimetry is less than 0.1% per apparent volume of the partition wall, are not enough pores having a pore size of 10 to 200 nm? Since many are present on the surface 6a of the base material 6 having a short contact time with the water to be treated, the effect of adsorbing and removing the dissolved organic matter becomes insufficient.
  • the total pore volume having a pore diameter of 10 to 200 nm measured by mercury porosimetry is preferably 0.5% or more per apparent volume of the partition wall, and more preferably 1.0% or more.
  • the apparent volume of the partition wall does not increase even if the metal oxide particles 7 are fixed to the inner surface 6b of the communication hole, the metal oxide particles 7 are fixed more to the inner surface 6b of the communication hole than the surface 6a of the substrate 6 In this case, the ratio of pore volume of 10 to 200 nm per apparent volume of partition wall becomes larger.
  • the upper limit of the ratio of pore volume of 10 to 200 nm per apparent volume of partition wall is not particularly limited, but if this ratio is too large, excessively fixed metal oxide particles 7 narrow communication hole 5 of partition 2, Not only does it prevent the passage of the water to be treated through the partition 2, but it does not contribute to an increase in the chance of contact between the water to be treated and the metal oxide particles 7. Therefore, the total pore volume having a pore diameter of 10 to 200 nm measured by mercury porosimetry is preferably 8% or less per apparent volume of the partition wall, and more preferably 6% or less.
  • the apparent volume of the partition wall is the total volume of the communication holes 5 constituting the partition wall 2, the base material 6, and the metal oxide particles 7 as shown by the frame 2s in FIG.
  • the alumina surface is positively charged in seawater having a near pH. Therefore, alumina having a positively charged surface can adsorb and remove dissolved organic matter such as polysaccharides. Further, since many oxygen atoms exist on the metal oxide such as alumina, the dissolved organic matter is adsorbed to the metal oxide by the hydrogen bond between these oxygen atoms and the hydroxyl group possessed by the dissolved organic matter.
  • the metal oxide particles 7 are preferably made of a material whose surface is positively charged when contacted with the water to be treated, and particularly preferably made of a material having an isoelectric point of pH 8 to 10. If the isoelectric point is pH 8 or more, the charge on the surface of the partition can be made positive in most of the treated water close to neutrality, and it becomes possible to adsorb and hold the negatively charged organic substance. In addition, since seawater etc. show a little alkalinity, when processing such treated water, it is preferable to select the metal oxide which has such an isoelectric point that the partition surface is positively charged in these treated waters. For example, it is preferable to apply a metal oxide having an isoelectric point of 8.2 or more.
  • the upper limit of the isoelectric point of the metal oxide is preferably pH 10.
  • the adsorption member of the type that adsorbs and removes foreign matter in the water to be treated as in the present invention if the adsorption performance decreases, the plus / minus of the surface charge is reversed during washing, and the adsorbed foreign matter is removed from the surface By peeling, the adsorption performance of the adsorption member can be regenerated.
  • a metal oxide having an isoelectric point of more than pH 10 is used, the surface charge can not be reversed to obtain sufficient repulsive force unless a stronger alkaline aqueous solution is used as a cleaning solution.
  • a strong alkali is used as the cleaning liquid, damage to the adsorption member and other members is increased. Therefore, in order to reduce the use of strong alkali as much as possible, the isoelectric point of the metal oxide is adjusted to pH 10 or less.
  • metal oxide particles examples include particles of ⁇ -alumina, ⁇ -alumina, zinc oxide, etc.
  • ⁇ -alumina and ⁇ -alumina having excellent adsorption ability for dissolved organic matter are preferable, and in particular, the isoelectric point is around 9.1 Alpha alumina is most preferable because it is also excellent in corrosion resistance.
  • a polysaccharide As a dissolved organic substance which exists in seawater, a polysaccharide is mentioned as a typical thing. For example, when a molecule having a molecular weight of 1,000,000 is considered as a polysaccharide, its molecular size (assumed to be a sphere with a density of 1 g / cm 3 ) is about 15 nm, and a molecule having a molecular weight of 5,000,000 is considered. The molecular size (assumed to be a sphere with a density of 1 g / cm 3 ) will be about 30 nm. Therefore, when many pores having a pore diameter of 10 to 200 nm formed by the metal oxide particles 7 exist, many surfaces on which these dissolved organic substances can be adsorbed exist, and the dissolved organic substances are efficiently adsorbed. It becomes possible to remove.
  • pore distribution is obtained by immersing and pressing a bulkhead sample placed in vacuum into mercury, and determining the relationship between the pressure at the time of pressurization and the volume of mercury pressed into the pores of the sample.
  • mercury intrusion measurement when the pressure is gradually increased, mercury is injected sequentially from the large diameter pore of the sample surface, and finally all the pores are filled with mercury.
  • measurement values obtained for pores of 6 nm or more are used The volume-based pore distribution (the relationship between the pore diameter of the partition wall and the cumulative pore volume) was determined. Therefore, the total pore volume is a value determined from the amount of mercury filled in the pores of 6 nm or more.
  • the pore diameter at the time when 50% of the total pore volume of mercury is injected is the median pore diameter (volume basis) measured by the mercury intrusion method. Furthermore, the relationship between the pore diameter of the partition wall and the cumulative pore surface area is determined, and from the curve, the pore diameter at a pore surface area corresponding to 50% of the total pore surface area is determined as the median pore diameter on a surface area basis.
  • the volume-based median pore diameter D 50 measured by mercury porosimetry is preferably 50 to 5000 times the surface-based median pore diameter d 50 , that is, 50 ⁇ D 50 / d 50 ⁇ 5000.
  • the volume-based median pore diameter D 50 is a value mainly reflecting a relatively large pore structure such as pores forming communication holes in partition walls, and is preferably in the range of 1 to 50 ⁇ m.
  • the median pore diameter d 50 on a surface area basis is significantly smaller than the median pore diameter D 50 on a volume basis Shift to the side.
  • the value of D 50 / d 50 becomes larger.
  • the value of D 50 / d 50 is less than 50, the number of pores having a pore diameter of 10 to 200 nm decreases, and the effect of adsorbing and removing the dissolved organic matter is significantly reduced.
  • the value of D 50 / d 50 is more than 5000, many finer pores less than 10 nm exist, and the effect of adsorbing the dissolved organic matter is saturated.
  • the value of D 50 / d 50 is more preferably 100 to 2500, and most preferably 150 to 1000.
  • the volume-based median pore diameter D 50 is a value mainly reflecting the pores forming the communicating holes in the partition wall, and is preferably in the range of 1 to 50 ⁇ m, and is 1 to 30 ⁇ m. Is more preferable, 5 to 25 ⁇ m is more preferable, and 10 to 20 ⁇ m is most preferable.
  • the volume-based median pore diameter D 50 is preferably in the range of 0.005 to 0.15 times the thickness d of the partition walls.
  • the median pore diameter D 50 on a volume basis is less than 1 ⁇ m and / or less than 0.005 times the thickness d of the partition walls, the diameter of the communication holes becomes too small, so the resistance when passing water (pressure loss) In addition, clogging by components other than the adsorptive component becomes remarkable, and may be damaged when a large pressure is applied to the water to be treated.
  • the volume-based median pore diameter D 50 is more than 50 ⁇ m and / or is more than 0.15 times the thickness d of the partition walls, the pores are too large, so the area of the inner surface of the through hole for fixing the metal oxide particles is It becomes smaller and the amount of metal oxide particles is reduced. Therefore, the ability to adsorb dissolved organic matter is reduced.
  • the adsorption member of the present invention removes dissolved organic matter by adsorption, even if the median pore diameter D 50 on a volume basis is in the range of 1 to 50 ⁇ m, it is dissolved in water with a size of 10 to 20 nm. It can remove organic matter. For this reason, unlike the pore blocking type filter (filtration membrane) which removes foreign substances by blocking foreign substances larger than the pore diameter by pores formed in the filter, small pressure loss and high removal performance of dissolved organic matter It is compatible.
  • the porosity of the partition walls 2 is preferably 25 to 70%.
  • the porosity of the partition wall 2 is determined by the pore volume of the communication hole 5 in the partition wall 2 of the substrate 6, the surface 6a of the substrate 6, the communication hole inner surface 6b, and the surface of the plugging portions 9a and 9b. It is calculated from the sum of the volume of fine pores of 1 ⁇ m or less formed by coating the particles 7. Since the pore volume of the communication holes 5 is larger than the volume of fine pores of 1 ⁇ m or less formed in the coating, the porosity is almost determined by the pore volume of the communication holes 5.
  • the porosity of the partition wall 2 When the porosity of the partition wall 2 is less than 25%, many pores which do not form the communication holes 5 will be present, and the amount of the communication holes 5 will be reduced. When the porosity of the partition wall 2 is more than 70%, the mechanical strength of the partition wall 2 is reduced, and there is a possibility of breakage when a large pressure is applied to the treated water.
  • the thickness d of the partition 2 is preferably 0.1 to 2 mm, and the ratio d / w of the thickness d to the width w of the flow path formed by the partition 2 is expressed by the equation: 0.20 ⁇ d / It is preferable to satisfy w ⁇ 1.25. If the thickness of the partition 2 is less than 0.1 mm and / or 0.20> d / w, the mechanical strength of the partition 2 is reduced, and there is a possibility of breakage when a large pressure is applied to the water to be treated. At the same time, the length of the communication hole 5 can not be secured sufficiently, and the amount of metal oxide particles is reduced, so that the adsorption performance is lowered.
  • the thickness of the partition 2 is more than 2 mm and / or d / w> 1.25, the pressure required to permeate the treated water becomes large (pressure loss increases), and time and energy for water treatment are increased. It takes The thickness d of the partition 2 and the width w of the flow path can be appropriately set by changing the dimension of the molding die.
  • the partition walls 2 be provided in a lattice shape or a mesh shape in the axial direction. Therefore, for example, when the partition walls 2 are provided in a lattice, the flow path 3 has a rectangular shape in the axial direction. In this case, the flow path 3 is preferably a square having a side of 0.5 to 8 mm in the axial direction. If one side of the flow path 3 is less than 0.5 mm, foreign matter other than the dissolved organic matter in the water to be treated may block the flow path 3a opened in the end face 10a on the inflow side of the ceramic honeycomb structure 4 Decreases.
  • the shape of the flow path 3 is not limited to a square as shown in FIG. 1, and may be a shape that can be filled on a plane such as another quadrilateral, triangle, hexagon, combination of octagon and quadrilateral, etc. .
  • the base material 6 of the partition 2 is made of ceramic mainly composed of alumina, silica, cordierite, titania, mullite, zirconia, spinel, silicon carbide, silicon nitride, aluminum titanate, lithium aluminum silicate, etc. Is preferred.
  • alumina or cordierite is preferable as the substrate 6, and cordierite is most preferable.
  • the main crystal phase may be cordierite, and other crystal phases such as spinel, mullite, and saphyrin, and may further contain a glass component. Therefore, as the adsorbing member of the present invention, it is preferable to use a substrate made of porous cordierite and particles of alumina coated on at least a part of the surface of the substrate and the inner surface of the communication hole.
  • the base material of the partition walls be cordierite and the metal oxide particles be alumina.
  • Cordierite is a substrate capable of easily forming pores, and contains alumina as a component, and therefore is effective in firmly fixing alumina.
  • Plugging portion The plurality of channels 3 of the ceramic honeycomb structure 4 are alternately plugged on the treated water inflow side or the treated water outflow side, and as a result, the end face on the inflow side of the treated water 10a is open, the first flow path 3a in which the end face 10b on the opposite side on the outflow side of treated water is plugged by the plugging portion 9a, and the end face 10b on the outflow side of treated water is open on the opposite side
  • the end face 10a on the inflow side of the water to be treated has a second flow path 3b plugged by a plugging portion 9b.
  • the first flow path 3a and the second flow path 3b are disposed adjacent to each other through the one partition wall 2, and the water to be treated flowing from the first flow path 3a is the partition wall 2 Treated water is configured to be discharged from the second flow passage 3b through the inner communication hole.
  • the plugged portions 9a and 9b may be formed of the same material as the porous ceramic honeycomb structure 4 (the base 6 of the partition 2), an organic material, or a material which does not dissolve in treated water such as other inorganic materials. it can.
  • the same material as the porous ceramic honeycomb structure 4 it can be formed by injecting a slurry made of a ceramic material into a predetermined end of the flow path and baking it.
  • examples of the organic material include materials such as polyimide, polyamide, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, Teflon (registered trademark), and the other inorganic materials include ceramics other than the ceramic constituting the partition 2 ( Alumina, silica, magnesia, titania, zirconia, zircon, cordierite, spinel, aluminum titanate, lithium aluminum silicate etc.), glass and the like can be mentioned. Further, the formation of the plugging portions 9a and 9b can be performed by using a known method.
  • the porosity of the plugged portions 9 a and 9 b is preferably 0 to 40%, and is preferably smaller than the porosity of the partition 2.
  • the axial length of the plugging portions 9 a and 9 b is preferably thicker than the thickness of the partition 2. If the porosity of the material used for the plugging portions 9a and 9b is more than 40% or higher than the porosity of the partition walls 2, the water to be treated passes through not only the partition walls 2 but also the plugging portions 9a and 9b The dissolved organic matter is discharged from the adsorption member without being adsorbed to the metal oxide particles 7.
  • porous ceramic structure 4 The method of forming the porous ceramic structure 4 will be described by taking the case of the porous ceramic structure 4 made of cordierite as an example. Prepare powders such as kaolin, talc, silica, alumina, etc. Cordierite so that the mass ratio is SiO 2 : 48-52%, Al 2 O 3 : 33-37%, and MgO: 12-15%. Preparation materials powder, adding additives such as pore former, binder such as methyl cellulose and hydroxypropyl methyl cellulose, if necessary, dispersant, surfactant, lubricant etc. after dry mixing well Add water and mix to make plasticized ceramic cups.
  • additives such as pore former, binder such as methyl cellulose and hydroxypropyl methyl cellulose
  • the clay is extruded using a molding die, cut and dried, and processing such as end face and outer periphery is performed as needed to obtain a dried body having a honeycomb structure.
  • the dried product is fired (for example, at 1400 ° C.), and then a coating agent containing cordierite particles and colloidal silica is applied to the outer periphery and fired, and the cross section partitioned inside the outer peripheral wall 8 by the partition 2 is
  • the cordierite porous ceramic honeycomb structure 4 is formed with a large number of rectangular channels 3.
  • the formation of the outer peripheral wall 8 may be performed after the formation of plugging portions described later.
  • a binder and a dispersion medium (solvent) are added to the cordierized raw material powder used for producing the porous ceramic structure 4 to prepare a slurry for forming plugged portions.
  • a plurality of nozzles are used to alternately plug the slurry into the flow path 3 of the porous ceramic honeycomb structure 4 at the inflow side end of the water to be treated and the end side at the outflow side of the process water.
  • the mixture is poured using a dispenser having the following, dried and fired to form the plugged portions 9a and 9b.
  • Screen printing can be used to form the plugged portions 9a and 9b, in addition to the dispenser.
  • a printing mask having a predetermined position opened is disposed in alignment with the predetermined position of the ceramic honeycomb structure 4, and a high viscosity slurry is injected through the opening of the printing mask, and then The resultant is dried and fired to form plugging portions 9a and 9b.
  • the plugged portions 9a and 9b may be formed of the same material as the porous ceramic honeycomb structure 4 or may be formed of another ceramic material.
  • organic polymer materials polyimide, polyamide, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, Teflon (registered trademark), etc.
  • inorganic materials glass etc.
  • ceramic particles alumina, silica, magnesia, titania, zirconia, zircon, etc. And cordierite, spinel, aluminum titanate, lithium aluminum silicate, etc.
  • the plugging portions 9a and 9b may be formed by pressing and fixing a plug prepared in advance with a material such as Teflon (registered trademark) with a rod or a syringe.
  • a material such as Teflon (registered trademark) with a rod or a syringe.
  • Teflon registered trademark
  • the temperature at which the plugging portions 9 a and 9 b are formed is lower than the temperature at which the partition wall 2 is formed.
  • the surface 6a and the communication hole inner surface 6b of the partition 2 of the porous ceramic honeycomb structure 4 and the plugging portion 9a , 9b are coated with metal oxide particles 7.
  • the coating of the metal oxide particles 7 can be carried out by the so-called washcoat method.
  • a slurry containing metal oxide particles 7 (for example, ⁇ -alumina, ⁇ -alumina) is drawn into the porous ceramic honeycomb structure 4 by suction, dried, and fired at 900 ° C. or less .
  • An inorganic binder such as alumina sol can be added to the slurry.
  • the temperature of firing after coating of the particles of metal oxide is 900 ° C. or less.
  • alumina powder having an average particle diameter of 0.1 to 1 ⁇ m is preferably used as the metal oxide particles 7 to be coated.
  • alumina powder having an average particle diameter of 0.1 to 1 ⁇ m
  • one obtained by grinding alumina A-26 manufactured by Sumitomo Chemical Co., Ltd. may, for example, be mentioned.
  • the binder an alumina sol having an average particle diameter of 100 to 500 nm is preferable, and specifically, Cataloid AS series manufactured by JGC Co., Ltd. can be mentioned.
  • the coating amount of the metal oxide particles 7 on the base material 6 of the partition wall 2 is preferably 0.2 to 5 ⁇ m as the thickness of the metal oxide particles 7 formed after firing, and is 0.5 to 2 ⁇ m. More preferable.
  • the total pore volume having fine pores of 1 ⁇ m or less formed by particles of metal oxide and having a pore size of 10 to 200 nm measured by mercury porosimetry is 0.1% or more per apparent volume of partition wall
  • the thickness of the metal oxide particles after firing is set to 0.2 ⁇ m or more.
  • the coating amount can be adjusted by the viscosity of the slurry, the particle concentration of the metal oxide, and the like.
  • the wash coating method may be repeated plural times.
  • the adsorption member 1 of the present invention is used, for example, in a water treatment equipment 100 as shown in the flow chart of FIG.
  • the water treatment facility 100 includes an adsorption module 101 incorporating the adsorption member 1 of the present invention, a water storage tank 102 for storing the water treated by the adsorption module 101, a water supply pump 103 for supplying water of the water storage tank 102, water supply
  • the reverse osmosis membrane module 104 provided with the reverse osmosis membrane 105 which removes a to-be-separated substance from the water sent from the pump 103 is provided.
  • the adsorption module 101 includes the adsorption member 1 of the present invention, and a filter support 110 supporting the treated liquid inflow side end surface and the treated water outflow side end surface of the adsorption member 1 via a holding member (not shown). It is comprised from the housing 111 (for example, the storage container made from an acryl) which accommodates the said adsorption
  • the filter support 110 may be made of any material or material that allows the water to be treated to pass without resistance, has a strength not to be easily deformed by the pressure of the water to be treated, and has no eluted material in water.
  • resin mesh spacers such as polyethylene, polypropylene, polyethylene terephthalate and polystyrene, metal meshes such as stainless steel and titanium, or punching metals can be used.
  • the adsorption module 101 is a primary treatment that has been processed to remove dust and the like through a screen, to add a coagulant to a fine suspension such as sand, and to remove sedimentation, and to decompose organic matter using microorganisms. Water is supplied, and the primary treated water contains salts and dissolved organic matter.
  • the primary treated water supplied to the adsorption module 101 passes through the adsorption member 1 to adsorb and remove foreign substances (dissolved organic matter etc.) in the water to be treated, passes through the water storage tank 102 and is pressurized by the water supply pump 103 while reverse osmosis It passes through the membrane 105, and is separated into permeate water from which organic matter and salts in treated water are removed and concentrated water in which organic matter and salts are concentrated.
  • the adsorbing member 1 of the present invention functions as a pretreatment step of selectively adsorbing and removing organic substances and the like attached to the surface of the reverse osmosis membrane 105, such a water treatment facility 100 is desalinated by seawater, a semiconductor Water treatment using reverse osmosis membrane 105 such as pure water production used for precision electronic device manufacture, advanced treatment of drinking water, regeneration treatment of sewage and drainage (including not using microorganism treatment etc.), especially seawater Application to the process of desalination is possible.
  • a semiconductor Water treatment using reverse osmosis membrane 105 such as pure water production used for precision electronic device manufacture, advanced treatment of drinking water, regeneration treatment of sewage and drainage (including not using microorganism treatment etc.), especially seawater Application to the process of desalination is possible.
  • suction members of the example (the present invention) and the comparative example were manufactured as follows.
  • Example 1 Preparation of powder of kaolin, talc, silica, aluminum hydroxide and alumina to make a cordierite raw material powder having a chemical composition of 50% by mass SiO 2 , 36% by mass Al 2 O 3 and 14% by mass MgO I got To this cordierite-forming raw material powder are added methylcellulose and hydroxypropyl methylcellulose as a forming aid, and thermally expandable microcapsules as a pore former, and a specified amount of water is injected to carry out sufficient kneading to form a honeycomb structure. An extrudable clay was prepared.
  • the obtained clay was extruded using a molding die to prepare a honeycomb structure molded body, and after drying, the peripheral portion was removed and processed, and fired at 1400 ° C. for 24 hours.
  • a plugging material made of cordierite-forming material so that the treated water inflow side end or the treated water outflow side end of the flow path is alternately plugged in the flow path of the ceramic honeycomb body after firing After filling the slurry, the plugging material slurry was dried and fired.
  • a coating agent containing cordierite particles and colloidal silica is coated, dried and fired on the outer periphery of the ceramic honeycomb structure after forming the plugged portions to form an outer peripheral wall, and the outer diameter is 285 mm, the total length 330
  • a porous ceramic honeycomb structure of 0.3 mm in thickness, 0.3 mm in partition wall thickness and 1.6 mm in cell pitch was obtained.
  • the porous ceramic honeycomb structure in which the plugging portions are formed is immersed in a slurry containing alumina fine particles originating from ⁇ -alumina and an alumina sol binder, and in the communication holes formed in the partition walls of the porous ceramic honeycomb structure. After the slurry is sufficiently infiltrated, the slurry is taken out of the slurry, dried, and fired at 500 ° C. for 5 hours, on the surface of the base of the partition wall of the porous ceramic honeycomb structure and the inner surface of the communicating hole, and on the surface of the plugging portion
  • the metal oxide particles (alumina fine particles) were coated to prepare an adsorption member of the present invention.
  • the layer of coated alumina particles ranged in thickness from 0.2 to 1 ⁇ m.
  • the coated alumina was confirmed to be ⁇ -alumina by electron beam diffraction.
  • Example 2 An adsorptive member of the present invention was produced in the same manner as in Example 1 except that alumina fine particles having ⁇ alumina as a source were used in place of the alumina fine particles having ⁇ alumina as a source in Example 1.
  • the layer of coated alumina particles had a thickness in the range of 0.3 to 0.8 ⁇ m.
  • the coated alumina was confirmed to be ⁇ -alumina by electron diffraction.
  • Example 3 An adsorptive member of the present invention was produced in the same manner as in Example 1, except that the alumina fine particles derived from ⁇ -alumina used in Example 1 were replaced with alumina fine particles derived from ⁇ -alumina.
  • the layer of coated alumina particles had a thickness in the range of 0.5 to 1.5 ⁇ m.
  • the coated alumina was confirmed to be ⁇ -alumina by electron diffraction.
  • Comparative Example 1 To ⁇ -alumina powder, add methylcellulose and hydroxypropyl methylcellulose as a forming aid, and a spherical resin with a hollow structure and an average particle diameter of 10 to 45 ⁇ m as a pore forming material, inject water in a specified amount, and sufficiently knead To prepare a honeycomb structure which can be extruded into a honeycomb structure. The obtained clay was extruded using a molding die to prepare a honeycomb structure molded body, and after drying, the peripheral portion was removed and processed, and fired at 1400 ° C. for 24 hours.
  • cordierite is formed in the same manner as in Example 1 so that the treated water inflow side end or the treated water outflow side end of the flow passage is alternately plugged in the flow passage of the ceramic honeycomb body after firing. After filling the plugging material slurry made of the raw material, the plugging material slurry was dried and fired.
  • a coating agent containing cordierite particles and colloidal silica is coated, dried and fired on the outer periphery of the ceramic honeycomb structure after forming the plugged portions to form an outer peripheral wall, and the outer diameter is 285 mm, the total length 330
  • a porous ceramic honeycomb structure made of alumina of mm, a partition wall thickness of 0.76 mm and a cell pitch of 2.66 mm was produced and used as an adsorption member. Coating of the metal oxide particles was not performed, and the thickness of the metal oxide particles was 0 ⁇ m.
  • Comparative example 2 An adsorption member made of porous cordierite was produced in the same manner as in Example 1 except that alumina was not coated on the surface of the partition wall and in the communicating hole. Coating of the metal oxide particles was not performed, and the thickness of the metal oxide particles was 0 ⁇ m.
  • Comparative example 3 The adsorption member obtained in Example 1 was further fired at 1400 ° C. for 24 hours to produce an adsorption member.
  • the layer of alumina particles had a thickness in the range of 0.2 to 1 ⁇ m before firing at 1400 ° C.
  • the surface of the ceramic honeycomb structure was reacted with the alumina particles by firing at 1400 ° C.
  • the thickness of the integrated layer of alumina particles was less than 0.2 ⁇ m.
  • the total pore volume is the total pore volume having a pore size of 6 nm or more.
  • the total pore volume having a pore diameter of 10 to 200 nm was determined from the volume-based pore distribution, and the ratio per apparent volume of the partition wall was shown.
  • the relationship between the pore diameter of the partition wall and the cumulative pore surface area (data of the pore distribution based on surface area) is determined, and from the curve, it corresponds to 50% of the total pore surface area
  • the pore diameter at the pore surface area was determined as the median pore diameter (d 50 ) based on the surface area.
  • the porosity was calculated from the measurement value of the total pore volume, assuming that the true specific gravity of cordierite is 2.52 g / cm 3 .
  • a solution to be treated is prepared by dissolving mannan, which is one of polysaccharides, in artificial seawater at a concentration of 6 mg / L, and is incorporated into an adsorption module as shown in FIG. 7 into a 25 mm diameter, 35 mm long adsorption member
  • the liquid to be treated was supplied at a volumetric flow rate (SV) of 120 L / hr.
  • the amount of mannan in the liquid to be treated at the inlet and outlet of the adsorption module (weight of carbon) measured with a TOC (total organic carbon) measuring instrument (TOC-L manufactured by Shimadzu Corporation), the amount of mannan adsorbed on the adsorption member
  • TOC-L total organic carbon measuring instrument
  • the adsorption members of Examples 1 to 3 in which the total pore volume having a pore diameter of 10 to 200 nm is 0.1% or more per apparent volume of partition wall have an adsorption amount of 1.0 mg or more in all It can be seen that the adsorption performance to dissolved organic matter is excellent.
  • the adsorption amount is 1.5 mg or more, and the adsorption performance is further excellent Recognize.
  • Kaolin, talc, silica, aluminum hydroxide and alumina powder are prepared to have a chemical composition of 50% by mass SiO 2 , 36% by mass Al 2 O 3 and The cordierized raw material powder which becomes 14 mass% MgO was obtained.
  • methylcellulose and hydroxypropyl methylcellulose as a forming aid, and thermally expandable microcapsules as a pore former, and a specified amount of water is injected to carry out sufficient kneading to form a honeycomb structure.
  • An extrudable clay was prepared.
  • the obtained clay was extruded using a molding die to prepare a honeycomb structure molded body, and after drying, the peripheral portion was removed and processed, and fired at 1400 ° C. for 24 hours.
  • a plugging made of cordierite-forming material so that the treated water inflow side end or the treated water outflow side end of the flow path is alternately plugged at the flow path end of the fired ceramic honeycomb body After filling the plug material slurry, the plugging material slurry was dried and fired.
  • a coating agent containing cordierite particles and colloidal silica is coated, dried and fired on the outer periphery of the ceramic honeycomb structure after forming the plugged portions to form an outer peripheral wall, and the outer diameter is 267 mm, the total length 185
  • a porous ceramic honeycomb structure having a diameter of 0.8 mm and a cell pitch of 1.9 mm was obtained.
  • Example 3 particles (alumina fine particles) of metal oxide were coated on the surface of the base of the partition wall of the obtained porous ceramic honeycomb structure and on the inner surface of the communicating hole to obtain the adsorption member of the present invention .
  • the layer of coated alumina particles had a thickness in the range of 0.5 to 1.5 ⁇ m.
  • the coated alumina was confirmed to be ⁇ -alumina by electron diffraction.
  • Water treatment system A (example of the present invention) In order to verify the fouling suppression effect of the reverse osmosis membrane by the produced adsorption member, actual seawater and the demonstration equipment which can add sewage to it were installed.
  • the seawater added with the sewage is used as raw water, and the adsorption members obtained in inexpensive sand filtration (SF) are combined to perform pretreatment with (sand filtration (SF) + adsorption member), and the treated water becomes a reverse osmosis membrane module Strain A was prepared to be sent.
  • SF inexpensive sand filtration
  • Water treatment system B (comparative example) Pretreatment was performed with existing ultrafiltration membrane (UF) using seawater added with sewage as raw water, and strain B was produced in which the treated water was sent to the reverse osmosis membrane module.
  • UF ultrafiltration membrane

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Press-Shaping Or Shaping Using Conveyers (AREA)

Abstract

Elément d'adsorption ayant une structure en nid d'abeille de céramique poreuse comportant une pluralité de canaux d'écoulement séparés par des parois de séparation poreuses et s'étendant dans une direction axiale, l'eau à traiter empruntant les nombreux canaux d'écoulement, de telle sorte que les impuretés de l'eau à traiter soient adsorbées et retirées. L'élément d'adsorption est caractérisé en ce que : dans les canaux d'écoulement, le côté dans lequel s'écoule l'eau à traiter et le côté duquel s'écoule les flux d'eau traités sont scellés en alternance ; les parois de séparation comportent des trous de raccordement auxquels sont reliés les canaux d'écoulement ; les parois de séparation sont constituées d'un matériau de base constitué de céramique poreuse, de particules d'oxyde métallique fixées à au moins une partie des surfaces internes des trous de communication et de la surface du matériau de base ; et le volume total des pores d'un diamètre de 10 à 200 nm, tel que mesuré par intrusion de mercure, est de 0,1 % minimum par volume apparent des parois de séparation.
PCT/JP2018/029284 2017-08-04 2018-08-03 Élément d'adsorption et procédé de fabrication WO2019027047A1 (fr)

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WO2021251401A1 (fr) * 2020-06-09 2021-12-16 日立金属株式会社 Élément d'adsorbtion et son procédé de fabrication
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US20210387126A1 (en) * 2020-06-15 2021-12-16 Metalmark Innovations, Inc. Porous materials for treating contaminants

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