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WO2008059618A1 - Appareil de traitement d'un liquide, et procédé de traitement d'un liquide, à l'aide d'une substance granulaire de type hydrotalcite - Google Patents

Appareil de traitement d'un liquide, et procédé de traitement d'un liquide, à l'aide d'une substance granulaire de type hydrotalcite Download PDF

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Publication number
WO2008059618A1
WO2008059618A1 PCT/JP2007/001245 JP2007001245W WO2008059618A1 WO 2008059618 A1 WO2008059618 A1 WO 2008059618A1 JP 2007001245 W JP2007001245 W JP 2007001245W WO 2008059618 A1 WO2008059618 A1 WO 2008059618A1
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WO
WIPO (PCT)
Prior art keywords
liquid
granular material
hydrotalcite
liquid processing
processing apparatus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/001245
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English (en)
Japanese (ja)
Inventor
Masahiko Matsukata
Takeo Asakura
Mutsuhiro Ono
Takashi Kajimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Waseda University
JDC Corp
Original Assignee
Waseda University
JDC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Waseda University, JDC Corp filed Critical Waseda University
Priority to JP2008544072A priority Critical patent/JP5363817B2/ja
Publication of WO2008059618A1 publication Critical patent/WO2008059618A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/10—Inorganic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

Definitions

  • the present invention relates to a liquid processing apparatus and a liquid processing method using a hydrophobic site-like granular material.
  • Hydrotalcite a type of layered clay mineral that exists in nature, is mainly composed of hydroxides of naturally abundant elements such as magnesium and aluminum, and its synthesis is relatively easy. Therefore, various synthesis methods have been disclosed.
  • magnesium hydroxide is used as a magnesium source, and a hydrolytic site is produced in an aqueous solvent (see, for example, Patent Document 1) or magnesium ions and aluminum ions are reacted in an aqueous solution in the presence of alkali. (For example, refer to Patent Document 2) and the like.
  • the hydrophobic site has an anion exchange action. And if this anion exchange action can immobilize arsenic, fluorine, boron, selenium, hexavalent chromium, nitrite ions, and other anionic harmful substances, waste safety improvement technology, harmless It is expected to contribute to improving the quality of contaminated water, preventing the release of harmful substances, improving soil, and promoting the stabilization of hazardous substances at waste disposal sites.
  • Patent Document 1 Japanese Patent Laid-Open No. 6_3 2 9 4 10
  • Patent Document 2 Japanese Patent Laid-Open No. 2 0 0 3 _ 2 6 4 1 8
  • a granular hydrosite that can adsorb and fix anionic toxic substances at a relatively low pressure in a small-scale facility.
  • the granular hydrosite needs to have a large particle size.
  • the present invention provides a liquid processing apparatus and a liquid processing method using a hydrophobic site-like granular material that is stable in form, has high anion exchange performance per unit volume, and can be manufactured at low cost.
  • the purpose is to provide.
  • a liquid processing apparatus of the present invention is a liquid processing apparatus for removing ions in a liquid, and has a chemical formula of M 2 X M 3+ X (OH) 2 ( A " x / n 'mH 2 0 Hydralsite-like substance (M 2+ is a divalent metal, M 3+ is a trivalent metal, A n -is an anion) and water at least A hydrotalcite-like granule obtained by drying a material containing the hydrotalcite-like substance at a temperature lower than or equal to the dehydration temperature of the hydrotalcite-like substance (temperature at which the crystal water of the hydrotalcite-like substance starts dehydration); And a contact portion for contacting the hydrophobic site-like granular material.
  • the liquid processing apparatus of the present invention is a liquid processing apparatus for removing ions in a liquid, and has a chemical formula of M 2 xM 3+ x (OH) 2 (A " x / n ⁇ Hydrate site-like substance represented by mH 20 (M 2+ represents a divalent metal, M 3+ represents a trivalent metal, and An ⁇ represents an anion).
  • a hydrousite-like granule obtained by drying at least a material having a moisture content of 70% or less at a temperature lower than the dehydration temperature of the hydrosite-like material, and the liquid and the hydrosite-like granule. And a contact portion for contacting.
  • the hydrophobic site-like granular material is dried at 90 ° C or higher 1
  • the product is produced by carrying out at 10 ° C. or lower.
  • the above mentioned hydrousite-like granular material is produced by performing the drying under conditions where the amount of water vapor in the atmosphere is close to the amount of saturated water vapor.
  • the liquid processing apparatus of the present invention is a liquid processing apparatus for removing ions in a liquid, and has a fluorine ion (F-) concentration of 1 16 mg / I at 20 ° C.
  • the amount of fluorine ion (F-) adsorbed is 8 mg / g or more when 100 g of a hydrotalcite-like granular material is added to 100 ml of the fluorine solution adjusted to 50 g and stirred for 60 minutes.
  • the hydrotalcite-like granular material, and a contact portion for bringing the liquid into contact with the hydrotalcite-like granular material are examples of fluorine ion (F-) adsorbed.
  • the hydrousite-like granular material has a water content of 10% or more.
  • the hydrotalcite-like granule contains chloride, and more preferably, the hydrotalcite-like granule contains Na CI.
  • the hydrotalcite-like granular material is produced from a hydrotalcite-like substance having a crystallite size of 20 nm or less.
  • the hydrousite-like granular material is one that adsorbs and fixes cations.
  • the particle size of the hydrophobic site-like granular material is 0.24 mm or more.
  • the stationary means may be formed in a net shape that encloses the hydrophobic site-like granular material.
  • a plurality of the contact portions may be connected.
  • a sampling channel for sampling the liquid in the contact portion may be provided.
  • the hide in the contact portion It is preferable to provide a stirring means for stirring the mouth talcite-like granular material.
  • flow rate varying means for changing the flow rate of the liquid flowing through the contact portion.
  • you may comprise the gas supply means which supplies gas to the said contact part.
  • the liquid treatment method of the present invention is a liquid treatment method for removing ions in a liquid, and has a chemical formula of M 2 xM 3+ x (OH) 2 (A " x / n ⁇ mH 2 0 high Dorotarusai Doo-like material (M 2+ is a divalent metal, M 3+ is a trivalent metal, a n - represents a Anion) represented a material containing at least a and the water, the high Dorotarusai preparative like substances It is characterized in that a hydrousite-like granule dried at a temperature lower than the dehydration temperature is brought into contact with the liquid.
  • the liquid processing method of the present invention is a liquid processing method for removing ions in a liquid, and has a chemical formula of M 2 xM 3+ x (OH) 2 (A " x / n ⁇ mH
  • the hydrous site-like substance represented by 20 (M 2+ represents a divalent metal, M 3+ represents a trivalent metal, and An ⁇ represents an anion). It is characterized in that the liquid site is brought into contact with a hydrous site-like granular material obtained by drying a material at a temperature lower than the dehydration temperature of the hydrous site-like material.
  • the hydrousite-like granular material is dried at 90 ° C or higher 1
  • the product is produced by carrying out at 10 ° C. or lower.
  • the above mentioned hydrousite-like granular material is produced by performing the drying under conditions where the amount of water vapor in the atmosphere is close to the amount of saturated water vapor.
  • the liquid treatment method of the present invention is a liquid treatment method for removing ions in a liquid, wherein the fluorine ion (F-) concentration is 1 16 mg / I at 20 ° C.
  • the amount of fluorine ion (F-) adsorbed is 8 mg / g or more when 100 g of a hydrotalcite-like granular material is added to 100 ml of the fluorine solution adjusted to 50 g and stirred for 60 minutes. This hydrotalcite-like granular material is brought into contact with the liquid.
  • the hydrotalcite-like granular material has a water content of 10% or more. Is preferable.
  • the hydrotalcite-like granule contains chloride, and more preferably, the hydrotalcite-like granule contains Na CI.
  • the hydrotalcite-like granular material is preferably produced from a hydrotalcite-like material having a crystallite size of 20 nm or less.
  • the hydrousite-like granular material is one that adsorbs and fixes cations.
  • the particle size of the hydrophobic site-like granular material is 0.24 mm or more.
  • the fixing means may be formed in a net shape that encloses the hydrophobic site-like granular material.
  • the hydrotalcite-like granular material is disposed, and a plurality of contact portions for contacting the liquid are connected, and the liquid body is sequentially brought into contact with the hydrotalcite-like granular material at these contact portions. It can also be made.
  • the crystallite size is 20 nm or less. Since the hydrotalcite-like granular material produced from the hydrotalcite-like substance is used, the adsorption amount of ions can be improved.
  • the hydrostatic site-like granular material can be prevented from flowing out from the contact portion by the fixing means.
  • ions in the liquid can be adsorbed in order from ions that are easily adsorbed. Ions can be selectively processed.
  • the liquid in the contact portion can be sampled, the type and concentration of ions in the liquid in the contact portion can be measured, and the hydrosite-like granularity in the contact portion can be measured.
  • the body condition can be accurately grasped.
  • FIG. 1 is a schematic front view showing a liquid processing apparatus of the present invention.
  • FIG. 2 is a schematic front view showing a liquid processing apparatus of the present invention.
  • FIG. 3 is a schematic front view showing a liquid processing apparatus of the present invention.
  • FIG. 4 is a schematic perspective view showing a liquid processing apparatus of the present invention.
  • FIG. 5 is a schematic front view showing a liquid processing apparatus of the present invention.
  • FIG. 6 is a graph when a solution is processed using the liquid processing apparatus of the present invention.
  • the present invention is a liquid processing apparatus 1 for removing cations and anions in a liquid 9, such as an aqueous solution containing various ions, which is described later. And the contact portion for bringing the liquid 9 into contact with the hydrophobic site-like granule 2.
  • the hydrotalcite-like granular material of the present invention comprises a material containing at least a hydrotalcite-like substance and water, and the dehydration temperature of the hydrotalcite-like substance (the crystal water of the hydrotalcite-like substance is dehydrated). Starting temperature) It is dried at the following.
  • the hydrosite-like substance is a kind of non-stoichiometric compound, and the chemical formula is represented by M 2 + 1 - X M 3+ X (OH) 2 (A " x / n ⁇ mH 2 0 M 2+ represents a divalent metal, Mg 2 ⁇ Fe 2+ , Zn 2+ , Ga 2+ , L i 2+ , Ni 2+ , Co 2 ⁇ Gu 2+ M 3+ represents a trivalent metal, such as AI 3+ , Fe 3 ⁇ Mn 3+, etc. A n- represents an anion ( where n is the valence of the anion). , X represents a numerical value between 0 and 1, and a general hydrosite material is 0.25 ⁇ ⁇ ⁇ 0.33. Any such hydrosite material may be used. For example, a product manufactured by the following method can be used.
  • the aluminum source of aluminum ions is not limited to a specific substance as long as it generates aluminum ion in water.
  • alumina, soda aluminate, aluminum hydroxide, aluminum chloride , Aluminum nitrate, pork site, alumina production residue from pork slag, aluminum sludge, etc. can be used. These aluminum sources may be used alone or in combination of two or more.
  • the magnesium source of magnesium ions is not limited to a specific substance as long as it is a substance that generates magnesium ions in water.
  • a blu-site, magnesium hydroxide, magnesite, or a burned product of magnesi lees can be used. These magnesium sources may be used either alone or in combination of two or more.
  • the aluminum compound as the aluminum source and the magnesium compound as the magnesium source do not need to be completely dissolved as long as aluminum ions and magnesium ions are present in the acidic solution. Therefore, even if an aluminum compound or a magnesium compound that is not dissolved in the acidic solution is contained, a hydrolytic site can be produced without any problem.
  • nitric acid or hydrochloric acid is preferably used.
  • the acidic solution containing aluminum ions and magnesium ions is mixed with an alkaline solution containing alkali.
  • This alkaline solution preferably has a pH of 8 to 11.
  • the acidic solution and alkaline solution can be mixed by adding the acidic solution to the alkaline solution at once, or mixing the acidic solution However, it is preferable to mix an acidic solution and an alkaline solution in appropriate amounts according to the stirring ability at the time of mixing. Of course, other methods may be used as long as the acidic solution and the alkaline solution can be sufficiently stirred.
  • the strength of the alkaline solution contained in the alkaline solution is not limited to a specific substance as long as the aqueous solution is made strong.
  • sodium hydroxide, calcium hydroxide, etc. can be used.
  • sodium carbonate, potassium carbonate, ammonium carbonate, aqueous ammonia, sodium borate, potassium borate and the like can also be used. These alkalis may be used alone or in combination of two or more.
  • the crystallite size (crystallite size) can be reduced without growing the crystals of the hydrotalcite-like substance. This is preferable in that a small hydrosite-like substance can be produced. In this case, because the crystallite size of the hydrotalcite-like substance is small, the solution becomes colloidal when mixed.
  • the pH of the mixed solution is lowered to a value at which the crystal growth of the hydrousite-like substance stops.
  • the maturation of the hydrated talcite-like substance represented by mH 2 0 can be stopped by setting the pH to 9 or less.
  • Aging can also be stopped by removing moisture. moisture In order to remove this, an appropriate method such as suction filtration or centrifugal separation can be used.
  • the crystallite size of the hydrotalcite-like substance represented by the general formula Mg 2 + I 3 + x (OH) 2 (A n _) x / n 'mH 2 0 should be 20 nm or less.
  • the pH of the mixed solution may be adjusted to 9 or less, preferably within 120 minutes after the mixing of the acidic solution and the alkaline solution is completed. Any method can be used to adjust the pH to 9 or less. For example, there is a method in which an acidic solution and an alkaline solution are mixed and then immediately diluted with water. Of course, the water may be removed by suction filtration or centrifugation within 120 minutes, preferably at the same time after mixing the acidic solution and the alkaline solution. Also, in order to prevent the aging from occurring, it is also possible to quickly wash the hydrousite-like substance after the mixing of the acidic solution and the alkaline solution is completed. In addition, chlorides such as Na CI produced in the synthesis process may be included.
  • the hydrotalcite-like substance thus produced is subjected to a predetermined pressure by a dehydrating device such as a filter press to remove moisture as much as possible, and then the dehydration temperature of the crystal water of the hydrotalcite-like substance. Dry with: In other words, only water outside the crystal of the hydrotalcite-like substance is dried. Specifically, a hydrotalcite-like substance having a moisture content of 70% or less, preferably 65% or less, and more preferably 60% or less is used. It is dried so that it is 10% or more and 20% or less, preferably 10% or more and 15% or less, and more preferably 11% or more and 12% or less.
  • the reason why the moisture content of the hydrousite-like granule is maintained at 10% or more is that when the moisture content of the hydrousite-like granule is less than 10%, it comes into contact with the solution etc. This is because the hydrated talcite-like granular material absorbs moisture and rapidly expands in volume, making it impossible to maintain the particle size.
  • the water content is the mass of water relative to the mass of the entire hydrotalcite-like substance containing water.
  • the mass of moisture contained in the hydrosite-like substance was measured according to the Japanese Industrial Standard “Method for testing moisture content of soil” (JISA 1203: 1 999).
  • the drying temperature may be any temperature as long as it is equal to or lower than the dehydration temperature of the crystal water of the hydrotalcite-like substance, but in order to increase the particle size of the hydrotalcite-like granule. It is preferable to dry at a relatively low temperature. However, if it is dried at a temperature that is too low, the hydrotalcite-like granular material is easily dissolved in water. Therefore, the specific drying temperature should be 25 ° C or higher and 125 ° C or lower, preferably 90 ° C or higher and 110 ° C or lower, more preferably 95 ° C or higher and 105 ° C or lower. .
  • this drying may be performed in any way, for example, a normal drying furnace may be used. Of course, it can be naturally dried at room temperature. In addition, it is better to adjust the humidity during drying to be high in terms of morphological stability of the hydrotalcite-like granules. For example, the amount of water vapor in the drying furnace may be adjusted to be close to the saturated water vapor amount (humidity is 90% to 100%).
  • the dried mouth talcite-like granular material may be sieved to remove the precipitated chloride and the like.
  • the particle size of the hydrousite-like granule may be adjusted according to its use.
  • the particle size of the hydrousite-like granular material is a size that does not pass through a stationary means described later, for example, 0.24 mm or more, preferably 0.36 mm or more, and more preferably 1 mm or more. 2 mm or less is good.
  • the particle size may be adjusted in any way, for example, by crushing with a hammer or the like and passing through a sieve having a target size.
  • the amount of adsorbed anions of the thus produced hydrotalcite-like granular material is high.
  • the adsorption amount of fluorine ions is at least 8 mg / g or more, preferably 8.5 mg / g or more, more preferably 8.7 mg / g or more.
  • the hydrotalcite-like granular material is preferably one that adsorbs and fixes cations such as force domium ions and lead ions.
  • the smaller the crystallite size of the hydrotalcite-like substance used as the material the higher the anion exchange property and the higher the amount of adsorption of fluorine ions. Therefore, the material is a hydrolytic site-like substance with a crystallite size of 20 nm or less, preferably 10 nm or less. It is good to use.
  • this hydrotalcite-like granular material has a relatively high amount of anion adsorption because it does not use a binder or the like for production.
  • the material of the contact part 3 may be any material as long as it does not react with the solution.
  • a resin such as polymethyl methacrylate (PMMA) or vinyl chloride, metal, wood, etc. can be freely used. Can be used.
  • any material can be used as long as the hydrophobic site-like granule 2 is disposed and the liquid 9 and the hydrous site-like granule 2 can be brought into contact with each other.
  • a container connected to a supply channel 3 1 for supplying the liquid 9 into the contact portion 3 and a discharge channel 3 2 for discharging the liquid 9 from the contact portion 3 What was formed in the shape can be used.
  • the position where the supply flow path 31 and the discharge flow path 3 2 are connected to the contact portion 3 may be anywhere. For example, as shown in FIG.
  • a plurality of supply channels and discharge channels should be provided.
  • the flow of the liquid 9 in the contact part 3 may be changed.
  • FIG. 3 it is of course possible to use the common flow path 33 that serves as both the supply flow path and the discharge flow path, and supply and discharge the liquid 9 through the common flow path 33-3 lines.
  • the contact portion 3 may be formed as a flow path itself.
  • the hydrophobic site-like granular material 2 may be arranged at the bottom 39 of the flow path.
  • the liquid treatment apparatus 1 circulates the liquid 9 and prevents it from flowing out from the contact portion 3 together with the liquid 9 in order to prevent the hydrophobic site-like granular material 2 arranged in the contact portion 3 from flowing out from the contact portion 3.
  • the stationary means for preventing the flow of the granular bodies 2 may be arranged on the liquid 9 discharge side or the liquid 9 supply side of the contact part 3.
  • a filter having a finer particle size than the particle size of the hydrophobic site-like granular material 2 can be used. In this case, this filter may be arranged at the connection portion between the contact portion 3 and the supply flow path 31 or the discharge flow path 3 2.
  • a reinforcing plate having a coarser grain than that of the filter 1 may be provided between the filter 1 and the hydrophobic site-like granular material 2.
  • the fixing means it is also possible to use a net having a finer particle size than the particle size of the hydrophobic site-like granular material 2.
  • the hydrophobic site-like granule 2 may be held by the net and placed in the contact portion 3.
  • a hydrotalcite-like granular material 2 encased in a net can be easily placed in a channel such as a river, and predetermined ions can be extracted from the water flowing through the channel. After removing and purifying the water, it can be easily removed from the waterway.
  • the liquid treatment apparatus 1 may be provided with a stirring means 4 that stirs the hydrophobic site-like granular material 2 in the contact portion 3.
  • a stirring means 4 that stirs the hydrophobic site-like granular material 2 in the contact portion 3.
  • the stirring means 4 for example, a flow rate adjusting means for changing the flow rate of the liquid 9 supplied into the contact portion 3, for example, a flow rate adjusting valve can be used.
  • changing the flow rate of the liquid 9 flowing to the contact portion 3 includes making the flow rate negative, that is, reversing the direction of the liquid 9 flowing into the contact portion 3.
  • a gas supply means for supplying gas to the contact portion 3 may be used so that the hydrophobic site-like granular material 2 in the contact portion 3 is uniformly dispersed.
  • the flow rate adjusting means and the gas supply means may be used in combination.
  • the liquid processing apparatus 1 is formed by connecting a plurality of contact portions 3 as shown in FIG. You may do it. If formed in this way, the hydrophobic site-like granular material 2 adsorbs ions in the liquid 9 in order from the ions that are likely to be adsorbed, so that the ions in the liquid 9 are selectively removed at each contact portion 3. can do.
  • the contact portion 3 on the supply side has a higher ion concentration in the liquid 9, and the adsorption capacity of the hydrotalcite-like granule 2 is likely to deteriorate. By removing the contact portion 3 on the side and connecting the contact portion 3 having the new hydrotalcite-like granule 2 on the discharge side, the hydrotalcite-like granule 2 can be used effectively.
  • each contact portion 3 may be provided with a sampling flow path 5 for sampling the liquid 9 in the contact portion 3.
  • a sampling flow path 5 for sampling the liquid 9 in the contact portion 3.
  • the measurement of the adsorption amount of fluorine ions is performed by the following method. First, prepare a fluorine solution 10 Om I prepared so that the fluorine concentration is 1 16 mg / I. Next, 10 g of the hydrousite-like granular material produced in each example is added, stirred for 1 hour with a magnetic stirrer, and then filtered using a filter. In addition, the particle size of the hydrotalcite-like granule was adjusted to 2 to 4.75 mm. Further, the adsorption of anions was performed in a constant temperature room at 20 ° C. by adjusting the temperature of the fluorine solution to 20 ° C. This change in the concentration of the fluorine solution was measured using an absorptiometer (DR. 1_80 £ 1_ 8 3 8_ 50) and a special reagent for this absorptiometer (LCK 3 2 3). And calculate the amount of anions adsorbed per gram of the hydrosite-like granular material. Adsorption amount.
  • the measurement of adsorption and fixation of force domum ions and lead ions is performed by the following method.
  • a force dome solution containing 2250 p pm (high concentration) and 1.6 p pm (low concentration) of cadmium (C d) and 885 p pm (high concentration) of lead (P b) and 1. 1 7 Prepare 10 Om I lead solutions containing p pm (low concentration).
  • the amount of powdery hydrosite-like substance added is adjusted to 0.1 wt%, 0.5 wt%, 1 wt%, and 5 wt%. This is stirred for 1 hour with a magnetic stirrer and then filtered using a filter.
  • Cadmium ions and lead ions were adsorbed and fixed in a constant temperature room at 20 ° C with the temperature of the fluorine solution adjusted to 20 ° C. Changes in the concentration of this cadmium solution and lead solution were measured using an absorptiometer (1_8_3_50 manufactured by Dr. 1_800) and a special reagent for this absorption altimeter. CK308 was measured using LCK306 as the lead ion (see Table 2). In addition, the residue (hydrated talcite-like substance) obtained by filtration was measured by XRD, SEM ⁇ EDS.
  • water permeability means the ease of water flow when water is flowed at a constant pressure in a cylindrical container filled with hydrotalcite-like granules, and the shape of the hydrousite-like granules is stable.
  • water permeability was measured as follows.
  • a PMMA plate (reinforcement plate) with holes of 5 mm in diameter arranged at a pitch of 7 mm is placed at the bottom of a cylindrical container (contact part) with a height of 250 mm and an inner diameter of 9 Omm.
  • the hydrotalcite-like granule was prepared to a particle size of 2 to 4.75 mm.
  • water with a head difference of 4 m was allowed to flow from the lower part to the upper part of this cylindrical container for 12 hours, and the water flow rate was measured to measure the water permeability. At this time, it is indicated as large, medium and small in order of increasing water permeability. Shown in 1.
  • Table 1 shows the amount of adsorption and the change in water permeability of Sample 2.
  • Table 1 shows the changes in the amount of adsorption and water permeability of Sample 3.
  • a material having a water content of about 63% was dried in a drying furnace at a temperature of 125 ° C. for 24 hours to produce a hydrosite-like granular material.
  • Table 1 shows the changes in the adsorption amount and water permeability of the specimen 5.
  • Table 1 shows that the hydrotalcite-like granule according to the present invention (samples 1 to 5) has a fluorine ion adsorption amount as compared to the sample material 6 formed into a spherical body using a binder. high.
  • the powdery hydrotalcite-like substance constituting the hydrotalcite-like granule according to the present invention reduces the concentration of cations, force domium ions and lead ions.
  • cadmium No diffraction peaks other than those in the hydrotalcite-like substance were detected after the on-site adsorption immobilization test.
  • a diffraction peak of lead hydroxide chloride (PbCIOH) was detected in the hydrotalcite-like substance after the lead ion adsorption and immobilization test, in addition to the hydrotalcite-like substance.
  • a supply port connected to the supply channel is formed at the bottom, a discharge port is formed at the top facing the bottom, and the height is 25 Omm and the inner diameter is 9 Om.
  • a cylindrical container was used. At the bottom of this cylindrical container (contact part), a PMMA pan with 5 mm diameter holes formed at a 7 mm pitch is placed as a reinforcing plate, and a 0.336 mm diameter hole is placed below it as a mounting means. PP mesh 40 (filter) with was placed.
  • the cylindrical container (contact portion) was filled with 5.0 kg of the hydrotalcite-like granular material of Test Material 4. Liquid is supplied from the supply port to this liquid treatment device at a flow rate of 1.5 I / min.
  • the uniform drainage standard for fluorine is 8 mg / I
  • the time required to exceed 8 mg / I is about 14 hours
  • the total amount of fluorine ion adsorption up to that time is 26, 91 6 mg
  • Adsorbed amount per gram of hydrated talcite-like granule is 5.4 mg.
  • the adsorption amounts of fluorine ions and sulfate ions almost became 0 at the same time, and the hydrousite-like granular material was saturated with respect to fluoride ions and sulfate ions. It was confirmed that the amount of fluoride ion adsorbed at this point was 12.1 mg / g.
  • the liquid treatment apparatus and the liquid treatment method of the present invention have high ion exchange performance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Analytical Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Des ions dangereux sont enlevés d'un liquide (9) à l'aide d'un appareil de traitement de liquide (1) comprenant une substance granulaire de type hydrotalcite (2) obtenue par séchage d'une matière contenant au moins une substance de type hydrotalcite de la formule chimique M2+1-xM3+x(OH)2(An-)x/nmH2O (M2+ est un métal bivalent, M3+ est un métal trivalent et An- est un anion) et de l'eau à la température de séchage absolu de la substance de type hydrotalcite ou au-dessous et comprenant une partie de contact (3) pour réaliser un contact du liquide (9) avec la substance granulaire de type hydrotalcite (2).
PCT/JP2007/001245 2006-11-17 2007-11-15 Appareil de traitement d'un liquide, et procédé de traitement d'un liquide, à l'aide d'une substance granulaire de type hydrotalcite Ceased WO2008059618A1 (fr)

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JP2011121786A (ja) * 2009-12-08 2011-06-23 Taki Chem Co Ltd 水分散型コロイド溶液及びその製造方法
JP2013112560A (ja) * 2011-11-28 2013-06-10 Jdc Corp 層状複水酸化物粒子群およびその製造方法、並びに層状複水酸化物分散液、層状複水酸化物添加樹脂
JP2013226530A (ja) * 2012-04-27 2013-11-07 Toshiba Corp 不純物吸着方法及び吸着装置
KR101556538B1 (ko) 2014-11-28 2015-10-02 한국해양과학기술원 토양에서 분리한 자성분리입자를 이용한 오염수 내의 인(p) 제거방법
KR101733471B1 (ko) * 2016-11-08 2017-05-10 (재)서해환경과학연구소 불소이온제거효율이 높은 이중층상수산화물 및 이의 제조방법, 불소이온 제거방법
JP2017119256A (ja) * 2015-12-28 2017-07-06 日本国土開発株式会社 シリカ吸着剤およびその製造方法
WO2018124191A1 (fr) * 2016-12-27 2018-07-05 日本国土開発株式会社 Corps de filtration utilisant un hydroxyde double lamellaire et procédé de fabrication dudit corps de filtration
WO2021117275A1 (fr) * 2019-12-12 2021-06-17 日本国土開発株式会社 Filtre à liquide et procédé de traitement de liquide
CN116355441A (zh) * 2023-03-28 2023-06-30 江西广源化工有限责任公司 一种黑滑石增白复合粉体及其制备方法
CN117504813A (zh) * 2023-11-27 2024-02-06 中南(上饶)冶金产业研究院有限公司 一种黑滑石制备重金属吸附材料的方法及重金属吸附材料

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JP2011121786A (ja) * 2009-12-08 2011-06-23 Taki Chem Co Ltd 水分散型コロイド溶液及びその製造方法
JP2013112560A (ja) * 2011-11-28 2013-06-10 Jdc Corp 層状複水酸化物粒子群およびその製造方法、並びに層状複水酸化物分散液、層状複水酸化物添加樹脂
JP2013226530A (ja) * 2012-04-27 2013-11-07 Toshiba Corp 不純物吸着方法及び吸着装置
KR101556538B1 (ko) 2014-11-28 2015-10-02 한국해양과학기술원 토양에서 분리한 자성분리입자를 이용한 오염수 내의 인(p) 제거방법
JP2017119256A (ja) * 2015-12-28 2017-07-06 日本国土開発株式会社 シリカ吸着剤およびその製造方法
KR101733471B1 (ko) * 2016-11-08 2017-05-10 (재)서해환경과학연구소 불소이온제거효율이 높은 이중층상수산화물 및 이의 제조방법, 불소이온 제거방법
CN110325256A (zh) * 2016-12-27 2019-10-11 日本国土开发株式会社 使用了层状双氢氧化物的过滤体及其制造方法
WO2018124192A1 (fr) * 2016-12-27 2018-07-05 日本国土開発株式会社 Corps moulé en hydroxyde double lamellaire et procédé de fabrication de celui
WO2018124191A1 (fr) * 2016-12-27 2018-07-05 日本国土開発株式会社 Corps de filtration utilisant un hydroxyde double lamellaire et procédé de fabrication dudit corps de filtration
CN110352088A (zh) * 2016-12-27 2019-10-18 日本国土开发株式会社 层状双氢氧化物成形体及其制造方法
JPWO2018124191A1 (ja) * 2016-12-27 2019-10-31 日本国土開発株式会社 層状複水酸化物を用いた濾過体およびその製造方法
JPWO2018124192A1 (ja) * 2016-12-27 2019-11-14 日本国土開発株式会社 層状複水酸化物成形体およびその製造方法
JP7042219B2 (ja) 2016-12-27 2022-03-25 日本国土開発株式会社 層状複水酸化物を用いた濾過体およびその製造方法
WO2021117275A1 (fr) * 2019-12-12 2021-06-17 日本国土開発株式会社 Filtre à liquide et procédé de traitement de liquide
JPWO2021117275A1 (fr) * 2019-12-12 2021-06-17
JP7309120B2 (ja) 2019-12-12 2023-07-18 日本国土開発株式会社 液体用フィルタならびに液体の処理方法
CN116355441A (zh) * 2023-03-28 2023-06-30 江西广源化工有限责任公司 一种黑滑石增白复合粉体及其制备方法
CN117504813A (zh) * 2023-11-27 2024-02-06 中南(上饶)冶金产业研究院有限公司 一种黑滑石制备重金属吸附材料的方法及重金属吸附材料

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