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WO2004096433A1 - Adsorbant et procede de production associe - Google Patents

Adsorbant et procede de production associe Download PDF

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Publication number
WO2004096433A1
WO2004096433A1 PCT/JP2004/006091 JP2004006091W WO2004096433A1 WO 2004096433 A1 WO2004096433 A1 WO 2004096433A1 JP 2004006091 W JP2004006091 W JP 2004006091W WO 2004096433 A1 WO2004096433 A1 WO 2004096433A1
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WO
WIPO (PCT)
Prior art keywords
water
adsorbent
rare earth
arsenic
earth element
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/JP2004/006091
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English (en)
Japanese (ja)
Inventor
Hiroaki Kurosawa
Haruhiko Ito
Toshio Yotsumoto
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Nihon Kaisui Co Ltd
Original Assignee
Nihon Kaisui Co Ltd
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Filing date
Publication date
Priority claimed from JP2003126379A external-priority patent/JP2004330012A/ja
Priority claimed from JP2003271850A external-priority patent/JP2005028312A/ja
Priority claimed from JP2004108704A external-priority patent/JP2005288363A/ja
Application filed by Nihon Kaisui Co Ltd filed Critical Nihon Kaisui Co Ltd
Priority to CN200480011614.4A priority Critical patent/CN1780692B/zh
Publication of WO2004096433A1 publication Critical patent/WO2004096433A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0207—Compounds of Sc, Y or Lanthanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F2101/103—Arsenic compounds
    • 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 an adsorbent that adsorbs at least one harmful substance of the group consisting of boron, arsenic, and fluorine contained in water, and a method for producing the same.
  • a method of treating the boron-containing wastewater in the service water as described above a method of removing boron as an insoluble precipitate in which boron is fixed to a boron fixing agent, a boron-selective chelating resin
  • a method of adsorbing with an adsorbent, a method of treating with a reverse osmosis membrane, and the like are known.
  • boron fixing agent aluminum sulfate or slaked lime is often used as a boron fixing agent.
  • these boron fixing agents have poor boron removal efficiency and require a low boron concentration.
  • zirconium is used as the boron fixing agent. A problem similar to the above-described boron fixing agent has occurred (for example, see Japanese Patent Application Laid-Open No. 10-277563).
  • Some of the boron removal methods using ion-exchange resins include boron-selective chelating resins (Rohm 'and' Haas Co., Ltd., Amberlite IRA-743; Mitsubishi Chemical Corporation, Diaion CRB02, registered trademark).
  • boron-selective chelating resins Rohm 'and' Haas Co., Ltd., Amberlite IRA-743; Mitsubishi Chemical Corporation, Diaion CRB02, registered trademark.
  • the carrier polystyrene is hydrophobic, boron dissolved in water is hardly diffused into the inside of the carrier, and has disadvantages such as a small adsorption capacity and a low adsorption speed.
  • concentration of boron in water is less than 5 r> pm, boron selectivity and adsorptivity are reduced in a short time, and the heat resistance of the resin is low
  • N-glucamine exchange group and its free base form as weakly basic ion exchange groups, or strong basic ion exchange groups are prepared in salt form to form high purity pure water or ultrapure water boron for semiconductor production.
  • a method for removing the carbon see, for example, Japanese Patent Application Laid-Open No. 8-238384.
  • the resin is dissolved in water, the total organic carbon (TOC) concentration is increased, and the boron selectivity and adsorptivity are reduced in a short time. There is a problem that cannot be used.
  • hydrated oxides of rare earth elements can be used as powders as they are
  • a boron adsorbent for example, see Japanese Patent Publication No. 3-22238 and Japanese Patent Publication No. 3-24431
  • a zirconium compound for example, see Japanese Patent Application Laid-Open No. 2002-38038
  • the hydrophilic resin is eluted with a boron adsorbent containing a hydrated oxide of a rare earth element in a hydrophilic polymer material.
  • the adsorption of boron to the hydroxide of the rare earth element is not sufficient, and boron cannot be removed efficiently.
  • the polymer material contains hydrous zirconium oxide, the ability to adsorb boron to the zirconium compound is low and the ability to remove boron is insufficient.
  • arsenic which is a cause of soil pollution, is eluted due to wind and rain and infiltration of groundwater, which may cause secondary environmental water pollution.
  • arsenic in the ground is liable to elute as pentavalent arsenate or trivalent arsenite, and a report from the Environment Agency, “2002 Groundwater Quality Measurement Results” (Ministry of the Environment, Environmental Management Bureau According to the Groundwater and Ground Environment Office of the Department of Soil and Environment Division, the Ground Environment Office (January 27, 1995), out of the 5,269 wells surveyed, the arsenic concentration in 1.5% of the groundwater quality standard (0 0 01 mg / 1), and its transcendence rate is by far higher than other pollutants.
  • Arsenic is carcinogenic and causes chronic poisoning if taken long term.
  • arsenic may be detected in hot spring water or mine runoff water, or may be constantly detected in groundwater or spring water in excess of water quality standards.
  • the water quality standards are set by the Canadian Insurance and Social Welfare Bureau to be less than 0.02 5111 ⁇ / 1, and the U.S. Environmental Protection Agency is planning to reduce 0.050 mg / l or less to 0.1 Olmg / 1 or less.
  • the arsenic concentration is 0.0 lmgZl or less according to the water standard and the water quality standard value in the domestic water supply law. If the arsenic concentration in the water exceeds this, it is necessary to remove arsenic from the water.
  • Conventional methods for removing arsenic in water include the coagulation sedimentation method (coprecipitation method) and the adsorption method.
  • coagulation sedimentation method coprecipitation method
  • an inorganic coagulant such as aluminum salt or iron salt is added; pH is adjusted to neutral to form coagulated flocs of metal hydroxide, resulting in turbidity. Quality, heavy metal ions, etc. Suspended substances, heavy metal ions, etc. Precipitates with heat.
  • arsenic is also taken up by flocculated flocs and precipitated. Precipitates are removed by gravity separation or the like.
  • the coagulation sedimentation method As a method for removing arsenic, the coagulation sedimentation method (coprecipitation method), which is generally used, adds an inorganic coagulant such as an aluminum salt or iron salt according to the turbid mass of the water to be treated, so that the turbid mass is large. In some cases, it may be necessary to administer large amounts of flocculant. Furthermore, there is the disadvantage that it takes a long time to remove flocculated flocs incorporating arsenic before they settle and settle in the sedimentation basin or sedimentation tank. There are drawbacks to the complexity of operating.
  • a separately prepared polymer flocculant or the like may be added to promote the sedimentation.
  • the bulk of the water to be treated contains arsenic more than the cloudy mass.
  • arsenic more than the cloudy mass.
  • trivalent arsenous acid cannot be directly incorporated in the coagulation sedimentation method (coprecipitation method). Therefore, an oxidizing agent such as sodium hypochlorite must be added as a pretreatment to change the form to pentavalent arsenic acid.
  • an oxidizing agent such as sodium hypochlorite must be added as a pretreatment to change the form to pentavalent arsenic acid.
  • Japanese Unexamined Patent Publication No. 8-2066663 discloses a method for separating flocculated floc comprising metal hydroxide and arsenic produced by coprecipitation by adding a flocculant with an ultrafiltration membrane or a microfiltration membrane. Is described. Although this method can reduce the installation area of the treatment facility, the amount of coagulant used is the same as in the conventional coagulation sedimentation method, and the sludge containing a large amount of suspended solids and coagulated flocs composed of metal hydroxide and arsenic is limited. There is a disadvantage that frequent washing of the filtration membrane is required because the filtration is performed with an external filtration membrane or a precision filtration membrane.
  • Adsorbents include natural soil, activated carbon, activated alumina, manganese dioxide, titanic acid, zirconium hydrate, lanthanum, Transition metal compounds such as thorium and cerium are used in the form of granules having a diameter of 1.0 to 2.0 mm.
  • the arsenic adsorption capacity generally reduces the adsorbent removal capacity. There is a drawback that the frequency of replacement and regeneration of the adsorbent becomes high.
  • activated alumina is an adsorbent that has the property that residual arsenic in wastewater increases almost in proportion to the volume of water passing through.
  • an adsorption tower for neutralizing a weakly acidic treatment liquid in order to quickly and efficiently remove arsenic in the water to be treated.
  • An arsenic removal device comprising: a neutralization means provided downstream; and a filter provided downstream of the neutralization means for capturing adsorbents and debris of the adsorbent.
  • Rare earth-based adsorbents such as lanthanum which are considered to have a high adsorption amount, are affected by the arsenic concentration in the water and rapidly equilibrate when the arsenic concentration reaches a concentration range of 1.0 mg / l or less. There was a drawback that the amount of adsorption was reduced. Activated alumina and activated carbon also had the disadvantage that the equilibrium adsorption amount was lower than that of rare earth adsorbents such as lanthanum.
  • an alumina carrier is used as an adsorbent, and an oxide or a hydroxide of a rare earth metal is 5 to 60% by weight. /.
  • an arsenic adsorption / removal method characterized by using a supported substance has been proposed, there has been a drawback that the adsorbent has a weak adsorption ability and cannot be said to have sufficiently achieved its purpose.
  • the invention described in Japanese Patent Publication No. Hei 4-45213 discloses an arsenic adsorbent characterized by using an organic polymer carrier loaded with 5 to 50% by weight of a hydrated oxide of a rare earth metal as an adsorbent.
  • the hydrophilic resin is used for the organic polymer carrier, and there is a drawback that the hydrophilic resin is eluted at the time of initial water flow.
  • the superficial superficial velocity at the time of passing water is assumed to be about 10 lZhr, but if the superficial superficial velocity is increased more than this, water does not sufficiently penetrate into the adsorbent, and as a result However, there is a drawback that is reduced.
  • a type of adsorbent that uses a hydrophilic resin may be used to wash the adsorbent with water to remove low-molecular components in the resin, which are the initial elution components.
  • a final treatment with activated carbon is required in addition to a treatment with an arsenic adsorbent even during actual use.
  • Wastewater such as smoke drainage often contains fluorine and other harmful and polluting substances.
  • two-stage flocculation and sedimentation by adding the above-mentioned flocculant is preferably used depending on the concentration of high-concentration dissolved fluorine and heavy metals from the wastewater.
  • the complexity of the two-stage operation is unavoidable.
  • the removal of effluents to a low concentration for example, 8 mg ZL based on water quality standards) for harmful and contaminants such as fluorine, requires aluminum-iron ferrite.
  • the above ion-exchange resin method is commercially available, for example, such as U-SELEC UR370, a trademark of U-Tika, and Orlite F, a trademark of Zirconia containing a product of Organo, but any adsorbent is acidic.
  • the above-mentioned activated alumina method is also a gelled aluminum hydroxide. In the case of low-concentration fluorine (20 to 50 mg / L concentration), there is a defect in low adsorption capacity that does not adsorb fluorine sufficiently.
  • the method using a rare earth metal-carrying resin in the above method has the drawback that the adsorbent rare earth element in the resin elutes into the wastewater treatment liquid and becomes a shell of only the resin, preventing fluorine from being adsorbed. .
  • the adsorbent of JP-A-2-2612 also has a fluorine adsorption performance because a large amount of cerium is eluted in the acidic region, but has the disadvantage that a large amount of resin must be replenished due to deterioration. there were.
  • oxidation Reducing substances may be mixed. For this reason, redox substances are neutralized and precipitated using sodium hypochlorite, etc., but trace amounts of sodium hypochlorite remain in the wastewater after the separation.
  • the present invention has excellent adsorption performance for boron, arsenic, and fluorine present in water as compared with conventional adsorbents, and functions effectively even when their concentrations are low.
  • the adsorbent has a long service life, is easy to maintain, and has no need for secondary purification means to remove the adsorbent and polymer substances because they do not elute into water. It is intended to do so.
  • the present inventors have conducted intensive research and have found that a rare-earth element hydroxide and / or a hydrated oxide are used as the boron, arsenic, and fluorine adsorbent components, and the polymer resin is used as a polymer resin.
  • a structure in which a thin layer of a water-resistant polymer resin, i.e., a skin layer, is used, and a large amount of rare-earth element hydroxides and Z or hydrated oxides with a large number of voids are contained in the skin layer of the parentheses As a result, it has been found that a large amount of adsorbent components can be included, and that the ability to adsorb the harmful substances can be significantly improved, thereby leading to the present invention.
  • the present invention relates to the following (1) to (10).
  • polymer resin is a resin selected from a fluororesin and an acetalized polyvinyl alcohol-based resin.
  • a rare earth element hydrated oxide and / or hydrated oxide having a water content of 1 to 40% by weight is heated and aged at 300 ° C. to 600 for 1 hour to 10 hours to obtain a crystallite diameter of 50 to 200.
  • a method for producing a fluorine adsorbent which comprises mixing the rare earth element hydroxide and / or hydrated oxide prepared in A with a water-resistant polymer resin.
  • FIG. 1 is a diagram showing the boron adsorption performance of the present invention, and is a diagram showing the relationship between the water penetration ratio and the boron concentration (mg / L) of the treatment liquid (Example 1, Comparative Example 1).
  • FIG. 2 is a graph showing the relationship between the amount of absorbed boron (g / g—CeO 2 ) and the concentration of liquid phase B (mg / L) (Example 2, Comparative Example 2).
  • FIG. 3 is a graph showing the relationship between the water penetration ratio in the presence of ions other than boron of the present invention and the boron concentration of the treatment liquid (Example 3, Comparative Example 3).
  • Figure 4 is a diagram showing the relationship between the liquid phase boron concentration (mg / L) and the amount of adsorption (g / L) (Example 4).
  • FIG. 5 is a graph showing the arsenic (A s (V)) adsorption performance of the present invention, and is a graph showing the relationship between the water passage ratio and the arsenic concentration (mg '/ l) of the treatment liquid.
  • FIG. 6 is a graph showing the arsenic (As ( ⁇ )) adsorption performance of the present invention, and is a graph showing the relationship between the water permeability and the arsenic concentration (mg / l) of the treatment liquid.
  • FIG. 7 is a diagram showing the relationship between the water passage magnification and the cerium concentration of the treatment liquid according to the present invention.
  • FIG. 8 is a graph showing the relationship between the liquid arsenic concentration (mg / 1) and the arsenic adsorption amount (gZl) of the present invention.
  • FIG. 9 is a relationship diagram between the liquid pH and the arsenic adsorption amount (mo 1/1) of the present invention.
  • FIG. 10 is a diagram showing the relationship between SV (1 / hr) and the arsenic removal rate according to the present invention.
  • FIG. 11 is a schematic diagram of the internal structure of the adsorbent of the present invention.
  • FIG. 12 is a photograph (100 times) of an internal split cross section of the adsorbent of the present invention.
  • the boron, arsenic, and fluorine adsorbent of the present invention is a mixture of a water-resistant polymer resin and a rare earth element hydroxide and / or hydrated oxide.
  • the mixture contains at least 600 parts by weight of a rare earth hydroxide and Z or a hydrated oxide per 100 parts by weight of the polymer resin. If the rare earth element content is less than 600 parts by weight, the amounts of boron, arsenic and fluorine adsorbed are not sufficient.
  • the upper limit is basically not limited from the viewpoint of the adsorbing ability of the adsorbent, and it is better that the amount of the rare earth element hydroxide and / or hydrated oxide is larger.
  • the porous membrane of the water-resistant polymer resin is coated with a rare earth element hydroxide and / or hydrated oxide, and the rare earth element hydroxide and / or hydrated oxide inside the porous membrane is formed in the central cavity. , And a minute void around it.
  • the mixture may be in the form of granules or a molded article having a shape allowing water to pass through. Any structure may be used as long as the mixture can be filled and used without impeding the passage of water. It is sufficient if the reticulated body meets the objectives. Also, if the particles are almost uniform and round, Diameter 0.2 mn! ⁇ 5. Omni is preferably used. A more preferred particle size is between 0.5 mm and 2.5 mm. When the particle size is 0.2 mm or less, the packing density is high, the water flow resistance is high, and the workability is likely to be inferior.When it is 5.0 mm or more, the contact area per unit time between the arsenic-containing water and the granular material is small. As a result, the ability to absorb boron, arsenic, and fluorine tends to be low.
  • the granulated product is prepared by dispersing a powder of rare earth element hydroxide and / or Z or hydrated hydroxide in a drier with a polymer resin and a polymer resin into a solvent and feeding the mixture into a granulator. I got it. The obtained granular molded body was washed with water until the elution of the solvent was no longer observed.
  • the water-resistant polymer resin used in the adsorbent of the present invention an organic polymer polymer resin or a derivative of the water-resistant organic resin having heat resistance higher than that of the cation-exchange resin and chelate resin, and having a water-resistance that does not elute in water.
  • the number average molecular weight is preferably 500 or more, more preferably 200 or more.
  • the water-soluble hydrophilic resin is not preferred in that it elutes, and at high temperatures the elution is further increased and there is no heat resistance.
  • Examples of the polymer resin used in the present invention include organic polymers, natural polymers, and derivatives thereof, which are excellent in synthetic or natural water resistance.
  • the water resistance means that the polymer resin does not elute in the treated water even at the initial stage of water passage to the adsorbent, or at least that there is no elution that causes a problem for beverages.
  • an olefin resin such as a polyethylene resin, a vinyl chloride resin, a vinylidene chloride resin, a styrene resin, and a polysulfone resin, can be used.
  • Particularly preferred polymer resins include fluorine resins and acetalized polyvinyl alcohol resins.
  • polyvinylidene fluoride resin vinylidene fluoride-6-propylene monofluoride copolymer resin, polytetrafluoroethylene resin, and polybutyl butyral resin.
  • These polymer resins are easy to contain high concentrations of rare earth element hydroxides and Z or hydrated oxides, and are excellent in water resistance and chemical resistance This is a particularly preferred resin.
  • the rare earth element hydroxide and / or hydrated oxide used in the adsorbent of the present invention is a group 3 (3A) rare earth element according to the periodic table of 1999 elements, which is scandium Sc, yttrium Y, lanthanoid.
  • Element Lanthanum La, Cerium Ce, Praseodymium Pr, Neodymium Nd, Promethium Pm, Samarium Sm, Euphyllium Eu, Power Dream Gd, Terbium Tb, Dysprosium Dy, Honoremium Ho, Erbium Er, Thulium Tm, ytterbium Yb, lutetium hydroxide and Z or hydrated oxide.
  • a preferred element in conformity with the object of the present invention is Ce, and tetravalent Ce is preferred. Mixtures of these rare earth hydroxides and / or hydrated oxides are also useful. Among them, those containing 5 wt% or less of Ywp in Ce are preferable.
  • the rare earth element hydroxide and / or Z or hydrated oxide used in the present invention are preferably those having excellent acid resistance, especially in the case of a fluorine adsorbent.
  • the term "acid resistance" as used herein means that 1 L of an aqueous solution containing 5 Omg ZL of fluoride ions is adjusted to pH 3.2 in advance, and the rare earth element hydroxide and Z or hydrated oxide are added with lO Omg. It is expressed by measuring the concentration of cerium in the solution using CCP after stirring for 4 hours at pH 3.0. In the present invention, the acid resistance is good when the cerium concentration is 7.5 mgZL or less.
  • the rare earth element hydroxide used contains water, and the water content is 1 to 30 parts by weight with respect to 100 parts by weight of Ce hydroxide. Parts by weight, preferably 5 to 18 parts by weight, more preferably 5 to 15 parts by weight.
  • This water content makes it impossible to imagine from the conventional level (400 parts by weight per 100 parts by weight of resin) of 600 parts by weight or more per 100 parts by weight of polymer resin and polymer resin, which was thought to be impossible in the past.
  • Adsorbents containing rare earth element hydroxides and / or hydrated oxides with a high content can be produced, and surprisingly 2 to 4 times the conventional adsorption capacity of boron and arsenic can be obtained. I was able to do things.
  • the adsorbent of the present invention has a saturated adsorption amount (equilibrium adsorption amount) as shown in FIGS. 4 and 8, which indicates an adsorption amount that cannot be achieved by the conventional technology.
  • the inclusion of water causes rare earth element hydroxide and Z or The fluidity of the hydrated oxide is improved and appropriate mixing with the resin is performed.As shown in Figs. 11 and 12, the polymer resin is porous on the surface of the rare earth element hydroxide and / or hydrated oxide particles.
  • the rare earth element hydroxide and / or hydrated oxide is retained inside the particles without flowing out, and the rare earth element hydroxide and / or water in which water is secondarily aggregated and / or The action of making the hydrated oxide a suitable particle size, creating voids in the secondary particles to enable the contact with the water containing boron and arsenic, and preventing the hydroxide from returning to the oxide As a result, it is estimated that the ability to adsorb boron and arsenic has increased.
  • the method for measuring the water content is to remove the resin from the resin-mixed particles with a resin dissolving agent and then volatilize or separate the solvent to remove the remaining water-containing rare earth hydroxide and / or hydroxide at 800 ° C. At a high temperature for 1 hour, and a value obtained by dividing the evaporation by a hydrated rare earth element hydroxide and / or hydrated oxide is expressed as a water content.
  • a hydroxide of a rare earth element having a crystallite diameter of 50 to 20 OA, Z or a hydrated oxide is particularly preferable.
  • the rare earth element hydroxide and the Z or hydrated oxide having a crystallite diameter of 50 to 20 OA according to the present invention have a water content defined below of 1 to 40 weight. /.
  • the rare earth element hydroxides and Z or hydrated oxides at a high temperature of 300 ° C. to 600 ° C. for 1 hour to 10 hours.
  • the condition of 350 to 420 ° C in air is required.
  • Heat aging for 2 to 10 hours may be performed to obtain a rare earth element hydroxide and / or hydrated oxide. If the temperature is less than 300 ° C., the crystallite size of the rare earth element hydroxide and / or hydrated oxide cannot satisfy the requirements of the present invention, the acid resistance is poor, and the elution of the rare earth element increases. On the other hand, when the temperature exceeds 600 ° C., some oxides are formed, and the fluorine treatment capacity is reduced.
  • the adsorbent of the present invention suppresses the amount of the rare earth element compound eluted into water by this high-temperature aging with less than half the amount of the conventional fluorine adsorbent.
  • the rare earth element compound for fluorine adsorption in which the elution amount is suppressed as described above, has not been known so far.
  • a rare earth having a heat loss of 5 to 30% by weight described in Japanese Patent Publication No. 2-17220 instead of the hydrated oxide having a specific crystallite diameter of the present invention, a rare earth having a heat loss of 5 to 30% by weight described in Japanese Patent Publication No. 2-17220. It is surprising that it was not known in the class oxides.
  • Rare earth element hydroxides and / or hydrated oxides and rare earth element oxides also have different thermal properties and show different absorption bands in infrared analysis.
  • the rare earth element hydroxide and / or hydrated oxide of the present invention which has been aged at a high temperature preferably has a water content of 0.1 to 20% by weight, more preferably 0.1 to 5. 0 weight. / 0 .
  • a value (heat loss) obtained by leaving the material at a high temperature of 800 ° C for 1 hour and dividing the evaporated content by the hydrated rare earth element hydroxide and _ or hydrated oxide (thermal loss) is expressed.
  • the rare earth element fluorine adsorbent of the prior art has a high water content and a small crystallite size of 20 to 40 A, the mixing state with the polymer resin is not good, and the elution of the rare earth element hydroxide and / or hydrated oxide
  • the crystal form of the rare earth element hydroxide and Z or the hydrated oxide of the present invention has a low water content due to this high-temperature heating aging, the crystallization is advanced and the crystallite diameter is large.
  • the skin layer of the polymer resin in the boron, arsenic, and fluorine adsorbent of the present invention preferably has a thickness of 0.01 to 2 xm, preferably 0.1 to 0.5 // m. If the thickness is less than 0.01 ⁇ , rare earth elements may be eluted. If the thickness exceeds 2 m, water may not easily penetrate into the adsorbent when passing water. Further, the inside of the polymer resin skin layer has a central cavity and a minute void surrounding the central cavity as shown in FIGS. The bulk density of the adsorbent has a bulk density of 0. 4 ⁇ 2. 0 g / cm 3 .
  • the secondary particles of the rare earth element hydroxide and / or hydrated oxide are aggregates of primary particles having an average particle size of 0.1 to 0.1 ⁇ m, and the secondary particles have an average particle size of 0.2 to 25 ⁇ is preferable, and for boron adsorbent, 0.5 to 10. ⁇ is preferable, and for arsenic adsorbent, 1 to 6 ⁇ is preferable. In the case of fluorine adsorbent, 0. 1 to 25 / im is preferred, and 0.5 to: LO. ⁇ is more preferred. If it is less than 0.2 ⁇ m, it may be wrapped with resin mixture and contact with these harmful substance-containing water may be insufficient. If it is more than 25 ⁇ , mixing with resin may not be good.
  • the rare earth element hydroxide and Z or the hydrated oxide used for the boron and arsenic adsorbent of the present invention have the water content of the rare earth element hydroxide and the Z or the hydrated oxide (dry matter) 10
  • Rare earth element hydroxides and Z or hydrated hydroxides are oxidized by adding an oxidizing agent such as hydrogen peroxide after performing an operation such as solvent extraction of the rare earth chloride compound, and neutralized to form hydroxides and hydroxides.
  • the purified hydrate may be washed with pure water to form a cake or a commercially available hydroxide cake. Since the cake-like rare earth element hydroxide and Z or hydrated oxide contain excess water, the content of the cake is reduced to 50 to 70 ° C. by using a normal heating device in order to obtain the specific water content of the present invention.
  • the treatment is carried out at a low temperature to adjust the water content to 1 to 30 parts by weight with respect to the rare earth element hydroxide and Z or hydrated oxide.
  • the rare earth element hydroxide and / or hydrated oxide containing a specific amount of water obtained as described above is subsequently mixed with a polymer resin to obtain the boron, arsenic, and fluorine adsorbent of the present invention. .
  • the boron / arsenic adsorbent of the present invention having a moisture content of 0.2 to 5.0 mm and a water content of 1 to 30 parts by weight with respect to the rare earth element hydroxide and / or hydrated oxide can be obtained.
  • the fluorine adsorbent can also be produced by the same operation using a hydrous oxide having a predetermined crystallite diameter after the above-mentioned heat aging.
  • the polymer resin may be mixed with the rare-earth element hydroxide and / or hydrated oxide in the organic solvent without previously dissolving the polymer resin in the organic solvent.
  • the solvent is not particularly limited as long as it can dissolve the polymer resin.
  • Rare earth element hydroxides and / or hydrated oxides can be obtained by performing a neutralization reaction of rare earth element oxides with hydroxyl groups.However, if the pH during the reaction is on the acidic side, unreacted A small amount of rare earth element nitroxide remains in the rare earth element hydroxide and / or hydrated oxide. Although the specific reason is not clear, as shown in Tables 2 and 4, it is assumed that 1 to 10 parts by weight of rare earth element hydroxide per 100 parts by weight of rare earth element hydroxide and / or hydrated oxide remains. In the course of the development, it was found that they had higher boron and arsenic adsorption performance, and were found to be preferable in solving the object of the present invention.
  • the particulate arsenic adsorbent of the present invention is filled in a predetermined container, and water containing arsenic (A s (V) and As (III)) ′ at a predetermined concentration is 1 to 200 with respect to the adsorbent capacity.
  • water containing arsenic (A s (V) and As (III)) ′ at a predetermined concentration is 1 to 200 with respect to the adsorbent capacity.
  • the water flow rate When a water volume of 00 times the volume is passed (referred to as the water flow rate), the arsenic concentration of the water that has passed through is maintained at less than 0.1 mg / l. Also, even if the superficial velocity at the time of passing water is 100 to 2001 / hr, which far exceeds the conventional level of 10 lZhr, it has sufficient adsorption performance.
  • the pH of the arsenic-containing water used for passing the water is 4 to 10 so that the adsorption ability of the adsorbent is activated and maintained.
  • the preferred pH is between 7 and 9.
  • the particulate fluorine adsorbent of the present invention is filled into a predetermined container, and a predetermined concentration of fluorine-containing water is passed through the adsorbent by a weight of 1 to 400 times the weight of the adsorbent (referred to as water permeation magnification). Then, the fluorine concentration of the passing water is maintained at a low concentration (for example, 2 mg / L or less).
  • a low concentration for example, 2 mg / L or less.
  • it is preferable to adjust the pH of the fluorine-containing water used for passing water to 3 to 6 so that the adsorption capacity of the adsorbent can be activated and maintained. This pH can be adjusted with hydrochloric acid or caustic soda.
  • the adsorbent of the present invention when it has a reduced adsorbability due to long-term use, it is subjected to a regenerating treatment by a known method (for example, by the method described in JP-A-2004-146626). The adsorption ability can be restored.
  • the SV in the text is the superficial velocity (space velocity-1), the water flow rate per adsorbent, and the water flow rate per adsorbent. For example, if the speed is 20 times the speed of the adsorbent per hour, it means that water passed at 201 hr.
  • the water flow rate means how many times water flows per adsorbent capacity.For example, a water flow rate of 200 with 11 adsorbents means that 200 1 water flowed. .
  • the saturated adsorption amount is a value indicating the maximum amount of adsorption when the adsorbent is adsorbed with a specific concentration of an aqueous solution of boron, arsenic, or fluorine, and varies depending on the concentration.
  • H 3 B0 3 reagent first grade (initial) concentration 20. 17 mg / L in tap water This is hereinafter referred to as tap water hydrogen-containing liquid.
  • PH8. 5 produced pure water by dissolving H 3 B0 3 reagent first grade (initial) solution to a concentration 20. 72 mg / L.
  • this is referred to as a pure water boron-containing liquid.
  • the hydrated hydroxide was dried at 70 ° C with a low-temperature drier of 20% moisture. /. Thus, a hydrated cellium powder was obtained.
  • This powder, vinylidene fluoride and propylene hexafluoride copolymer resin were mixed and dispersed in a solvent N-methyl_2-pyrrolidone to obtain a dispersion.
  • this dispersion was granulated with a granulator and washed with water to obtain rounded particles having an average particle diameter of 0.7 Omm in a ratio of 700 parts by weight of cerium hydroxide to 100 parts by weight of the resin. .
  • this particle is called READ-B.
  • the sampling method was sampling with a pure water boron-containing liquid at a water flow rate of 200 times, and the TOC value was determined from the difference between the pure water boron-containing liquid and the water flowing liquid.
  • the results are shown in Figure 1 and Table 1.
  • Table 1 shows that the adsorbent of the present invention clearly prevents the dissolution of dissolved substances into water even in comparison with Comparative Example 1 (O ppb in Example 1), and there is no problem for beverages and ultrapure water From Fig. 1, it can be seen that the poor adsorptivity of boron in water, the slow adsorption rate, the short-term decrease of the adsorptivity over time, and the low heat resistance are solved. Also, there was no need for multi-stage large-scale equipment, so there was no complicated operation, and there was no problem of large amounts of adsorbed sediment sludge because there was no precipitation with powder.
  • the measurement was performed while changing the amount of the boron adsorbent used.
  • the read- B is highly any liquid phase B concentration compared to commercially available resin CRB 02 boron adsorption across the (mg / L) (g / g- C e 0 2) I understood that.
  • Example 1 and Comparative Example 1 are the same as those in Example 1. 0 3. Omg / L to (H 3 B 0 3), or other S 0 4 ion 5, 00 Omg / L, CL and 1 0, OO Omg / L, S 2 0 6 to 300 mg ZL, M All operations were the same except that g was contained at 300 mg / L. Figure 3 shows the results.
  • the adsorbent of the present invention firmly adsorbs B, and has a superior boron adsorption in water, which is extremely superior to commercially available resins. It was found that the performance exhibited no deterioration over a short period of time.
  • Arsenate disodium hydrogen heptahydrate in tap water (Na 2 HAs O 4. 7H 2 0) was prepared and dissolved to (initial) solution was A s (V) concentration lmg / 1 and pH 7. 0 Ensure Was.
  • This is hereinafter referred to as tap water arsenate-containing liquid.
  • a cerium nitrate aqueous solution and a sodium hydroxide aqueous solution were subjected to a neutralization reaction, purified and dehydrated to obtain a water-containing cerium oxide powder having a water content of 30 to 40% by weight. Next, this powder was dried with a low-temperature dryer at 70 ° C.
  • a water-containing hydroxide powder having a water content of 16% by weight.
  • 833 parts by weight of this powder and 100 parts by weight of polyvinyl butyral resin were dispersed in 700 parts by weight of a solvent N-methyl-1-pyrrolidone to obtain a dispersion.
  • this dispersion was charged into a granulator, and rounded particles having an average particle diameter of 0.7 Omm were obtained at a ratio of 700 parts by weight of cerium hydroxide to 100 parts by weight of the resin.
  • FIGS. 11 and 12 When a cross section of the particle was observed with a microscope, it was as shown in FIGS. 11 and 12.
  • these particles are referred to as adsorbent A.
  • an arsenic adsorbent described in Japanese Patent Application Laid-Open No. 61-18793 (trade name: Hisokyu, manufactured by Chiyoda Chemical Works, Ltd.) was prepared as a comparative example.
  • the TOC concentration of adsorbent B in Table 3 is the value at the beginning of water passage, and the elution of the dissolved substance disappears shortly after water passage. Therefore, if the adsorbent was washed beforehand and the treated water was further treated with activated carbon, there was no problem in practical use, but it was thought that elution itself should be improved.
  • Table 2 clearly shows that the adsorbent of the present invention can prevent the dissolution of the dissolved substance into water easily and has no problem for beverages. This indicates that high adsorption performance is maintained.
  • Trioxide arsenic anhydride in tap water was confirmed (A s 2 0 3) was dissolved (initial) A s (IE) to prepare a liquid to a concentration lmg / 1 p H 7. 0 .
  • the adsorbent A after the completion of the water flow was regenerated with sodium hydroxide, and then the As (A) concentration was measured under the water flow conditions described above.
  • One cycle of regenerated water was performed twice. As shown in Fig. 6, it was found that trivalent arsenite, which cannot be incorporated by the coagulation sedimentation method (coprecipitation method), was adsorbed, and that the adsorption performance after the regeneration treatment did not decrease.
  • Example 9 A solution was prepared by dissolving disodium hydrogen arsenate heptahydrate (Na 2 HAs 04. 7H 2 O) in pure water to make (initial) As (V) concentration l O OmgZl: pH 7.0 was confirmed. Further, it was confirmed p H 7. 0 to produce pure water 3 by dissolving oxide 2 arsenic anhydride (As 2 0 3) (Initial) As ( ⁇ ) solution was concentration l O OmgZl. 2 ml of the adsorbent A of Example 6 was added to each of the arsenic-containing liquids 11 and stirred for 48 hours. Figure 8 shows the results. It was found that the adsorbent of the present invention effectively adsorbed arsenic from a low concentration to a high concentration.
  • the arsenic acid-containing liquid in tap water ((initial) As (V) concentration lmgZl) of Example 6 was diluted to prepare (initial) As (V) concentrations of 0.5 mg / l and 0.1 mgZl, respectively. PH 7.0 was confirmed.
  • the conditions other than the SV were the same as in Example 1, and a water passage test was carried out while changing the SV, and the arsenic removal rate was calculated from the As (V) concentration in the passed water.
  • Fig. 10 shows the results.
  • the pH during the neutralization reaction was adjusted to obtain hydrated cerium oxide powder having different residual cerium nitrate concentrations.
  • Table 4 shows that the higher the residual cerium nitrate concentration in the hydrated cerium oxide, the higher the arsenic adsorption performance.
  • the adsorbent of the present invention has significantly improved arsenic adsorption performance as compared with the conventional adsorbent.
  • it is possible to purify arsenic-contaminated water in large quantities at high speed, and to efficiently purify water to be treated containing low-concentration arsenic, and to increase the adsorption activity. Because it can be maintained for a long period of time, maintenance is easy, and in addition, adsorbents and resin components do not elute.
  • Na F (reagent grade) is dissolved in pure water to prepare a solution with an initial fluorine concentration of 50 mg / L, and hydrochloric acid is added to obtain an aqueous solution adjusted to pH 3.0.
  • the cerium hydroxide was aged in the air under the conditions shown in Table 1 in an electric furnace to obtain cerium hydroxide powder having a large crystallite diameter as shown in Table 5. Heat loss weight of this hydrous cerium oxide. /. (Heat loss (%); moisture content when treated at 800 ° C. for 1 hour in an electric furnace) The moisture content was measured. / 0 was the value in Table 5.
  • Example 13 As a comparative example, the heat treatment was performed at a heating temperature of 70 to 300 for 1 to 4 hours to obtain a weight loss by weight (moisture percentage; Ig—1 oss) of the crystallite diameter in Table 5. The same operation was performed to obtain the same powder granules.
  • Comparative Example 1 1 70 4 25 30.3
  • S sample factor half-width FW
  • K is the average crystallite form factor
  • Sampled amount X (atomic weight of cerium Z molecular weight of cerium oxide)
  • the Ce elution rate can be calculated from the following formula based on the amount of cerium in unused hydrous cerium and the concentration of cerium in the treatment solution.
  • Dissolution rate (%) measured value of cell concentration Z amount of collected cell X 100
  • the boron, arsenic, and fluorine adsorbents of the present invention are made of a porous polymer resin as a skin layer, and can contain a large amount of a rare-earth metal hydroxide and / or hydrated oxide having a large amount of voids therein.
  • harmful substances is much better than conventional sorbents I have.
  • contaminated water with a low concentration of these harmful substances can be efficiently purified.
  • fluorine works effectively even at about 20 to 5 Omg ZL.
  • the adsorption activity can be maintained for a long period of time, maintenance is easy.

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Abstract

L'invention concerne un adsorbant d'arsenic qui présente des propriétés d'adsorption de bore, d'arsenic et de fluor supérieures à des adsorbants classiques, qui est efficace y compris lorsque les concentrations en bore, arsenic et fluor sont faibles, et qui bénéficie d'une longue durée de vie. Cet adsorbant est facile d'entretien, et les composants de résine et d'adsorbant ne se dissolvent pas. Ledit adsorbant comprend un hydroxyde et/ou un oxyde hydraté d'un élément du groupe des terres rares et une résine polymère résistant à l'eau servant de revêtement pour la surface de l'hydroxyde et/ou de l'oxyde hydraté, et est caractérisé en ce que l'hydroxyde et/ou l'oxyde hydraté présente un vide central et des micropores entourant ce vide central, et en ce que la résine polymère servant de revêtement pour la surface de l'hydroxyde et/ou de l'oxyde hydraté constitue une couche de peau poreuse.
PCT/JP2004/006091 2003-05-01 2004-04-27 Adsorbant et procede de production associe Ceased WO2004096433A1 (fr)

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US7686976B2 (en) 2003-01-29 2010-03-30 Molycorp Minerals, Llc Composition for removing arsenic from aqueous streams
US8066874B2 (en) 2006-12-28 2011-11-29 Molycorp Minerals, Llc Apparatus for treating a flow of an aqueous solution containing arsenic
US8252087B2 (en) 2007-10-31 2012-08-28 Molycorp Minerals, Llc Process and apparatus for treating a gas containing a contaminant
CN102698716A (zh) * 2011-03-28 2012-10-03 清华大学 一种金属氧化物颗粒吸附剂及其制备方法
US8349764B2 (en) 2007-10-31 2013-01-08 Molycorp Minerals, Llc Composition for treating a fluid
US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
EP3305403A4 (fr) * 2015-06-04 2019-02-13 Ebara Corporation Adsorbant pour l'adsorption de composés d'iode et/ou d'antimoine, procédé de préparation dudit adsorbant, et procédé et appareil de traitement de déchet liquide radioactif au moyen dudit adsorbant
CN118255476A (zh) * 2022-12-28 2024-06-28 中国石油天然气集团有限公司 改性火山渣滤料及去除地下水中铁锰氟的工艺系统

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Publication number Priority date Publication date Assignee Title
US7686976B2 (en) 2003-01-29 2010-03-30 Molycorp Minerals, Llc Composition for removing arsenic from aqueous streams
US8066874B2 (en) 2006-12-28 2011-11-29 Molycorp Minerals, Llc Apparatus for treating a flow of an aqueous solution containing arsenic
US8252087B2 (en) 2007-10-31 2012-08-28 Molycorp Minerals, Llc Process and apparatus for treating a gas containing a contaminant
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US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
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US10577259B2 (en) 2014-03-07 2020-03-03 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
EP3305403A4 (fr) * 2015-06-04 2019-02-13 Ebara Corporation Adsorbant pour l'adsorption de composés d'iode et/ou d'antimoine, procédé de préparation dudit adsorbant, et procédé et appareil de traitement de déchet liquide radioactif au moyen dudit adsorbant
CN118255476A (zh) * 2022-12-28 2024-06-28 中国石油天然气集团有限公司 改性火山渣滤料及去除地下水中铁锰氟的工艺系统

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