WO1998036831A1 - Matiere composite renfermant du zeolite et du charbon actif, preparation et utilisation de celle-ci pour le traitement de l'eau - Google Patents

Matiere composite renfermant du zeolite et du charbon actif, preparation et utilisation de celle-ci pour le traitement de l'eau Download PDF

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Publication number
WO1998036831A1
WO1998036831A1 PCT/US1998/003786 US9803786W WO9836831A1 WO 1998036831 A1 WO1998036831 A1 WO 1998036831A1 US 9803786 W US9803786 W US 9803786W WO 9836831 A1 WO9836831 A1 WO 9836831A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
composition according
binder
heavy metals
colloidal
Prior art date
Application number
PCT/US1998/003786
Other languages
English (en)
Inventor
Thomas J. Shaniuk
Robert V. Russo
Original Assignee
Engelhard Corporation
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
Priority claimed from US09/021,642 external-priority patent/US6107354A/en
Application filed by Engelhard Corporation filed Critical Engelhard Corporation
Priority to EP98908750A priority Critical patent/EP0968051A1/fr
Priority to AU66700/98A priority patent/AU6670098A/en
Publication of WO1998036831A1 publication Critical patent/WO1998036831A1/fr

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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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
    • 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
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/018—Granulation; Incorporation of ion-exchangers in a matrix; Mixing with inert materials

Definitions

  • This invention relates to novel ion exchange/carbon composite materials, methods for their preparation and processes for the removal of heavy metals and other contaminants such as volatile organic compounds (VOC's), chlorine, etc. from aqueous systems 0 utilizing said composite materials.
  • VOC's volatile organic compounds
  • Ion exchangers both organic and inorganic, including crystalline molecular sieve zeolites, are known to remove certain metals from aqueous systems such as drinking water.
  • Activated carbon is also used in water purification or remediation processes. Activated carbon improves taste, odor and smell by adsorbing ionic metals, organic molecules and colloidal particles and also removes chlorine.
  • the purification of drinking water is commonly accomplished at its point of use, e.g., under-the- counter, on-the-counter, whole house systems, under- the-tap, or free standing gravity flow carafe type device.
  • point of use e.g., under-the- counter, on-the-counter, whole house systems, under- the-tap, or free standing gravity flow carafe type device.
  • packed bed systems are typically used.
  • Flow rates vary depending the system. For example, flow rates typically vary from 0.05 gallons per minute (gpm) for gravity-flow pour-through carafes to 1.0 gpm or more, e.g., 3.0 gpm- 8.0 gpm for devices connected directly to household pressurized water lines.
  • gpm gallons per minute
  • This invention relates to composite material compositions suitable for use in the removal of heavy metals from aqueous systems, a process for preparing said composite materials and a process for the removal of heavy metals using said composite materials.
  • this invention relates to formed particulate composite materials comprised of (A) at least one ion exchange material; (B) at least one activated carbon; and, optionally, (C) at least one binder material.
  • this invention relates to a method for preparing said composite material compositions which comprises first mixing components (A) , (B) and, optionally, (C) , then forming particles from said mixture.
  • this invention relates to a method for removing heavy metals from aqueous systems containing one or more heavy metals which comprises contacting said aqueous system with one or more of said composite materials until said heavy metals are substantially removed from said aqueous system.
  • this invention relates to composite material compositions suitable for use in the removal of heavy metals such as lead, cadmium, zinc, copper, chromium, arsenic and mercury from aqueous systems containing one or more of said metals.
  • heavy metals such as lead, cadmium, zinc, copper, chromium, arsenic and mercury.
  • the aqueous systems to which the method of the instant invention is typically applied are industrial, municipal or residential water streams. A preferred use for this method is in the treatment of drinking water.
  • Heavy metal removal from aqueous streams can be complicated by the presence of other contaminants, i.e., competing ions.
  • competing ions include alkaline earth metals, particularly calcium or magnesium sulfates, phosphates and halide ions such as chlorides or fluorides.
  • alkaline earth metals particularly calcium or magnesium sulfates, phosphates and halide ions such as chlorides or fluorides.
  • these -competing ions in amounts of from about 10 ppm up to about 800 ppm, commonly from about 50 ppm up to about 800 ppm, in many cases from about 200 up to about 300 ppm and more typically from about 50 up to about 200 ppm.
  • the presence of these competing ions can make heavy metal removal from aqueous systems much more difficult.
  • the other ions present will compete for available adsorption sites on the adsorbent materials and lower the heavy metal removal efficiency.
  • the most common competing cations are calcium, magnesium, iron from rusty pipes and copper from plumbing as well as anions such as sulphate, phosphate, chloride and fluoride ions.
  • the ion exchange materials useful for the purposes of this invention may be amorphous or crystalline.
  • Preferred ion exchange materials are the amorphous hydrated metal oxide and silicate gels, and the crystalline zeolite materials.
  • the preferred hydrated metal oxide and silicate gels are those described in US Patents 5,277,931 and 5,053,139, which are hereby incorporated herein by reference for the teachings regarding of such materials and methods for their preparation.
  • the zeolite materials useful in making the composite material compositions of this invention are those in powdered form and zeolites present in such materials may be natural or synthetic zeolites, or combinations thereof.
  • Crystalline zeolites are characterized by an aluminosilicate tetrahedral framework and have ion exchangeable large cations and loosely held water molecules permitting reversible dehydration.
  • the general formula for a zeolite is as follows: O-Al 2 0 3 -nSi0 2 -xH 2 0, where M is Na, K, Ca, Sr or Ba and- n and x are integers.
  • the natural zeolites include Analcime, Chabazite, Erionite, Mordenite, Phillipsite, Clinoptilolite, and Faujasite.
  • Synthetic zeolites are particularly useful for the purposes of this invention and are illustrated by zeolite A (U.S. Patent No. 2,882,243), zeolite X (U.S. Patent No. 2,882,244), zeolite Y (U.S. Patent No. 3,130,007), zeolite ZK-5 (U.S. Patent No. 3,247,195), zeolite ZK-4 (U.S. Patent No. 3,314,752), zeolite ZSM-5 (U.S. Patent No. 3,702,886), zeolite ZSM-11 (U.S. Patent No. 3,709,979), zeolite ZSM-12 (U.S. Patent No. 3,832,449), zeolite ZSM-20 (U.S. Patent No. 3,972,983), zeolite ZSM-23 (U.S. Patent No. 4,075,842), zeolite
  • zeolite materials wherein the zeolite in said material has a silica/alumina ratio of less than 20/1, preferably from about 1/1 up to about 5/1, and more preferably of about 1/1. Synthetic zeolite materials are preferred.
  • the zeolite materials useful for the purposes of this invention may be 100% zeolite, but typically contain other components such as kaolin microspheres .
  • the zeolite materials usually contain at least about 25% by weight zeolite and, preferably from 50 up to about 95% by weight zeolite.
  • the ion exchange materials useful for the purposes of this invention are in powdered form.
  • the average particle size of suitable ion exchange materials is less than 200 microns, although usually less than 100 microns; preferably less than 30 microns; and more preferably less than 25 microns. It may be necessary to reduce the size of the particles of the ion exchange material by grinding or otherwise into the powdered form.
  • the BET (nitrogen method) surface area of zeolites useful for the purposes of this invention is typically from about 400 up to about 600 M 2 /g, preferably from about 450 up to about 550 M 2 /g.
  • Activated carbon suitable for the purposes of this invention include those based on coal, wood, coconut shell and peat. A variety of different particle sizes of carbon are suitable for use in this invention. In a preferred embodiment, carbon within 80x325 mesh particle size results in a substantially clear filtered water.
  • the composite materials of this invention will typically contain a minor amount of at least one binder material, preferably a water dispersible binder. As used herein, a "water dispersible binder" shall mean that under typical process conditions, the binder is soluble in water or other liquid medium or is sufficiently dispersed or suspended therein.
  • Binders suitable for use within the context of the present invention include materials such as alginates, dextrin, glucose, gums, starch, waxes, glues; polymer compounds such as polyvinyl acetate, polyolefins such as polyethylene and polyprophylene, and polyvinyl alcohol; mineral acids such as sulfuric acid and phosphoric acid; phosphates such as ammonium phosphate; silica compounds such as alkaline silicates and silica hydrosol; and colloidal clays. These binder materials are typically present in an amount up to about 10% by weight of the composite materials on a moisture-free basis, preferably 1% to about 5% by weight.
  • the polymer compound, if present as the only binder is present in an amount up to about 20%, preferably 15% by weight of said composite material on a moisture-free basis; the silica compound, if present as the only binder, is present in an amount up to about 3% by weight of said composite material on a moisture-free basis; and the colloidal clay, if present as the only binder, is present in an amount up to about 5% by weight of said microsphere on a moisture-free basis. Amounts in excess of that necessary to achieve the desired particle strength may be present as fillers.
  • colloidal clay refers to metallo-aluminum silicate which disperses in water into particles having an average particle size less than one-half micron, as determined by centrifugal sedimentation.
  • the range of possible binders can be extended beyond those mentioned above by those skilled in the art.
  • Colloidal clays typically suitable for use in the instant invention are colloidal attapulgite, colloidal sodium bentonite, colloidal montmorillonite and mixtures thereof.
  • the compositions of the instant invention are preferably spherical granules having particles sizes within the range of about 12x60 mesh (U.S. Standard), preferably about 16x40 mesh.
  • the composite material useful for the purposes of this invention is comprised of at least 5% by weight on a moisture-free basis of ion exchange material, typically from about 5 up to about 25%, at least about 25% by weight on a moisture-free basis of activated carbon, typically from about 25 up to about 75%, and, when present, at least 3% by weight on a moisture free basis of binder material, typically from about 3 up to about 15%.
  • said composite material comprises from about 10 up to about 15% by weight on a moisture-free basis of ion exchange material, from about 50 up to about 60% by weight on a moisture-free basis of activated carbon and from about 3 up to about 10% by weight on a moisture free basis of binder material.
  • Additional binder material, preferably clays may be present in said composites as filler.
  • a moisture-free basis shall be determined by heating at 500°C to a constant weight.
  • compositions of the instant invention are prepared by a process which comprises first mixing components (A) , (B) and, optionally, (C) , then forming particles from said mixture.
  • the process preferably involves intimately mixing the components to insure uniform distribution of the components in the formed composite when combined into a granule.
  • the ion exchange material, activated carbon and binder are the same as, and used in the same amounts, as described above.
  • the mixture may be prepared by combining the components in any order.
  • the composite materials are preferably prepared by mixing powders of the ion exchange material, activated carbon and binder in the presence of water so as to form granules.
  • the powders can also be formed into 1/32" to 1/8" diameter extrudates or pressed into tablets.
  • the formed composite materials are dried. The drying step is typically conducted at 100°C to 120°C. in order to impart sufficient "green strength" so that the formed particles can be handled and transported.
  • the dried particles may be screened to a desired mesh size.
  • thermally fixing or setting the binder is preferred so that the formed particles maintain their integrity when in contact with water.
  • the formed particles are either dried again at 130-190°C, preferably 130-150°C, or calcined in an inert atmosphere, e.g., nitrogen, at 350-700°C, preferably 400-500°C.
  • the specific temperature needed to fix the binder depends upon the specific binder being used. For example polymer compounds are set at 140°C, whereas ceramic binders such as colloidal clays or silica compounds are set at 500°C.
  • thermal fixation e.g. calcination
  • Another benefit of thermal fixation is the development of a high degree of particle integrity to ensure handling without attrition in the dry state.
  • the mixture may be shaped into particles by methods well known in the art. Such methods include extrusion compounding, prilling, tableting and spray drying.
  • the particles of this invention are formed spheres prepared by spheridization on a rotati-ng inclined plate.
  • the shaping of components (A) , (B) and, preferably, with optional component (C) into spheres in the presence of a liquid medium such as water can be carried out by spray drying, flash drying, or other conglomeration techniques such as the use of a high-shear mixer. Agglomeration in a mechanical mixer followed by drum or dish granulators is a preferred method.
  • Spray drying techniques are well-known. As a reference, consult, e.g., Atomization and Spray Drying, by . R. Marshall (Chemical Engineering Monograph Series, No. 2, Vol. 50 (1954)), which is hereby incorporated by reference for its teachings in this regard.
  • a minor amount of a dispersing agent or a flocculating agent may also be incorporated into the mixture to facilitate dispersion/suspension of the particles in the liquid medium.
  • materials for example, aluminas and silicas, other than (A) , (B) and (C) may be incorporated into the mixture.
  • the mixture of ion exchange material, activated carbon, liquid (preferably water) , optional binder and other optional ingredients can be agglomerated in a mechanical mixer.
  • a preferred type of mixer employs pins or blades mounted radially on a rotating shaft, so that the tip of the pin or blade, traveling at high speed, causes solid particles, binder and water to impinge upon or contact each other in such a way as to form an agglomerate.
  • nominally spherical particles tend to grow larger and larger. This phenomenon is enhanced by the tips of the blades or pins coming very close to a stationary wall or to a solid -object (e.g., another blade or pin) moving at a different relative rate.
  • the vortexes set up by this shearing motion tend to enhance the sphericity of the growing particles.
  • This invention provides improved products which meet or exceed EPA drinking water requirements for the removal heavy metals as well as providing improved taste, color and odor, chlorine removal, and have flow rates which are commercially acceptable.
  • the formed composite materials are typically packed into a fixed-bed column or container.
  • the heavy metal containing aqueous stream moves through the adsorbent bed system.
  • Treated water with significantly reduced levels of heavy metals will flow out of the system.
  • Empty bed contact times need to be from one to about 50 seconds. Preferably, the contact time should be five minutes or greater for best results.
  • Lead concentrations in the effluent needs to be less than 15 ppb (micrograms/liter) to be considered substantially removed, however, the effluent concentrations can be as low as 2 ppb.
  • the capacity of the composite material will be higher with higher levels of lead permitted in the effluent stream.
  • the composite material is used as a free-flowing granular media, filled into a cartridge with holes on the top to permit entry of the contaminant solution, which is allowed to trickle through the bed of the composite material and then exit through holes on the bottom of the cartridge, possibly into a reservoir to hold the treated water.
  • Examples of this invention are included hereinbelow. Of course, these examples are not intended as limiting this invention as modification of the examples by ordinary expedient will be readily apparent to those of ordinary skill in the art. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight on a moisture- free basis, temperatures are in degrees Celsius, pressures are at or near atmospheric. Example 1
  • a composite material having the formulation: 55% activated carbon, 12% zeolite, 25.5% attapulgite clay, and 7.5% Si02 coming from Nalco 1140 colloidal silica is prepared by mixing 611 parts of Barnebey & Sutcliffe activated carbon #B&S 3025 (80x325 mesh), 156 parts of a Na alumino-silicate zeolite having a Si/Al ratio of 1/1 and 301 parts of Attagel® 30 attapulgite clay for ten minutes in a bench-scale Eirich mixer.
  • a mixture of 185 parts of Nalco 1140 colloidal silica and 800 parts of deionized water is sprayed onto the dry powders while mixing in the Eirich mixer over a 15 minute period.
  • the mixer is operated in a manner to produce 18 x 40 mesh granules.
  • the wet granules are dried at 110°C for 16 hours and then sieved to 18 x 40 mesh size.
  • the resultant granules are calcined at 500°C -for one hour with a nitrogen gas purge.
  • Example 2 A composite material having the formulation: 55% activated carbon, 12% zeolite, 23% attapulgite clay, and 10% polyolefin powder is prepared by mixing 611 parts of Barnebey & Sutcliffe activated carbon # B&S 3025 (80x325 mesh), 156 parts of a Na alumino-silicate zeolite having a Si/Al ratio of 1/1, 270 parts of Attagel 30 attapulgite clay, and 100 parts of Microthene FN510-00 for ten minutes in a bench-scale Eirich mixer. Then 800 parts of deionized water is sprayed onto the dry powders while mixing in the Eirich mixer over a 15 minute period.
  • the mixer is operated in a manner to produce 18 x 40 mesh granules.
  • the wet granules are dried at 110°C for 16 hours and then sieved to 18 x 40 mesh size.
  • the resultant granules are then placed into an oven at 140°C for 1-2 hours.
  • a composite material having the formulation: 55% activated carbon, 12% zeolite material, 13% attapulgite clay, and 20% calcium silicate is prepared by mixing 611 parts of Barnebey & Sutcliffe activated carbon #B&S 3025 (80x325 mesh) , 156 parts of a Na alumino-silicate zeolite having a Si/Al ratio of 1/1, 153 parts of Attagel® 30 attapulgite clay, and 184.5 parts of calcium hydroxide for ten minutes in a bench-scale Eirich mixer.
  • a mixture of 314 parts of Nalco 1034A colloidal silica and 950 parts of deionized water is sprayed onto the dry powders while mixing in the Eirich mixer over 15 minute period.
  • the mixer is operated in a manner to produce 18 x 40 mesh granules.
  • the wet granules are dried at 110°C for 16 hours and then sieved to 18 x 40 mesh size.
  • the resultant granules are calcined at 500°C for one hour with a nitrogen gas purge.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

L'invention a trait à des compositions de matières composites formées, qui sont utilisées pour éliminer des métaux lourds de systèmes aqueux, à un procédé de préparation desdites matières composites et à un procédé permettant d'éliminer des métaux lourds au moyen desdites matières. Les compositions de matières composites particulaires formées sont constituées de (A) au moins une matière échangeuse d'ions, de préférence un zéolyte; (B) au moins un charbon actif; et (C) au moins une matière liante. Le procédé de préparation desdites compositions de matières composites comporte les étapes consistant à mélanger tout d'abord les éléments (A), (B) et (C), et former ensuite des particules à partir dudit mélange. Le procédé permettant d'éliminer des métaux lourds de systèmes aqueux renfermant un ou plusieurs métaux lourds comporte les étapes consistant à mettre en contact ledit système aqueux avec une ou plusieurs des matières composites, jusqu'à ce que les métaux lourds soient sensiblement éliminés du système aqueux.
PCT/US1998/003786 1997-02-21 1998-02-18 Matiere composite renfermant du zeolite et du charbon actif, preparation et utilisation de celle-ci pour le traitement de l'eau WO1998036831A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98908750A EP0968051A1 (fr) 1997-02-21 1998-02-18 Matiere composite renfermant du zeolite et du charbon actif, preparation et utilisation de celle-ci pour le traitement de l'eau
AU66700/98A AU6670098A (en) 1997-02-21 1998-02-18 Composite material based on zeolite and active carbon, preparation and use thereof in water treatment

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US80321197A 1997-02-21 1997-02-21
US08/803,211 1997-02-21
US09/021,642 US6107354A (en) 1997-02-21 1998-02-10 Composite material, preparation and use thereof
US09/021,642 1998-02-11

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Publication Number Publication Date
WO1998036831A1 true WO1998036831A1 (fr) 1998-08-27

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EP (1) EP0968051A1 (fr)
AU (1) AU6670098A (fr)
WO (1) WO1998036831A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2833984A4 (fr) * 2012-04-05 2016-01-06 3M Innovative Properties Co Milieux d'échange ionique composites pour des systèmes de filtration liquide
JP2017500189A (ja) * 2013-11-27 2017-01-05 ノースウェスタン ユニバーシティ 重金属及び貴金属イオンの捕捉用カラム材料
JP2020157247A (ja) * 2019-03-27 2020-10-01 太平洋セメント株式会社 水質浄化材

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4994191A (en) * 1989-10-10 1991-02-19 Engelhard Corporation Removal of heavy metals, especially lead, from aqueous systems containing competing ions utilizing wide-pored molecular sieves of the ETS-10 type
DE4015555A1 (de) * 1989-06-15 1991-11-21 Bettina Affonso Verfahren zur herstellung von kuenstlicher aktivkohle
DD299622A5 (de) * 1990-10-01 1992-04-30 Karl-Marx-Universitaet,De Geformte hydrophobe mischadsorbentien und verfahren zu ihrer herstellung
US5320773A (en) * 1990-05-31 1994-06-14 Aquatechnica Inc. Composition and method for purifying water
EP0684210A1 (fr) * 1993-12-13 1995-11-29 Suntory Limited Materiau de purification d'eau, procede de production d'un tel materiau, et installation de purification d'eau

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4015555A1 (de) * 1989-06-15 1991-11-21 Bettina Affonso Verfahren zur herstellung von kuenstlicher aktivkohle
US4994191A (en) * 1989-10-10 1991-02-19 Engelhard Corporation Removal of heavy metals, especially lead, from aqueous systems containing competing ions utilizing wide-pored molecular sieves of the ETS-10 type
US5320773A (en) * 1990-05-31 1994-06-14 Aquatechnica Inc. Composition and method for purifying water
DD299622A5 (de) * 1990-10-01 1992-04-30 Karl-Marx-Universitaet,De Geformte hydrophobe mischadsorbentien und verfahren zu ihrer herstellung
EP0684210A1 (fr) * 1993-12-13 1995-11-29 Suntory Limited Materiau de purification d'eau, procede de production d'un tel materiau, et installation de purification d'eau

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2833984A4 (fr) * 2012-04-05 2016-01-06 3M Innovative Properties Co Milieux d'échange ionique composites pour des systèmes de filtration liquide
US10576466B2 (en) 2012-04-05 2020-03-03 3M Innovative Properties Company Composite ion exchange media for liquid filtration systems
JP2017500189A (ja) * 2013-11-27 2017-01-05 ノースウェスタン ユニバーシティ 重金属及び貴金属イオンの捕捉用カラム材料
EP3074128A4 (fr) * 2013-11-27 2017-08-02 Northwestern University Matériau de colonne pour la capture d'ions de métaux lourds et de métaux précieux
US10549270B2 (en) 2013-11-27 2020-02-04 Northwestern University Column material for the capture of heavy metal and precious metal ions
JP2020157247A (ja) * 2019-03-27 2020-10-01 太平洋セメント株式会社 水質浄化材
JP7287813B2 (ja) 2019-03-27 2023-06-06 太平洋セメント株式会社 水質浄化材

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EP0968051A1 (fr) 2000-01-05
AU6670098A (en) 1998-09-09

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