WO2016014480A1 - Filtre et procédés de remédiation des métaux lourds de l'eau - Google Patents

Filtre et procédés de remédiation des métaux lourds de l'eau Download PDF

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Publication number
WO2016014480A1
WO2016014480A1 PCT/US2015/041268 US2015041268W WO2016014480A1 WO 2016014480 A1 WO2016014480 A1 WO 2016014480A1 US 2015041268 W US2015041268 W US 2015041268W WO 2016014480 A1 WO2016014480 A1 WO 2016014480A1
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Prior art keywords
stage
filter
article
water
adsorbent
Prior art date
Application number
PCT/US2015/041268
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English (en)
Inventor
William Peter Addiego
Benedict Yorke Johnson
Lingyan Wang
Original Assignee
Corning Incorporated
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Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to CN201580040848.XA priority Critical patent/CN106536420A/zh
Publication of WO2016014480A1 publication Critical patent/WO2016014480A1/fr

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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
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • 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
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/60—Use in several different columns
    • B01J2220/603—Use in several different columns serially disposed columns
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes

Definitions

  • NANOPARTICLES mentions a method for making carbon-supported transition metal- based nanoparticles, the method comprising: mixing at least one carbon feedstock, at least one transition metal-containing feedstock, at least one organic binder, and at least one resin binder to form a feedstock mixture; extruding the feedstock mixture; and heating the extruded feedstock mixture at a temperature and for a time sufficient to carbothermally reduce the at least one transition metal-containing feedstock.
  • the application also mention technologies that have been employed to fabricate water filters for removing heavy metals from drinking water (i.e., tap water). Extensive testing has been conducted in mixed metal ion solutions to assess the feasibility of the filter samples for heavy metal remediation.
  • the disclosure relates to a filter article and methods for heavy metal remediation of water with the article.
  • the disclosure provides a filter article and methods for heavy metal remediation of water.
  • FIG. 1 shows a schematic of a filter article having two-stage adsorbent bed for removing toxic metals from a contaminated water stream.
  • compositions, articles, and methods of the disclosure can include any value or any combination of the values, specific values, more specific values, and preferred values described herein, including explicit or implicit intermediate values and ranges.
  • Nanoscale zero valent iron ( ZVI) is emerging as a promising option for removal of heavy metals from contaminated water.
  • NVI zero valent iron
  • ZVI nanoparticles possess various chemical properties derived from their different oxidation states, they have the ability to degrade a wide variety of toxic pollutants in soil and water, such as perchloroethene (PCE), trichloroethene (TCE), carbon tetrachloride (CT), nitrate, energetic munitions such as TNT and RDX, legacy organohalide pesticides such as lindane and DDT, and heavy metals such as chromium, lead, mercury, cadmium, and other inorganics such as selenium and arsenic. Processes employing ZVI nanoparticles may also provide cost savings compared to conventional pump-and-treat or permeable reactive barrier methods.
  • NZVI in powder, granular, and fibrous forms are used in batch reactors and column filters.
  • ZVI nanoparticles in a reactor or filter rapidly fuses into a mass due to formation of iron oxides. This fusion significantly reduces the hydraulic conductivity of the iron bed.
  • To prevent NZVI aggregation and rapid deactivation several technologies have been developed in the art that immobilize iron nanoparticles on particulate supports such as silica, sand, alumina, activated carbon, titania, zeolite powder, etc. The main issue with these technologies is that like the free standing NZVI nanoparticles, they require a follow up filtration.
  • the present disclosure provides a liquid filter article, comprising: a housing having an inlet, an outlet, and an adsorbent bed there between, the bed comprising:
  • first stage having a first adsorbent, the first adsorbent including an activated carbon honeycomb infused with a plurality of zero valent iron nanoparticles ("Fe-AC"); and
  • a second stage having a second adsorbent, the second adsorbent being selected from iron oxide particles supported on activated carbon honeycomb ("FEOX-AC”), iron oxide particles supported on activated alumina honeycomb (“FeOX-AA”), or a combination thereof, wherein the first stage is in fluid communication with the second stage.
  • FEOX-AC activated carbon honeycomb
  • FeOX-AA iron oxide particles supported on activated alumina honeycomb
  • the iron oxide particles in the second stage can be, for example, magnetite.
  • the plurality of zero valent iron nanoparticles is from 15 to 40 wt% based on the total weight of the activated carbon based honeycomb in the first stage.
  • the iron oxide particles supported on the activated carbon honeycomb in the second adsorbent can be present, for example, in from 20 to 40 wt% based on the total weight of the activated carbon honeycomb.
  • the liquid filter article can further comprise a high surface area of, for example, from 300 to 4,000 m 2 per gram.
  • the iron oxide particles supported on the activated alumina honeycomb in the second adsorbent can be present, for example, present in from 20 to 40 wt% based on the total weight of the activated alumina honeycomb.
  • the fluid communication between the first stage and the second stage is direct physical contact between the first and second stage.
  • the fluid communication between the first stage and the second stage is indirect and having an enclosed spatial gap (140) between the first and second stage.
  • a flow control material can be selected, for example, from a fiber (e.g., glass wool), a mesh (e.g., woven or non-woven material), granules (such as sand, beads, etc.), a honeycomb structure, static mixing packings, such as rings, balls, miniliths, "Sultzer” -type packings, and like materials, or a combination thereof.
  • the flow control material can be disposed in the article, for example: before (105), after (107), or between (109) the first stage and the second stage. The flow control material facilitates redistribution of the liquid flow into the article, through the article, exiting the article, or a combination thereof.
  • the disclosure provides a method of removing heavy metals from water using the abovementioned filter article, comprising: contacting the first stage of the filter and a water influent having, or suspected of having, at least one heavy metal contaminant present; and
  • the contacting the first stage of the filter and the water influent having at least one heavy metal contaminant removes the at least one heavy metal contaminant from the water.
  • the contacting the effluent of the first stage of the filter and the second stage of the filter removes exchanged iron from the effluent of the first stage.
  • the at least one heavy metal contaminant is selected, for example, from cadmium, chromium, copper, lead, mercury, nickel, zinc, semi-metals, and like metals, or a combination thereof.
  • the contacting the first stage of the filter and the water influent, and contacting the effluent of the first stage of the filter and the second stage of the filter comprises providing relative motion between the filter and the water influent and the effluent.
  • the contacting the first stage of the filter and the water influent can comprise at least one of any situation that provides for relative motion between the filter article and the liquid being filtered, for example:
  • the disclosure provides improved methods, compositions, and articles for removing heavy metals from contaminated drinking water streams without significant release of iron into the water streams.
  • the disclosure provides a filter article having a two-stage adsorbent bed for removing heavy metals from contaminated drinking water, and without releasing significant iron into the drinking water.
  • the adsorbent bed comprises an adsorbent material in each adsorption stage selected to provide effective adsorption characteristics for the contaminants present in the water at that stage.
  • heavy metal-laden drinking water is passed through a bed of activated carbon (AC) honeycomb infused with zero valent iron nanoparticles (Fe-AC).
  • the Fe-AC adsorbent adsorbs the heavy metals present in the water and releases Fe (III) into the water.
  • the iron-rich water is passed into a second-adsorption stage, which contains an adsorbent material selected for effective adsorption of iron.
  • This second adsorbent is used to strip iron and the remaining heavy metals, and provide a purified drinking water product having a concentration of the toxic metals and iron below their respective maximum contaminant levels (MCLs).
  • the adsorbent material in the second stage can be, for example, an activated carbon honeycomb or an activated alumina honeycomb infused with iron oxide, preferably magnetite.
  • the disclosure provides improved methods, compositions, and articles, for removing heavy metals from drinking water streams using iron-based adsorbents without releasing significant amount of iron into the water stream.
  • Fig. 1 shows a schematic of an exemplary filter (100) comprised of a housing (101) having a two-stage (1 10, 120) adsorbent bed for removing toxic metals from a metal contaminated water source (130) or stream.
  • a metal contaminated water is introduced into stage one (1 10) containing adsorbent material A.
  • Adsorbent material A can be, for example, ZVI-nanoparticles supported on activated carbon honeycomb (Fe-AC).
  • Fe-AC activated carbon honeycomb
  • the toxic metals are adsorbed by Fe-AC, and subsequently or consequently, dissolved and particulate iron are introduced into the intermediate water stream such as in spatial gap (140).
  • the filter article can have an optional chamber, for example, before (105), after (107), between (109), or a combination thereof, with respect to each of the first stage (110) and the second stage (120).
  • the optional chamber(s) can be, for example, vacant, or can be occupied by a flow control material that can redistribute the liquid flow within and through the article, such as with a static mixing packing.
  • the carbon based honeycomb adsorbents can be prepared according to the aforementioned commonly owned and assigned application USSN 13/927,857, and USSN 14/252,174, from a substantially homogeneous mixture made by blending, according to conventional methods, the four main ingredients: an organic filler material; an iron compound(s); a binder selected from cellulose ethers; and a resinous binder.
  • the activated carbon supported NZVI or iron oxide honeycomb is prepared in a one-step process that involves pyrolyzing the extruded body to carbonize and activate the carbon precursor and convert the iron compound into elemental iron (Fe°) or iron oxide depending on the heat treatment applied.
  • the alumina supported iron oxide particles can be prepared by at least two methods.
  • the extrusion batch compositions for alumina honeycombs such as described in US 6677261
  • an iron precursor material such as an Fe (II) salt (e.g., Fe (II) oxalate), Fe (III) salt (e.g., Fe (N0 3 ) 3 , and iron oxide) and then extruding and firing the extrudate according to the methods described in US 6677261.
  • iron oxide particles can be deposited in the pores and on the walls of extruded alumina honeycomb by conventional impregnation methods, such as wash coating.
  • an adsorption column was separately packed with adsorbent A and B, and the tap water or mixed metal iron solution was passed through the column at a flow rate of 100 mL/min.
  • a column containing only adsorbent A was tested under identical test conditions.
  • a fixed bed adsorption column is a column in which the adsorbent material is held in place and does not move relative to the fluid.
  • Tap water was pumped, using a peristaltic pump, through the column at flow rate of 100 mL/min.
  • the effluent water was sampled (8 mL) at 10 min intervals.
  • the concentration of iron in the influent and effluent water was measured by ICP-MS and compared. Table 1 shows the concentration of iron in the effluent water of adsorption column with no iron-removing media.
  • Table 1 provides the iron concentration of an effluent water of an adsorption column (as defined above) without an iron-removing media as a control.
  • the second stage FeOX-AC adsorbent was effective in removing the iron that was leached out from the first stage (stage one), with the iron concentration in the effluent water significantly reduced below the EPA's MCL of Fe in drinking water (300 ppb).
  • the effectiveness of the adsorbent in removing iron was further confirmed by the clarity of the effluent water, which was colorless, and which compares very well with the clarity of tap water.
  • the iron concentration in the final effluent water was significantly reduced below the EPA's MCL of iron in drinking water (300 ppb).
  • Heavy metal adsorption performance of the two-stage adsorbent bed The metal removal performance of the two-stage adsorbent bed was evaluated in a column adsorption test using a mixed metal ion solution as the source of contaminated water.
  • the test solution was prepared by spiking tap water with measured amounts of selected heavy metal salts (control).
  • the test solution was passed through the adsorption column at a flow rate of 100 mL/min using a peristaltic pump. The adsorption time was 15 minutes.
  • Table 4 provides the concentration of toxic metals in the effluent water after a two-stage adsorbent bed containing Fe nanoparticles supported on activated carbon honeycomb (Fe-AC) in the first stage and Fe 3 0 4 nanoparticles supported on activated carbon honeycomb (FeOX-AC) in the second stage.
  • the adsorption test results support the conclusion that the two-stage adsorbent bed was effective in removing both heavy metals and iron.
  • the primary phase is elemental iron (i.e., Fe°), with small amounts of FeO and FeC in the final product.
  • a size calculation based on the XRD data indicated a particle size of about 160 nm for the zero-valent iron nanoparticles.
  • Table 5 Feedstock Composition for Fe-AC Adsorbent.
  • X-ray diffraction (XRD) analysis is expected to determine crystalline phases in the sample that resemble a mixture of iron oxide particles supported on activated carbon (“FEOX-AC”) and iron oxide particles supported on activated alumina (“FeOX-AA").
  • FEOX-AC activated carbon
  • FeOX-AA iron oxide particles supported on activated alumina

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

L'invention concerne un article de filtre à liquide, qui comprend : un boîtier ayant une entrée, une sortie et un lit adsorbant entre les deux. Le lit comprend : un premier étage ayant un premier adsorbant, le premier adsorbant contenant un nid d'abeille en carbone actif infusé avec une pluralité de nano-particules de fer à valence zéro (« Fe-Ac ») ; et un second étage ayant un second adsorbant, le second adsorbant étant choisi parmi des particules d'oxyde de fer supportées sur un nid d'abeille en carbone actif (« FeOX-AC »), des particules d'oxyde de fer supportées sur un nid d'abeille en alumine active (« FeOX-AA ») ou une combinaison de celles-ci, le premier étage étant en communication fluidique avec le second étage. L'invention concerne également un procédé d'utilisation de l'article de filtre à liquide afin de remédier aux métaux lourds dans l'eau.
PCT/US2015/041268 2014-07-22 2015-07-21 Filtre et procédés de remédiation des métaux lourds de l'eau WO2016014480A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580040848.XA CN106536420A (zh) 2014-07-22 2015-07-21 用于水的重金属治理的过滤器和方法

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US201462027576P 2014-07-22 2014-07-22
US62/027,576 2014-07-22

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Cited By (2)

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CN107970890A (zh) * 2017-11-30 2018-05-01 华南理工大学 一种羟基铁改性活性炭复合材料及其制备方法
CN115093003A (zh) * 2022-07-06 2022-09-23 重庆大学 一种限域体系驱动六价铬瞬时还原的方法

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WO2017218366A1 (fr) * 2016-06-12 2017-12-21 Liangjie Dong Compositions et procédés pour l'élimination d'arsénic et de métaux lourds à partir d'eau
CN111807635A (zh) * 2020-07-23 2020-10-23 河北林江环境科技发展有限公司 污水、饮用水重金属去除工艺

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US20100307978A1 (en) * 2009-04-25 2010-12-09 John Sawyer Apparatus and method for contaminant removal from aqueous solution
US20130105400A1 (en) * 2011-10-04 2013-05-02 Hyoyoung Lee Composite containing metal component supported on graphene, preparing method of the same, and uses of the same

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CN107970890A (zh) * 2017-11-30 2018-05-01 华南理工大学 一种羟基铁改性活性炭复合材料及其制备方法
CN115093003A (zh) * 2022-07-06 2022-09-23 重庆大学 一种限域体系驱动六价铬瞬时还原的方法
CN115093003B (zh) * 2022-07-06 2023-06-09 重庆大学 一种限域体系驱动六价铬瞬时还原的方法

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