WO2001010786A1 - Procede de filtration sur sable utilisant de la poudre de fer pour le traitement de l'eau contaminee par des metaux lourds et des composes organiques - Google Patents

Procede de filtration sur sable utilisant de la poudre de fer pour le traitement de l'eau contaminee par des metaux lourds et des composes organiques Download PDF

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Publication number
WO2001010786A1
WO2001010786A1 PCT/US2000/017693 US0017693W WO0110786A1 WO 2001010786 A1 WO2001010786 A1 WO 2001010786A1 US 0017693 W US0017693 W US 0017693W WO 0110786 A1 WO0110786 A1 WO 0110786A1
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WO
WIPO (PCT)
Prior art keywords
water
iron
heavy metals
filter
filtration device
Prior art date
Application number
PCT/US2000/017693
Other languages
English (en)
Inventor
Xiaoguang Meng
George P. Korfiatis
Original Assignee
Trustees Of Stevens Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Trustees Of Stevens Institute Of Technology filed Critical Trustees Of Stevens Institute Of Technology
Priority to CA002380843A priority Critical patent/CA2380843A1/fr
Priority to US10/049,107 priority patent/US6942807B1/en
Priority to AU60567/00A priority patent/AU6056700A/en
Priority to JP2001515260A priority patent/JP2003506214A/ja
Priority to EP00946872A priority patent/EP1216209A4/fr
Publication of WO2001010786A1 publication Critical patent/WO2001010786A1/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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • Zero valent iron is an effective and economic reagent for removal of heavy metals and for destruction of chlorinated organic compounds in water because of its high reduction potential. It is known that zero valent iron can be used to recover copper, silver and mercury in water by electrochemical reduction or iron concentration (Case, O.P. 1974. In: Metalli c Recovery from Waste Waters Utilizing Cementation . EPA-670/2-74-008 , 9-23; Gold, J.P. et al . 1984. WPCF 56:280-286) . Other heavy metals such as lead, nickel, cadmium, chromium, arsenic, and selenium can also be removed from water using iron by reduction and precipitation (U.S.
  • Uranyl (U0 2 +2 ) and pertechnetate (Tc0 4 " ) can be effectively removed by iron through reductive precipitation (Cantrell, K.J. et al . 1995. J. Hazard . Mater. 42:201-212).
  • Zero valent iron has also been used to remediate nitrate- contaminated water (Zawaideh, L.I. and T.C. Zhang. 1998. Wat . Sci . Tech . 38:107-115) .
  • Iron is also known to be effective for dechlorination of toxic organic compounds such as carbon tetrachloride and trichloroethylene (Gilham, R. . and S.F. O'Hannesin. 1994. Groundwa ter 32:985-967; Helland, B.R. et al . 1995. J. Hazard . Mater. 41:205-216).
  • Zero valent iron in powder, granular, and fibrous forms can be used in batch reactors, column filters, and permeable reactive barriers installed in groundwater aquifers for water treatment and metals recovery.
  • iron particles in a filter rapidly fuse into a mass due to formation of iron oxides and deposition of the heavy metals. This fusion significantly reduces the hydraulic conductivity of the iron bed.
  • a mixture of iron and inert material such as sand has been used in filter columns (Shokes, T.E. and G. Moller. 1999. Environ . Sci . Technol . 33:282-287).
  • the mixed bed cannot be backwashed because iron and sand will be separated into different layers.
  • Sand filtration alone is not effective in removing heavy metals, especially arsenic and chromate, mainly because sand filter media have a low sorptive capacity for heavy metals.
  • the sand surface of the filter is coated with iron or aluminum hydroxide, the adsorption capacity of the filter media can be significantly enhanced (Meng, X.G. 1993. Effect of Component Oxide Interaction on the Adsorption Properti es of Mixed Oxides, Ph.D. Thesis, Department of Civil and Environmental Engineering, Syracuse University, Syracuse, NY) .
  • Microfiltration (Martin, J.F. et al . 1991. J. Air Waste Manage . Assoc . 41:1653-1657) and adsorption and magnetic filtration (Chen, W.Y. et al . 1991. Res . J. Water Pollut . Control Fed. 63:958-964) have also been studied as means of removing heavy metals from water.
  • the microfiltration process includes precipitation and filtration in two steps. The main difference between this process and the traditional precipitation and filtration treatment is that the heavy metal precipitates are removed directly through a membrane filter, eliminating the coagulation step.
  • the adsorption and magnetic filtration process heavy metals are adsorbed onto fine magnetic particles coated with ferrihydrite . The magnetic particles are then collected using a magnetic filter.
  • the magnetic particles are regenerated by metal desorption and then reused.
  • a water filtration device has now been developed for removal of heavy metals and organic compounds, such as pesticides, from drinking water, waste water and soil washing solutions.
  • the process for filtering water via this device is based on use of a vibrating iron bed filter and a sand filter.
  • the present invention is a water filtration device for removal of heavy metals and organic compounds from contaminated drinking water, waste water and soil treatment solutions.
  • the device comprises at least one iron filter connected in series to a sand filter. Removal of contaminants from water is enhanced by the application of a source of vibratory energy and/or an auger system to the iron filter.
  • the auger system may be used either in place of or in conjunction with the vibratory energy source.
  • Oxidizers and coagulants may be mixed with the water after passage through the iron filter and before passage through the sand filter to increase efficiency of contaminant removal from water.
  • Also provided are methods for removal of heavy metals and organic compounds from raw water using a water filtration device of the present invention.
  • Another object of the present invention is a water filtration device for removal of heavy metals and organic compounds from contaminated water that employs on-line addition of iron solution with an in-line injection port and a sand filter or multi-media filter, thereby eliminating the use of an iron filter.
  • This system can be used for treatment of water containing low levels of heavy metals. Iron solution is added upstream of the sand filter to form a co-precipitate with the contaminants. The co- precipitate is removed directly by the sand filter.
  • Figure 1 provides a schematic of one embodiment of a water filtration device of the present invention wherein the iron filter is subjected to vibration via an external source .
  • Figure 2 depicts a process diagram for in-line injection.
  • contaminated water enters the inflow, passes to an in-line mixer, mixing chamber and sand filter, and emerges as treated water.
  • the present invention is a water filtration device which comprises a continuously or intermittently vibrated iron bed filter or filters and a sand filter.
  • a continuously or intermittently vibrated iron bed filter or filters and a sand filter.
  • the fusion of iron particles in the filter is prevented by continuous or intermittent vibration with an external or internal source of vibratory energy or by continuous mixing with an auger.
  • Most of the water pollutants are removed by the iron filter or filters.
  • the residual pollutants in the iron filter effluent are further precipitated with ferric ions generated by corrosion of iron particles and oxidation.
  • the precipitates are removed directly by the sand filter.
  • the iron filter can also be eliminated from the system to form a direct co-precipitation filtration process for the treatment of water containing low levels of contaminants .
  • the device of the present invention consists of at least two filters in series, an iron filter 2 and a sand bed filter 3, as shown in Figure 1.
  • a device which comprises two or more iron filters and one or more sand filters in series can also be used.
  • water for filtration is first collected in a container.
  • the filtration device of the present invention can be placed directly on line with a water supply source.
  • the water to be filtered via the device of the present invention is contaminated with heavy metals and/or organic compounds that are harmful to human health and is commonly referred to as "raw water” .
  • Examples of heavy metals and organic compounds which often contaminate the water include, but are not limited to, arsenic, chromium, nickel, selenium, lead, cadmium, copper, PCBs, chlorinated organic compounds and pesticides.
  • the raw water is passed through the iron filter which comprises iron filings or particles. The size of these particles can vary from fine powder to large granules and chips depending on the type of contaminant and water flow rate.
  • the chemical processes that take place within the iron filter include reduction, precipitation, adsorption, dechlorination, and combinations thereof. Since the incoming raw water generally contains dissolved oxygen, up to saturation level of 8 mg/L, oxidation of the iron surface takes place immediately.
  • a source of vibratory energy 4 is applied to the granular iron.
  • the vibration is applied either continuously or intermittently.
  • the vibrations keep the iron particle in motion and thus prevent the cementation of the matrix by oxide formation.
  • the frequency and the magnitude of the vibrations applied depends on the filter size, the type of granular iron used, and the types and concentration of contaminants present in the water, and can vary from low frequencies to ultrasonic frequencies.
  • the vibrations can be applied either externally as depicted in Figure 1 (i.e.. applying vibration on the filter housing with a commercially available vibrator) or internally directly on the iron powder with a vibratory probe.
  • a set of ribs or baffles can be added to the vibratory probe.
  • a combination of externally and internally applied vibration can also be used.
  • applied vibration is used to regenerate the iron filter.
  • the vibration frees the iron precipitates which are formed during the oxidation process and the finer particulates are carried by the water to the sand filter where they are retained and recovered during backwashing .
  • an augering system which is embedded in the iron and slowly circulates the iron can be used. The number and size of the augers required depends upon the size of the filter, where augering, like vibration keeps the iron filter continuously regenerating.
  • a combination of both vibration and circulation via an auger is employed.
  • the core shaft of the auger consists of a vibratory probe and the combination of vibration and circulation provides an improved separation of iron particles within the filter.
  • small of amounts of iron filings and granular iron can be added into the vibrating iron filter, continuously or intermittently to maintain sufficient reactivity of the iron bed.
  • the iron bed can also be replaced partially or completely when its reactivity decreases to a desirable level .
  • Chemicals such as acids, bases, and oxidizing and reducing reagents such as ozone or hydrogen peroxide can be added to the water before it flows into the vibrating iron filter. The addition of the chemicals can control the reactivity of the iron bed and improve the removal and destruction of contaminants.
  • on-line addition of iron solution and a sand filter can be used for the treatment of water which contains only low levels, in the order of less than 1 ppm, of heavy metals.
  • the iron solution is added to the water upstream of the sand filter to form a co-precipitate with the contaminants. These co- precipitates are then removed directly by passage of the water through the sand filter.
  • the sand filter 3 of the present invention is located downstream of the iron filter 2.
  • the sand filter has a dual function in that it facilitates precipitation of contaminants that are not removed in the iron filter, such as heavy metals, and it acts as a particulate filter cleaning the water from any produced solids. For example, small amounts of ferrous ions are released from the iron particles due to corrosion. Ferrous ions in the effluent coming out of the iron filter are oxidized by dissolved oxygen and form ferric hydroxide precipitate. At the same time, residual heavy metals in the effluent form co- precipitates with ferric hydroxide rapidly and are removed by the sand filter. The process continues until the permeability of the sand filter is reduced. This is detected by a pressure drop across the filter.
  • the pressure is automatically monitored and when it exceeds a specified value the sand filter undergoes a backwash cycle by reversing the water flow as is done in conventional filter backwashing procedures .
  • the iron filter 2 can be eliminated from the system to form a direct co- precipitation filtration process.
  • the direct coprecipitation filtration process eliminates the iron filter in the iron powder-sand filter system ( Figure 1) .
  • Ferric solution and other chemicals such oxidants and coagulants are added into the water pipe and other water distribution systems directly or through an on-line mixer, or through other device such as an injection port.
  • the injection port is located upstream of the sand filter 3 so that the chemicals can mix with the water and convert the contaminants from soluble to particulate form before the water enters the sand filter bed 3.
  • a conventional in-line mixer can be used to enhance the mixing process. Therefore, this distance between the injection port and the sand filter is a chamber for mixing of the water and the iron solution in order to form a co-precipitate.
  • a direct co-precipitation filtration process has lower costs and less total area requirements for the treatment process. It eliminates the need for flocculation reactor (s) that are usually required in the direct filtration process.
  • additional oxidizers such as potassium permanganate and chlorite salts, or coagulants, such as iron chloride and iron sulfate, are used to achieve complete removal of target contaminants from water.
  • coagulants and oxidizers can be added on-line by means such as a metering pump 5 placed between the iron filter 2 and sand filter 3 as shown in Figure 1.
  • the efficiency of the iron filter can also be improved by increasing the retention time of water in the iron bed.
  • the ability of the device of the present invention to process contaminated water was demonstrates in water spiked with chromate ions (1000 ⁇ g/L of Cr(VI)). Cr(VI) concentration was reduced to approximately 20 ⁇ g/L by the iron column. The sand filter further reduced Cr concentration to less than 3 ⁇ g/L. After 27 days of treatment, the flow rate was increased from 0.34 gpm/ft 2 to 2.7 gpm/ft 2 . The effluent Cr concentration increased slightly to approximately 5 ⁇ g/L. Cr (VI) was effectively removed at a similar flow rate to the conventional sand filters.
  • the hydraulic retention time or the location of the iron injection port in the direct co-precipitation filtration process is determined by the rate of co- precipitation of contaminants with ferric hydroxide.
  • the results show that removal of As (V) and iron is a function of time of co-precipitation.
  • the mixed water was filtered through a 0.1 micron membrane filter to remove the co- precipitate.
  • As (V) concentration was reduced from 50 ⁇ g/L in the influent to 3.3 ⁇ g/L within 1 minute of mixing.
  • iron concentrations were reduced from 1000 ⁇ g/L to 50 ⁇ g/L. Data showed that less than 10 minutes was required for the removal of As (V) by co-precipitation with ferric hydroxide with the device of the present invention.

Abstract

L'invention concerne un dispositif de filtration (3) et un procédé pour retirer les métaux lourds et les composés organiques de l'eau non traitée.
PCT/US2000/017693 1999-08-06 2000-06-28 Procede de filtration sur sable utilisant de la poudre de fer pour le traitement de l'eau contaminee par des metaux lourds et des composes organiques WO2001010786A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002380843A CA2380843A1 (fr) 1999-08-06 2000-06-28 Procede de filtration sur sable utilisant de la poudre de fer pour le traitement de l'eau contaminee par des metaux lourds et des composes organiques
US10/049,107 US6942807B1 (en) 1999-08-06 2000-06-28 Iron powder and sand filtration process for treatment of water contaminated with heavy metals and organic compounds
AU60567/00A AU6056700A (en) 1999-08-06 2000-06-28 An iron powder and sand filtration process for treatment of water contaminated with heavy metals and organic compounds
JP2001515260A JP2003506214A (ja) 1999-08-06 2000-06-28 重金属および有機化合物で汚染された水の処理のための鉄粉末および砂濾過方法
EP00946872A EP1216209A4 (fr) 1999-08-06 2000-06-28 Procede de filtration sur sable utilisant de la poudre de fer pour le traitement de l'eau contaminee par des metaux lourds et des composes organiques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14770899P 1999-08-06 1999-08-06
US60/147,708 1999-08-06

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/803,170 Continuation-In-Part US20050016928A1 (en) 1999-08-06 2004-03-17 Apparatus and method for water treatment by a direct co-precipitation/filtration process

Publications (1)

Publication Number Publication Date
WO2001010786A1 true WO2001010786A1 (fr) 2001-02-15

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Country Status (5)

Country Link
EP (1) EP1216209A4 (fr)
JP (1) JP2003506214A (fr)
AU (1) AU6056700A (fr)
CA (1) CA2380843A1 (fr)
WO (1) WO2001010786A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1094036A2 (fr) * 1999-10-19 2001-04-25 Malcolm Robert Snowball Traitement de liquide par filtration et des vibrations
US7713426B2 (en) * 2008-01-11 2010-05-11 Blue Water Technologies, Inc. Water treatment
US7713423B2 (en) 2002-12-04 2010-05-11 Idaho Research Foundation, Inc. Reactive filtration
US7744764B2 (en) 2002-12-04 2010-06-29 Idaho Research Foundation, Inc. Reactive filtration
US8071055B2 (en) 2002-12-04 2011-12-06 Blue Water Technologies, Inc. Water treatment techniques
US8080163B2 (en) 2002-12-04 2011-12-20 Blue Water Technologies, Inc. Water treatment method
EP2447220A1 (fr) * 2010-11-02 2012-05-02 Montanuniversität Leoben Suppression de contaminants de liquides aquatiques
US8741154B2 (en) 2008-10-17 2014-06-03 Remembrance Newcombe Water denitrification
CN104326607A (zh) * 2014-11-12 2015-02-04 云南昆钢水净化科技有限公司 一种处理焦化纳滤浓盐水的方法
DE10392330C5 (de) * 2002-02-14 2015-07-16 Trustees Of Stevens Institute Of Technology Verfahren zur Herstellung eines oberflächenaktivierten Titanoxidprodukts und zur Verwendung desselben in Wasseraufbereitungsverfahren
CN109231676A (zh) * 2018-10-15 2019-01-18 佛山市思特四通化工有限公司 一种化学工业用重金属废水处理装置及其操作方法
CN112850976A (zh) * 2019-11-26 2021-05-28 韩国科学技术研究院 电容式脱盐工序的预处理装置

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ITMI20052150A1 (it) * 2005-11-11 2007-05-12 Enitecnologie Spa Processo per il trattamento di acque contaminate mediante un sistema bifunzionale costituito da ferro e zeoliti
JP4630237B2 (ja) * 2006-06-27 2011-02-09 株式会社神戸製鋼所 ヒ素除去用鉄粉の再生方法
JP4808093B2 (ja) * 2006-06-27 2011-11-02 株式会社神戸製鋼所 ヒ素除去用鉄粉の再生方法
JP2008100177A (ja) * 2006-10-19 2008-05-01 Kobe Steel Ltd 被処理水からのヒ素の除去方法
JP6118571B2 (ja) * 2012-02-07 2017-04-19 株式会社神戸製鋼所 汚染土壌の処理方法
CN105121095B (zh) * 2013-04-04 2018-04-27 株式会社可乐丽 浆料再生装置、浆料再生方法以及再生浆料
JP6275003B2 (ja) * 2014-08-25 2018-02-07 株式会社 エー・イー・エル 放射能汚染土壌の洗浄方法
JP6457328B2 (ja) * 2015-04-28 2019-01-23 鹿島建設株式会社 地下水の浄化設備、及び浄化方法
CN106316004B (zh) * 2016-11-07 2017-09-01 江西盖亚环保科技有限公司 一种高浓度有机废水直接深度净化的方法

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2359073A (en) * 1999-10-19 2001-08-15 Malcolm Robert Snowball Fluid treatment comprising vibration of a filter media
EP1094036A3 (fr) * 1999-10-19 2001-12-05 Malcolm Robert Snowball Traitement de liquide par filtration et des vibrations
GB2359073B (en) * 1999-10-19 2003-10-29 Malcolm Robert Snowball Fluid treatment
EP1094036A2 (fr) * 1999-10-19 2001-04-25 Malcolm Robert Snowball Traitement de liquide par filtration et des vibrations
DE10392330C5 (de) * 2002-02-14 2015-07-16 Trustees Of Stevens Institute Of Technology Verfahren zur Herstellung eines oberflächenaktivierten Titanoxidprodukts und zur Verwendung desselben in Wasseraufbereitungsverfahren
US7744764B2 (en) 2002-12-04 2010-06-29 Idaho Research Foundation, Inc. Reactive filtration
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AU6056700A (en) 2001-03-05
EP1216209A1 (fr) 2002-06-26

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