WO1994029228A1 - Water purification system and removal of halides - Google Patents

Water purification system and removal of halides Download PDF

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Publication number
WO1994029228A1
WO1994029228A1 PCT/US1994/005849 US9405849W WO9429228A1 WO 1994029228 A1 WO1994029228 A1 WO 1994029228A1 US 9405849 W US9405849 W US 9405849W WO 9429228 A1 WO9429228 A1 WO 9429228A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
water
iodine
activated carbon
per cent
Prior art date
Application number
PCT/US1994/005849
Other languages
English (en)
French (fr)
Inventor
Moshe A. Frommer
Israël DALVEN
Original Assignee
Purotech International Inc.
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 Purotech International Inc. filed Critical Purotech International Inc.
Priority to BR9406788A priority Critical patent/BR9406788A/pt
Priority to US08/556,910 priority patent/US6071415A/en
Priority to KR1019950705404A priority patent/KR960702817A/ko
Priority to JP7501845A priority patent/JPH08510958A/ja
Priority to EP94919230A priority patent/EP0723526A4/en
Publication of WO1994029228A1 publication Critical patent/WO1994029228A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C02F1/505Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/18Removal of treatment agents after treatment
    • C02F2303/185The treatment agent being halogen or a halogenated compound

Definitions

  • Methods for impregnating activated carbon with silver to yield silver loadings much higher than that available commercially are provided, which provide products useful for purifying water, especially from iodides and bromides which may be eluted from iodinated and halogenated disinfecting resins, lowering the concentrations, of the contaminating halides to levels acceptable for continuous drinking applications and enabling regeneration of the silver and possibly also of iodine from the precipitated silver halides.
  • Silver impregnated activated carbon (Ag-GAC) is a well known product, used widely for purifying process-water and drinking-water.
  • the function of the silver bound to the activated carbon is to avoid bacterial growth on the carbon bed and in the water in contact with it.
  • Filter cartridges containing Ag-GAC do not kill bacteria during normal filtration rates. For this reason Ag-GAC is described as a Bacteriostatic medium and not a Bactericide.
  • the maximum admissible concentration of silver in drinking water is : 0.05 mg/L (50ppb) in the USA and Canada and 0.01 mg/L (10 ppb) in the EEC. Therefore, in order to enable application of Ag-GAC for purifying drinking water, the loading of silver on the carbon is low, usually lower than one percent. The highest silver loading offered commercially is 1.05%. Recently iodinated and halogenated resins have been introduced as water purifiers capable of "instantaneously" killing bacteria and viruses upon contact between the treated water and the disinfecting resin.
  • AADI adjusted acceptable daily intake
  • the concentrations of iodine/iodide eluted to the treated water by commercial disinfecting resins vary between 2 to 15 ppm (mg/L), depending on the type of the resin and on the salinity and temperature of the treated water. Therefore, application of equipment containing iodinated resins for purifying drinking water for continuous consumption can be possible only if the drinking water purifier contains means which reduce the concentration of iodine/iodide in the product water to 1.19 ppm and preferably considerably lower.
  • Iodides can be removed almost absolutely from aqueous solutions by precipitating them with silver ions.
  • the solubility product of Agl at 25°C is 1.5x10 -1 ⁇ , a million times lower than that of AgCl (1.56x10 "" ⁇ ) at the same temperature. Therefore, iodides can effectively be eliminated from drinking water via precipitation as Agl, even in the presence of a large excess of chloride ions such as those existing in drinking water.
  • Metallic silver or silver chloride can generate sufficient concentrations of silver ions for precipitating iodides.
  • the surface area of the silver-ion generating solid must be very large. Otherwise it will very quickly be coated with Agl precipitate and become "blind" to the aqueous solution.
  • Granular Activated Carbon (GAC) has a large surface area and can be an efficient "carrier” for silver. Indeed, Ag-GAC has proven to be effective in removing iodide ions from drinking water.
  • the present invention relates to a purification device for producing potable water for drinking by humans, comprising a sequence of a bed of a halogenated resin, followed by a bed or separate container containing silver-impregnated activated carbon, loaded with more than two weight per cent of silver.
  • the carbon is preferably loaded with from 4 to 14 weight-% of silver and a filter is provided for filtering out particulate material.
  • the invention further relates to a process for the purification of water and for the purpose of converting it to water fit for human consumption comprising passing feed water through a sequence of a halogenated resin, followed by a bed of silver-impregnated activated carbon containing at least two weight per cent of silver.
  • the resin used is an iodinated one, and preferably the impregnated carbon contains between 4 and 14 weight per cent silver.
  • the invention also relates to the novel silver impregnated activated carbon containing at least two percent by weight of silver.
  • the system is useful for the purification or treatment of water for reducing the concentration of iodide/iodine in water and also for reducing the concentration of bromide/bromine, or of mixed iodide/bromide in water. It can be used as a post treatment for water disinfected by passage through an iodinated or halogenated resin. It can be used in conjunction with iodinated resins, utilizing the precipitated silver iodide for regenerating silver and iodine.
  • Ag-GAC loaded with at least 3% silver is therefore desired for practical elimination of iodine/iodide from water disinfected by iodinated resins.
  • Such a product also enables a considerable reduction of the cost of water purification by disinfecting resins, because both the expensive silver and the expensive iodine when precipitated as Agl can easily be trapped (filtered out) by a coarse post filter and regenerated.
  • placement of Ag-GAC treatment down-stream the iodinated-resin-filter guarantees that the concentrations of both silver and iodine will be lower than the maximum permissible levels for continuous drinking applications.
  • Fig. 1 illustrates total iodine elimination of AG/GAC against quantity of water passed through the filter, according to Example 1.
  • Fig. 2 is a similar graph, relating to Example 2
  • Fig. 3 is a similar graph, relating to Example 3
  • Fig. 4 is a similar graph, relating to Example 4
  • Fig. 5 illustrates the effectivity of activates carbon with different silver content in reducing iodine content
  • Fig. 6 illustrates the use of 10 per cent silver impregnated active carbon with prefiltration in a water purifier. E x a m p l e s .
  • Example 1 25.8 g Silver nitrate, 70 ml water, and 31 ml of a 25% Ammonia (as NH3) solution and were combined and stirred until dissolved. The solution was added slowly in 10 ml portions to 165 g 20-50 mesh granulated activated carbon, which had been previously washed with nitric acid and dried. Agitation between additions was necessary to assure an even mixture. After standing 15 minutes a solution of 15 g fructose in 80 ml of water was added. The mixture was placed in an 80°C oven for 68 hrs. The small amount of supernatant liquid showed no precipitate with HC1. The product was rinsed well with water and dried at 250°C. The yield was 181.2 g, corresponding to 9% silver.
  • a 25% Ammonia as NH3
  • Example 2 81 g of nitric-acid-washed, dried GAC and 25 ml of a cold 1.65 M Hydrazine solution were combined and mixed. A solution chilled to - 8°C containing 12.6 g silver nitrate, 5 g EDTA, 45 ml water and 20 ml of a 25% ammonia solution was added. The mixture was left at room temperature for one hour. The supernatant liquid was tested with 0.1 N HC1 and no precipitate was observed, indicating complete reaction. The product GAC was washed and dried at 250°C, yielding 97.6 g, corresponding to 8.2% silver.
  • Example 3 To 90 g of nitric-acid-washed, dried GAC was added 18 g silver nitrate dissolved in 50 ml water with gentle stirring. The mixture was let stand for 15 min. A solution containing 100 ml water, 8.5 g sodium hydroxide and 26 g sodium dithionite (sodium hydrosulfite, 85% min assay) was added rapidly and mixed gently. After 1 hr the GAC is rinsed with water and dried at 250°C. The yield was 103 g, corresponding to 11.1% silver; however, it appeared that some silver was lost during the rinse.
  • Example 4 To 170 ml of nitric-acid-washed, dried GAC (91.4 g) was added a solution a solution of 10.8 g silver nitrate in 100 ml water giving a moist mixture with no free solution. This mixture is added slowly with stirring to a solution of 50 g sodium chloride in 500 ml deionized water. The supernatant solution was filtered, revealing only 0.7 g of residue (mostly carbon fines). After rinsing and drying the weight was 100.8 g corresponding to 6.8% silver as silver chloride.
  • Figure 1 is a graph of total iodine content in feed water and treated water as a function of the quantity of water passed through a sample of example 1.
  • Figure 2 is a similar graph relating to example 2.
  • Figure 3 is a similar graph relating to example 3.
  • Figure 4 is a similar graph relating to example 4.
  • Figure 5 is a graph of the same parameters, relating to four samples of commercially prepared compositions of the invention.
  • Figure 6 is a graph of eluted iodine and iodide versus the quantity of water passed through a Counter-Top water purifier containing disinfecting resin (PDR) and an EC-10 Ag/GAC sample of figure 5.
  • PDR disinfecting resin
  • Figures 1 to 4 demonstrate the effectiveness of the samples of Ag-GAC prepared according to Examples 1 to 4, above in reducing the concentrations of iodine/iodide contained in water treated by PuroTech Disinfecting Resin (PDR - a commercial iodinated resin) to levels permissible for continuous human drinking applications.
  • PDR PuroTech Disinfecting Resin
  • the water treated is Tel-Aviv City tap water, having a conductivity of 950-1,600 ⁇ S/cm, and at a temperature of 21-25°C.
  • the water was passed through a chamber containing PDR and then through 150-160 ml of the Ag-GAC sample at a rate of 2 liters/min. Samples were taken of water entering and leaving the Ag-GAC chamber, as shown in the individual graphs.
  • Figure 5 demonstrates the effectiveness of various types of 5-10% Ag-GAC, produced specially for these tests by manufacturers of activated carbon and of Ag-GAC, in reducing the concentrations of iodine/iodide contained in Tel-Aviv City tap water treated by PDR, as described above, to levels permissible for continuous human drinking applications.
  • the relevant properties of the Ag-GAC samples tested in this experiment, and their actual performance, are summarized in the Table below. In these tests, 120 ml samples were treated with the same feed stream at a flow rate of 0.72 liters/min each.
  • Figure 6 illustrates the practical use of 10% silver impregnated granular activated carbon together with 5 ⁇ prefiltration and iodinated resin disinfection in a single 10" standard CounTertop drinking water purifier.
  • the amount of Ag-GAC used in this example was 280 ml.
  • the capacity of the filter is limited by the permissible maximum or average level of iodide in the product water.
  • AADI "adjusted acceptable daily intake"
  • the capacity of the filter is approximately 5,000 liters. At the average daily use of 4 liters per person, this capacity is sufficient for a family of four for over nine months or a family of seven for six months, both practical figures, common to many popular water filtration devices.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
PCT/US1994/005849 1993-06-03 1994-05-25 Water purification system and removal of halides WO1994029228A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9406788A BR9406788A (pt) 1993-06-03 1994-05-25 Dispositivo de purificação para produzir água potável processo para a purificação de água e para a finalidade de converter a mesma em água própria para consumo humano carvão ativado impregnado com prata e uso do mesmo
US08/556,910 US6071415A (en) 1993-06-03 1994-05-25 Water purification system and removal of halides
KR1019950705404A KR960702817A (ko) 1993-06-03 1994-05-25 정수 시스템 및 할로겐화물의 제거 방법 (water purification system and removal of halides)
JP7501845A JPH08510958A (ja) 1993-06-03 1994-05-25 水精製装置及びハロゲン化物の除去
EP94919230A EP0723526A4 (en) 1993-06-03 1994-05-25 WATER PURIFICATION SYSTEM AND HALOGENIDE REMOVAL

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL105905 1993-06-03
IL105905A IL105905A (en) 1993-06-03 1993-06-03 Water purification facility and process

Publications (1)

Publication Number Publication Date
WO1994029228A1 true WO1994029228A1 (en) 1994-12-22

Family

ID=11064906

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/005849 WO1994029228A1 (en) 1993-06-03 1994-05-25 Water purification system and removal of halides

Country Status (7)

Country Link
EP (1) EP0723526A4 (ko)
JP (1) JPH08510958A (ko)
KR (1) KR960702817A (ko)
BR (1) BR9406788A (ko)
CA (1) CA2163857A1 (ko)
IL (1) IL105905A (ko)
WO (1) WO1994029228A1 (ko)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997029995A1 (en) * 1996-02-12 1997-08-21 Aqua System A/S Plant for production of drinking water from unfiltered water
WO2000003953A1 (en) * 1998-07-17 2000-01-27 Worldwide Water Technologies Pty Ltd Water treatment apparatus and components
US7402239B2 (en) 2001-01-09 2008-07-22 Ionics Perpetual, Inc. Water purification apparatus and method of using the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294572A (en) * 1963-03-08 1966-12-27 Pittsburgh Activated Carbon Co Impregnation of carbon with silver
US4151092A (en) * 1977-07-11 1979-04-24 Teledyne Industries, Inc. Portable water filter
US4187183A (en) * 1975-03-28 1980-02-05 Aqua-Chem, Inc. Mixed-form polyhalide resins for disinfecting water
US4298475A (en) * 1980-07-18 1981-11-03 Gartner William J Water purification system
US4461711A (en) * 1981-03-10 1984-07-24 Gesellschaft Fur Strahlen- Und Umweltforschung Mbh Method for separating and collecting iodine
US4769143A (en) * 1987-02-17 1988-09-06 Or-Tsurim Device for purifying water
US4995976A (en) * 1990-05-31 1991-02-26 Water Technologies Corporation Water purification straw

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2215325B (en) * 1988-02-29 1991-10-16 Pre Mac Portable water-purifying devices

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294572A (en) * 1963-03-08 1966-12-27 Pittsburgh Activated Carbon Co Impregnation of carbon with silver
US4187183A (en) * 1975-03-28 1980-02-05 Aqua-Chem, Inc. Mixed-form polyhalide resins for disinfecting water
US4151092A (en) * 1977-07-11 1979-04-24 Teledyne Industries, Inc. Portable water filter
US4298475A (en) * 1980-07-18 1981-11-03 Gartner William J Water purification system
US4461711A (en) * 1981-03-10 1984-07-24 Gesellschaft Fur Strahlen- Und Umweltforschung Mbh Method for separating and collecting iodine
US4769143A (en) * 1987-02-17 1988-09-06 Or-Tsurim Device for purifying water
US4995976A (en) * 1990-05-31 1991-02-26 Water Technologies Corporation Water purification straw

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0723526A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997029995A1 (en) * 1996-02-12 1997-08-21 Aqua System A/S Plant for production of drinking water from unfiltered water
WO2000003953A1 (en) * 1998-07-17 2000-01-27 Worldwide Water Technologies Pty Ltd Water treatment apparatus and components
US7402239B2 (en) 2001-01-09 2008-07-22 Ionics Perpetual, Inc. Water purification apparatus and method of using the same

Also Published As

Publication number Publication date
BR9406788A (pt) 1996-01-30
IL105905A0 (en) 1993-10-20
JPH08510958A (ja) 1996-11-19
EP0723526A1 (en) 1996-07-31
CA2163857A1 (en) 1994-12-22
EP0723526A4 (en) 1996-12-18
IL105905A (en) 2006-04-10
KR960702817A (ko) 1996-05-23

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