WO2003066531A1 - Procede de traitement des eaux et produit - Google Patents

Procede de traitement des eaux et produit Download PDF

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Publication number
WO2003066531A1
WO2003066531A1 PCT/IB2003/000836 IB0300836W WO03066531A1 WO 2003066531 A1 WO2003066531 A1 WO 2003066531A1 IB 0300836 W IB0300836 W IB 0300836W WO 03066531 A1 WO03066531 A1 WO 03066531A1
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WO
WIPO (PCT)
Prior art keywords
water
citrate
chitosan
polyphosphate
aminated polysaccharide
Prior art date
Application number
PCT/IB2003/000836
Other languages
English (en)
Inventor
Mats Anderson
Lars Adolfsson
Original Assignee
Medicarb Ab
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 Medicarb Ab filed Critical Medicarb Ab
Priority to AU2003209537A priority Critical patent/AU2003209537A1/en
Publication of WO2003066531A1 publication Critical patent/WO2003066531A1/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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/002—Processes for the treatment of water whereby the filtration technique is of importance using small portable filters for producing potable water, e.g. personal travel or emergency equipment, survival kits, combat gear
    • 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
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • This invention relates to a method of treating water, particularly to make it potable, and to products and mixtures for use in such treatment. Background of the invention
  • Access to potable water is important, but often not easy, for people and farm animals in developing countries, for travellers to such countries, for people in disaster situations, e.g. flooding, and also for military personnel.
  • the raw water available in such situations may be contaminated ter alia with microorganisms, algae, humus, clay, organic and inorganic particulates and unwanted chemicals, e.g. heavy metals or chlorinated organic compounds such as pesticides.
  • Many of the existing means of purifying water in such conditions require the use of sterilising agents, e.g. halogen containing agents which are potentially toxic or have undesirable environmental effects.
  • effervescent tablet comprising a complex seven component mixture (US Patent 5,681,475) comprising a number of undesirable ingredients, e.g. organo chlorine compounds and aluminium sulphate.
  • Kawabata Prog. Polym. Sci. V 7, 1-34, 1992 in which microorganisms and viruses are captured and coagulated by the use of a solid cross-linked poly (N-benzyl-4-vinylpyridinium halide) used alone.
  • N-benzyl-4-vinylpyridinium halide N-benzyl-4-vinylpyridinium halide
  • Kawabata describes an attempt to impart biodegradability by the incorporation of N-benzyl-4-pyridinium groups into the biodegradable poly(methylmethacrylate).
  • Chitosan is a linear polysaccharide which is generally prepared by the alkaline deacetylation of chitin.
  • Chitin itself is a naturally occurring polysaccharide which can be obtained from a number of sources, but is generally obtained on an industrial scale from crustacea , e.g. crab
  • Chitosan is composed of 1,4-beta-linked D-glucosamine and
  • Chitosan has been widely used in a number of water treatment processes, e.g. in swimming pools, in the treatment of waste water and in the preparation of drinking water.
  • the addition of chitosan to. waste water initiates a flocculatiqn process in which the microorganism impurities are removed by sedimentation and/or filtration.
  • the chitosan binds strongly to toxic and environmentally undesirable (heavy) metals, e.g. Hg, Cd and Pb, and transition metals, e.g. Cr, Ni, Mn and Cu.
  • Chitosan also has the ability to remove polychlorinated. compounds, such as PCBs, from water.
  • water soluble chitosan i.e. chitosan in its salt form
  • US Patent 6,071,417 describes a method for removing water soluble macromolecular compounds from aqueous fermentation products to which the macromolecular compounds have been added as flocculants. This method comprises adding a polyphosphate and an alkaline earth metal salt to the fermentation product, then adding kaolin and filtering.
  • Chitosan has been used in combination with, for exmple carboxymethyl cellulose (CMC), to increase flocculation and sedimentation in water purification, but we have found that chitosan in combination with a variety of CMCs or with a number of other polymeric ahionic species ⁇ e.g..,alginates and dextran sulphates, does not give quantitative or near quantitative precipitation of the chitosan or of its complexes with the added polymers. Furthermore such precipitates as were obtained from the combinations with these polymers were not removed easily by filtration or sedimentation.
  • a large number of small anionic species e.g. tartrates, oxalates, sulphates etc. do not provide satisfactory results in that they either give no precipitate or only a partial precipitate which is difficult to remove by filtration when admixed with an aqueous solution of chitosan
  • a method for the removal of pathogenic materials from water which comprises treatment of the water with an aminated polysaccharide and either a citrate or a polyphosphate both the aminated polysaccharide and the citrate or polyphosphate being in water soluble form.
  • kits for the purification of water which comprises an aminated polysaccharide and a citrate or a polyphosphate both the aminated polysaccharide and the citrate or polyphosphate being in water soluble form.
  • the aminated polysaccharide may be an aminated derivative of starch (e.g. such as can be obtained by treating starch with N-(3-chloro-2-hydroxypropyl) trimethylammonium chloride) or of cellulose, or a partially deacetylated homopolymer of N-acetyl glucosamine, e.g. those derived from chitin.
  • the aminated polysaccharide is preferably a chitosan.
  • the water solubility of the aminated polysaccharide depends on molecular weight, the pH of the solution (i.e. whether the polysaccharide is in salt form) and, in the case of chitosan, on the degree of acetylation,.
  • the form of aminated polysaccharide, e.g. chitosan, used should be such as to have sufficient water solubility for the present purposes.
  • aminated polysaccharide to be present in solution at from 0.01 to 4.0% w/w, and preferably from 0.05 to 2.0% w/w.
  • a relatively high concentration of aminated polysaccharide e.g. above about 0.25g, preferably above about 0.5- g, per litre and most preferably above about 1 g per litre.
  • the upper limit of the aminated polysaccharide concentration will be set by the solubility of the particular aminated polysaccharide used.
  • aminated polysaccharide may be in the form of a salt with a mono basic anion, e.g. an
  • organic anion such as acetate or propionate or preferably a glutamate or asparaginate.
  • a salt e.g. a chitosan salt
  • an inorganic anion e.g. a halo anion, especially the chloride anion which latter imparts relatively little smell or taste to the
  • the chitosan has a degree of deacetylation of from about 40-100%, preferably from about 75-95%.
  • the chitosan has a molecular weight in the range 3,000 to 2,000,000D, and preferably 10,000 to 2,000,000D.
  • the aminated polysaccharide to be of a reasonable commercial purity, e.g. not to contain excessive levels of heavy metals or other potentially toxic contaminants.
  • the citrate is preferably in the form of a salt; e.g. a salt with the ammonium or, preferably, an alkali metal cation, e.g. the sodium cation. "
  • a salt with the ammonium or, preferably, an alkali metal cation, e.g. the sodium cation.
  • an alkali metal cation e.g. the sodium cation.
  • citrate When a citrate is used we prefer to use from 1 to 5:1, and more preferably from 1.5 to 2.5:1 equivalents of citrate to aminated polysaccharide calculated on the free amino functions in the aminated polysaccharide and the anionic groups of the citrate.
  • the number of free amino functions will depend on its degree of deacetylation.
  • the polyphosphate may be of low molecular weight and preferably to be a tri-, tetra- or penta-polyphosphate.
  • the polyphosphate may be in the form of a salt with the ammonium cation, or more preferably and giving a better taste in the final product, a salt with an alkali metal, e.g. the sodium, cation.
  • a polyphosphate we prefer to use from 0.5 to 5.0:1, preferably from 0.5 to 1.5:1 equivalents of polyphosphate to aminated polysaccharide calculated on the free amino functions in the aminated polysaccharide and the anionic groups of the polyphosphate.
  • anionic polymer e.g. an alginate or CMC
  • the proportion of anionic polymer used can be much less than would neutralise the amino groups on the aminated polysaccharide. These low proportions of anionic polymer are such that in the absence of the citrate and/or polyphosphate no, or only an incomplete, precipitate would normally be formed.
  • the anionic polymer should be in readily soluble solid form, or, if in a liquid, e.g. solution, form should be of such a viscosity that it is easily, and preferably quickly, soluble in water.
  • the anionic polymer is preferably in salt form, e.g. an alkali metal salt such as the sodium salt.
  • the proportion of the anionic polymer should be such that it corresponds to no more than 0.5, preferably no more than 0.2,
  • aminated polysaccharide calculated on the free amino functions in the aminated polysaccharide and the anionic groups of the
  • anionic polymer When an anionic polymer is used the amount of citrate and/or
  • polyphosphate may reduced correspondingly.
  • an anionic polymer is particularly useful when the aminated polysaccharide is of high water solubility, e.g. when a chitosan of low molecular weight and/or high degree of deacetylation, is used.
  • a suitable CMC is one having a molecular weight of about 90 KD and an average of about 0.75 carboxymethyl groups per glucose residue.
  • the pH For hard raw water containing relatively high proportions of magnesium and/or calcium, it is desirable to adjust the pH before, or during the application of the method, or the using of the ⁇ kit of the invention.
  • a relatively, high, concentration of the aminated polysaccharide salt e.g. theliydrochloride (which if necessary can be achieved by the addition of more, e.g. two or more units, of the salt) will lower the pH of most waters to within the desired range.
  • a buffering agent e.g. citric acid or mono sodium citrate
  • Any such buffering agents must, of course, be non toxic.
  • pH of the product water is within the range of palatably potable water.
  • the method of the invention may be carried out continuously, e.g. by mixing the aminated polysaccharide and the citrate and/or polyphosphate with the water to be treated on a
  • flocculating agent or anionic polymer such as CMC is used, but can readily be ascertained by
  • kits which can be easily carried by a soldier, or which can be supplied to individuals in the case of an emergency.
  • Such kits would contain one or more, say up to 10, units, each unit comprising the desired dosage of at least the aminated polysaccharide, e,g: chitosan,; and citrate or polyphosphate and opti ⁇ nally*also : comprising the anionic : polymer, e.g. CMC, and/or a buffering agent.
  • the components of the kit may be packaged as separate sub-units. Each such unit of the kit is designed to be suitable for the treatment of from about 1 to 25 litres of water.
  • the kit can also suitably comprise a container in which to mix the water and the ingredients, although any suitable container will serve, e.g. a soldier's billy can, and also means of filtering the treated water, e.g. a funnel made of plastics material and a supply of conventional filter paper such as is used in coffee making or in laboratories.
  • a container in which to mix the water and the ingredients
  • any suitable container will serve, e.g. a soldier's billy can, and also means of filtering the treated water, e.g. a funnel made of plastics material and a supply of conventional filter paper such as is used in coffee making or in laboratories.
  • the units or sub-units may be put up as sachets in foil or plastics material, the sachets preferably being water impervious.
  • the units may be arranged so as to facilitate the addition of the aminated polysaccharide and the citrate/polyphosphate in the order desired, e.g. the aminated polysaccharide before the citrate/polyphosphate.
  • the citrate or polyphosphate is dissolved in the water.
  • solid aminated polysaccharide it is therefore desirable to add the aminated polysaccharide to the water before the addition of the citrate or polyphosphate.
  • the kit is also desirably provided with instructions (written and/or pictorial) as to how it should be used, such instructions preferably being printed on the container, e.g. the sachet.
  • the instructions should, when solid aminated polysaccharide is used, indicate that the aminated polysaccharide be added to the water before the citrate/polyphosphate.
  • the cpmponents for.useiin the method and kit according to the invention maybe in liquid, > e.g..solution or suspension, form, , but are, preferably in solid, e.g., dry form.
  • citrate and/or polyphosphate with an anionic polymer, e.g. CMC in its sodium salt form.
  • anionic polymer e.g. CMC in its sodium salt form.
  • the particle size of the solid components should be such that they will dissolve readily in water. We prefer the components to be such that they will dissolve within a few minutes of addition to well stirred water. Thus we prefer finely divided, but easily flowable dry forms of
  • aminated polysaccharide optionally together with any buffering agent, to be added to and dissolved in the water before the addition of the citrate and/or polyphosphate.
  • citrate and/or polyphosphate we prefer the citrate and/or polyphosphate to be dissolved in the water before any anionic
  • citrate/polyphosphate will tend to dissolve more rapidly than the anionic polymer thus providing the desired sequence of dissolution.
  • the time required after the aminated polysaccharide and the citrate and/or polyphosphate have been added to the water before the water can be used will vary depending on the quality of the raw water, the specific nature and ratio of the active ingredients, and the volume and degree of mixing of water. This time can easily be ascertained by simple observation, e.g. of the formation of a precipitate and/or a clear supernatant.
  • the method and kit according to the invention may be used to remove-bacteria, e.g. E. coli, salmonella and ETEC. coli from the raw water. They may also be used to remove other pathogenic microorganisms, e.g. viruses, such as HSN, hepatitis C, HIN, polio and rota viruses, and parasites, e.g.Giardia lamblia and Cr ⁇ ptosporidium. Additionally they may be used to remove heavy and/or radioactive metals. The method and kit may be used to extract such metals from waters, e.g. effluent or mining waters, containing them. The method and kit may also be used to remove colour and other contaminants, e.g. particulates, dyes, turbidity and polychlorinated compounds such as PCB from the water.
  • pathogenic microorganisms e.g. viruses, such as HSN, hepatitis C, HIN, polio and rota viruses
  • parasites
  • precipitated aminated polysaccharide complex forms a three dimensional structure or net that
  • chitosans preferably in the form of their hydrochloride salts, citrate, especially sodium citrate, and CMC.
  • chitosan hydrochloride 250 Mg chitosan hydrochloride is dissolved in 250 ml of the water to be purified with agitation until complete dissolution, giving a pH of 4.2.
  • Sodium citrate (approx. 250 mg) is added to the solution giving a charge ratio between the chitosan and the citrate of approx. 1:2.
  • Precipitation starts almost immediately and after a short period the precipitate settles to provide a clear water phase having a pH of about 6.4.
  • the pH of the product can be adjusted by conventional means if desired.
  • 250 Mg chitosan hydrochloride is dissolved in 250 ml of the water to be purified with agitation, the resulting solution having a pH of 4.2.
  • Pentasodium tripolvphosphate (approx. 100 mg) is added to the solution giving a charge ratio between the chitosan and the pentasodium tripolvphosphate of approx. 1:1.
  • Precipitation starts almost immediately and after a short period the precipitate settles to provide a clear water phase having a pH of about 6.4.
  • the pH of the product can be adjusted by conventional means if desired.
  • Example 3 Use of other polvanions to try to form filterable complexes with chitosan
  • filtrate further precipitates were produced indicating that not all of the chitosan had been removed in the initial precipitate.
  • sample 2 the water to be purified, and a small sample (sample 1) withdrawn. 750 Mg of sodium citrate was then added to the flask with shaking. 30 Min. after the addition of the citrate the precipitated complex was filtered off and a second sample (sample 2) was withdrawn from the water phase.
  • sample 1 contained 1 mg/ml of chitosan (the expected value), whereas in sample 2, even after concentration 20 times, no chitosan could be found.
  • the detection limit of the analytical method is 3.0 ⁇ g/ml.
  • Example 6 Treatment of different kinds of tap water with chitosan/sodium citrate
  • the treated water (Uppsala) was after filtration freeze dried and the residue was analysed by
  • 500 Mg of chitosan hydrochloride is dissolved in 250 g of water from a dirty river (Ballstaan, Bromma, Sweden; turbidity: 38.1 FNU) and the pH adjusted to 4.5 with dilute hydrochloric acid.
  • 500 Mg of sodium citrate was added and within a few minutes precipitation occurred giving a water of the appearance of normal tap water (turbidity: 0.46 FNU), all the colour having been removed. Turbidity was analysed at the same time on a sample of water for injection (WFI, turbidity: 0.10).
  • Uricult sticks a culture based system for detection of bacteria in urine
  • E.Coli (ATCC 25922) was added to 250 ml of water to a concentration of about 10 8 cfu/ml. compared to a McFarland suspension (a suspension of barium sulphate in water where the optical density corresponds approx. to a bacterial suspension. Different concentration of barium sulphate corresponds to different concentrations of bacteria).
  • 250 Mg of chitosan hydrochloride were then dissolved in the water, 250 mg of sodium citrate were then added and the resulting solution left to stand for 30 mins. and then filtered.
  • the water before and after treatment was tested using Uricult sticks as in Example 7 above. The water before treatment caused the stick to be 80-90% covered with bacterial colonies: the water after treatment produced no colonies on the stick.
  • ETEC Coli (E55:l) was added to 250 ml of water to a concentration of about 3x10 3 cfu/ml.
  • the concentration of the bacteria in the water before and after treatment was measured by culturing on agar dishes.
  • the treatment yielded water containing no ETEC Coli (100% removal) and 80 cfu ml of salmonella (99.96% removal) respectively.
  • Example 10 Treatment of water with chitosan and sodium citrate in combination with CMC
  • Example 11 Treatment of water with chitosan and sodium citrate in combination with CMC
  • Example 12 Treatment of water with chitosan and sodium citrate in combination with alginic acid sodium salt
  • the kit compromises 10 each of separate sachets containing 1) 2.0 g of chitosan hydrochloride and 2) 1.6 g of sodium citrate in admixture with 0.4 g CMC sodium salt with instructions to dissolve the contents of one chitosan sachet in 1 L of the water to be purified followed by one citrate/CMC sodium salt sachet; to await the formation of a precipitate and the clearing of the supernatant water and then either to decant the supernatant water ready for use, or to filter it using the filters provided.
  • These filters are no. 3 filter papers or similar.
  • the kit also comprises a funnel to support the filter papers.
  • kit may include vessels/flasks to contain the water to be treated and the treated product water.

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  • 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

La présente invention concerne un procédé et un kit pour le retrait des matériaux pathogènes de l'eau. L'invention a aussi pour objet un procédé et un kit comprenant (a) du polysaccharide aminé et (b) un citrate ou polyphosphate. Ces deux éléments (a) et (b) se présentant sous forme soluble dans l'eau.
PCT/IB2003/000836 2002-02-07 2003-01-31 Procede de traitement des eaux et produit WO2003066531A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003209537A AU2003209537A1 (en) 2002-02-07 2003-01-31 Water treatment method and product

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0202882A GB2385050A (en) 2002-02-07 2002-02-07 Removing pathogens from water
GB0202882.7 2002-02-07

Publications (1)

Publication Number Publication Date
WO2003066531A1 true WO2003066531A1 (fr) 2003-08-14

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AU (1) AU2003209537A1 (fr)
GB (1) GB2385050A (fr)
WO (1) WO2003066531A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4928115B1 (fr) * 1967-09-16 1974-07-23
US5393435A (en) * 1993-09-17 1995-02-28 Vanson L.P. Removal of organic contaminants from aqueous media
US6217780B1 (en) * 1998-01-23 2001-04-17 Zodiac Pool Care, Inc. Biocidal compositions for treating water
WO2001038230A1 (fr) * 1999-11-26 2001-05-31 Health By Nature As Agent d'amelioration de l'eau contenant du sable corallien

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19642874C1 (de) * 1996-10-17 1998-05-07 Henkel Kgaa Desodorierende Zubereitungen
GB2364047A (en) * 2000-06-27 2002-01-16 Procter & Gamble Water treatment composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4928115B1 (fr) * 1967-09-16 1974-07-23
US5393435A (en) * 1993-09-17 1995-02-28 Vanson L.P. Removal of organic contaminants from aqueous media
US6217780B1 (en) * 1998-01-23 2001-04-17 Zodiac Pool Care, Inc. Biocidal compositions for treating water
WO2001038230A1 (fr) * 1999-11-26 2001-05-31 Health By Nature As Agent d'amelioration de l'eau contenant du sable corallien

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 197433, Derwent World Patents Index; Class A91, AN 1974-59325V, XP002243593 *

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GB2385050A (en) 2003-08-13
GB0202882D0 (en) 2002-03-27
AU2003209537A1 (en) 2003-09-02

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