WO2019001875A1 - Composition for purification of turbid water - Google Patents
Composition for purification of turbid water Download PDFInfo
- Publication number
- WO2019001875A1 WO2019001875A1 PCT/EP2018/063978 EP2018063978W WO2019001875A1 WO 2019001875 A1 WO2019001875 A1 WO 2019001875A1 EP 2018063978 W EP2018063978 W EP 2018063978W WO 2019001875 A1 WO2019001875 A1 WO 2019001875A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- water
- polymer
- repeating units
- alkyl
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
Links
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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating 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
- C02F1/52—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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
Definitions
- the invention relates to a composition for purification of impure water, especially turbid water which usually contains particulate impurities.
- groundwater is a major source of drinking water at home, especially in developing countries, but groundwater is often contaminated with sediments and other particulates which makes the water turbid. Not only is turbid water less appetizing to drink, but in some cases it contains harmful bacteria and suspended solids which may damage the appliances, such as dishwashers and washing machines which use such water.
- a flocculent like alum (potassium aluminum sulfate dodecahydrate or aluminium sulphate).
- a flocculent like alum (potassium aluminum sulfate dodecahydrate or aluminium sulphate).
- the electrostatic repellent forces which keep the solids suspended get neutralised and the solids agglomerate to form larger particles called 'floes' which settle slowly to the bottom of the container which holds the water.
- alum as the flocculent is that the performance is substantially compromised at lower temperature and there is poorer efficiency towards attracting organic suspended solids. A relatively large dose becomes necessary.
- Adding excess amount of coagulant beyond the charge-neutralization point results in formation of metal coagulant precipitates by sweep flocculation.
- Some examples are metal hydroxides e.g., AI(OH)3, Fe(OH)3 and FeC .
- Al-based salts or Fe-based salts are added in sufficient amount so that they form amorphous particles of AI(OH)3 or Fe(OH)3. These amorphous particles entrap suspended solids thereby reducing the turbidity of water.
- AI(OH)3 or Fe(OH)3 particles with entrapped suspended solids called sweep floes are generally 100 ⁇ or lower. At this size, it is still difficult to separate them from the water by, e.g. filtration or decantation.
- the rate of settling of the sweep floes is very slow.
- ferric chloride is good at attracting inorganic solids, it is observed that the tendency to attract organic solids is lower.
- the kinetics can be improved by adding a polymeric flocculent, such as
- polyacrylamides including acrylamide-acrylate copolymers.
- This type of flocculation includes the addition of a polymer flocculent with molecular weight of at least 100 kDa. These polymers are believed to adsorb on the sweep floes and thereby bring the sweep floes together to form bigger and stronger floes. This phenomenon is known as "bridging flocculation". This bridging mechanism helps increase the settling velocity of the floes for faster purification of water.
- US 8,883,262 BB (RHODIA RECHERCHES AND TECH, 2014) describes a hard surface cleaning composition comprising a combination of (a) a sulphobetaine or carboxybetine zwitterionic polymer and (b) at least one cationic polymer.
- the US patent further describes hard surface cleaning compositions containing a combination of (a) a phosphobetaine zwitterionic polymer and (b) at least one anionic polymer.
- Metal-free flocculation/coagulation compositions are not widely known/used due to their inability to clarify/purify dirty turbid water.
- EP 16192021.0 (Unilever, unpublished) discloses a composition comprising an anionic polymeric flocculent (polyacrylamide), an amphoteric polymer having carbo/sulpho betaine units. The application is particularly effective against turbid water.
- composition comprising a polymeric flocculent (such as polyacrylamide) along with a polymer having repeating units of particular type is able to provide the desired technical effect in soft as well as hard water.
- a polymeric flocculent such as polyacrylamide
- ingredients interact synergistically with each other to purify the turbid water which may be hard or soft. Usually such compositions are effective in either of the situation but not both.
- turbidity refers to the cloudiness or haziness of a fluid caused by a large number of individual particles.
- NTU Nephelometric Turbidity Units
- the nephelometer is preferably calibrated by using the standard formazin solutions as recommended by the instrument manufacturer. The nephelometer measures the propensity of particles to scatter a light beam focused on them.
- inert filler refers to particulate component(s) in the composition that do not significantly contribute to the clarification of turbid water.
- hardness of water is the French hardness and indicated as FH.
- polyacrylamide refers to a polymer derived from acrylamide, and derivatives thereof (such as N,N- dimethacrylamide and N-isopropylacrlyamide) and/or methacrylamide and derivatives thereof.
- composition of the invention comprises:
- Coagulation is generally understood as the process whereby the forces holding the solids in suspension are overcome or neutralized. In other words, the suspended solids are destabilized.
- Flocculation is the process whereby destabilized suspended solids are brought together to form larger aggregates.
- Flocculation results in aggregation of particles or groups of particles into larger groups of particles or floes.
- flocculation is defined to include the process of particle destabilization and collection into larger aggregates.
- the anionic polymer B is selected from polysaccharides, poly(meth)acrylates, proteins, modified cellulose, and polyacrylamide.
- the weight average molecular weight of the anionic polymer B is at least 0.5 Million Daltons. More preferably it is 1 to 10 Million Daltons. It is preferred that the molecular weight of the anionic polymer B does not exceed 20 Million Da.
- the unit Da (Dalton) as used herein refers to atomic mass unit (amu, the less commonly used SI unit).
- anionic polymer, as used herein refers to any type of polymer comprising functional groups that can carry one or more negative charges in aqueous systems, e.g.
- anionic polysaccharides can be derived from any source and/or may be obtained by modification, e.g. derivatization, of a polysaccharide.
- the anionic polysaccharides Preferably the anionic
- polysaccharides according to the present invention is selected from the group comprising carrageenans, alginates, agar, pectins, modified pectins, gellan gum, xanthan gum, furcellaran, dextran sulphate, modified starches, exopolysaccharides and mixtures thereof.
- the polysaccharides are non-cellulosic in origin.
- the polymer B is polyacrylamide.
- the polyacryamide is anionic in nature. Alternatively, it is nonionic. Some useful trademarked materials icnklude the Magnafloc® and Dynafloc® grade of polymers.
- suitable poly(meth)acrylate polymers include polyacrylates, acrylate copolymers or alkali swellable emulsion acrylate copolymers (e.g., ACULYN® and CARBOPOL®.
- a commercially available cross-linked acrylic acid copolymer includes the CARBOPOL® Ultrez series and CARBOPOL® Aqua SF-1 .
- modified celluloses examples include alkyl or carboxyalkyl celluloses such as hydroxyethyl cellulose, sodium carboxymethyl cellulose, methyl cellulose and hydroxypropyl cellulose.
- Other preferred modified celluloses include ethyl hydroxyethyl cellulose (EHEC), carboxymethylhydroxyethyl cellulose (CMHEC), hydroxypropyl hydroxyethyl cellulose (HPHEC), methylhydroxypropyl cellulose (MHPC),
- methylhydroxyethyl cellulose (MHEC), carboxymethyl methyl cellulose (CMMC), hydrophobically modified carboxymethyl cellulose (HMCMC), hydrophobically modified hydroxyethyl cellulose (HMHEC), hydrophobically modified hydroxypropyl cellulose (HMHPC), hydrophobically modified ethyl hydroxyethyl cellulose (HMEHEC), hydrophobically modified carboxymethylhydroxyethyl cellulose (HMCMHEC), hydrophobically modified hydroxypropyl hydroxyethyl cellulose (HMHPHEC), hydrophobically modified methyl cellulose (HMMC), hydrophobically modified methylhydroxypropyl cellulose (HMMHPC), hydrophobically modified
- HMMHEC methylhydroxyethyl cellulose
- HMCMMC hydrophobically modified carboxymethyl cellulose
- cationic HMHEC methylhydroxyethyl cellulose
- the polymer B is water-soluble. By that it means solubiliy of the polymer in water at 25 degC is at least 40 mg/litre.
- polymer B For a list of other suitable polymers that may be used as polymer B, reference may be to the polymers described in Kirk-Othmer Encyclopedia of Chemical Technology or any other equivalent standard reference book.
- the polymer "A” comprises repeating units a and ⁇ in which,
- R1 represents a hydrogen atom or a linear or branched C1 to C6 alkyl group
- R2 and R3 independently of each other, represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C1 to C6 alkyl;
- - X represents a negatively charged functional group selected from carboxylate, sulphonate, sulphate or phosphate,
- the X is a carboxylate group.
- R1 is methyl or ethyl group.
- R is methyl group.
- R3 is methyl group.
- n 1 to 3.
- p 1 to 3.
- the X is a carboxylate group in a and ⁇ , but it is possible that X is a carboxylate group in a and the same X is sulphonate group in ⁇ .
- the negatively charged entity e.g., COO " or SO3 " are always accompanied by the corresponding cationic counter ion (e.g. Na + ) so that the charges are balanced, but the counter ion is not included in the structure in this description.
- the polymer identified as A may or not be commercially available but the same could be easily prepared using methods which are known in the art.
- the first stage involves synthesis of polydimethylaminoethylmethacrylate (pDMAEMA)
- the pDMAEMA polymer is synthesized by free radical polymerization.
- a 50 % aqueous (w/w) solution of the DMAEMA monomer is stirred at room temperature under nitrogen atmosphere for 30 minutes.
- 2.5 wt% of potassium persulfate (initiator) is added to this mixture and the temperature is raised to 40 °C.
- the reaction is carried out for 20 hours (or until completion).
- the homopolymer is isolated by precipitation in hexane followed by re- dispersion of the sticky polymeric mass in water to obtain a 50% aqueous solution of the polymer.
- the process involves post-polymerization modification of the pDMAEMA polymer, synthesized as above.
- a one-pot reaction is done by contacting pDMAEMA with appropriate molar equivalent (variable as per need or requirement) of sodium monochloroacetate. The reaction is carried out at 80 °C for 10 hours (or until complete conversion has been achieved). The final polymer A can be isolated by precipitation in acetone, followed by vacuum drying at 40 °C and re-dispersion in water to obtain a 50% aqueous dispersion of polymer A for further use.
- the number of repeating units of repeating units a and ⁇ may vary. However, it is preferred that a accounts for 10 to 90 parts by weight of said polymer A, the balance being accounted for by the repeating units ⁇ . Further preferably, a accounts for 20 to 80 parts by weight of said polymer A, the balance being accounted for by the repeating units ⁇ -
- compositions of the invention comprise from 1 to 20 wt% of the polymer A and from 0.5 to 10 wt% of the polymer B. More preferably the compositions comprise 2 to 10 wt% of the polymer A and 0.5 to 5 wt% of the polymer B.
- compositions of the invention comprise not more than 1 wt% metal-based flocculent based on the total weight of the composition.
- metal-based flocculent is a salt comprising at least one of Al or Fe.
- Examples include ferrous sulphate, ferric sulfate, aluminium sulfate, aluminium chloride and polyaluminium chlorides.
- compositions of the invention preferably further comprise inert inorganic filler having surface area up to 10 m 2 /g and porosity upto 30 volume %.
- suitable examples include of feldspar, sand, calcium carbonate, talc, kaoline, bentonite, attapulgite, alumina or MgO.
- Surface area measurements can be done using the BET method (Brunauer et al. "Adsorption of Gases in Multimolecular Layers". Journal of the American Chemical Society (1938) 60(2): 309-319.)
- Porosity can be measured using mercury porosimetry about which reference may be made to the following website. (http://www.micromeritics.com/Repository/Files/Mercury_Porosemitry_Theory_poster_. pdf)
- Filler according to the invention may be any inorganic material which preferably is non- reactive to any other ingredients present in the system. It is typically a solid with high density. For the sake of clarity, the filler is not the same as metal based flocculent.
- the inorganic filler is preferably selected from natural or synthetic clays and water insoluble inorganic salts.
- Preferred fillers include feldspar (KAISi308), kaoline, bentonite and Attapulgite, as well as alumina (including silica alumina compositions) and MgO. It is particularly preferred that the compositions of the invention comprise feldspar as the filler.
- the inorganic filler is believed to increase the number of particles.
- the increased particle number density results in faster floe formation.
- the floes formed are also heavier due to the extra mass of the filler and therefore settle faster. Due to its higher density, it is thought to increase the settling velocity of the floe and improve the overall flocculation kinetics.
- the inorganic filler is present in the composition in a concentration of 5 to 95 wt%.
- the inorganic filler is preferably present in a concentration of 20 to 95 wt%.
- dolomite clay (CaMg(CC>3)2) is not used in a large amount, preferably not more than 10 percent by weight of the filler material, more preferably less than 5 percent, still more preferably less than 1 percent, or even 0 percent by weight of the filler material.
- Dolomite is found to cause effervescence when producing pastes probably reacting with acidic salts present in the formulation. This happens more specifically in presence of moisture or if some formulation ingredient contains water, which is thought to hamper the clarification of some wash or rinse liquors.
- MgO is reactive to many compounds, as generally known to the skilled person. It may cause exothermic reaction, causing heat formation and may give processing problems in some compositions, especially in the presence of water which in turn affects the efficiency of formulation.
- 2:1 clays e.g. attapulgite, bentonite are known to retain more liquid in its structure which is thought to be the reason to delay the release of a cationic material in the desired time scale which affects the efficiency of formulation. Therefore, 2:1 clays are less preferred in the compositions according to the invention. Consequently, attapulgite, MgO and/or dolomite are not preferred in a large amount, preferably not more than 10 wt% of the composition.
- the most preferred fillers are 1 :1 clays, most preferably kaolin or feldspar.
- the inert filler preferably has a mass weighted mean particle size in the range of 5 to 500 micrometer, more preferably in the range of 10 to 150 micrometer, most preferably in the range of 50 to 90 micrometer.
- the inert filler preferably has a surface area of up to 1 m 2 /g and a porosity of up to 30 vol.%.
- the composition according to the present invention may be provided, for instance, in the form of a solid (e.g. a powder or tablet), a paste or a gel.
- the water clarification composition is a powder.
- the water purification composition preferably is a powder having a mass weighted mean particle size in the range of 10 to 100 micrometers, more preferably in the range of 50 to 90 micrometers.
- the composition is preferably dosed at a dosage level of 0.2 to 5 grams per litre water. More preferably the dosage level is 0.5 to 5 grams per litre water and most preferably it is 0.5 to 3 grams per litre water.
- Dispersing of the composition in the water to be clarified can be achieved by agitating the water, example by stirring. It is preferred that water is agitated for at least 10 seconds, more preferably for 15 to 60 seconds and most preferably for 15 to 50 seconds. Different patterns of stirring may be followed applied, e.g. stirring-pause- stirring or stirring-pause or variations thereof.
- the separation of the floes from the water is preferably performed by filtration, decantation and combinations thereof. More preferably the separation of the precipitate from the water is performed by filtration.
- Turbidity of the purified water is about 5 and preferably less than 5 NTU.
- the water to be purified may have initial turbidity of about 60 NTU.
- Example 1 Purification of water using compositions according to the invention
- pCBMA poly(carboxybetaine methacrylate)
- pDMAEMA poly(dimethylaminoethyl methacrylate)
- repeating units a account for 30 parts by weight of said polymer A, balance accounted by repeating units ⁇
- repeating units a account for 50 parts by weight of said polymer A, balance accounted by repeating units ⁇
- compositions outside the invention failed to meet the required standards because turbidity of treated/purified water was more than 5 NTU in at least one of the two situations. Even an admixture of the two polymers (Composition Reference 3) did not provide expected results.
- composition according to the invention met the required standards of turbidity less than 5 NTU and this was an unexpected technical effect, especially considering the fact that, referring particularly to Composition 3, the same effect was not provided by the constituents of the Polymer A (i.e. two separate polymers made up solely by the a and ⁇ units).
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
Claims
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR112019027193-7A BR112019027193A2 (en) | 2017-06-29 | 2018-05-29 | composition for water purification and process for water purification |
| MX2019015216A MX2019015216A (en) | 2017-06-29 | 2018-05-29 | Composition for purification of turbid water. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17178635 | 2017-06-29 | ||
| EP17178635.3 | 2017-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2019001875A1 true WO2019001875A1 (en) | 2019-01-03 |
Family
ID=59258059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2018/063978 Ceased WO2019001875A1 (en) | 2017-06-29 | 2018-05-29 | Composition for purification of turbid water |
Country Status (3)
| Country | Link |
|---|---|
| BR (1) | BR112019027193A2 (en) |
| MX (1) | MX2019015216A (en) |
| WO (1) | WO2019001875A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2021106899A1 (en) * | 2019-11-28 | 2021-06-03 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040168980A1 (en) * | 2002-01-04 | 2004-09-02 | Musale Deepak A. | Combination polymer treatment for flux enhancement in MBR |
| EP1734011A1 (en) * | 2005-06-01 | 2006-12-20 | Nalco Company | A method for improving flux in a membrane bioreactor |
| US20090272691A1 (en) * | 2008-05-02 | 2009-11-05 | Musale Deepak A | Method of conditioning a mixed liquor containing nonionic polysaccharides and/or nonionic organic molecules |
| US20140158633A1 (en) | 2013-11-27 | 2014-06-12 | Psmg, Llc | Particle suspensions of flocculating polymer powders and powder flocculant polymer blends |
| US8883262B2 (en) | 2006-03-03 | 2014-11-11 | Rhodia Operations | Modification of solid surfaces by application of polymer associations thereon |
-
2018
- 2018-05-29 BR BR112019027193-7A patent/BR112019027193A2/en not_active IP Right Cessation
- 2018-05-29 WO PCT/EP2018/063978 patent/WO2019001875A1/en not_active Ceased
- 2018-05-29 MX MX2019015216A patent/MX2019015216A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040168980A1 (en) * | 2002-01-04 | 2004-09-02 | Musale Deepak A. | Combination polymer treatment for flux enhancement in MBR |
| EP1734011A1 (en) * | 2005-06-01 | 2006-12-20 | Nalco Company | A method for improving flux in a membrane bioreactor |
| US8883262B2 (en) | 2006-03-03 | 2014-11-11 | Rhodia Operations | Modification of solid surfaces by application of polymer associations thereon |
| US20090272691A1 (en) * | 2008-05-02 | 2009-11-05 | Musale Deepak A | Method of conditioning a mixed liquor containing nonionic polysaccharides and/or nonionic organic molecules |
| US20140158633A1 (en) | 2013-11-27 | 2014-06-12 | Psmg, Llc | Particle suspensions of flocculating polymer powders and powder flocculant polymer blends |
Non-Patent Citations (1)
| Title |
|---|
| BRUNAUER ET AL.: "Adsorption of Gases in Multimolecular Layers", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, no. 2, 1938, pages 309 - 319, XP000572670, DOI: doi:10.1021/ja01269a023 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2021106899A1 (en) * | 2019-11-28 | 2021-06-03 | ||
| WO2021106899A1 (en) * | 2019-11-28 | 2021-06-03 | 京セラ株式会社 | Copolymer, determination device, and carrier for determination |
| CN114981326A (en) * | 2019-11-28 | 2022-08-30 | 京瓷株式会社 | Copolymer, measuring device and measuring carrier |
| CN114981326B (en) * | 2019-11-28 | 2023-12-22 | 京瓷株式会社 | Copolymers, measuring devices and measuring carriers |
| EP4067396A4 (en) * | 2019-11-28 | 2024-01-10 | Kyocera Corporation | COPOLYMER, DETERMINATION DEVICE AND DETERMINATION SUPPORT |
| JP7443396B2 (en) | 2019-11-28 | 2024-03-05 | 京セラ株式会社 | Copolymers, measuring devices and measuring carriers |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112019027193A2 (en) | 2020-06-30 |
| MX2019015216A (en) | 2020-02-05 |
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