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ZA200107959B - Higher actives dispersion polymer to aid clarification, dewatering, and retention and drainage. - Google Patents

Higher actives dispersion polymer to aid clarification, dewatering, and retention and drainage. Download PDF

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Publication number
ZA200107959B
ZA200107959B ZA200107959A ZA200107959A ZA200107959B ZA 200107959 B ZA200107959 B ZA 200107959B ZA 200107959 A ZA200107959 A ZA 200107959A ZA 200107959 A ZA200107959 A ZA 200107959A ZA 200107959 B ZA200107959 B ZA 200107959B
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South Africa
Prior art keywords
alkyl
group
water
monomers
acrylamide
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ZA200107959A
Inventor
Elise E Maury
Rudolf Buelte
Cathy C Johnson
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Nalco Chemical Co
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Priority to ZA200107959A priority Critical patent/ZA200107959B/en
Publication of ZA200107959B publication Critical patent/ZA200107959B/en

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Description

HIGHER ACTIVES DISPERSION POLYMER TO AID CLARIFICATION,
DEWATERING, AND RETENTION AND DRAINAGE
Field of Invention
The invention is a method for clarifying industrial waste water or paper furnish with an effective amount of at least one dispersion of a water soluble cationic polymer flocculant wherein the improvement comprises the addition of said polymer which has a concentration of at least twenty five percent to said waste water or paper furnish. The industrial waste is preferably food processing waste water, oily waste water, paper mill waste water and inorganic contaminated waste water. The : paper furnish may be an aqueous cellulosic suspension.
Background of the Invention
This invention relates to polymers that are of particular value as flocculants for suspensions of organic matter of a proteinaceous or cellulosic nature such as are to be found in sewage and industrial plant treatment effluents or in paper mills.
It is commonly accepted that such suspended . materials which are hydrophilic in nature and which often ) have specific gravities quite close to that of the aqueous liquors in which they are suspended, contrast in a marked way with the more hydrophobic mineral suspensions in that they are frequently found to be much more difficult to flocculate economically with chemical reagents prior to a physical dewatering step such as filtration, flotation, sedimentation, dewatering or in the retention of such materials for processing. These difficulties are particularly noticeable when higher proportions of suspended matter are present, commonly involving concentrations of 0.5 percent by weight and upwards wherein the suspensions take on a paste-like consistency and are commonly described as sludges or paper furnishes.
It is well known that the clarification or dewatering of sewage and industrial sludges and similar organic suspensions may be aided with the use of chemical reagents, added in order to induce a state of coagulation or flocculation which facilitates the process of solid/liquid or liquid/liquid separation from water. For this purpose, lime or salts of iron or aluminum have been utilized. More recently synthetic polyelectrolytes, particularly certain cationic copolymers of acrylamide, have been found to be of interest.
Cationically charged water soluble or water dispersible polymers are utilized in a variety of processes that involve the separation of solids or immiscible liquids dispersed or suspended in water from water, and the dewatering of solids containing water.
These types of polymers, which may be natural or synthetic, are broadly termed coagulants and flocculants.
These polymers can be utilized in such diverse processes as emulsion breaking, sludge dewatering, raw water clarification, drainage and retention aids in the manufacture of pulp and paper, flotation aids in mining processing and color removal.
Polymers of this type generally work by neutralizing the anionic charge of the suspended solids, or liquids, which are to be removed. These solids or liquids may be waste which must be removed from water, Or desirable products which are recovered from aqueous systems, such as coal fines, which can be coagulated or flocculated and sold as fuel.
In the water treatment field of solids/liquid separation, suspended solids are removed from water by a variety of processes, including sedimentation, straining, flotation, filtration, coagulation, flocculation, and emulsion breaking among others. Additionally, after
> suspended solids are removed from the water they must often be dewatered so that they may be further treated or properly disposed of. Liquids treated for solids removal often have as little as several parts per billion of suspended solids or dispersed oils, or may contain large amounts of suspended solids or oils. Solids being dewatered may contain anywhere from 0.25 weight percent solids, to 40 or 50 weight percent solids material.
Solids/ligquid or liquid/liquid separation processes are designed to remove solids from liquids, or liquids from liquids.
While strictly mechanical means have been used to effect solids/liquid separation, modern methods often rely on mechanical separation techniques which are augmented by synthetic and natural cationic polymeric materials to accelerate the rate at which solids can be removed from water. These processes include the treatment of raw water with cationic coagulant polymers which settle suspended inorganic particulates and make the water usable for industrial or municipal purposes.
Other examples of these processes include the removal of colored soluble species from paper mill effluent wastes, the use of organic flocculant polymers to flocculate industrial and municipal waste materials, sludge recovery and emulsion breaking.
Regarding the mechanism of separation processes, particles in nature have either a cationic or anionic charge. Accordingly, these particles often are removed py a water soluble coagulant or flocculant polymer having a charge opposite to that of the particles. This is referred to as a polyelectrolyte enhanced solids/liquid separation process, wherein a water soluble or dispersionable jonically charged polymer is added to neutralize the charged particles or emulsion droplets to pe separated. The dosage of these polymers is critical to the performance of the process. Too little ionically charged polymer, and the suspended particles will not be charge neutralized and will thus still repel each other.
Too much polymer, and the polymer will be wasted, or worse, present a problem in and of itself.
Examples of such cationic polymers for dewatering include U. S. Patent No. 3,409,546 which describes the use of N- (amino methyl) -polyacrylamides in conjunction with other cationic polymers for the treatment of sewage sludges; U. S. Patent No. 3,414,514 which describes the use of a copolymer of acrylamide and a quaternized cationic methacrylate ester, JP 61-106072 which describes water-soluble copolymers and another class of cationic polymers used to dewater sludges described in U.S. Patent
No. 3,897,333. Utilization of polyethyleneimines and homopolymers of cationic acrylates and methacrylates and other cationic polymers such as polyvinyl pyridines is also known.
Another example of a cationic polymer useful for sludge treatment is U. S. Patent No. 4,191,645, in which cationic copolymers prepared from a nonionic monomer, such as acrylamide, and a cationic monomer, such as trimethylammonium ethylmethacrylate methyl sulfate guaternary (TMAEM.MSQ) or dimethylaminoethylacrylate methyl sulfate quaternary (DMAEA.MSQ) are disclosed.
Further examples of polymeric treatments for sludge dewatering include the 1,4-dichloro-2-butene dimethylamine ionene chloride polymer as disclosed in U.
S. Patent No. 3,928,448 and the block copolymers disclosed in U. S. Patent No. 5,234,604. among treatments useful for improving retention and drainage are those described in U.S. Patent Nos. 5,126,014 and 5,266,164.
.
Notwithstanding the variety of commercially : © available polymers which have been found to be capable of flocculating or coagulating solids sludges, there are various circumstances which tend to limit the usefulness of these reagents. While for certain sludges economical treatments with these known reagents are feasible, more often sludges require very high and cost-ineffective dosages of reagents for successful treatment. Moreover, variations often occur in sludge from any one source.
For example, variations in the supply of material to the waste water/sludge/paper furnish process water and/or in the oxidizing conditions that may be involved in the production of these waters lead to a variety of particle types which must be removed. Furthermore, it is not uncommon to encounter sludges which are, for some reason, not amenable to flocculation by any of the known polymeric flocculating agents. It is therefore an object of the invention to provide to the art a superior method for the dewatering of sludge-containing industrial waste waters or in the retention of industrial processing aids.
Summary of the Invention
The invention is a method for clarifying industrial waste water or paper furnish with an effective amount of at least one dispersion of a water soluble cationic polymer flocculant wherein the improvement comprises the addition of said polymer which has a concentration of at least twenty five percent to said waste water or paper furnish. The industrial waste is preferably food processing waste water, oily waste water, paper mill waste water and inorganic contaminated waste water. The paper furnish may be an aqueous cellulosic suspension.
Description of the Invention
Methods for manufacturing the polymer dispersion used in the invention are described in detail in U. S.
Pat. Nos. 5,006,590 and 4,929,655, assigned to Kyoritsu
Yuki Co., Ltd., Tokyo, Japan, and U.S Patent Nos. 5,708,071 and 5,587,415 assigned to Hymo Corporation of
Tokyo, Japan. The disclosures of these two patents are incorporated herein by reference.
This invention represents a substantial improvement in the art of treatment of aqueous ‘systems with dispersion polymers. As will be shown in the Examples, the lower concentration dispersion polymers presently utilized and disclosed are inferior to those dispersion polymers at higher concentrations disclosed herein. The superiority of the polymers disclosed herein is much more than an incremental additive effect which would be normally expected by those skilled in the art. The
Examples will illustrate this unexpectedly greater activity at much lower dosage, which was previously unforeseeable.
The Monomers
According to the invention, the polymer dispersion used to treat the produced water is prepared from a water-soluble monomer mixture containing at least 5 mole 2 of a cationic monomer represented by the general formula (I):
R, Rj
R, AN yd :
A £10 a zs
B, 0 1 wherein R; is H or CHi3; Ry and Rj; are each an alkyl group having 1 to 2 carbon atoms; A; is an oxygen atom or NH; Bj is an alkyl group having 2 to 4 carbon atoms or a hydroxypropyl group and Xi is a counter anion. The above water-soluble monomer mixture is soluble in the aqueous solution of the anionic salt. The polymer generated from the monomer mixture is, however, insoluble in the aqueous anionic salt solution. The polymer of the monomer mixture can also be used as the seed polymer. The seed polymer is described in detail below.
The above cationic monomer represented by the ’ general formula (I) preferably is a quaternary ammonium salt obtained by the reaction of benzyl chloride and : dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminohydroxypropyl acrylate, dimethylaminopropyl acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylaminopropyl methacrylamide.
Monomers preferably copolymerized with the cationic monomer represented by the general formula (I) includes acrylamide, methacrylamide or other N-substituted (meth) acrylamides and the cationic monomers represented by the general formula (II):
Rs Re
Ng al
AN yd ON
Sha
O 11 wherein Rs is H or CH3; Rs and Rg are each an alkyl group having 1 to 2 carbon atoms; R; is H or an alkyl group having 1 to 2 carbon atoms; A, is an oxygen atom or NH; B: is an alkyl group having 2 to 4 carbon atoms or a hydroxypropyl group and X; is a counter anion. Xi; and X may be anionic counterions such as halides, pseudohalides, -S050CH3, and -OC(O)CH; among others.
Preferable monomers represented by the formula (ITI) include the ammonium salts of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide and dimethylhydroxypropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide and dimethylhydroxypropyl methacrylate or other N-substituted (meth)acrylamides as well as the methylated and ethylated quaternary salts. Among the more preferable cationic monomers represented by the general formula (IT) are the salts and methylated quaternary salts of dialkylaminoethyl acrylate and dialkylaminoethyl methacrylate. The concentration of the above-mentioned monomers in the polymerization reaction mixture is suitably in the range of 5 to 30% by weight.
The Anionic Salts
The anionic salt to be incorporated in the aqueous solution according to the present invention is suitably a sulfate, a phosphate, a chloride or a mixture thereof.
Preferable salts include ammonium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, ammonium chloride, sodium chloride, ammonium hydrogen phosphate, sodium hydrogen phosphate and potassium hydrogen phosphate. In the present invention, these salts may be each used as an agueous solution thereof having a combined concentration of 10% or above.
The Dispersants
A dispersant polymer (also referred to as stabilizer polymer) is present in the aqueous anionic salt solution in which the polymerization of the above monomers OCCUrS.
The dispersant polymer is a water-soluble high molecular weight cationic polymer. The dispersant polymer is at least partially soluble in the above-mentioned aqueous salt solution. The dispersant polymer is preferably used in an amount of from 1 to 10% by weight based on the total weight of the monomers. The dispersant polymer is composed of 5 mole % or more of a diallyldialkyl ammonium halide or of a cationic monomer unit represented by the formula I or II. Preferably, the residual mole % is acrylamide or methacrylamide or other N-substituted : (meth)acrylamides or diallyldimethyl ammonium chloride.
The performance of the dispersant is not greatly affected by molecular weight. However, the molecular weight of the dispersant is preferably in the range of 10,000 to 10,000,000. According to one embodiment of the invention, a multifunctional alcohol such as glycerin or polyethylene glycol or a chain transfer agent such as sodium formate is coexistent in the polymerization system. The deposition of the fine particles is smoothly carried out in the presence of these agents.
The Dispersion Polymers ” For the polymerizations, a usual water-soluble radical-forming agent can be employed, but preferably water-soluble azo compounds such as 2,2'-azobis (2- amidinopropane) hydrochloride and 2,2'-azobis(N,N'- dimethyleneisobutylamine) hydrochloride are used.
According to one embodiment of the invention, a seed polymer may be added before the beginning of the polymerization of the above monomers for the purpose of obtaining a fine dispersion. The seed polymer is a water-soluble cationic polymer insoluble in the aqueous solution of the anionic salt. The seed polymer is preferably a polymer prepared from the above monomer mixture by the process described herein. Nevertheless, the monomer composition of the seed polymer need not

Claims (30)

Claims
1. In a method for clarifying waste water with an effective clarifying amount of at least one dispersion of a water soluble cationic polymer flocculant; wherein said water soluble flocculant is added to said waste water in an effective amount to flocculate suspended solids, the suspended solids are removed, and a clarified water is obtained, said dispersion of said water soluble cationic polymer flocculant formed from polymerizing vinylic monomers under free-radical forming conditions in a medium containing water, monomers, stabilizer polymer, and an aqueous anionic salt solution; wherein said water-soluble cationic polymer flocculant is polymerized from a) at least 5 mole es of a cationic monomer selected from the group consisting of: monomers of general formula (I) R; Rs R, AN J A £10 NE Co 0 I wherein R; is. selected from the group consisting of H and CHs, R; and Rj; are selected from the group consisting of Ci alkyl and C, alkyl, A; is selected from the group consisting of O and NH, By is selected from the group consisting of C, alkyl, C3 alkyl and hydropropoxy groups, and Xi is an anionic counterion and monomers of general formula II: Rs Re I NN £ At AN ye On Sh Y II wherein Ry; is selected from the group consisting of H and CHs;, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; Ry is selected from the group consisting of hydrogen atom, Ci; alkyl and C; alkyl; A; is selected from the group consisting of an oxygen atom and NH; Bz is selected from the group consisting of C; alkyl, Cz alkyl, Cq alkyl and hydroxypropyl and Xz = is an anionic counterion with b) at least 5 mole % of a monomer selected from the group consisting of C;-C;p N-alkyl acrylamide, C;-Cjo N,N-dialkyl arylamide, Ci-
Cip N-alkylmethacrylamide, C;-Cip N,N- dialkylmethacrylamide, N-aryl acrylamide, N,N-diaryl acrylamide, N-aryl methacrylamide, N,N-diaryl methacrylamide, N-arylalkyl acrylamide, N,N-diarylalkyl acrylamide, N-arylalkyl methacrylamide, N,N-diarylalkyl methacrylamide, acrylamide and methacrylamide;
and wherein said stabilizer polymer is a cationic polymer which is at least partially soluble in said aqueous solution of said anionic salt, wherein the improvement comprises the addition of said water-soluble cationic flocculant polymer dispersion to said waste water at a concentration of at least twenty-five weight percent polymer dispersion in water.
2. The improvement of claim 1 wherein said stabilizer polymer is polymerized from at least 5 mole % of cationic monomers selected from the group consisting of : monomers of general formula I R; R; R; AN J A § 1 DES Co O I wherein R; is selected from the group consisting of H and CHi3, R; and R3 are selected from the group consisting of C; alkyl and C; alkyl, A; is selected from the group consisting of O and NH, B; is selected from the group consisting of C; alkyl, C3 alkyl and hydropropoxy groups, and Xi” is an anionic counterion, diallyldialkyl ammonium halides, monomers of general formula II: Rs Rg Ry AN J SN ve * Ry oO II wherein Rs is selected from the group consisting of H and CH3, Rs and Re are selected from the group consisting of C; alkyl and C; alkyl; Ry; is selected from the group consisting of hydrogen atom, C; alkyl and C, alkyl; A, is selected from the group consisting of an oxygen atom and NH; B; is selected from the group consisting of C; alkyl, Cs; alkyl, C4 alkyl and hydroxypropyl and X; is an anionic counterion, and combinations thereof.
3. The improvement of claim 1 wherein said waste water is selected from the group consisting of industrial wastewater and municipal wastewater.
4. The improvement of claim 1 wherein said anionic salt is selected from the group consisting of phosphates, sulfates, chlorides and mixtures thereof.
5. The improvement of claim 1 including the further step of adding an effective amount of at least one coagulant to the waste water.
6. The improvement of claim 3 wherein said industrial wastewater is selected from the group consisting of food processing waste water, oily waste water, paper mill waste water and inorganic-contaminated waste water.
7. In a method for dewatering waste water with an effective dewatering amount of at least one dispersion of a water soluble cationic polymer flocculant; wherein said water soluble flocculant is added to said waste water in an effective amount to dewater suspended solids, the ] suspended solids are removed, and a clarified water is obtained, said dispersion of said water soluble cationic polymer flocculant formed from polymerizing vinylic monomers under free-radical forming conditions in a medium containing water, monomers, stabilizer polymer, and an aqueous anionic salt solution; wherein said water-soluble cationic polymer flocculant is polymerized from a) at least 5 mole % of a cationic monomer selected from the group consisting of:
monomers of general formula I° R, R3 R; AN ye £ A x0 oo 0 I wherein R; is selected from the group consisting of H and CHi, R; and Rj are selected from the group consisting of C; alkyl and Cp alkyl, A; is selected from the group consisting of O and NH, B; is selected from the group consisting of C; alkyl, Cs; alkyl and hydropropoxy groups, and Xi)” is an anionic counterion and monomers of general formula II: Rs Re : Ry AN yd 4S A ON O 11 wherein R; is selected from the group consisting of H and CHs, Rs and Re are selected from the group consisting of C; alkyl and C; alkyl; Rs is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; Az is selected from the group consisting of an oxygen atom and NH; B; is selected from the group consisting of C; alkyl, Cs; alkyl, C, alkyl and hydroxypropyl and Xp; is an anionic counterion with b) at least 5 mole % of a monomer selected from the group consisting of C;-Cjpo N-alkyl acrylamide, C3-Cjo N,N-dialkyl arylamide, Ci-Cio N-alkylmethacrylamide, Ci1-Cio
N,N-dialkylmethacrylamide, N-aryl acrylamide, N,N-diaryl acrylamide, N~aryl methacrylamide, N,N-diaryl methacrylamide, N-arylalkyl acrylamide, N,N-diarylalkyl acrylamide, N-arylalkyl methacrylamide, N,N-diarylalkyl methacrylamide, acrylamide and methacrylamide; and wherein said stabilizer polymer is a cationic polymer which is at least partially soluble in said agueous solution of said anionic salt; wherein the improvement comprises the addition of said water-soluble cationic flocculant polymer dispersion to said waste water at a concentration of at least twenty-five weight percent polymer dispersion in water.
8. The improvement of claim 7 wherein said stabilizer polymer contains at least 5 mole % of cationic monomers selected from the group consisting of monomers of the general formula I R, Rj R, AN yd £ 1 Ay yd © oo 0 I wherein R; is selected from the group consisting of H and CH;, R, and R; are selected from the group consisting of C; alkyl and C; alkyl, A: is selected from the group consisting of O and NH, B; is selected from the group consisting of C: alkyl, C3 alkyl and hydropropoxy groups, and X; is an anionic counterion, diallyldialkyl ammonium halides,
monomers of general formula II: Rs Rg Rs AN / ® Ay ya ON / NaN 0 II . wherein Rs is selected from the group consisting of H and CHs, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; R; is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; A; is selected from the group consisting of an oxygen atom and NH; By is selected from the group consisting of Cz; alkyl, C3 alkyl, Ci alkyl and hydroxypropyl and X, © is an anionic counterion, and combinations thereof.
9. The improvement of claim 7 wherein said waste water is selected from the group consisting of industrial wastewater and municipal wastewater.
10. The improvement of claim 7 wherein said anionic salt is selected from the group consisting of phosphates, sulfates, chlorides and mixtures thereof.
11. The improvement of claim 7 including the further step of adding an effective amount of at least one coagulant to said waste water.
12. The improvement of claim 9 wherein said industrial wastewater is selected from the group consisting of food processing waste water, oily waste water, paper mill waste water and inorganic contaminated waste water. -
13. In a method for improving retention and drainage of process water in pulp and paper production with an effective amount of at least one dispersion of a water soluble cationic polymer flocculant; wherein said water soluble flocculant is added to said process water in an effective amount to improve retention and drainage, said dispersion of said water soluble cationic polymer flocculant formed from polymerizing vinylic monomers under free-radical forming conditions in a medium containing water, monomers, stabilizer polymer, and an aqueous anionic salt solution; wherein said water-soluble cationic polymer flocculant is polymerized from a) at least 5 mole % of a cationic monomer selected from the group consisting of: monomers of general formula I R, R3 R; AN ya A £1 ™ zs B, Oo I wherein R; is selected from the group consisting of H and CHi3, R; and Rj; are selected from the group consisting of C; alkyl and C; alkyl, A; selected from the group consisting of O and NH, B; is selected from the group consisting of C; alkyl, C3; alkyl and hydropropoxy groups, and X; is an anionic counterion and monomers of general formula II:
Rs Rg \ ® ™ / ON, . B, 7 0 11 wherein R, is selected from the group consisting of H and CHs, Rs and Rg are selected from the group consisting of Ci alkyl and Cz; alkyl; Rs; is selected from the group consisting of hydrogen atom, C; alkyl and C: alkyl; A; is selected from the group consisting of an oxygen atom and NH; B: is selected from the group consisting of Cz alkyl, Cs alkyl, C4 alkyl and hydroxypropyl and X; = 1s an anionic counterion with b) at least 5 mole % of a monomer selected from the group consisting of C;-Cjo N-alkyl acrylamide, C1-Cjo N,N-dialkyl arylamide, Ci-Cio N-alkylmethacrylamide, C;-Cjo N,N-dialkylmethacrylamide, N-aryl acrylamide, N,N-diaryl acrylamide, N-aryl methacrylamide, N,N-diaryl methacrylamide, N-arylalkyl acrylamide, N,N-diarylalkyl acrylamide, N-arylalkyl methacrylamide, N,N-diarylalkyl methacrylamide, acrylamide and methacrylamide; and wherein said stabilizer polymer is a cationic polymer which is at least partially soluble in said aqueous solution of said anionic salt; wherein the improvement comprises the addition of said water-soluble cationic flocculant polymer dispersion to said waste water at a concentration of at least twenty-five weight percent polymer dispersion in water.
14. The improvement of claim 13 wherein said stabilizer polymer is polymerized from at least 5 mole %
of cationic monomers selected from the group consisting of monomers of the general formula I R, AN yd © N® Ay ya © oo 0 1 wherein R; is selected from the group consisting of H and CHi;, R, and R; are selected from the group consisting of C; alkyl and C; alkyl, A; is selected from the group consisting of O and NH, B; is selected from the group consisting of C; alkyl, C3 alkyl and hydropropoxy groups, and X; is an anionic counterion, diallyldialkyl ammonium halides, monomers of the general formula II: Rs Rs "Ry N J Bo a Z * Bs 0 II wherein Ry; is selected from the group consisting of H and CHi;, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; Ry is selected from the group consisting of hydrogen atom, Ci alkyl and C; alkyl; A, is selected from the group consisting of an oxygen atom and NH; By is selected from the group consisting of C; alkyl, C3 alkyl, Cs; alkyl and hydroxypropyl and X; ~ is an anionic counterion and combinations thereof.
15. The improvement of claim 13 wherein said anionic salt is selected from the group consisting of :phosphates, sulfates, chlorides and mixtures thereof.
16. In a method for clarifying waste water with an effective clarifying amount of at least one dispersion of a water soluble cationic polymer flocculant; wherein said water soluble flocculant is added to said waste water in an effective amount to flocculate suspended solids, the suspended solids are removed, and.a clarified water is obtained, said dispersion of said water soluble cationic polymer flocculant formed from polymerizing vinylic monomers under free-radical forming conditions in a medium containing water, monomers, stabilizer polymer, ’ and an agueous anionic salt solution; wherein said water-soluble cationic polymer flocculant is polymerized from a) at least 5 mole % of a cationic monomer selected from the group consisting of: monomers of general formula (I) R, Rj Rj AN / A &@ ™ 50 B; 0 I wherein R; is selected from the group consisting of H and CH;, R; and R3 are selected from the group consisting of C; alkyl and C; alkyl, A is selected from the group consisting of O and NH, B; is selected from the group consisting of C; alkyl, C3; alkyl and hydropropoxy groups, and Xj; is an anionic counterion and monomers of general formula II: Rs Re Ry AN J At A; ya On / NN 0 II wherein Ry; is selected from the group consisting of H and CH;, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; Ry; is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; A, is selected from the group consisting of an oxygen atom and NH; Bp is selected from the group consisting of C, alkyl, C3 alkyl, C4 alkyl and hydroxypropyl and X» = is an anionic counterion with b) at least 5 mole % of a monomer selected from the group consisting of Ci-Cjo N-alkyl acrylamide, C;-Cio N,N-dialkyl arylamide, C;-Cip N-alkylmethacrylamide, Ci-Cipo N,N-dialkylmethacrylamide, N-aryl acrylamide, N,N-diaryl acrylamide, N-aryl methacrylamide, N,N-diaryl methacrylamide, N-arylalkyl acrylamide, N,N-diarylalkyl acrylamide, N-arylalkyl methacrylamide, N,N-diarylalkyl methacrylamide, acrylamide and methacrylamide; and wherein said stabilizer polymer is a cationic polymer which is at least partially soluble in said aqueous solution of said anionic salt, wherein the improvement comprises the addition of said water-soluble cationic flocculant polymer dispersion to said waste water at a concentration of twenty-five weight percent polymer dispersion in water.
17. The improvement of claim 16 wherein said stabilizer polymer is polymerized from at least 5 mole % of cationic monomers selected from the group consisting of : monomers of general formula I R, Rj Ry AN / £ Ay yd © d Ng Xi . 0) I wherein R; is selected from the group consisting of H and CH3, Ry; and R; are selected from the group consisting of Cy; alkyl and C; alkyl, A; isselected from the groupgroup consisting of C; alkyl, Cz alkyl and hydropropoxy groups, and X;~ is an anionic counterion, . diallyldialkyl ammonium halides, monomers of general formula II: Rs Rg a NN 4 as A; J SN / NN 0 11 wherein Ry; is selected from the group consisting of H and CHs;, Rs and Rg are selected from the group consisting of C; alkyl and Cp alkyl; Rs is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; A; is selected from the group consisting of an oxygen atom and NH; Ba: is selected from the group consisting of C; alkyl, C3 alkyl, C4 alkyl and hydroxypropyl and X; = is an anionic counterion, and combinations thereof.
18. The improvement of claim 16 wherein said waste water is selected from the group consisting of industrial wastewater and municipal wastewater.
19. The improvement of claim 16 wherein said "anionic salt is selected from the group consisting of phosphates, sulfates, chlorides and mixtures thereof.
20. The improvement of claim 16 including the further step of adding an effective amount of at least one coagulant to the waste water.
21. The improvement of claim 18 wherein said industrial wastewater is selected from the group consisting of food processing waste water, oily waste water, paper mill waste water and inorganic-contaminated waste water.
22. In a method for dewatering waste water with an effective dewatering amount of at least one dispersion of a water soluble cationic polymer flocculant; wherein said water soluble flocculant is added to said waste water in an effective amount to dewater suspended solids, the suspended solids are removed, and a clarified water is obtained, said dispersion of said water soluble cationic polymer flocculant formed from polymerizing vinylic monomers under free-radical forming conditions in a medium containing water, monomers, stabilizer polymer, and an aqueous anionic salt solution; wherein said water-soluble cationic polymer flocculant is polymerized from a) at least 5 mole % of a cationic monomer selected from the group consisting of: monomers of general formula I
R; Rj R; AN / £1 NE O I : wherein R; is selected from the group consisting of H and CHs, R; and Rj are selected from the group consisting of C; alkyl and Cp alkyl, A; isselected from the group consisting of O and NH, B; is selected from the group consisting of Cz alkyl, Cj alkyl and hydropropoxy : groups, and Xi” is an anionic counterion and monomers of general formula II: Rs Re I N AE in IN Sh 0 11 wherein Rs is selected from the group consisting of H and CHi, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; Ry; is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; A, is selected from the group consisting of an oxygen atom and NH; Bz is selected from the group consisting of C, alkyl, C3 alkyl, C; alkyl and hydroxypropyl and X; = is an anionic counterion with b) at least 5 mole % of a monomer selected from the group consisting of C;-C;o N-alkyl acrylamide, C;- Cio N,N-dialkyl arylamide, C;-Cj;o N~alkylmethacrylamide, C1-Cjo N,N-dialkylmethacrylamide, N-aryl acrylamide, N,N- diaryl acrylamide, N-aryl methacrylamide, N,N-diaryl methacrylamide, N-arylalkyl acrylamide, N,N-diarylalkyl acrylamide, N-arylalkyl methacrylamide, N,N-diarylalkyl methacrylamide, acrylamide and methacrylamide; and wherein said stabilizer polymer is a cationic polymer which is at least partially soluble in said aqueous solution of said anionic salt; wherein the improvement comprises the addition of said water-soluble cationic flocculant polymer dispersion to said waste water at a concentration of twenty-five weight percent polymer dispersion in water. :
23. The improvement of claim 22 wherein said stabilizer polymer contains at least 5 mole $% of cationic monomers selected from the group consisting of monomers of the general formula I : R, R; R; AN 4 § Aj ye C) a O I wherein R; is selected from the group consisting of H and CHi;, R, and Rj; are selected from the group . consisting of C; alkyl and C; alkyl, A; isselected from the group consisting of O and NH, B; is selected from the group consisting of C; alkyl, C3; alkyl and hydropropoxy groups, and XX,” is an anionic counterion,diallyldialkyl ammonium halides, monomers of general formula II: Rs R¢ Ry NL J SN ™ VE 0 11 wherein Rs is selected from the group consisting of H and CH;, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; R; is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; Az is selected from the group consisting of an oxygen atom and NH; Bp is selected from the group consisting of C, alkyl, C3 alkyl, C4 alkyl and hydroxypropyl and X; = is an anionic counterion, and combinations thereof.
24. The improvement of claim 22 wherein said waste water is selected from the group consisting of industrial wastewater and municipal wastewater.
25. The improvement of claim 22 wherein said anionic salt is selected from the group consisting of phosphates, sulfates, chlorides and mixtures thereof.
26. The improvement of claim 22 including the further step of adding an effective amount of at least one coagulant to said waste water.
27. The improvement of claim 24 wherein said industrial wastewater is selected from the group consisting of food processing waste water, oily waste water, paper mill waste water and inorganic contaminated waste water.
28. In a method for improving retention and drainage of process water in pulp and paper production with an effective amount of at least one dispersion of a water soluble cationic polymer flocculant; wherein said water soluble flocculant is added to said process water in an effective amount to improve retention and drainage, said dispersion of said water soluble cationic polymer flocculant formed from polymerizing vinylic monomers under free-radical forming conditions in a medium containing water, monomers, stabilizer polymer, and an aqueous anionic salt solution; wherein said water-soluble cationic polymer flocculant is polymerized from a) at least 5 mole % of a cationic monomer selected from the group consisting of:
monomers of general formula I R, Rj R, AN yd ts B, 0 I wherein R; is selected from the group consisting of H and CHs, R; and R3 are selected from the group consisting of C; alkyl and C; alkyl, A; is selected from the group consisting of O and NH, B; is selected from the group consisting of Cz alkyl, Cs alkyl and hydropropoxy groups, and X; is an anionic counterion and monomers of general formula II: Rs R¢ Ry NL yd AE A; yd SO d ANE 0 II wherein Ry; is selected from the group consisting of H and CHs, Rs and Re are selected from the group consisting of C; alkyl and Cp alkyl; Rs is selected from the group consisting of hydrogen atom, C; alkyl and C: alkyl; A, is selected from the group consisting of an oxygen atom and NH; B; is selected from the group consisting of C; alkyl, C3 alkyl, C, alkyl and hydroxypropyl and X; = is an anionic counterion with b) at least 5 mole % of a monomer selected from the group consisting of Ci1-Cio N-alkyl acrylamide, C;-Cjo N,N-dialkyl arylamide, Cy1-Cio N-alkylmethacrylamide, C1-Cjo
N,N-dialkylmethacrylamide, N-aryl acrylamide, N,N-diaryl acrylamide, N-aryl methacrylamide, N,N-diaryl methacrylamide, N-arylalkyl acrylamide, N,N-diarylalkyl acrylamide, N-arylalkyl methacrylamide, N,N-diarylalkyl methacrylamide, acrylamide and methacrylamide; and wherein said stabilizer polymer is a cationic polymer which is at least partially soluble in said aqueous solution of said anionic salt; wherein the improvement comprises the addition of said water-soluble cationic flocculant polymer dispersion to said waste water at a concentration of twenty-five weight percent polymer dispersion in water.
29. The improvement of claim 28 wherein said stabilizer polymer is polymerized from at least 5 mole % of cationic monomers selected from the group consisting of monomers of the general formula I Ro R3 R; AN J £ 1) as 0) I wherein R; is selected from the group consisting of H and CH;, R, and Rj; are selected from the group consisting of C; alkyl and C; alkyl, A; is selected from the group consisting of O and NH, B; is selected from the group consisting of Cp alkyl, C3 alkyl and hydropropoxy groups, and X;” is an anionic counterion, diallyldialkyl ammonium halides,
monomers of the general formula II: Rs Re Ry AN J At A; ye ON / NN 0 11 wherein Ry is selected from the group consisting of H and CHs, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; R; is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; A; is selected from the group consisting of an . oxygen atom and NH; Bz is selected from the group consisting of C, alkyl, C3 alkyl, Cs alkyl and " hydroxypropyl and X; = 1s an anionic counterion and combinations thereof.
30. The improvement of claim 28 wherein said anionic salt is selected from the group consisting of phosphates, sulfates, chlorides and mixtures thereof.
AMENDED CLAIMS [received by the International Bureau on 10 August 1999 (10.08.99), original claims 1 — 30 replaced by new claims 1 - 7 (4 pages)]
1. A method for the treatment of water with an effective clarifying amount of at least one dispersion of a water soluble cationic polymer flocculant; wherein said water soluble flocculant is added to said water in an effective amount to flocculate suspended solids, the suspended solids are removed, and a clarified water is obtained, said dispersion of said water soluble cationic polymer flocculant formed from polymerizing vinylic monomers under free-radical forming conditions in a medium containing water, monomers, stabilizer polymer, and an aqueous anionic salt solution; wherein said water-soluble cationic polymer flocculant is polymerized from a) at least 5 mole % of a cationic monomer selected from the group consisting of: monomers of general formula (I) R, Ry R; AN J £ A yas oo 0
I . wherein R; is selected from the group consisting of H and CH;, R; and R3 are selected from the group consisting of C; alkyl and C; alkyl, A; is selected from the group consisting of O and NH, B; is selected from the group consisting of C, alkyl, C3 alkyl and hydropropoxy groups, and X; is an anionic counterion and AMENDED SHEET (ARTICLE 19)
monomers of general formula II: Rs Rg Ry AN / Ane? Ay J On / NTN 0 II wherein R; is selected from the group consisting of H and CHs, Rs and Rg are selected from the group consisting of C, alkyl and C; alkyl; R; is selected from the group consisting of hydrogen atom, C; alkyl and C, alkyl; A; is selected from the group consisting of an oxygen atom and NH; B; is selected from the group consisting of C; alkyl, C3; alkyl, C4 alkyl and hydroxypropyl and X, = 1s an anionic counterion with b) at least 5 mole % of a monomer selected from the group consisting of C;-C;p N-alkyl acrylamide, C;-Cio N,N- dialkyl arylamide, Ci- Cio N-alkylmethacrylamide, C;-Cjo N,N- dialkylmethacrylamide, N-aryl acrylamide, N,N-diaryl acrylamide, N-aryl methacrylamide, N,N-diaryl methacrylamide, N-arylalkyl acrylamide, N,N-diarylalkyl acrylamide, N- arylalkyl methacrylamide, N,N-diarylalkyl methacrylamide, acrylamide and methacrylamide; and wherein said stabilizer polymer is a cationic polymer which is at least partially soluble in said aqueous solution of said anionic salt, wherein the addition of said water- soluble cationic flocculant polymer dispersion to said waste water at a concentration of at least twenty-five weight percent polymer dispersion in water.
2. The method of claim 1 wherein said anionic salt is . selected from the group consisting of phosphates, sulfates, chlorides and mixtures thereof. AMENDED SHEET (ARTICLE 19)
3. The method of claim 2 wherein that said stabilizer polymer is polymerized from at least 5 mole % of cationic monomers selected from the group consisting of : monomers of general formula I R, Rj Ry AN J NO Aq ye © X, d ™ B, 0 I wherein R; is selected from the group consisting of H and CH;, R; and Rj; are selected from the group consisting of C; alkyl and C, alkyl, A; is selected from the group consisting of 0 and NH, B; is selected from the group consisting of C, alkyl, Cs; alkyl and hydropropoxy groups, and X; is an anionic counterion, diallyldialkyl ammonium halides, monomers of general formula II: Rs Re Ry AN / ® Ay J 2 @ ANE ON oy O II wherein Ry is selected from the group consisting of H and CH3, Rs and Rg are selected from the group consisting of C; alkyl and C; alkyl; R; is selected from the group consisting of hydrogen atom, C; alkyl and C; alkyl; A; is selected from the group consisting of an oxygen atom and NH; B; is selected from the group consisting of C, alkyl, Ci; alkyl, Cs, alkyl and hydroxypropyl and X; = is an anionic counterion, and combinations thereof.
AMENDED SHEET (ARTICLE 19)
4. The method of claim 3 wherein the further step of adding an effective amount of at least one coagulant to the waste water.
5. The method of claim 4 wherein said water is selected from the group consisting of industrial wastewater and municipal wastewater. ]
6. The method of claim 5 wherein said industrial wastewater is selected from the group consisting of food processing waste water, oily waste water, paper mill waste water and inorganic-contaminated waste water. :
7. The method of claim 6 wherein the water to be treated is selected from clarifying waste water, the dewatering of waste water and the improvement of retention and drainage of process water in pulp and paper production. AMENDED SHEET (ARTICLE 19)
ZA200107959A 2001-09-27 2001-09-27 Higher actives dispersion polymer to aid clarification, dewatering, and retention and drainage. ZA200107959B (en)

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