CN101993139B - Method of removing a coloring component - Google Patents
Method of removing a coloring component Download PDFInfo
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- CN101993139B CN101993139B CN201010243612.5A CN201010243612A CN101993139B CN 101993139 B CN101993139 B CN 101993139B CN 201010243612 A CN201010243612 A CN 201010243612A CN 101993139 B CN101993139 B CN 101993139B
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Abstract
The invention is a method of removing a coloring component. The invention provides a method of effectively removing hard biolysis water-solubility coloring components remained in activated sludge by using a small amount of organic high molecule flocculant. The method is characterized by adding a coloring component removing agent into an activated sludge mixed liquor in which a color intensity of the hard biolysis water-solubility coloring component is more than 50 under a condition that a floating solid component is more than 500mg/L, then performing solid-liquid separation, wherein the coloring component removing agent adopts at least one polymer selected from water-solubility and/or water-absorbability cation polymers (a, b), as well as a water-solubility and/or water-absorbability amphiprotic polymer (c) containing units represented by a prescribed formula, as an active ingredient.
Description
Technical field
The present invention relates to remain in the method for removing of the water-soluble coloring composition of the difficult Biodegradable in the active sludge of draining.
Background technology
The activated sludge treatment method of organic drainage is, in aerator tank, draining and active sludge is (following, sometimes referred to as " mud ") mix, carry out aeration, separated sludge in the solid-liquid separation tank such as settled layer, floating layer of mud, discharges using parting liquid as processing water, on the other hand, a part for mud after separating is back in aerator tank as returned sluge, and rest part is discharged as excess sludge.This activated sludge treatment method, by centered by the bacterial flora such as zoogloea, assemble have the flocs unit (active sludge) of various microorganisms to carry out decomposing organic matter, but in organic drainage during containing the water-soluble coloring material of Biodegradable in distress, remaining coloring components sometimes in the supernatant liquor in solid-liquid separation tank.
In the present invention, the water-soluble coloring composition of difficult Biodegradable refers to the anionic property that is difficult to remove in common active sludge treatment or has the organism of both sexes functional group, be soil ulmin, xylogen decomposition product, bilirubin formula material, other the pollution substance such as the water-soluble coloring polymer substance generating by amino-carbonyl reaction, refer to that BOD (biological oxygen demand)/CODMn (by the chemical oxygen demand (COD) of potassium permanganate process) is below 0.1 and the colourity of counting the 10mg/L aqueous solution taking carbon component is more than 20 materials.
With regard to the water-soluble coloring composition of the difficult Biodegradables such as soil ulmin,, shown in non-patent literature 1 and non-patent literature 2, be for example material contained in draining, underground water etc., owing to having wetting ability and hydrophobicity concurrently, thereby be dissolved in the water, cannot remove by coagulative precipitation.In addition, these coloring components are decomposed by microorganism owing to being difficult to, and being therefore difficult to by common treatment process is that activated sludge process etc. is removed.Although it is possible utilizing the adsorption treatment of gac etc., cost is high.
In the water-soluble coloring composition of above-mentioned difficult Biodegradable, bilirubin formula material refers to the metabolite of hemochrome contained in fecaluria, livestock products draining, except the bilirubin as gall pigment russet, also comprises stercobilinogen, urobilin.Bilirubin formula material can be by chemical process processing, but because being implemented in of existing known method is difficult economically, thereby practical situation are dilute and discharge, so seeking the treatment process that carrying capacity of environment is few.
The painted draining of the water-soluble coloring composition containing Biodegradable in distress as above, even reach the benchmark values such as BOD by the processing etc. that utilizes activated sludge process, COD sometimes also can be high.In addition, even if its content of these coloring components is little, also demonstrate painted.Therefore, sewage, fecaluria, livestock products draining, food mfg draining and papermaking draining etc. by the drainings after treatment such as active sludge (processing water) in, the water-soluble coloring composition that contains this difficult Biodegradable, therefore, the draining that contains these compositions is just given off so, can cause the pollution of water resources, and, if discharge this painted draining, can cause the complaint from periphery resident etc.
And then, when the coloring components such as soil ulmin are carried out to chlorine germicidal treatment etc., contain and can form the precursor substance of harmful trichloromethane, if be discharged in river etc., worry can make the diversion water quality deterioration of tap water.
In addition, even if known above-mentioned coloring components is using in the filtration treatment such as filter membrane, also become the reason of fouling, cause the reduction of strainability.
Under the increasingly valued present situation of environmental pollution, process relevant draining regulation owing to further having strengthened to this draining, therefore, the necessity of processing more to heavens draining is increased, expect to develop the water treatment method of low cost, excellent in efficiency.
So, the various treatment processs of the draining that contains above-mentioned coloring components have been proposed, for example can enumerate: there is ozonize operation and by the drainage processing method of the accelerated oxidation treatment process of ozone interpolation and uviolizing use (for example, patent documentation 1, non-patent literature 3), (for example make its method that contacts to remove with ion exchange resin, patent documentation 2), adding load has method that the porous plastid of titanium removes (for example, patent documentation 3), to the method for adding inorganic flocculant and organic polymer flocculation agent in active sludge treatment water (for example, patent documentation 4, patent documentation 5) etc.But these method operations are numerous and diverse, from removing viewpoint of efficiency, economy etc., can't say gratifying method.
In addition, in patent documentation 6, disclose: the polyvinylamine as one of cation property copolymer can be in the decolouring purposes of dyeing draining.
Prior art document
Patent documentation 1: TOHKEMY 2006-224065 communique
Patent documentation 2: TOHKEMY 2000-254488 communique
Patent documentation 3: TOHKEMY 2005-238174 communique
Patent documentation 4: TOHKEMY 2003-181491 communique
Patent documentation 5: Japanese kokai publication hei 6-226265 communique
Patent documentation 6: Japanese kokai publication hei 8-81519 communique
Non-patent literature 1: the upper positive people in field, slope literal sense is clear: Gang sorption Trees fat The is got と specificity analysis (using the getting of underground water soil ulmin of rigidity polymeric adsorbent to collect and specificity analysis) with the rotten Zhi Wu of い underground water Quality Mining, atomic power バ Star Network エ Application De research (research of atomic power end), vol.12No.1-2 (2006)
Non patent literature 2: Nokami Yusaku, South Arita Chiko, Miyanaga Masako: the life drain of the activated sludge treatment of water in COD and I, we? In acids shadow <img TranNum= "92" file= "BSA00000214907400031.GIF" he= "59" img-content= "drawing" img-format= "TIF" inline= "yes" orientation= "portrait" wi= "57" / > (influence on life rich acid drainage activated sludge water COD), water and Fei water (use of water and wastewater), vol.43No.12 (2001)
Non-patent literature 3: gloomy Bodhidharma, Qi Yuan road man's work: new い decolouring skill Intraoperative (new decolouring technology), livestock products research (research of livestock industry) the 57th No. 1st, volume (2003)
Summary of the invention
The problem that invention will solve
Known method as above, as the method for water-soluble coloring composition of removing the difficult Biodegradable in draining, can't say gratifying method.For example, the method for utilizing ozone to process of recording in patent documentation 1, because not only cost is high, and need to adjust reaction conditions, and draining kind that therefore can be applicable is restricted.In addition, that in patent documentation 2,3, records adsorbs the method for removing coloring components with solids component, because loading capacity is limited, therefore needs to wash frequently, change filter material.And then, the interpolation inorganic flocculant of being recorded as patent documentation 4,5 and the method for organic polymer flocculation agent, not only need very large flocculation agent addition, and need a large amount of alkali in order to adjust pH value, have the such problem of a large amount of waste residues after treatment that produces.About patent documentation 6, object is limited to dyeing draining, fails to learn that it can remove the coloring components of other draining.
The object of the invention is to, provide a kind of in the process of water-soluble coloring composition of removing difficult Biodegradable remaining in active sludge, use the polymer coagulant fewer than previous methods, can low cost and easy and remove this coloring components with little waste residue generation, reduce the method for its concentration.
The means of dealing with problems
The present invention relates to effectively remove the method for water miscible difficult Biodegradable coloring components remaining in active sludge, its main points are the method for removing of the coloring components in the active sludge intermixture of following characteristics: be under condition more than 500mg/L at the existence solids component that swims, the colourity of coloring components remover being added to the water-soluble coloring composition that contains Biodegradable in distress is in more than 50 active sludge intermixtures, then carry out solid-liquid separation, described coloring components remover is with the water-soluble and/or absorptive cation property copolymer (a) from containing the amidine structural unit that amidine structural unit that aftermentioned general formula (1) represents and/or aftermentioned general formula (2) represent, water-soluble and/or the absorptive cation property copolymer (b) that the monomer polymerization that aftermentioned general formula (3) represents forms, and at least any polymkeric substance of selecting in water-soluble and/or absorptive amphiphilic polymers (c) is as effective constituent.
Preferred method as the inventive method can be enumerated following mode, that is, the principal constituent of the coloring components of described active sludge intermixture is not dyestuff; The water-soluble coloring composition of described difficult Biodegradable comprises and is selected from soil ulmin, xylogen decomposition product, bilirubin formula material and passes through at least one in water-soluble coloring polymer substance that amino-carbonyl reaction generates; Add the described coloring components remover of 0.1～2000mg/L with respect to described active sludge intermixture.
And then, can enumerate following mode as preferred mode, described amphiphilic polymers (c) is to contain the amphiphilic polymers of monomeric unit that monomeric unit that aftermentioned general formula (4) represents and aftermentioned general formula (5) represent; The amidine structural unit that the amidine structural unit that the aftermentioned general formula (1) that described cation property copolymer (a) contains 5～90 % by mole represents and/or aftermentioned general formula (2) represent; The unit of the monomer that derives from aftermentioned general formula (3) expression that described cation property copolymer (b) contains 10～100 % by mole; Described amphiphilic polymers (c) is the amphiphilic polymers of the monomeric unit that represents of the monomeric unit that represents of the aftermentioned general formula (4) that contains 10～98 % by mole and the aftermentioned general formula (5) of 2～30 % by mole.
Invention effect
The method according to this invention, use from least any polymkeric substance as still less selecting water-soluble and/or absorptive cation property copolymer (a), (b) and the amphiphilic polymers (c) of the organic polymer flocculation agent of usage quantity than previous methods, just can reduce the concentration of the water-soluble coloring composition of difficult Biodegradable remaining in active sludge with low cost and few waste residue generation.In addition, according to the present invention, because only add organic polymer coagulant in active sludge, therefore do not increase treatment process and just can remove easily above-mentioned coloring components.
Embodiment
Method of the present invention is to utilize coloring components remover to remove the method for the water-soluble coloring composition of the difficult Biodegradable in active sludge intermixture, coloring components remover is so-called polymer coagulant, is that at least any polymkeric substance to select from water-soluble and/or water-absorbent cation property copolymer and/or amphiphilic polymers is as the material of principal constituent.
Water-soluble and/or the absorptive cation property copolymer using as the composition of painted remover of the present invention is at least one being selected from the cation property copolymer (b) that the cation property copolymer (a) that contains the amidine structural unit that amidine structural unit that following general formula (1) represents and/or following general formula (2) represent and the monomer polymerization that following general formula (3) represents form.In addition, this polymkeric substance can be also bridging property gel.
[Chemical formula 1]
[Chemical formula 2]
[in formula (1), (2), R
1～R
2be hydrogen atom or methyl independently of one another, can be the same or different.X
-the negatively charged ion of respectively doing for oneself, can be the same or different.]
[Chemical formula 2]
[in formula (3), Z
-represent negatively charged ion.]
Water-soluble and/or the absorptive cation property copolymer (a) using in the present invention is to contain the cation property copolymer of amidine structural unit that amidine structural unit that above-mentioned general formula (1) represents and/or following general formula (2) represent.In above-mentioned general formula (1) and (2), as with X
-the negatively charged ion representing, specifically can enumerate Cl
-, Br
-, 1/2SO
4 2-, CH
3(CO) O
-, H (CO) O
-deng.Wherein, preferred Cl
-.
As the manufacture method of this cation property copolymer (a), be not particularly limited, for example can enumerate following methods: manufacture has primary amino and maybe can generate the ethylene unsaturated monomer of substituted-amino of primary amino and the multipolymer of the nitrile of vinyl cyanide or methacrylonitrile by conversion reaction, carry out after acid hydrolysis, primary amino is reacted with the cyano group in this multipolymer, carry out the method for amidineization.
As above-mentioned ethylene unsaturated monomer, preferably with general formula CH
2=CR
a-NHCOR
b(in formula, R
arepresent hydrogen atom or methyl, R
brepresent alkyl or the hydrogen atom of carbonatoms 1～4) compound that represents.In the multipolymer of nitrile, the substituted-amino that derives from related compound can be changed into primary amino easily by hydrolysis or alcoholysis.And then this primary amino reacts with adjacent cyano group, carry out amidineization.As this compound, can exemplify N-vinyl formamide (R
a=H, R
b=H), N-vinyl acetamide (R
a=H, R
b=CH
3) etc.
The polymerization mol ratio of these ethylene unsaturated monomers and nitrile is generally 20:80～80:20, but according to expectation, also can adopt this extraneous polymerization mol ratio, for example, and the polymerization mol ratio that the ratio of ethylene unsaturated monomer is larger.Conventionally, amidine structural unit shared ratio in water-soluble and/or water-absorbent cation property copolymer is larger, and the performance during as coloring components remover is more excellent.In addition, can think, vinyl amine structural unit is also conducive to the performance as coloring components remover.Therefore, provide the polymerization mol ratio of this ethylene unsaturated monomer and the nitrile of suitable multipolymer as coloring components remover, be generally 20: 80～80: 20, be particularly preferably 40: 60～60: 40.
As the method for ethylene unsaturated monomer and nitrile copolymerization, can use common radical polymerization, any means such as mass polymerization, aqueous solution precipitation polymerization, suspension polymerization, letex polymerization can be used.In solvent when polymerization, be generally 5～80 quality %, be preferably 20～60 quality % and implement polymerization with starting monomer concentration.Polymerization starter can use common radical polymerization initiator, and preferably azo-compound, can exemplify 2, the hydrochloride of 2 '-azo two (2-amidine propane) etc.In addition, polyreaction under inert gas flow, is implemented in the temperature of 30～100 DEG C conventionally.The multipolymer obtaining can be directly for amidineization reaction solution, or reacts for amidineization after dilution.In addition, also can carry out desolventizing, dry by known method, after separating multipolymer as solid, again dissolve, react for amidineization.
In amidineization reaction, while using N-ethenyl amide compound prodn that above-mentioned general formula represents as ethylene unsaturated monomer, the substituted-amino of multipolymer is converted into primary amino, then, the primary amino generating is reacted with adjacent cyano group, generate amidine structure, by carrying out such two-stage reaction, can manufacture the water-soluble and/or absorptive cation property copolymer (a) using in the present invention.
In addition, also can, by multipolymer under the existence of strong acid, in water, heat, make it generate amidine structure with a stage.In this case, can think: first, primary amino generates as intermediate structure.
As the actual conditions of amidineization reaction, for example can pass through with respect to the substituted-amino in multipolymer, conventionally add 0.1～5.0 times, preferably strong acid, the preferred hydrochloric acid of 0.5～3.0 times of equivalent, conventionally 80～150 DEG C, preferably at the temperature of 90～120 DEG C, conventionally heating 0.5～20 hour, forms the cation property copolymer with amidine structural unit.Conventionally, the equivalence ratio of strong acid and substituted-amino is larger, and temperature of reaction is higher, more promotes amidineization.In addition, when amidineization, preferably make to exist in reaction system with respect to be generally for the multipolymer of reaction 10 quality % above, preferred water more than 20 quality %.
About the water-soluble and/or absorptive cation property copolymer (a) using in the present invention, the most typically, preferably manufacture as follows according to above-mentioned explanation: make N-vinyl formamide and acrylonitrile compolymer and generate multipolymer, this multipolymer, conventionally with form heating in the presence of hydrochloric acid of aqueous suspension, is formed to amidine structural unit by substituted-amino and adjacent cyano group.Then, the amidineization condition by selection for the N-vinyl formamide of copolymerization and the mol ratio of vinyl cyanide and multipolymer, can obtain the water-soluble and/or absorptive cation property copolymer (a) of various compositions.
With regard to the water-soluble and/or absorptive cation property copolymer (a) so obtaining, in 100 % by mole of this cation property copolymers, the amidine structural unit that the amidine structural unit that above-mentioned general formula (1) represents and/or above-mentioned general formula (2) represent, as repeating unit, preferably contains 5～90 % by mole.If the content of these amidine structural units is lower than 5 % by mole, can be because the content of amidine structural unit is very few, thereby in the time using coloring components remover, usage quantity increases.On the other hand, if the content of amidine structural unit exceedes 90 % by mole, be difficult to manufacture with aforesaid method.The lower value of the content of amidine structural unit more preferably more than 10 % by mole, more preferably more than 15 % by mole, is particularly preferably more than 20 % by mole.In addition, the higher limit of the content of amidine structural unit is more preferably more than 85 % by mole, more preferably more than 80 % by mole.
Cation property copolymer (a) is if manufactured by aforesaid method, except described amidine structural unit, sometimes also can contain at least one being selected from the represented unit of arbitrary general formula of following general formula (6)～(8).
[chemical formula 3]
In general formula (6)～(8), R
11, R
13, R
14be hydrogen atom or methyl independently of one another, can be the same or different.
R
12for alkyl or the hydrogen atom of carbonatoms 1～4.
Q
-for negatively charged ion.As negatively charged ion, identical with illustrative negatively charged ion in the explanation of above-mentioned general formula (1), (2).
When cation property copolymer of the present invention (a) contains the unit that in above-mentioned general formula (6)～(8), arbitrary general formula represents, conventionally, in 100 % by mole of this cation property copolymers (a), 0～70 % by mole of the repeating unit of 0～40 % by mole of the repeating unit that contains above-mentioned general formula (6) expression, 0～70 % by mole of the repeating unit that above-mentioned general formula (7) represents, above-mentioned general formula (8) expression.
The composition of the unit that arbitrary general formula of the amidine structural unit that above-mentioned general formula (1) represents, the amidine structural unit that above-mentioned general formula (2) represents and above-mentioned general formula (6)～(8) represents can be adjusted by the condition (temperature, time) of the polymerization mol ratio of ethylene unsaturated monomer and nitrile, amidineization reaction.
In addition, their composition, can be by measuring cation property copolymer
13c-NMR (
13c nucleus magnetic resonance) obtain, particularly, can be corresponding by each repeating unit
13the integrated value of the peak value (signal) of C-NMR wave spectrum calculates.
The cation property copolymer (b) using in the present invention is the cation property copolymer that the monomer polymerization of above-mentioned general formula (3) expression forms, and it contains the unit that derives from this monomer.
Cation property copolymer (b) preferably contains 10～100 % by mole of unit that derive from the monomer that above-mentioned general formula (3) represents.
In general formula (3), Z
-what the negatively charged ion that represents was concrete is expressed as F
-, Cl
-, Br
-deng halide-ions.
Cation property copolymer (b) is specifically preferably the homopolymer of diallyl amine cation monomer as follows.
As the diallyl amine cation monomer using in the present invention, can enumerate the quaternary ammonium salts such as the inorganic salt of the tertiary amines such as the inorganic salt of the secondary amine such as diallyl amine, DMAA or organic acid salt, diallyl methylamine, diallyl ethylamine, diallyl butylamine or organic acid salt, chlorination diallyl dimethyl ammonium, bromination diallyl dimethyl ammonium, chlorination diallyl diethyl ammonium, bromination diallyl diethyl ammonium, chlorination diallyl dibutyl ammonium, bromination diallyl dibutyl ammonium.Wherein, chlorination diallyl dimethyl ammonium particularly preferably.
Then, the water-soluble and/or absorptive amphiphilic polymers using in the present invention is described.
This amphiphilic polymers (c) preferably has the Amphiphatic high polymer of the monomeric unit of following general formula (4) expression and the ethene base system of the monomeric unit that following general formula (5) represents.
[chemical formula 4]
[in formula (4), R
3represent hydrogen atom or methyl, R
4represent the alkylidene group of carbonatoms 1～4, R
5represent the alkyl of carbonatoms 1～4, R
6represent alkyl or the benzyl of hydrogen atom, carbonatoms 1～4, represent-O-of A or-NH-, Y
-represent negatively charged ion.]
[chemical formula 5]
[in formula (5), R
7, R
8represent hydrogen atom, methyl or-COO
-m '
+(M '
+represent hydrogen ion or other positively charged ions.), B represents alkylidene group, the phenylene ,-COOR of singly-bound, carbonatoms 1～2
9-(R
9represent the alkylidene group of carbonatoms 2～6) or-CONHR
10-(R
10represent the alkylidene group of carbonatoms 2～6) linking group, W
-expression-COO
-or-SO
3 -, M
+represent hydrogen ion or other positively charged ion.]
As the vinyl cation monomer of the monomeric unit raw material shown in above-mentioned general formula (4), for example can enumerate dimethylamino (methyl, ethyl, propyl group or butyl) acrylate or methacrylic ester, diethylamino (methyl, ethyl, propyl group or butyl) acrylate or methacrylic ester, diη-propyl amino (methyl, ethyl, propyl group or butyl) acrylate or methacrylic ester, diisopropylaminoethyl (methyl, ethyl, propyl group or butyl) acrylate or methacrylic ester, di-n-butyl amino (methyl, ethyl, propyl group or butyl) acrylate or methacrylic ester, di-sec-butyl amino (methyl, ethyl, propyl group or butyl) acrylate or methacrylic ester, diisobutyl amino (methyl, ethyl, propyl group or butyl) (methyl) acrylic acid dialkyl aminoalkyl ester class such as acrylate or methacrylic ester, dimethylamino (methyl, ethyl, propyl group or butyl) acrylamide or Methacrylamide, diethylamino (methyl, ethyl, propyl group or butyl) acrylamide or Methacrylamide, diη-propyl amino (methyl, ethyl, propyl group or butyl) acrylamide or Methacrylamide, diisopropylaminoethyl (methyl, ethyl, propyl group or butyl) acrylamide or Methacrylamide, di-n-butyl amino (methyl, ethyl, propyl group or butyl) acrylamide or Methacrylamide, di-sec-butyl amino (methyl, ethyl, propyl group or butyl) acrylamide or Methacrylamide, diisobutyl amino (methyl, ethyl, propyl group or butyl) dialkyl aminoalkyl (methyl) acrylic amide such as acrylamide or Methacrylamide by hydrogen halide, sulfuric acid, nitric acid, organic acid etc. form in and salt, by halon, benzyl halide, methyl-sulfate, the quaternary salt that ethyl sulfate etc. form etc.These ethene base system monomers can use a kind, also two or more can be used in combination.
Y in general formula (4)
-the negatively charged ion representing, is expressed as Cl particularly
-, Br
-, 1/2SO
4 2-.
In addition, as the vinyl cation monomer of the monomeric unit raw material shown in above-mentioned general formula (5), can exemplify vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, vinyl sulfonic acid, allyl sulphonic acid, methacrylic sulfonic acid, styrene sulfonic acid, 2-acrylamide ethane sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, 2-Methacrylamide ethane sulfonic acid, 2-Methacrylamide-2-methyl propane sulfonic acid, 2-acryloxy ethane sulfonic acid, 3-acryloxy propane sulfonic acid, 4-acryloxy butane sulfonic acid, 2-methacryloxy ethane sulfonic acid, 3-methacryloxy propane sulfonic acid, 4-methacryloxy butane sulfonic acid, and their basic metal, the metal-salts such as alkaline-earth metal or ammonium salt.These anionic property monomers can use a kind, also two or more can be used in combination.
In addition, in general formula (5), M '
+, M
+represent independently of one another hydrogen ion or other positively charged ion.This other positively charged ion specifically can be enumerated Na
+, K
+deng alkalimetal ion, alkaline-earth metal ions, ammonium ion etc.
And then, in described amphiphilic polymers (c), also can contain the monomeric unit that derives from non-ionic monomer, as non-ionic monomer, can enumerate the nonionic vinyl monomer of (methyl) acrylamide, (methyl) acrylate, (methyl) vinyl cyanide, jealous woman acid ethene alcohol ester etc., other energy copolymerization.In non-ionic monomer, particularly preferably acrylamide.This monomeric unit that derives from non-ionic monomer can contain 0～90 % by mole, preferably 0～80 % by mole conventionally.
For the manufacture method of above-mentioned water-soluble and/or absorptive amphiphilic polymers (c), be not particularly limited, can adopt the known manufacture method such as aqueous solution polymerization, dispersion polymerization, emulsion polymerization high polymer modification.About the ratio of the each composition in amphiphilic polymers (c), general formula (4) represent monomeric unit be 10～98 % by mole, be preferably 15～95 % by mole, contain general formula (5) represent monomeric unit be 2～30 % by mole, be preferably 5～25 % by mole.If beyond this scope, insufficient as the effect of coloring components remover, be therefore unaccommodated.
In addition, as the manufacture method of water-absorbing polymer (cation property copolymer and amphiphilic polymers), can exemplify to add in the starting monomer mixtures such as cationic monomer as oxalic dialdehyde, the multi-functional linking agent such as di-epoxy compounds carries out the method for polymerization, carries out crosslinked method after making to react with water-soluble polymers with the multi-functional material of polymer reaction, heating water soluble polymer makes its crosslinked method etc.
Coloring components remover of the present invention contains at least any polymkeric substance of selecting water-soluble and/or absorptive cation property copolymer (a), (b) and amphiphilic polymers (c) effective constituent amount, from as principal constituent, also can contain other composition.As other composition, for example, can enumerate formic acid, ammonium chloride etc.
In addition, in the present invention, " effective constituent amount " refers to the total content of water-soluble and/or absorptive cation property copolymer (a), (b) and amphiphilic polymers (c) in coloring components remover 100 quality %, conventionally preferably contains 10～100 quality %.
When coloring components remover contains other composition, can, manufacturing the use level that after above-mentioned cation property copolymer (a), (b), amphiphilic polymers (c), other composition of interpolation is extremely expected, also can make in advance other composition be blended in the manufacture raw material of these (being total to) polymkeric substance.
Cation property copolymer (b) and amphiphilic polymers (c) that the principal constituent-amidine structural unit that contains above-mentioned general formula (1) expression of coloring components remover of the present invention and/or the cation property copolymer (a) of the amidine structural unit of above-mentioned general formula (2) expression and the monomer polymerization being represented by above-mentioned general formula (3) form are, the reduced viscosity of 25 DEG C while making the solution of 0.1g/dL with the salt solution of 1 equivalent is preferably 0.01～10dL/g, more preferably 0.1～8dL/g.If lower than 0.01dL/g, having the manufacture of coloring components remover, reduced viscosity becomes difficulty, or the tendency of coloring components remover function reduction.On the other hand, if reduced viscosity higher than 10dL/g, the viscosity of the aqueous solution of coloring components remover becomes too high, thereby in the time adding, has the uncomfortable situation of occurring.
In addition, above-mentioned reduced viscosity, can control by the adjustment of the molecular weight of coloring components remover, ionic ratio, molecular weight distribution, manufacture method, composition distribution etc.For example, if increase the molecular weight of coloring components remover, reduced viscosity has the tendency of increase.
In method of the present invention, coloring components remover as above is added to the solids component and be in more than 50 active sludge intermixtures containing the colourity of the water-soluble coloring composition of Biodegradable in distress of swimming existing more than 500mg/L, then carry out solid-liquid separation, thereby remove the described water-soluble coloring composition remaining in active sludge.
In the inventive method, in active sludge intermixture, exist under the state of the solids component that swims to a certain degree,, exist under state more than 500mg/L, by adding coloring components remover, can make described water-soluble coloring composition condense together with the solids component that swims, remove as coagulative precipitation thing.
With regard to adding the active sludge intermixture of coloring components remover in method of the present invention, the situation that to have recorded the principal constituent of contained hard-decomposed water-soluble coloring composition in patent documentation 6 be dyestuff can be used polyvinylamine, is preferably other composition in the present invention.
In addition, with regard to active sludge intermixture, preferably include and be selected from soil ulmin, xylogen decomposition product, bilirubin formula material and pass through at least one the water-soluble coloring composition as difficult Biodegradable in water-soluble coloring polymer substance that amino-carbonyl reaction generates.If other composition beyond these, coloring components remover has the possibility that can not play one's part to the full.
Here, more than " water-soluble " refers to and dissolve 0.1mg/L in the water of 20 DEG C.
About the interpolation of coloring components remover, can be added in active sludge and use, also can add in solid-liquid separation tank after active sludge treatment or thickened sludge and use.Use if added in thickened sludge, because the coloring components in dehydration filtrate is removed, therefore can reduce the load to the active sludge after refluxing.
In addition, coloring components remover of the present invention, not damaging in the scope of its effect, also can and use with other discoloring agent or inorganic flocculant, polymer coagulant.
In the present invention, so-called " adding active sludge intermixture to ", refer to the arbitrary site adding in active sludge treatment system, it is contacted with the microorganism in active sludge, for example can adopt and add in former tank together with active sludge and import the method for aerator tank, directly add method in aerator tank to, in the equipment with the anaerobic groove taking denitrogenation etc. as object, directly add method in anaerobic groove etc. to, in addition, remove effect as long as there is the water-soluble coloring composition of difficult Biodegradable, can adopt any means.And then, also can add in the stream such as lateral sulcus, pipe arrangement that is connected with each groove or add to being arranged in these each grooves Flow-rate adjustment groove before to.
(in active sludge, adding)
In the inventive method, while adding coloring components remover to active sludge in advance, the addition of coloring components remover, with respect to active sludge intermixture, is preferably 0.1～2000mg/L, more preferably 0.1～1000mg/L.If addition is less than 0.1mg/L, can become the effect that is difficult to fully obtain coloring components remover.On the other hand, if addition exceedes 2000mg/L, may be to the microorganisms detrimentally affect in active sludge.
Embodiment
Below, illustrate the present invention by embodiment, but not exceeding in the scope of purport of the present invention, the present invention is not limited to these embodiment.
In following test example (embodiment and comparative example), the evaluation of coloring components remover is that the colourity by measuring active sludge supernatant liquor is carried out.
The mensuration > of < colourity
So-called colourity, to represent be present in or be present in the caused faint yellow extremely filemot degree of material in water with colloidal state because dissolving, utilize ultraviolet-visible pectrophotometer (Shimadzu science (strain) is manufactured UV-3100) to measure near the absorbancy of 390nm, calculated by the typical curve of reference liquid.
In addition, the mensuration of colourity is to carry out according to ordinary method (water drain association of Japan of Corporation compiles, " rolling up version in 1997 on water drain test method(s) " p95 " 2. transmitted light assay method ").
The judgement that coloring components is removed effect is that the rate of removing by calculate coloring components by following formula is carried out.
Remove rate (%)=(1-D
2/ D
1) × 100
(D
1: the colourity of processed painted draining, D
2: the colourity after coloring components is removed)
The mensuration > of <pH
What the mensuration of pH was used is the method for recording in JIS K0102, specimen temperature is adjusted to 23 DEG C and measures.
The blanket table 1 that is shown in of the cation property copolymer using in test example and amphiphilic polymers.
[cation property copolymer (a)]
As the cation property copolymer (a) using in coloring components remover of the present invention, use be the cation property copolymer (A1, A2, A3) of manufacturing by the following method.
The manufacture > of < cation property copolymer A1
In the four-hole boiling flask of 50ml that stirrer, nitrogen ingress pipe, prolong are installed, pack mixture (mol ratio 55: the 45) 6g of vinyl cyanide and N-ethylene carboxamide and the mixture of de-salted water 34g into.Warming while stirring to 60 DEG C in nitrogen, adds 2 of 10 quality %, and 2 hydrochloride aqueous solution 0.12g of 2 '-azo two (2-amidine propane), further keep 3 hours, obtain separating out in water the thing that is suspended of polymkeric substance.Be suspended and in thing, add 20g water at this, and then with respect to the formyl radical of polymkeric substance, add the concentrated hydrochloric acid of 2 equivalents, keep 4 hours at 100 DEG C, obtain yellow high viscosity liquid.This liquid is added in a large amount of acetone, polymkeric substance is separated out, fritter the polymkeric substance obtaining, after 60 DEG C of dry nights, pulverize, obtain water-soluble cationic polymer powder.
(composition of cation property copolymer A1)
Water-soluble cationic polymer A 1 is dissolved in heavy water, by NMR spectrometer (NEC society manufactures, 270MHz) mensuration
13c-NMR wave spectrum.Pass through
13the integrated value at the corresponding peak of each repeating unit in C-NMR wave spectrum calculates the composition of each unit.Wherein, need not distinguish the structural unit of above-mentioned general formula (1) and (2), obtain as its total amount.The results are shown in table 1.
In addition, each unit contained in the cation property copolymer A1 so obtaining is, in above-mentioned general formula [(1), (2), (6)～(8)], and R
1～R
2and R
11～R
14for hydrogen atom, X
-, Q
-for chloride ion.
(mensuration of the reduced viscosity of cation property copolymer A1)
0.1g cation property copolymer A1 is dissolved in the salt solution 100mL of 1 equivalent, makes the solution of 0.1g/dL.Measure the reduced viscosity of 25 DEG C of this solution with ostwald's viscometer (manufacture of society of institute of Harry Austria (Ha リ オ)).The results are shown in table 1.
The manufacture > of < cation property copolymer A2
In the four-hole boiling flask of 500ml that stirrer, nitrogen ingress pipe, prolong are installed, pack 40g de-salted water, 1.2g PEG 20000,0.2g sodium hypophosphite into, be warming up to 70 DEG C, under nitrogen gas stream, with the 70 quality % aqueous solution 120g that drip the mixture (mol ratio 50: 50) of vinyl cyanide and N-vinyl formamide for 2 hours.During this period, by 2 of 10 quality %, 2 hydrochloride aqueous solution 12.6g of 2 '-azo two (2-amidine propane) divide portion-wise addition 5 times.And then slaking, after 2 hours, adds concentrated hydrochloric acid (being equivalent to respect to formyl radical is 100 % by mole), is warming up to 90 DEG C, places 3 hours.Added in a large amount of acetone, polymkeric substance is separated out, frittered the polymkeric substance obtaining, after 60 DEG C of dry nights, pulverized, obtained cation property copolymer.
(composition of cation property copolymer A2)
Carry out same operation with cation property copolymer A1, measure
13c-NMR wave spectrum, calculates the composition of each unit.Wherein, need not distinguish the structural unit of above-mentioned general formula (1) and (2), obtain as its total amount.The results are shown in table 1.
In addition, each unit contained in the cation property copolymer A2 so obtaining is, in above-mentioned general formula [(1), (2), (6)～(8)], and R
1～R
2and R
11～R
14for hydrogen atom, X
-, Q
-for chloride ion.
(reduced viscosity of cation property copolymer A2)
Carry out same operation with cation property copolymer A1, measure reduced viscosity.The results are shown in table 1.
The manufacture > of < cation property copolymer A3
Make above-mentioned cation property copolymer A1 that the polymkeric substance that crosslinking reaction obtains occur by heat treated (120 DEG C, 5 hours), its reduced viscosity is carried out same operation with cation property copolymer A1 and is measured.The results are shown in table 1.
[cation property copolymer (b) and amphiphilic polymers (c)]
Use the cation property copolymer (B1) of manufacturing using following method as cation property copolymer of the present invention (b), and from commercially available grade, selected both sexes flocculation agent (C1～C3) as amphiphilic polymers (c).About the composition of each polymkeric substance, in heavy water, dissolve each polymkeric substance, by NMR spectrometer (NEC society system, 270MHz) mensuration
13c-NMR wave spectrum.Pass through
13the integrated value at the corresponding peak of each repeating unit in C-NMR wave spectrum calculates the composition of each unit.
The reduced viscosity of each polymkeric substance is carried out same operation with cation property copolymer A1 and is measured.
Composition and the reduced viscosity of polymkeric substance are shown in table 1.
The manufacture > of < cation property copolymer B1
In 300mL detachable flask, pack diallyldimethylammonium chloride 32.3g (0.2 mole) and deionized water 64.7g into, be dissolved as evenly.This aqueous solution is stirred on limit, and 2,2,6,6-tetramethyl--piperidino oxyradical (TEMPO) 20.3mg (0.03 mmole) is dissolved in the solution forming in 1.0mL methyl alcohol by limit interpolation, and TEMPO is dispersed in the aqueous solution.Then,, in ice bath, with 500mL/ minute logical nitrogen 3 hours, remove and in the aqueous solution that contains monomer mixture, dissolve the oxygen existing.This aqueous solution is stirred on limit, ammonium persulphate 22.8mg (0.1 mmole) is dissolved in the solution forming in deionized water 1.0mL by limit interpolation, and then, add sodium sulfite 19.0mg (0.1 mmole) is dissolved in to the solution forming in deionized water.Add this redox initiator after 3 hours, this aqueous solution is carried out to polymerization in 24 hours in 60 DEG C of heating, obtain gelatinous polymkeric substance.The limiting viscosity of this polymkeric substance is 1.6dL/g.
(composition of cation property copolymer B1)
Carry out same operation with cation property copolymer A1, measure
13c-NMR wave spectrum, calculates the composition of each unit.The results are shown in table 1.
(reduced viscosity of cation property copolymer B1)
Carry out same operation with cation property copolymer A1, measure reduced viscosity.The results are shown in table 1.
In addition, as a comparative example, used commercially available polymer coagulant: DIAFLOC K-415 (Dia-Nitrix (strain) makes, contains acrylic acid series cationic polymers 41wt%), DIAFLOC KP-201G (Dia-Nitrix (strain) system, dimethylaminoethyl methacrylate quaternary salt polymkeric substance).
Table 1
AAm: acrylamide unit
DMC: methacryloxyethyl trimethyl ammonium chloride unit
DADMAC: diallyldimethylammonium chloride unit
DMQ: acryloxy ethyl-trimethyl salmiac unit
Amidine: amidine hydrochloride unit
NVF:N-vinyl formamide unit
AN: acrylonitrile unit
VAM: vinyl amine hydrochloride unit
AA: acrylic acid units
[test 1]
< embodiment 1>
In beaker, pack active sludge (pH6.2, the colourity 314) 200ml in the sewage farm after painted into, by the coloring components remover shown in table 2 with the water-soluble aqueous interpolation specified amount of 0.1 quality % after, be uniformly mixed 2 minutes, leave standstill a night.Afterwards, for supernatant liquor, measure the absorbancy of wavelength 390nm, by calculated the colourity of supernatant liquor by measured value, judge the effect of removing of coloring components.The results are shown in table 2.
< comparative example 1>
Except not adding coloring components remover, carry out same operation with embodiment 1, judgement coloring components is removed effect.The results are shown in table 2.
< comparative example 2>
Except using commercially available poly aluminium chloride flocculation agent (Gao Shan Pharmaceutical Co., Ltd system, PAC: contain Al
2o
3composition 10～11%) in addition, carry out same operation with embodiment 1, judgement coloring components is removed effect.The results are shown in table 2.
< comparative example 3>
Except using commercially available polymer coagulant (Dia-Nitrix (strain) system, DIAFLOC K-415), carry out same operation with embodiment 1, judgement coloring components is removed effect.The results are shown in table 2.
Table 2
[test 2]
< embodiment 2>
Except using active sludge (pH6.7, the colourity 175) 200ml that urine after painted processes, carry out same operation with embodiment 1, judge its effect of removing with the coloring components remover shown in following table 3.And then using the hydrochloric acid of 0.1 equivalent is pH5.5 by the pH regulator of active sludge, carries out same operation with embodiment 1, judgement coloring components is removed effect.The results are shown in table 3.
Wherein, the solid of the active sludge constituent concentration that swims is 2,400mg/L.
< comparative example 4>
Except not adding coloring components remover, carry out same operation with embodiment 2, judgement coloring components is removed effect.The results are shown in table 3.
Table 3
[test 3]
< embodiment 3>
Except using active sludge (pH6.8, the colourity 84) 200ml that the draining in the paper mill after painted processes, carry out same operation with embodiment 1, judge its effect of removing with the coloring components remover shown in following table 4.The results are shown in table 4.
Wherein, the solid of the active sludge constituent concentration that swims is 6,100mg/L.
< comparative example 5>
Except not adding coloring components remover, carry out same operation with embodiment 3, judgement coloring components is removed effect.The results are shown in table 4.
< comparative example 6>
Except using commercially available poly aluminium chloride flocculation agent (Gao Shan Pharmaceutical Co., Ltd system, PAC: contain Al
2o
3composition 10～11%) in addition, carry out same operation with embodiment 3, judgement coloring components is removed effect.The results are shown in table 4.
< comparative example 7>
Except using commercially available polymer coagulant (Dia-Nitrix (strain) system, DIAFLOC K-415), carry out same operation with embodiment 3, judgement coloring components is removed effect.The results are shown in table 4.
Table 4
Claims (4)
1. the method for removing of the coloring components in an active sludge intermixture, it is characterized in that, be under condition more than 2000mg/L at the existence solids component that swims, the colourity of coloring components remover being added to the water-soluble coloring composition that contains Biodegradable in distress is in more than 50 active sludge intermixtures, then carry out solid-liquid separation
Described coloring components remover also to contain at least one the water-soluble and/or absorptive cation property copolymer (a) of selecting from the represented unit of following general formula (6)～(8) any one as effective constituent except containing the amidine structural unit that amidine structural unit that following general formula (1) represents and/or following general formula (2) represent
The water-soluble coloring composition of described difficult Biodegradable comprises and is selected from soil ulmin, xylogen decomposition product, bilirubin formula material and passes through at least one in water-soluble coloring polymer substance that amino-carbonyl reaction generates,
[Chemical formula 1]
In formula (1), (2), R
1～R
2be independently of one another hydrogen atom or methyl, identical or different, X
-the negatively charged ion of respectively doing for oneself, identical or different;
[chemical formula 3]
In general formula (6)～(8), R
11, R
13, R
14be hydrogen atom or methyl independently of one another, can be the same or different,
R
12for alkyl or the hydrogen atom of carbonatoms 1～4,
Q
-for negatively charged ion.
2. the method for removing of the coloring components of recording according to claim 1, wherein, the principal constituent of the water-soluble coloring composition of the contained described difficult Biodegradable of described active sludge intermixture is not dyestuff.
3. the method for removing of the coloring components of recording according to claim 1, wherein, adds the described coloring components remover of 0.1～2000mg/L with respect to described active sludge intermixture.
4. the method for removing of the coloring components of recording according to claim 1, wherein, 5～90 % by mole of the amidine structural units that the amidine structural unit that described cation property copolymer (a) contains above-mentioned general formula (1) expression and/or above-mentioned general formula (2) represent.
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| JP2010147578A JP2011050946A (en) | 2009-08-05 | 2010-06-29 | Method for removing coloring component |
| JP2010-147578 | 2010-06-29 |
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| CN1222489A (en) * | 1997-12-18 | 1999-07-14 | 纳尔科化学公司 | Amphoteric polymer/polyamine combinations for color removal and clarification of paper mill waste water |
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| CN101323472A (en) * | 2007-06-15 | 2008-12-17 | 南京理工大学 | Polymeric ferric sulfate-poly-dimethyl-diallyl-ammonium chloride composite flocculent, preparation and use method thereof |
| CN101405226A (en) * | 2006-03-24 | 2009-04-08 | 大野绿水株式会社 | Water treatment method |
-
2010
- 2010-07-30 CN CN201010243612.5A patent/CN101993139B/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN1222489A (en) * | 1997-12-18 | 1999-07-14 | 纳尔科化学公司 | Amphoteric polymer/polyamine combinations for color removal and clarification of paper mill waste water |
| CN101405226A (en) * | 2006-03-24 | 2009-04-08 | 大野绿水株式会社 | Water treatment method |
| JP2008055391A (en) * | 2006-09-04 | 2008-03-13 | Daiyanitorikkusu Kk | Dehydration method of sludge |
| CN101323472A (en) * | 2007-06-15 | 2008-12-17 | 南京理工大学 | Polymeric ferric sulfate-poly-dimethyl-diallyl-ammonium chloride composite flocculent, preparation and use method thereof |
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