CN110422915A - It is a kind of to remove turbid composite flocculation agent and its preparation method and application applied to waste water dephosphorization - Google Patents
It is a kind of to remove turbid composite flocculation agent and its preparation method and application applied to waste water dephosphorization Download PDFInfo
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- CN110422915A CN110422915A CN201910026092.3A CN201910026092A CN110422915A CN 110422915 A CN110422915 A CN 110422915A CN 201910026092 A CN201910026092 A CN 201910026092A CN 110422915 A CN110422915 A CN 110422915A
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- composite flocculation
- flocculation agent
- agent
- natural macromolecule
- water
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- 238000005189 flocculation Methods 0.000 title claims abstract description 49
- 230000016615 flocculation Effects 0.000 title claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000002351 wastewater Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000008394 flocculating agent Substances 0.000 claims abstract description 34
- 229920002521 macromolecule Polymers 0.000 claims abstract description 28
- 239000000701 coagulant Substances 0.000 claims abstract description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229920002472 Starch Polymers 0.000 claims description 17
- 239000008107 starch Substances 0.000 claims description 17
- 235000019698 starch Nutrition 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 6
- 229920000881 Modified starch Polymers 0.000 claims description 5
- 239000004368 Modified starch Substances 0.000 claims description 5
- 235000019426 modified starch Nutrition 0.000 claims description 5
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical group CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 1
- 150000004676 glycans Chemical class 0.000 claims 1
- 229920000609 methyl cellulose Polymers 0.000 claims 1
- 239000001923 methylcellulose Substances 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 17
- 239000011574 phosphorus Substances 0.000 abstract description 17
- 239000010865 sewage Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 241000195493 Cryptophyta Species 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229920001661 Chitosan Polymers 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 description 5
- 229920005615 natural polymer Polymers 0.000 description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003053 toxin Substances 0.000 description 4
- 231100000765 toxin Toxicity 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 229920006319 cationized starch Polymers 0.000 description 3
- -1 chloro- 2- hydroxypropyl Chemical group 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 208000024827 Alzheimer disease Diseases 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 244000085413 Aphanizomenon flos aquae Species 0.000 description 1
- 235000013781 Aphanizomenon flos aquae Nutrition 0.000 description 1
- 241000192700 Cyanobacteria Species 0.000 description 1
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 1
- 241000192534 Dolichospermum flos-aquae Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010019695 Hepatic neoplasm Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229940054349 aphanizomenon flos-aquae Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Abstract
A kind of to remove turbid composite flocculation agent applied to waste water dephosphorization, it is a kind of natural macromolecule flocculating agent and the mixing of inorganic salt coagulant and a kind of curing composite flocculation agent obtained.The composite flocculation agent is added directly Removal of Phosphorus in Wastewater.In the water for reaching the requirement of four this water standard of class water of earth's surface under the condition (TP < 0.3mg/L) of total phosphorus content, water outlet SS value can be down to 10mg/L or less using the composite flocculation agent, and it is unable to reach this target only with inorganic coagulant, it ensure that water outlet meets state sewage emission standard.The invention discloses its preparation methods.
Description
Technical field
The present invention relates to modified natural polymer flocculants and inorganic coagulant to prepare composite flocculation agent through curing, to reach
Phosphorus containg substances in water body are removed simultaneously and the effect of turbidity is effectively reduced.
Background technique
Recently as the steady promotion of China's economic level, the public starts that environmental protection neck gradually is put into the visual field
Domain.Key areas one of of the Dealing with Water-Area Pollution as environmental improvement, the even more hot topic of environmental protection instantly.Environmental improvement
In the process, not only to guarantee that being discharged result reaches national requirements, entire governance process should also meet harmless green, using environmental protection
Administer material and process.
P elements are nutrients present in common waste water, meanwhile, be also constitute the substances such as ATP element it
One.For the angle of plant growth, plant nutrient is a dvielement indispensable in plant growth, however, mistake
More P elements enter the natural water in the ecosystem, then can bring serious harm, cause the eutrophication of water body.It is " rich
Nutrient laden " is a concept in limnology, studies have shown that a big important feature of water body aging is eutrophication.It is natural
Nutrient in water body excessively increases, and will cause the excessive proliferation of water plant and algae, leads to aquatic animal in water body
Living space is smaller and smaller by squeezing.Simultaneously as excessive increment leads to the Species Competition between algae, so that Measures of Algae in Water Body
Type reduce and individual amount increases sharply.Algae excessive propagation can largely consume already existing dissolved oxygen in water body, make
The content for obtaining oxygen in water is lower and lower, and along with the respiration of a large amount of algae and dead decomposition, what is consumed is molten
Solution oxygen increases sharply, and water body will be in severe depletion of oxygen state, seriously affects the existence of remaining animals and plants, and water body is further sent out
Exhibition is dry ground.
Simultaneously as the mass propagation of algae substances, algae can secrete a large amount of algae toxin into water body.These are not easy to disappear
The toxin of solution enters water body, will cause health hazard to human body and aquatile.The algae for generating algae toxin is mostly cyanobacteria,
In, microcystic aeruginosa, section ball algae, Anabaena Flos-aquae, aphanizomenon flos aquae toxicity are maximum.Microcystin is to be distributed so far most
Extensively, a most complicated toxoid, and the toxin for having most apparent facilitation to the formation of liver tumour being currently known.
In recent years, by adding molysite reagent into phosphorus-containing wastewater, such as: iron chloride, ferric sulfate and bodied ferric sulfate
Deng so that the technique that P elements form precipitating removal with ferric ion in water has obtained widely answering in numerous sewage treatment plants
With, and achieve better effect.However, during practical engineering application, after which exposes process,
The shortcomings that SS value (index Suspended Matter in Water content) in water is higher, is unable to reach sewage discharge requirement.To using the technique
Sewage treatment is carried out, how to improve the problem of reaching optimal treatment effect as urgent need to resolve in prior art.And
Flocculation process becomes the big method for solving the problems, such as this because of its high removal effect to SS value.
Flocculation is the first step and a most key step process of conventional water treatment process.In this process, flocculant
Selection directly determine the quality of flocculating effect.For now, inorganic flocculating agent material (based on aluminium salt and molysite), because
The good, relative low price with effect, the advantages such as from a wealth of sources, has obtained extremely wide application in the flocculation treatment of water.
But this kind of flocculant is when in use, and micro metal ion will necessarily be made to remain in water body, if people's long-term drinking this
Kind water, inherently damages health.The Alzheimer disease (senile dementia) being widely reported in recent years be by aluminium from
The sub a kind of illness for depositing and causing in human body.Meanwhile inorganic salts flocculant material is larger to environmental hazard, to temperature,
The conditions such as pH are very sensitive, and are difficult to remove lesser particle, these disadvantages all hinder the further of inorganic flocculating agent material
Development.In addition, Syn-Organic flocculants, such as polyacrylamide, effect is better than inorganic flocculating agent, and dosage is few,
But price is higher, and although high polymer itself without toxicity, does not participate in the list of reaction inside be included in high polymer
Body, such as acrylamide but have very big toxicity.Therefore, now it is believed that should be cautiously using inorganic in water treatment technology
Carry out purifying water body with synthetic polymeric flocculant.
Natural polymer is the macromolecular in nature in animal and plant and microbial resources, they by after discarded very
It is readily decomposed to water, carbon dioxide etc., and source is wide, nonhazardous, is environment-friendly material, such as: cellulose, starch, chitosan
Etc..Formula 1 is a kind of natural macromolecular material that source is very extensive --- the molecular structural formula of starch.In addition, more worth
One is mentioned that, natural macromolecular material is a kind of renewable resource for completely disengaging petroleum resources, it may be said that is inexhaustible use
It is inexhaustible.There are above-mentioned excellent properties just because of natural macromolecular material, at present in biology, medicine and food processing etc.
It has had a wide range of applications in numerous areas.It is a large amount of due to being dispersed on natural polymer strand in water treatment field
Free hydroxyl group, amido isoreactivity group, have the function of good water body purification, have been considered as the green flocculant of 21 century.This
Outside, due to containing above-mentioned activity functional groups on natural polymer strand, it is suitable for chemical modification.By to natural polymer into
Nature high molecular flocculant is made in row chemical modification appropriate, further increases its flocculating property, undoubtedly has important
Realistic meaning.
However, natural macromolecule flocculating agent is during dephosphorization goes turbid, not easily settled etc. ask there is also wadding body density is lower
Topic, is undoubtedly a practical way to enhance its dephosphorization to go turbid performance with other high density inorganic coagulant Material claddings.This hair
Bright people has found that natural macromolecule flocculating agent (such as: starch, cellulose, chitosan, alginic acid and its derivative) and inorganic salts are mixed
Solidifying agent is compound, can give full play to natural macromolecule flocculating agent and the respective feature and advantage of inorganic salt coagulant, and it is close to improve wadding body
Degree reinforces its settling property, enhances practical dephosphorization and goes turbid effect.
Summary of the invention
The object of the present invention is to provide a kind of natural macromolecule flocculating agents and inorganic salt coagulant synthesizing new composite flocculation
Agent and its preparation method, using to achieve the effect that while remove phosphorus containg substances in water body and turbidity is effectively reduced in sewage；Meanwhile
The injected volume of inorganic salts in water body is reduced, and does not introduce other potential organic pollutants, guarantees the cleaning and safety of water body.
The purpose of the present invention is what is realized by following technical proposal:
A kind of to remove turbid composite flocculation agent applied to waste water dephosphorization, it is that a kind of natural macromolecule flocculating agent and inorganic salts are mixed
Solidifying agent mixing and a kind of curing composite flocculation agent obtained.
Above-mentioned composite flocculation agent, the natural macromolecule flocculating agent can be neutrality, cationic, anionic or
The natural macromolecule flocculating agent of amphoteric.
Above-mentioned composite flocculation agent, the natural macromolecule flocculating agent can be commercially available or homemade.
Above-mentioned composite flocculation agent, the neutral natural macromolecule flocculating agent can be chitosan.
Above-mentioned composite flocculation agent, the cationic natural macromolecule flocculating agent can be the chloro- 2- hydroxypropyl three of 3-
Ammonio methacrylate modified starch (St-CTA).
Above-mentioned composite flocculation agent, the anionic natural macromolecule flocculating agent can be starch graft polyacrylate
(St-g-PAA) flocculant.
Above-mentioned composite flocculation agent, it is poly- that the amphoteric natural macromolecule flocculating agent can be carboxymethyl cellulose grafting
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (CMC-g-PDMC).
A kind of preparation method of above-mentioned composite flocculation agent, it is that natural macromolecule flocculating agent and inorganic salt coagulant difference is molten
Yu Shuizhong, after completely dissolution, natural macromolecule flocculating agent mass concentration are as follows: 1%-10%, inorganic salt coagulant mass concentration are as follows:
Then 1%-7.5% presses inorganic salt coagulant aqueous solution with natural macromolecule flocculating agent aqueous solution: 1-100:1 volume ratio is mixed
It closes, and cures 0.5-5h under the conditions of 30-80 DEG C to get final composite flocculation agent product is arrived.
Inorganic salt coagulant and natural macromolecule flocculating agent mass ratio are 7.5:1-30:1 in final products.This is compound
Flocculant is added directly Removal of Phosphorus in Wastewater.The result shows that handling actual domestic wastewater using this process, reaching earth's surface four
In the water that this water standard of class water requires under the condition (TP < 0.3mg/L) of total phosphorus content, meanwhile, it can using the combination process
Will water outlet SS value be down to 10mg/L hereinafter, and be unable to reach this target only with inorganic coagulant, it ensure that water outlet meet
State sewage emission standard.
Detailed description of the invention
Fig. 1 is starch and modified version starch flocculant infrared spectrogram.
Fig. 2 is that turbid effect diagram is gone in composite flocculation agent dephosphorization, and Fig. 2-1 is that iron chloride dosage and total phosphorus remain magnitude relation
Figure；Fig. 2-2 is turbidity relational graph after iron chloride dosage and processing.
Specific embodiment
The present invention is further illustrated by the following examples.
Embodiment 1:
Using the homemade 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modified starch of ferric chloride hexahydrate (commercially available) and laboratory
(St-CTA) it carries out dephosphorization and goes turbid experiment.St-CTA is made from starch, and is etherificate with 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride
Agent obtains required medicament St-CTA (referring to Flocculation and antimicrobial by one-step method etherification reaction
properties of a cationized starch,Zhouzhou Liu,Mu Huang,Aimin Li,Hu Yang,
Water Research,2017,119,57-66.).Starch and modified version starch flocculant infrared spectrogram are shown in Fig. 1, starch
(St) in 982,2925 and 3298cm-1There is apparent characteristic peak at place, is belonging respectively to C-H bending vibration, CH2Deformation and-OH are flexible
Vibration.It is different from starch, Starch Modified Flocculant St-CTA is in 1478cm-1Place there is new absorption peak, this mainly by
In the absorption of vibrations of c h bond on the quaternary ammonium salt group introduced with CTA etherificate.This illustrates that starch is successfully etherified with CTA
Reaction.
Take respectively certain volume St-CTA (mass concentration are as follows: 1%) and ferric chloride hexahydrate (mass concentration are as follows:
7.5%) aqueous solution, according to volume ratio: 1:1 is sufficiently mixed, and cures 0.5h under the conditions of 30 DEG C to get final products.Wherein,
Ferric chloride hexahydrate quality and St-CTA mass ratio are 7.5:1.
Phosphorus-containing wastewater is the homemade potassium dihydrogen phosphate in laboratory and aqueous suspension ofkaolin, and the initial total phosphorus of simulated wastewater is
2.5mg/L, initial haze 30NTU.This technique observes that products obtained therefrom is practical to be removed by spectrophotometer (wavelength 700nm at)
Phosphorus effect；It, which is observed, by transmissometer practical goes turbid effect.Fig. 2 is that composite flocculation agent removes turbid effect picture to the dephosphorization of the water sample.
As we can see from the figure when composite flocculation agent dosage is in 9mg/L, total phosphorus in water content is reduced to four class water effluent index
(0.3mg/L), delivery turbidity value are 0.5NTU, and water outlet SS value is 1.5mg/L；13.5mg/L phase need to be added with iron chloride is used only
Than about 33.3% iron chloride medicament can be saved；Meanwhile for going turbid effect, composite flocculation agent is used so that going turbid effect
Fruit has further promotion.
Embodiment 2:
Compound obtained composite flocculation agent is carried out using ferric sulfate (commercially available) and chitosan are (commercially available).Specific steps: it takes respectively
And ferric sulfate aqueous solution (mass concentration are as follows: 1%), according to body the chitosan aqueous solution (mass concentration are as follows: 10%) of certain volume
Product ratio: 1:100 is sufficiently mixed, and cures 0.5h under the conditions of 80 to get final products.Wherein, sulfuric acid weight of iron and chitosan
Mass ratio is 10:1.It is processing water sample, the similar reality of performance with the homemade potassium dihydrogen phosphate in laboratory and aqueous suspension ofkaolin
Apply example 1, it may be assumed that use simulated water sample same as Example 1, when composite flocculation agent dosage is in 10mg/L, total phosphorus in water contains
Amount is reduced to four class water effluent index (0.3mg/L), and delivery turbidity value is 0.8NTU, and water outlet SS value is 2.4mg/L.
Embodiment 3:
Compound be made again is carried out using poly-ferric chloride (commercially available) and homemade starch graft polyacrylate (St-g-PAA)
Close flocculant.St-g-PAA is made from starch, and using acrylic acid as monomer, ammonium persulfate is initiator, is grafted by one-step method
Copolyreaction obtains required medicament St-g-PAA (referring to Evaluation of the structural morphology on
the scale-inhibition efficiency of starch-graft-poly(acrylic acid),Wei Yu,
Yawen Wang,Aimin Li,Hu Yang,Water Research,2018,141,86-95.).Turbid step is gone in specific dephosphorization:
And poly-ferric chloride (mass concentration are as follows: 1%) aqueous solution is pressed the St-g-PAA (mass concentration are as follows: 1%) of certain volume is taken respectively
According to volume ratio: 1:10 is sufficiently mixed, and cures 2h under the conditions of 60 DEG C to get final products.Wherein, polyaluminium weight of iron with
St-g-PAA mass ratio is 10:1.It is processing water sample, property with the homemade potassium dihydrogen phosphate in laboratory and aqueous suspension ofkaolin
It can similar embodiment 1, it may be assumed that simulated water sample same as Example 1 is used, when composite flocculation agent dosage is in 10mg/L, water body
Middle total phosphorus content is reduced to four class water effluent index (0.3mg/L), and delivery turbidity value is 1.1NTU, and water outlet SS value is 3.3mg/L.
Embodiment 4:
Polymethyl acyloxyethyl trimethyl ammonia chloride is grafted using aluminium chloride (commercially available) and homemade carboxymethyl cellulose
Ammonium (CMC-g-PDMC) carries out compound obtained composite flocculation agent.CMC-g-PDMC is using cellulose as raw material, first using monoxone as ether
Agent prepares carboxymethyl cellulose to improve the water solubility of cellulose, then with MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride for singly
Body, ammonium ceric nitrate are initiator, obtain required medicament CMC-g-PDMC (referring to Evaluation of by graft copolymerization
chain architectures and charge properties of various starch-based flocculants
for flocculation of humic acid from water,Hu Wu,Zhouzhou Liu,Hu Yang,Aimin
Li,Water Research,2016,96,126-135.).Turbid step is gone in specific dephosphorization: taking the CMC-g- of certain volume respectively
PDMC (mass concentration are as follows: 10%) and aluminium chloride (mass concentration are as follows: 1%) aqueous solution, according to volume ratio: 1:150 is sufficiently mixed,
And 3h is cured under the conditions of 50 DEG C to get final products.Wherein, aluminium chloride quality and CMC-g-PDMC mass ratio are 15:1.
Be processing water sample, the similar embodiment 1 of performance with the homemade potassium dihydrogen phosphate in laboratory and aqueous suspension ofkaolin, it may be assumed that using with
The identical simulated water sample of embodiment 1, when composite flocculation agent dosage is in 9.5mg/L, total phosphorus in water content is reduced to four class water
Effluent index (0.3mg/L), delivery turbidity value are 0.6NTU, and water outlet SS value is 1.8mg/L.
Embodiment 5:
Using the homemade 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modified starch flocculant of aluminum sulfate (commercially available) and laboratory
Compound obtained composite flocculation agent is carried out (referring to Flocculation and antimicrobial properties of a
cationized starch,Zhouzhou Liu,Mu Huang,Aimin Li,Hu Yang,Water Research,2017,
119,57-66.).And aluminum sulfate turbid step is gone in specific dephosphorization: taking the St-CTA (mass concentration are as follows: 1%) of certain volume respectively
(mass concentration are as follows: 3%) aqueous solution, according to volume ratio: 1:10 is sufficiently mixed, and cures 3h under the conditions of 40 DEG C to get final
Product.Wherein, aluminum sulfate quality and St-CTA mass ratio are 30:1.It is outstanding with the homemade potassium dihydrogen phosphate in laboratory and kaolin
Turbid is processing water sample, the similar embodiment 1 of performance, it may be assumed that uses simulated water sample same as Example 1, works as composite flocculation agent
For dosage in 8mg/L, total phosphorus in water content is reduced to four class water effluent index (0.3mg/L), and delivery turbidity value is 0.4NTU,
Water outlet SS value is 1.2mg/L.
Embodiment 6:
Using the homemade 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modified starch wadding of aluminium polychloride (commercially available) and laboratory
Solidifying agent carries out compound obtained composite flocculation agent (referring to Flocculation and antimicrobial properties of
a cationized starch,Zhouzhou Liu,Mu Huang,Aimin Li,Hu Yang,Water Research,
2017,119,57-66.).Turbid step is gone in specific dephosphorization: taking the St-CTA (mass concentration are as follows: 1%) and poly- of certain volume respectively
Conjunction aluminium chloride (mass concentration are as follows: 7.5%) aqueous solution, according to volume ratio: 1:1 is sufficiently mixed, and cures 2h under the conditions of 50 DEG C,
Up to final products.Wherein, aluminium polychloride quality and St-CTA mass ratio are 7.5:1.With the homemade di(2-ethylhexyl)phosphate in laboratory
Hydrogen potassium and aqueous suspension ofkaolin are processing water sample, the similar embodiment 1 of performance, it may be assumed that use simulation water same as Example 1
Sample, when composite flocculation agent dosage is in 9.5mg/L, total phosphorus in water content is reduced to four class water effluent index (0.3mg/L), out
Water turbidity value is 0.9NTU, and water outlet SS value is 2.7mg/L.
Claims (9)
1. a kind of remove turbid composite flocculation agent applied to waste water dephosphorization, it is characterized in that: it be a kind of natural macromolecule flocculating agent and
Inorganic salt coagulant mixing and a kind of curing composite flocculation agent obtained.
2. composite flocculation agent according to claim 1, it is characterized in that: the natural macromolecule flocculating agent is neutral, sun
The natural macromolecule flocculating agent of ionic, anionic or amphoteric.
3. composite flocculation agent according to claim 1, it is characterized in that: the natural macromolecule flocculating agent be commercially available or
It is homemade.
4. according to the above-mentioned composite flocculation agent of claim 2, it is characterized in that: the neutral natural macromolecule flocculating agent is shell
Glycan.
5. composite flocculation agent according to claim 2, it is characterized in that: the cationic natural macromolecule flocculating agent is
3- chloro-2-hydroxypropyl-trimethyl ammonium chloride modified starch (St-CTA).
6. composite flocculation agent according to claim 2, it is characterized in that: the anionic natural macromolecule flocculating agent is
Starch graft polyacrylate (St-g-PAA) flocculant.
7. composite flocculation agent according to claim 2, it is characterized in that: the amphoteric natural macromolecule flocculating agent is carboxylic
Methylcellulose is grafted polymethyl acyloxyethyl trimethyl ammonium chloride (CMC-g-PDMC).
8. a kind of preparation method of composite flocculation agent described in claim 1, it is characterized in that: it is by natural macromolecule flocculating agent and nothing
Machine salt coagulant difference is soluble in water, after completely dissolution, natural macromolecule flocculating agent mass concentration are as follows: 1%-10%, inorganic salts
Coagulant mass concentration are as follows: 1%-7.5%, then by inorganic salt coagulant aqueous solution and natural macromolecule flocculating agent aqueous solution
It presses: the mixing of 1-100:1 volume ratio, and 0.5-5h is cured under the conditions of 30-80 DEG C to get final composite flocculation agent product is arrived.
9. the application described in claim 1 for going turbid composite flocculation agent to be gone in turbid in waste water dephosphorization applied to waste water dephosphorization.
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| CN201910026092.3A CN110422915A (en) | 2019-01-10 | 2019-01-10 | It is a kind of to remove turbid composite flocculation agent and its preparation method and application applied to waste water dephosphorization |
| PCT/CN2019/114520 WO2020143282A1 (en) | 2019-01-10 | 2019-10-31 | Composite flocculant for removing phosphorus and turbidity of waste water, preparation method therefor and use thereof |
| ZA2021/02733A ZA202102733B (en) | 2019-01-10 | 2021-04-23 | Composite flocculant for removing phosphorus and turbidity of waste water, preparation method therefor and use thereof |
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| CN102531119A (en) * | 2011-10-27 | 2012-07-04 | 常州大学 | Preparation method and application of composite flocculant |
| CN103087265A (en) * | 2013-02-17 | 2013-05-08 | 南京大学 | Preparation method of grafted amphoteric starch flocculants |
| CN104017136A (en) * | 2014-03-05 | 2014-09-03 | 南京大学 | Preparation method of amphoteric grafting-type modified cellulose flocculant |
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| CN102658097B (en) * | 2012-05-09 | 2014-03-26 | 中国地质大学（北京） | Preparation method of efficient dephosphorizing porous particle adsorbent |
| WO2017089330A1 (en) * | 2015-11-27 | 2017-06-01 | Kemira Oyj | Improve phosphorus precipitation and membrane flux in membrane bioreactors |
| CN106882860A (en) * | 2015-12-16 | 2017-06-23 | 营口渤海科技有限公司 | A kind of preparation method of magnesia-starch Complex Flocculant |
| CN106746068B (en) * | 2016-11-29 | 2020-11-17 | 广东工业大学 | Treatment method of wastewater containing high-concentration organic phosphorus |
| CN109665610A (en) * | 2018-12-05 | 2019-04-23 | 南京大学 | Turbid technique is gone in a kind of natural macromolecule flocculating agent and the dephosphorization of molysite combined depth |
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|---|---|---|---|---|
| CN102531119A (en) * | 2011-10-27 | 2012-07-04 | 常州大学 | Preparation method and application of composite flocculant |
| CN103087265A (en) * | 2013-02-17 | 2013-05-08 | 南京大学 | Preparation method of grafted amphoteric starch flocculants |
| CN104017136A (en) * | 2014-03-05 | 2014-09-03 | 南京大学 | Preparation method of amphoteric grafting-type modified cellulose flocculant |
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| CN114477712A (en) * | 2021-09-07 | 2022-05-13 | 南京大学 | Green and efficient composite sludge dewatering process of natural polymeric flocculant and clay material |
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