CN115626703A - Method for efficiently removing algae by using monochloramine preoxidation enhanced coagulation - Google Patents
Method for efficiently removing algae by using monochloramine preoxidation enhanced coagulation Download PDFInfo
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- CN115626703A CN115626703A CN202211343449.9A CN202211343449A CN115626703A CN 115626703 A CN115626703 A CN 115626703A CN 202211343449 A CN202211343449 A CN 202211343449A CN 115626703 A CN115626703 A CN 115626703A
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- ammonia nitrogen
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- 241000195493 Cryptophyta Species 0.000 title claims abstract description 124
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000005345 coagulation Methods 0.000 title claims abstract description 64
- 230000015271 coagulation Effects 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 119
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000460 chlorine Substances 0.000 claims abstract description 49
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 45
- 230000000694 effects Effects 0.000 claims abstract description 45
- 239000003651 drinking water Substances 0.000 claims abstract description 13
- 235000020188 drinking water Nutrition 0.000 claims abstract description 13
- 239000000701 coagulant Substances 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 52
- 230000003647 oxidation Effects 0.000 claims description 51
- 230000008569 process Effects 0.000 claims description 25
- 230000001590 oxidative effect Effects 0.000 claims description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 5
- 239000002352 surface water Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 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 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical group ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 33
- 239000007800 oxidant agent Substances 0.000 description 13
- 239000012286 potassium permanganate Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003834 intracellular effect Effects 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 241000192710 Microcystis aeruginosa Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000195663 Scenedesmus Species 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 150000004982 aromatic amines Chemical group 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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Images
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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a method for efficiently removing algae by using chloramine to preoxidize, strengthen and coagulate, belonging to the technical field of water treatment and comprising the following steps: adding monochloramine or ammonia nitrogen and chlorine into the algae-containing water source water at the water intake of a drinking water plant, reacting for more than 3 hours, adding a coagulant, and coagulating and precipitating to obtain the product. The method of the invention uses monochloramine to selectively oxidize the extracellular attached organic matters of the algae cells, reduces the negative charges on the surfaces of the algae cells, further promotes the electric neutralization of the coagulant and the algae cells, improves the separation effect of the algae cells in water, and can improve the efficiency of removing the algae by coagulation by multiple times.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a method for efficiently removing algae by using chloramine to preoxidize, strengthen and coagulate.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, the water pollution caused by algae in various parts of China is more and more intense, and the cyanobacterial bloom of part of lakes and reservoirs (such as the Yunnan Erhai) is in a normal state. The water bloom not only damages the balance of a lake reservoir water ecosystem, but also seriously influences the availability of a water source, damages the normal operation of a water plant and threatens the safety of drinking water.
Coagulation is the most important algae removal unit in the water purification process, and algae cells generate a large amount of extracellular organic matters, so that the efficiency of removing algae by coagulation is low. The pre-oxidation is an effective technology for strengthening coagulation and removing algae, but the prior common pre-oxidant has the problems of high algae breaking effect or influence on the operation of subsequent processes. The activity of the oxidant has important influence on the pretreatment effect of the high algae content water, and the algae cell rupture (such as chlorine, chlorine dioxide and ozone) is easily caused by the over-strong oxidizing capability in the pretreatment process, namely the algae breaking effect is high, so that the release of algae toxin and intracellular organic matters is caused. Potassium permanganate is mild in algae oxidation activity, and small in algae breaking effect under the condition of low dosage, but in practical engineering application, the fact that manganese oxide is accumulated in a filter tank due to long-term addition of potassium permanganate is found, the filter tank flux is reduced, and the backwashing effect is reduced. In addition, the coexisting natural organic matters in water often contain electron-rich functional groups (such as phenolic hydroxyl groups, aromatic amine groups, aldehyde groups and the like), so that the consumption of potassium permanganate can be accelerated, the algae breaking rate can be increased if the dosage of potassium permanganate is increased, and the water chromaticity can be increased, so that the sensory index exceeds the standard.
In order to reduce the impact of high algae content water on the conventional water purification process (coagulation-precipitation-filtration-disinfection) and ensure the safety of drinking water, a pretreatment technology which has good modified algae effect, low algae breaking effect, economy and convenient use and does not influence the operation of each unit of the conventional treatment process is urgently needed so as to improve the coagulation algae removal efficiency, reduce the influence of algae organic matters on the subsequent treatment process and improve the quality of outlet water.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a method for efficiently removing algae by using monochloramine preoxidation reinforced coagulation.
In order to realize the purpose, the technical scheme of the invention is as follows:
in one aspect, a method for efficiently removing algae by using monochloramine preoxidation reinforced coagulation comprises the following steps:
s1, measuring the ammonia nitrogen concentration in water to be treated, wherein the ammonia nitrogen concentration in the water to be treated is lower than 0.3mg/L, and adding ammonia nitrogen to ensure that the ammonia nitrogen concentration is higher than 0.3mg/L; the concentration of ammonia nitrogen in the water to be treated is higher than 0.3mg/L, and ammonia nitrogen does not need to be added;
s2, adjusting the pH value of the water obtained in the step S1 to be more than 6.5;
s3, adding chlorine into the water obtained in the S2, and pre-oxidizing the water by controlling the mass ratio of the chlorine to the ammonia nitrogen to be 4.5-7.6;
and S4, adding a coagulant into the water obtained in the step S3 after the pre-oxidation is finished to perform coagulation and algae removal.
The method of the invention realizes the selective oxidation modification of extracellular organic matters by using the monochloramine generated in situ, promotes the algae cells to be more easily destabilized and removed in the coagulation process, and improves the efficiency of coagulation algae removal from 33 percent to 90 percent. Under the condition of the same oxidant dosage, the efficiency of coagulating and removing algae is respectively improved by 20 percent and 12 percent compared with the pre-oxidation of potassium permanganate and chlorine. The method provided by the invention has the advantages that the damage to the integrity of algae cells is obviously lower than the preoxidation of chlorine and potassium permanganate, and the residual monochloramine can be used for subsequent disinfection, so that the method has an important effect on improving the water bloom impact resistance of the conventional water purification process and ensuring the safety of drinking water.
The invention has the beneficial effects that:
(1) The invention utilizes ammonia nitrogen contained in water to be treated or adds a small amount of ammonia nitrogen to react with chlorine to generate monochloramine in situ as a pre-oxidant, and utilizes the monochloramine to realize selective oxidation modification of extracellular organic matters, so that algae cells are more easily destabilized and removed in the coagulation process, the efficiency of coagulating and removing algae is improved from 33% to 90%, and the invention is a pretreatment technology which has good algae modification effect, low algae breaking effect, economy and convenient use, does not influence each unit of the conventional treatment process, can reduce the influence of algae organic matters on the subsequent water treatment process, and improves the quality of outlet water. Under the condition of the same oxidant dosage, the efficiency of coagulating and removing algae is respectively improved by 20 percent and 12 percent compared with the pre-oxidation of potassium permanganate and chlorine. The invention adopts the monochloramine oxidant, the products of the reaction are ammonia nitrogen and chloride ions, and 1.0mg/L monochloramine (in terms of Cl) is added 2 Calculated) about 0.2mg/L of ammonia nitrogen is introduced, and the ammonia nitrogen is treated in the sanitary Standard for Drinking Water (GB 5749-2022) in ChinaThe limit of (2) is required to be 0.5mg/L. Therefore, the problem of excessive ammonia nitrogen in water can not be caused by adopting monochloramine for pre-oxidation. The surface water usually contains more chloride ions (dozens of mg/L), so the added chloride ions (<5 mg/L) did not significantly affect the chloride ion concentration in the water.
(2) The oxidant monochloramine adopted by the invention is a soluble micromolecular oxidant, is a disinfectant commonly used for drinking water treatment, does not influence the operation of a conventional water treatment unit, and the preoxidation residual monochloramine is beneficial to the subsequent disinfection of water to be treated, thereby playing an important role in improving the water bloom impact resistance of a conventional water purification process and ensuring the safety of drinking water.
(3) The preoxidant monochloramine adopted by the invention has low algae-breaking effect, avoids release of intracellular organic matters, and is beneficial to reducing generation of disinfection byproducts in the subsequent disinfection process. Meanwhile, the flocculant also has the functions of coagulation aiding and filtration aiding, reduces the turbidity of precipitated effluent and filtered effluent, and prolongs the filtration period.
(4) The invention utilizes the water pipeline to carry out reaction, does not need an additional processing unit, and is applied to the prior art without modifying the process. And the monochloramine causes little corrosion to the pipe network, and is suitable for carrying out preoxidation reaction in the water delivery pipeline.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the improvement effect of chloramine pre-oxidized high algae content water on aluminum salt coagulation algae removal in example 1 of the present invention;
FIG. 2 is a graph showing the improvement effect of chloramine pre-oxidation of high algae content water on aluminum salt coagulation algae removal in example 2 of the present invention;
FIG. 3 is a graph showing the improvement effect of chloramine pre-oxidized high algae content water on aluminum salt coagulation algae removal in example 3 of the present invention;
FIG. 4 is a graph showing the effect of chloramine pre-oxidation of high algae water on the increase of the surface potential of algae cells in example 1 of the present invention;
FIG. 5 is a graph showing the effect of chloramine pre-oxidation of high algae content water on the change of cell surface potential of algae in example 3;
FIG. 6 is a graph showing the effect of chloramine preoxidation and coagulation on dissolved organic carbon in water in high algae-laden water in example 1;
FIG. 7 is a graph showing the effect of chloramine preoxidation and coagulation on dissolved organic carbon in water in high algae-laden water in example 3 of the present invention;
FIG. 8 is a graph showing the enhanced effect of chloramine pre-oxidation, chlorine pre-oxidation and potassium permanganate pre-oxidation on coagulation algae removal in comparative example 1 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the impact of high algae content water on the conventional water purification process and the influence on the quality of drinking water, the invention provides a method for efficiently removing algae by using chloramine to preoxidize, strengthen and coagulate.
The invention provides a method for efficiently removing algae by using monochloramine preoxidation reinforced coagulation, which comprises the following steps:
s1, measuring the ammonia nitrogen concentration in water to be treated, wherein the ammonia nitrogen concentration in the water to be treated is lower than 0.3mg/L, and adding ammonia nitrogen to ensure that the ammonia nitrogen concentration is higher than 0.3mg/L; the concentration of ammonia nitrogen in the water to be treated is higher than 0.3mg/L, and ammonia nitrogen does not need to be added;
s2, adjusting the pH value of the water obtained in the S1 to be more than 6.5;
s3, adding chlorine into the water obtained in the S2, and controlling the mass ratio of the chlorine to the ammonia nitrogen to be 4.5-7.6;
and S4, adding a coagulant into the water obtained in the step S3 after the pre-oxidation is finished to perform coagulation and algae removal.
Coagulation is the most important algae removal unit in the water purification process, and algae cells generate a large amount of extracellular organic matters, so that the efficiency of coagulation algae removal is low. The specific gravity of algae cells is small, the algae cells are difficult to sink, the surface of the algae cells is generally negatively charged, the Zeta potential is different from minus 10mV (such as chlorella) to minus 35mV (such as scenedesmus and crescent algae), the isoelectric point is generally between pH3 and 4, and the algae cells are mostly in a colloid form in raw water. Inorganic metal salt coagulants (iron salt, aluminum salt and the like) commonly used in drinking water treatment, metal ions or hydrolysis products of the metal ions are positively charged, algal cells are destabilized mainly through the actions of electric double layer compression, electrostatic attraction, electric neutralization and the like, and are coagulated with the coagulants to form flocs, so that the flocs are removed in the subsequent precipitation process. The metabolic secretion and apoptosis ablation of algae cells result in water containing a large amount of extracellular organic matters, such as proteins, polysaccharides, nucleic acids, grease and other small molecular organic matters, which are the main components of soluble organic matters in high algae water. After the extracellular organic matter is attached to the surface of the algae cell colloid, the colloid electronegativity can be improved, the electrostatic repulsion among particles is increased, the colloid stability is increased, and the coagulation effect is reduced. The decrease of the coagulation effect can increase the difficulty of subsequent solid-liquid separation, which causes the problems of high water content of sediments, blockage of the filter, penetration of algae cells into the filter and the like, and further causes the deterioration of the quality of drinking water. Before raw water enters a water plant for treatment, an oxidant is added into the raw water for preoxidation to enhance the coagulation algae removal effect, organic matters in the oxidizing solution and attached to the surfaces of algae cells can reduce the surface negative charges of the algae cells, promote the algae cells to destabilize and separate from the water phase more easily, and thus the purpose of enhancing coagulation is achieved. However, the currently common pre-oxidant has the problems of high algae breaking effect or influence on the operation of the subsequent process.
The invention utilizes the method of the chloramine for pre-oxidation, strengthening coagulation and high-efficiency algae removal, and utilizes the chloramine to successfully solve the problems, and the mechanism of the invention is as follows: extracellular organisms contain more fatty amine and amide structures, and monochloramine can selectively react with these two chemical structures. The extracellular organic matter is oxidized by monochloramine, the structure is changed, and the extracellular organic matter falls off from the surface of algae cells, so that the Zeta potential on the surface of the algae cells is increased from-20 mV to-3.8 mV, and the extracellular organic matter is subjected to unstable sedimentation after being electrically neutralized by coagulant metal ions or hydrolysate of the metal ions. In addition, the cell structure prevents the monochloramine from reacting with intracellular organic matters, and the monochloramine is prevented from destroying the intracellular structure to cause death and rupture of algae. Due to the weak oxidation activity of monochloramine, although extracellular organic matters can be oxidized and modified, the oxidized extracellular organic matters still keep macromolecular states, small molecular organic matters are difficult to remove in the coagulation process, and a small amount of macromolecular organic matters (> 10 kDa) have the coagulation aiding effect, so that the coagulation algae removal effect is further enhanced.
In some embodiments of this embodiment, the method further comprises: the algae removal effect of the monochloramine preoxidation reinforced coagulation is evaluated by measuring the removal rate of algae in the coagulation process.
In some examples of this embodiment, the water to be treated is surface water affected by algae.
In some embodiments of this embodiment, the ammonia nitrogen concentration is ammonia nitrogen mass concentration, in terms of N.
In some embodiments of this embodiment, the ammonia nitrogen is added as a pre-dissolved ammonium salt stock solution. Wherein the solvent in the stock solution is distilled water, natural surface water or tap water; the ammonium salt is ammonium chloride, ammonium sulfate or ammonium nitrate.
In some examples of this embodiment, the pH is adjusted to 7.0 or higher in S2. Because monochloramine can be converted into dichloramine under an acidic condition, the dichloramine has strong oxidizing property under the acidic condition, and the high pH value ensures that the generated chloramine exists in the form of monochloramine, ensures that the algae breaking effect is low, avoids the release of intracellular organic matters, and enhances the coagulation algae removal effect.
In some embodiments of this embodiment, the chlorine is hypochlorous acid, or a stock solution of hypochlorite. Wherein the hypochlorite is sodium hypochlorite, calcium hypochlorite, lithium hypochlorite, or potassium hypochlorite; the solvent in the stock solution is distilled water.
In this embodimentIn some examples, the mass concentration of chlorine in S3 is Cl 2 And (6) counting.
In some examples of this embodiment, the pre-oxidation process is performed in a water conduit, specifically: ammonia nitrogen and chlorine are added at a water inlet of a drinking water plant, the ammonia nitrogen and the chlorine are effectively mixed by utilizing the flow of water in a water pipeline, and the pre-oxidation treatment of the water to be treated is realized.
In some examples of this embodiment, in S3, the mass ratio of chlorine to ammonia nitrogen is 4.5 to 5.0; the pre-oxidation time is not less than 3h.
In the invention, the key points of the method are the mass ratio of chlorine to ammonia nitrogen and the reaction time.
When the mass ratio of the chlorine to the ammonia nitrogen is less than 4.5, part of the ammonia nitrogen is not effectively converted into monochloramine and cannot play an oxidation role. When the mass ratio of chlorine to ammonia nitrogen is more than 5.0, excessive chlorine will continue to react with monochloramine to generate dichloramine and part of nitrogen, the concentration of residual chlorine is reduced, and the pre-oxidation effect is reduced. When the mass ratio of the chlorine to the ammonia nitrogen reaches 7.6-9.0, the chlorine is directly converted into ineffective chloride ions, the ammonia nitrogen is converted into nitrogen, and the system loses the oxidation effect. When the ratio of chlorine to ammonia nitrogen is further increased, the oxidant in water exists in the form of free chlorine, and the preoxidation of the chlorine easily causes the rupture of algae cells, the release of intracellular organic matters and the destruction of water quality.
Lower monochloramine redox potential (E) than currently used pre-oxidants 0 ＝1.13V NHE ) It is a weak oxidizing agent, which does not react with extracellular organic substances at a high rate, and usually requires a reaction time of 3 hours or more to effectively convert the extracellular organic substances. However, most drinking water sources in China are in the suburbs of cities, and the situation that water purification plants take water from lakes and reservoirs in a long distance is common. Taking the common water delivery economic flow rate of 1.0 m/s in the pipeline as an example, the water delivery time of 10-20 kilometers from a water source to a water plant is about 3-6 hours, which provides conditions for implementing the high-efficiency algae removal by using the water delivery process through the preoxidation, reinforced coagulation of monochloramine.
In some embodiments of this embodiment, the coagulant is an aluminum salt, an iron salt, or polyacrylamide. Wherein the aluminum salt comprises aluminum chloride, aluminum sulfate, polyaluminum chloride and polyaluminum sulfate; the iron salt includes ferric chloride, ferric sulfate, polymeric ferric chloride, and polymeric ferric sulfate.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
In the following examples, the monochloramine pre-oxidation process is performed in a water pipeline in a method for enhancing coagulation and efficiently removing algae by using the monochloramine pre-oxidation.
Example 1
The method for efficiently removing algae by using the monochloramine preoxidation reinforced coagulation comprises the following specific steps:
the pH of the water to be treated was 7. And if the ammonia nitrogen concentration in the water to be treated is higher than 0.3mg/L, adding chlorine into the water at a water intake according to the mass concentration ratio of the chlorine to the ammonia nitrogen of 4.5-5.0. If the ammonia nitrogen concentration in the water to be treated is lower than 0.3mg/L, adding extra ammonia nitrogen to adjust the ammonia nitrogen concentration to 0.3mg/L, and then adding chlorine to the water at a water intake to ensure that the concentration of monochloramine in the water to be treated is (as Cl) 2 Calculated) is 1.35 to 1.5mg/L. The mixing of ammonia nitrogen and chlorine and the oxidation of algae are implemented by utilizing the water delivery process. The time for pre-oxidation of monochloramine is different according to the distance between the water intake and the water plant. After pre-oxidation is carried out for 1, 2, 3, 4, 5, 6 and 7 hours, aluminum chloride (calculated by aluminum) is added into water, so that the concentration of the aluminum chloride (calculated by aluminum) in the water to be treated is 1.5mg/L, the water is quickly stirred for 1 minute, then the water is slowly stirred for 10 to 15 minutes, and the water is kept still for precipitation for 30 minutes, so that the removal rate of algae is increased from 37 percent to 48 percent, 66 percent, 63 percent, 80 percent, 89 percent and 90 percent compared with the coagulation algae removal process without the mono-chloramine pre-oxidation. Specific effects the comparative data are shown in fig. 1. The embodiment shows that the method can obviously improve the coagulation algae removal effect.
Detecting the change of the cell surface potential of the algae in the oxidation process of monochloramine. Pre-oxidation with monochloramine for 1, 4, and 7 hours increased the surface charge of the algal cells from-20.2 mV to-14.7, -6.9, and-3.8 mV. Specific effects comparison data are shown in fig. 4.
Detecting the change of the concentration of the soluble organic carbon in the water to be treated in the oxidation process of the monochloramine. After pre-oxidation for 0, 1, 2, 3, 4, 5, 6 and 7 hours, the concentrations of the soluble organic matters in the water to be treated after coagulation and algae removal are respectively 5.7, 5.5, 6.4, 6.9, 6.7, 7.1, 7.2 and 7.7mg/L. Specific effects comparative data are shown in fig. 6.
Example 2
Method for efficiently removing algae by using monochloramine preoxidation enhanced coagulation
This example differs from example 1 in that: the concentration of ammonia nitrogen is adjusted to be 0.4mg/L, and the adding amount condition of chlorine is as follows: the concentration in the water to be treated reached 2.0mg/L. After pre-oxidation for 1, 2, 3, 4, 5, 6 and 7 hours, the coagulation algae removal efficiency reaches 54%, 63%, 64%, 75%, 84%, 91% and 91%, respectively. Specific effects the comparative data are shown in fig. 2.
Example 3
Method for efficiently removing algae by using preoxidation enhanced coagulation of monochloramine
This example differs from example 1 in that: the concentration of ammonia nitrogen is adjusted to be 0.5mg/L, and the adding amount condition of chlorine is as follows: the concentration of chlorine in the water to be treated reached 2.5mg/L. After pre-oxidation for 1, 2, 3, 4, 5, 6 and 7 hours, the coagulation algae removal efficiency reaches 65%, 71%, 89%, 91%, 86% and 64% respectively. The reduction of the coagulation algae removal effect caused by the long-term oxidation of the high-concentration monochloramine is caused by the rupture of algae cells due to the oxidation. Specific effects the comparative data are shown in fig. 3.
Detecting the change of the cell surface potential of the algae in the oxidation process of monochloramine. Monochloramine pre-oxidation 3 raised the surface charge of the algal cells from-20.2 mV to-5.0 mV, while pre-oxidation for 7 hours resulted in a surface potential change to-13.5 mV. The high-concentration monochloramine is oxidized for a long time to cause the algae cells to break, and intracellular organic matters are adsorbed on the surfaces of the algae cells after being released, so that the surface potential of the algae cells after 7 hours of pre-oxidation is lower than that of the algae cells after 3 hours of pre-oxidation. Specific effects comparative data are shown in fig. 5.
And detecting the change of the concentration of the soluble organic carbon in the water to be treated in the oxidation process of the monochloramine. After pre-oxidation for 1, 2, 3, 4, 5, 6 and 7 hours, the concentrations of the soluble organic matters in the water to be treated after coagulation and algae removal become 5.7, 5.8, 5.9, 6.7, 7.3, 9.5 and 11.5mg/L respectively. The high concentration monochloramine oxidation for a long time leads to the rupture of algae cells and the release of intracellular organic matters, thereby leading to the significant increase of the concentration of soluble organic matters in water after 7 hours of pre-oxidation. Specific effects the comparative data are shown in fig. 7.
Comparative example 1
This example differs from example 1 in that: chlorine (the chlorine is added in an amount that the concentration of the chlorine in the water to be treated reaches 1.5 mg/L) and potassium permanganate (the potassium permanganate is added in an amount that the concentration of the potassium permanganate in the water to be treated reaches 4.0 mg/L) are respectively added into the water to be treated, and the pre-oxidation time is 7 hours. Specific effects the comparative data are shown in fig. 8. The efficiency of monochloramine preoxidation and coagulation algae removal is 21 percent higher than that of chlorine preoxidation and coagulation algae removal, and 12 percent higher than that of potassium permanganate preoxidation and coagulation algae removal. The embodiment shows that the method for improving the coagulation algae removal effect is higher than the traditional chlorine pre-oxidation and potassium permanganate pre-oxidation effects.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for efficiently removing algae by using the monochloramine preoxidation reinforced coagulation is characterized by comprising the following steps of:
s1, measuring the ammonia nitrogen concentration in water to be treated, wherein the ammonia nitrogen concentration in the water to be treated is lower than 0.3mg/L, and adding ammonia nitrogen to ensure that the ammonia nitrogen concentration is higher than 0.3mg/L; the ammonia nitrogen concentration in the water to be treated is higher than 0.3mg/L, and ammonia nitrogen does not need to be added;
s2, adjusting the pH value of the water obtained in the step S1 to be more than 6.5;
s3, adding chlorine into the water obtained in the S2, and pre-oxidizing the water by controlling the mass ratio of the chlorine to the ammonia nitrogen to be 4.5-7.6;
and S4, adding a coagulant into the water obtained in the S3 after the pre-oxidation is finished to perform coagulation and algae removal.
2. The method for removing algae with high efficiency by using the pre-oxidation enhanced coagulation of monochloramine according to claim 1, further comprising the following steps: the algae removal effect of the monochloramine preoxidation reinforced coagulation is evaluated by measuring the removal rate of algae in the coagulation process.
3. The method for efficiently removing algae by using the pre-oxidation enhanced coagulation of monochloramine according to claim 1, wherein the water to be treated is surface water affected by algae.
4. The method for efficiently removing algae by using the preoxidation-enhanced coagulation of monochloramine according to claim 1, wherein the ammonia nitrogen concentration is the mass concentration of ammonia nitrogen, and is counted by N;
preferably, the ammonia nitrogen is added by adding a pre-dissolved ammonium salt stock solution, and further preferably, a solvent in the stock solution is distilled water, natural surface water or tap water; further preferably, the ammonium salt is ammonium chloride, ammonium sulfate or ammonium nitrate.
5. The method for removing algae with high efficiency by using the preoxidation enhanced coagulation of the monochloramine according to claim 1, wherein the pH value in the S2 is adjusted to be greater than or equal to 7.0.
6. The method for removing algae with high efficiency by using the preoxidation reinforced coagulation of the monochloramine as claimed in claim 1, wherein the chlorine is hypochlorous acid or a stock solution of the hypochlorite;
preferably, the hypochlorite is sodium hypochlorite, calcium hypochlorite, lithium hypochlorite, or potassium hypochlorite;
preferably, the solvent in the stock solution is distilled water.
7. The method for removing algae with high efficiency by using the preoxidation enhanced coagulation of the monochloramine as claimed in claim 1, wherein the mass concentration of chlorine in S3 is Cl 2 And (6) counting.
8. The method for efficiently removing algae by using the preoxidation enhanced coagulation of the monochloramine according to claim 1, wherein the preoxidation process is performed in a water pipeline, and specifically comprises the following steps: ammonia nitrogen and chlorine are added at a water inlet of a drinking water plant, the ammonia nitrogen and the chlorine are effectively mixed by utilizing the flow of water in a water pipeline, and the pre-oxidation treatment of the water to be treated is realized.
9. The method for efficiently removing algae by using the preoxidation enhanced coagulation of the monochloramine according to claim 1, wherein in the S3, the mass ratio of chlorine to ammonia nitrogen is 4.5-5.0;
the pre-oxidation time is not less than 3h.
10. The method for efficiently removing algae by using the preoxidation reinforced coagulation of monochloramine as claimed in claim 1, wherein the coagulant is aluminum salt, iron salt or polyacrylamide;
preferably, the aluminum salt includes aluminum chloride, aluminum sulfate, polyaluminum chloride, polyaluminum sulfate;
preferably, the iron salt includes ferric chloride, ferric sulfate, polymeric ferric chloride, polymeric ferric sulfate.
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