WO2023181430A1 - Agent d'agrégation de sels métalliques - Google Patents
Agent d'agrégation de sels métalliques Download PDFInfo
- Publication number
- WO2023181430A1 WO2023181430A1 PCT/JP2022/023668 JP2022023668W WO2023181430A1 WO 2023181430 A1 WO2023181430 A1 WO 2023181430A1 JP 2022023668 W JP2022023668 W JP 2022023668W WO 2023181430 A1 WO2023181430 A1 WO 2023181430A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal salt
- ions
- salt flocculant
- flocculant
- water
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 106
- 150000003839 salts Chemical class 0.000 title claims abstract description 106
- 230000004931 aggregating effect Effects 0.000 title abstract 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 84
- -1 aluminum ions Chemical class 0.000 claims abstract description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 79
- 239000010802 sludge Substances 0.000 claims description 49
- 241000588724 Escherichia coli Species 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- 239000002351 wastewater Substances 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 244000000010 microbial pathogen Species 0.000 claims description 14
- 230000001877 deodorizing effect Effects 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- 239000002781 deodorant agent Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 30
- 239000008394 flocculating agent Substances 0.000 description 22
- 239000003814 drug Substances 0.000 description 21
- 239000010865 sewage Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 229940079593 drug Drugs 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000005189 flocculation Methods 0.000 description 7
- 230000016615 flocculation Effects 0.000 description 7
- 239000000701 coagulant Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000003311 flocculating effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000249 desinfective effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010797 grey water Substances 0.000 description 2
- 239000010800 human waste Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000009287 sand filtration Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- JLPUXFOGCDVKGO-TUAOUCFPSA-N (-)-geosmin Chemical compound C1CCC[C@]2(O)[C@@H](C)CCC[C@]21C JLPUXFOGCDVKGO-TUAOUCFPSA-N 0.000 description 1
- 239000001075 (4R,4aR,8aS)-4,8a-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-4a-ol Substances 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- LFYXNXGVLGKVCJ-FBIMIBRVSA-N 2-methylisoborneol Chemical compound C1C[C@@]2(C)[C@](C)(O)C[C@@H]1C2(C)C LFYXNXGVLGKVCJ-FBIMIBRVSA-N 0.000 description 1
- LFYXNXGVLGKVCJ-UHFFFAOYSA-N 2-methylisoborneol Natural products C1CC2(C)C(C)(O)CC1C2(C)C LFYXNXGVLGKVCJ-UHFFFAOYSA-N 0.000 description 1
- 241000223935 Cryptosporidium Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001263478 Norovirus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JLPUXFOGCDVKGO-UHFFFAOYSA-N dl-geosmin Natural products C1CCCC2(O)C(C)CCCC21C JLPUXFOGCDVKGO-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229930001467 geosmin Natural products 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Definitions
- the present invention relates to metal salt flocculants and various chemicals containing iron ions and aluminum ions used in wastewater treatment.
- the present invention also relates to a metal salt flocculant and various drugs that also have the effect of removing E. coli.
- iron-based and aluminum-based metal salt flocculants are applied to the water being treated to improve the quality of effluent water, reduce the amount of waste, ensure smooth operation, and extend the life of the facility. It is used by inserting it into the Typical iron-based flocculants include ferric chloride, polyferric sulfate, and ferrous sulfate solutions, and aluminum-based flocculants include aluminum sulfate, aluminum chloride, and polyaluminum chloride. .
- Ferric polysulfate is one of the representative examples of iron-based inorganic flocculants, and is widely used in sewage treatment plants and human waste treatment because it has deodorizing and dephosphorizing effects.
- Polyferric sulfate is represented by the general formula ([Fe 2 (OH)n(SO 4 ) 3-n/2 ]m, where 0 ⁇ n ⁇ 2, m is a natural number), and is composed of ferric sulfate, which is an iron-based raw material. It can be obtained by a method such as adding sodium nitrite and an oxidizing agent as a catalyst to a monoferric (FeSO 4 ) solution to allow an oxidation reaction to proceed (Patent Document 1).
- Polyaluminum chloride (commonly known as PAC) is one of the representative examples of aluminum-based inorganic flocculants.It has a high ability to treat suspended solids and soluble organic matter, has a wide optimum pH range, and is not affected by water temperature. It is widely used in water treatment plants because it is possible to reduce the concentration of coagulant added and the water after treatment is not colored.
- inorganic flocculants with a high concentration of the main inorganic component have a higher flocculating effect, which makes it possible to reduce the amount of chemicals used and is also advantageous in terms of transportation.
- polyferric sulfate a higher concentration (total iron concentration of 12.5% or more) compared to regular products (total iron concentration of 11.0 to 12.5%) and reducing the water content, , has high flocculation ability and dewatering ability, and can reduce product transportation costs.
- Patent Documents 5 and 6 disclose a method for producing a highly basic aluminum chloride solution with an Al 2 O 3 concentration of 5 to 25 wt%
- Patent Document 6 discloses a method for producing a highly basic aluminum chloride solution with an Al 2 O 3 concentration of 16 to 25%.
- a highly concentrated flocculant containing aluminum as a main ingredient is disclosed.
- Patent Documents 7 and 8 disclose an inorganic flocculant having an Al/Fe weight ratio of 1/30 to 1/2
- Patent Document 8 discloses an iron-containing flocculant having an Al/Fe molar ratio of 0.06 to 1.0. Discloses a flocculant using waste hydrochloric acid.
- a metal salt flocculant containing iron ions and aluminum ions is that adding iron-based polyferric sulfate to reducing wastewater may cause some coloring, so to prevent this, aluminum chloride or It is known to use a flocculant containing sulfuric acid. Additionally, in paper factories and the like, iron-based flocculants are sometimes mixed with the aluminum-based chemicals that are mainly used in order to impart a deodorizing effect. However, it is known that problems may occur depending on the combination. For example, a combination of aluminum chloride and ferric polysulfate provides a high aggregation effect, but is highly corrosive and has storage stability problems such as alum precipitation due to temperature drop.
- Patent Documents 7 and 8 Furthermore, in metal salt flocculants containing iron ions and aluminum ions, in Patent Documents 7 and 8, the main cation is iron ions, but metal salt flocculants with a composition in which aluminum ions are present in a large amount relative to iron ions are used. The preparation of the iron-containing polyaluminum chloride has not been previously reported.
- the first objective of the present invention is to mix and combine polyferric sulfate and polyaluminum chloride, both of which are known to have high flocculation ability, compared to when each is used alone.
- a second object of the present invention is to provide a metal salt flocculant that also has the effect of removing E. coli.
- the metal salt flocculant of the present invention is composed of the following technical means.
- a metal salt flocculant in which the total content of aluminum ions and iron ions is 5.7 moles or less in 1 liter of the metal salt flocculant, and the molar ratio of chloride ions to iron ions (Cl/ Fe) is 28 or more, the molar ratio of aluminum ions (SO 4 /Al 2 O 3 ) in terms of sulfate ions and aluminum oxide is 0.15 or less, and the removal rate of E. coli is higher than 83%. Flocculant.
- [2] The metal salt flocculant according to [1], wherein the molar ratio of chloride ions to iron ions (Cl/Fe) is 50 or more and 104 or less.
- the metal salt flocculant according to [1] or [2] which has an E. coli removal rate of higher than 90%.
- the metal salt flocculant according to [1] or [2] which has a pH of 3.7 to 4.2 (100 times diluted solution) and a specific gravity of 1.35 to 1.45.
- [6] A water quality improving agent containing the metal salt flocculant according to [1] or [2].
- a method for treating sludge wastewater comprising the step of adding the metal salt flocculant according to [1] or [2] to sludge wastewater.
- a method for purifying and deodorizing water the method comprising the step of adding the metal salt flocculant described in [1] or [2] to water in which pathogenic microorganisms are thought to be present.
- the metal salt flocculant of the present invention by mixing and combining polyferric sulfate and polyaluminum chloride, which are known to have a high flocculating ability, the metal salt flocculant has a high flocculating ability.
- a metal salt flocculant containing iron ions and aluminum ions which has excellent storage stability and can be applied to a wide range of treated wastewater having various characteristics.
- a metal salt flocculant which, in addition to the above-mentioned effects, further has an E. coli removing effect.
- FIG. 1 is a processing flow diagram of a sewage treatment plant (actual test field 1).
- FIG. 2 is a processing flow diagram of a sewage treatment plant (actual test field 2).
- FIG. 3 is a diagram showing the sludge capacity index (SVI) of the reaction tank.
- FIG. 4 is a diagram showing the change in TP concentration in the final sedimentation tank overflow water.
- Metal salt flocculant 1 The present inventors have discovered that by adding and mixing a predetermined amount of polyferric sulfate to polyaluminum chloride, a metal containing iron ions and aluminum ions has high storage stability and excellent water treatment performance. It was discovered that a salt flocculant can be obtained.
- the present invention provides a metal salt flocculant in which the total content of aluminum ions and iron ions is 5.7 moles or less in 1 liter of the metal salt flocculant, and the molar ratio of chloride ions to iron ions is (Cl/Fe) is 28 or more, and the molar ratio of aluminum ions (SO 4 /Al 2 O 3 ) in terms of sulfate ions and aluminum oxide is 0.15 or less.
- the gelation reaction of the polyaluminum chloride proceeds as the pH decreases.
- iron ions in the ferric polysulfate generate iron hydroxide and become insolubilized as the pH increases.
- sulfate ions necessary for stabilizing polyaluminum chloride are replenished and gelation is suppressed.
- stability can be maintained for iron ions in ferric polysulfate by reducing the supply of alkali.
- whether a water treatment agent can exist stably in a solution state (storage stability) is often determined by the cation concentration and the molar ratio of anions to cations.
- polyaluminum chloride as a flocculant often contains sulfate ions, and it is thought that these sulfate ions contribute to the flocculating properties and chemical stability of polyaluminum chloride.
- the chemical stability of the mixed solution is not only improved, but although it has not been confirmed.
- the proportion of a certain polynuclear complex may be high, and this may contribute to the improvement of the water treatment properties of the metal salt flocculant of the present invention. We estimate that it may be contributing.
- the metal salt flocculant of the present invention is a flocculant that has significant effects over a wide range of areas.
- the polyaluminum chloride used in the present invention preferably has an Al concentration in the range of 2 to 6 mol/L.
- the Fe concentration of the ferric polysulfate is preferably in the range of 2 to 4 mol/L. If the amount of ferric polysulfate added is small, the stability of the iron-containing polyaluminum chloride will be poor and it will not be possible to exhibit good flocculation ability. Moreover, if the amount added is large, the hydrolysis of the ferric polysulfate will progress and iron-based precipitates will precipitate as a by-product, which is not preferable.
- the metal salt flocculant obtained in the present invention preferably has a pH of 3.7 to 4.2 (100 times diluted solution) and a specific gravity of 1.35 to 1.45.
- the metal salt flocculant obtained by mixing is not only effective as a flocculant, but also has excellent performance in removing phosphorus, nitrogen, COD, or SS, and is effective in deodorization, dehydration, color reduction, bacteria and virus removal, and fluorine. It also has excellent performance in removing TOC. Therefore, by taking advantage of these properties, it can be used not only as a flocculant but also as a wide variety of wastewater treatment agents.
- the metal salt flocculant according to the first embodiment can be injected with the same equipment as ordinary polyaluminum chloride, as is clear from the actual machine test in the chromaticity reduction test described below. Additionally, since the amount of medicine used can be reduced, the frequency of transportation and reception by lorries will be reduced. This leads to reductions in required labor and personnel costs.
- Metal salt flocculant 2 Although the present invention has been mainly described with respect to the metal salt flocculant according to the first embodiment, the present invention is not limited to the above content. The differences from the metal salt flocculant according to the first embodiment will be mainly explained.
- metal salt flocculants in addition to the above-mentioned basic performance, also have the function of an E. coli remover. .
- the metal salt flocculant according to the second embodiment is a metal salt flocculant in which the total content of aluminum ions and iron ions is 5.7 mol or less in 1 liter of the metal salt flocculant.
- the molar ratio of chloride ions to iron ions (Cl/Fe) is 28 or more
- the molar ratio of aluminum ions (SO 4 /Al 2 O 3 ) in terms of sulfate ions and aluminum oxide is 0.15 or less
- E. coli The present invention relates to a metal salt flocculant having a removal rate of higher than 83%.
- sludge settling, etc. and E. coli removal can be performed in one step using one type of chemical, thereby simplifying the entire water treatment process. can. Furthermore, by making the chemicals used for water treatment multi-functional, the amount of chemicals used in the overall water treatment can be suppressed, and as a result, the energy required for transporting the chemicals can be reduced.
- the area has a high concentration of chlorine ions.
- the molar ratio of chloride ions to iron ions is preferably 28 or more, more preferably 50 or more and 104 or less. This is because if it is less than 28, the chemical stability of the drug is low and iron hydroxide is precipitated. This is because if it exceeds 104, side effects due to the coexistence of iron ions will be reduced, and there is a risk that residual chlorine contained in the treated water will be in an excessive amount.
- the removal rate of E. coli is more preferably higher than 90%. There is no upper limit to the removal rate of E. coli, and it is 100% or less or about 98%.
- the present invention is not limited to metal salt flocculants, but also relates to various methods that take advantage of the characteristics of the metal salt flocculants 1 and 2 described above.
- the present invention relates to sludge treatment and wastewater treatment in sewage treatment. That is, the present invention relates to a method for treating sludge wastewater, which includes a step of adding the metal salt flocculant 1 or 2 described above to the sludge wastewater.
- Metal Salt Flocculant 1 or 2 as described later in the Examples section, the following items are achieved: phosphorus/nitrogen removal performance, deodorizing property (hydrogen sulfide suppression effect), color reduction, and sludge settling property (SV value). It has good effects.
- the sedimentation properties of sludge are improved at an addition rate of about 50% of the added mass of polyaluminum chloride, and the phosphorus removal performance is equivalent to that of polyaluminum chloride.
- the metal salt flocculant 2 When the metal salt flocculant 2 is added, in addition to the above-mentioned performance, it also has the effect of removing pathogenic microorganisms, such as Escherichia coli.
- the removal rate of E. coli becomes higher than 83%, preferably higher than 90%.
- the removal rate of E. coli when polyaluminum chloride is added as a drug is about 75%
- Metal Salt Flocculant 2 although the amount added is less than 50% of the added mass of polyaluminum chloride, , the removal rate of E. coli can be greatly improved.
- sludge sedimentation, etc. and E. coli removal can be performed in one step using one type of chemical, so that it is possible to simultaneously simplify the work process and reduce the amount of chemicals used in the overall water treatment.
- the present invention also relates to a method for purifying and deodorizing waste water such as tap water and gray water. That is, the present invention also relates to a method for purifying and deodorizing water, which includes the step of adding the metal salt flocculant 1 or 2 described above to water in which pathogenic microorganisms are thought to be present. Despite the small amount of chemicals added, it is possible to purify and deodorize water due to its phosphorus and nitrogen removal performance, deodorizing properties (hydrogen sulfide suppression effect), color reduction, and pathogenic microorganism removal properties.
- the present invention has been described by way of embodiments, but the statements and drawings that form part of this disclosure should not be understood as limiting the present invention.
- the metal salt flocculant described in the embodiments can be used in a new usage method. That is, the present invention provides a new method for using a metal salt flocculant in which the metal salt flocculant 1 or 2 described above is used to remove pathogenic microorganisms in waste water, and a new method for using the metal salt flocculant 1 or 2 in the removal of pathogenic microorganisms in waste water.
- Metal salt flocculant 1 The following experiment was conducted on the metal salt flocculant according to the first embodiment. (Characteristics evaluation) The properties of the prepared metal salt flocculant were evaluated from the following viewpoints.
- Sludge settling property Activated sludge was filled in a 1-liter graduated cylinder, each drug to be evaluated was added thereto, and the sludge settling ability of each drug was evaluated based on the height of the sludge separated from solid and liquid after being allowed to stand for a predetermined period of time.
- SV in SVn represents the sludge volume
- n represents the elapsed time (minutes) after standing.
- the total amount of aluminum ions and iron ions in 1L is 5.7 moles or less
- the molar ratio of chloride ions to iron ions (Cl/Fe) is 28 or more
- the sedimentation properties (SV 10 , SV 30 ) of the sludge were measured after standing for 10 minutes and after standing for 30 minutes.
- M 3+ represents the total concentration of trivalent metal ions (ie, Al 3+ and Fe 3+ ) contained in the drug.
- the supernatant water after being left standing for 1 hour was analyzed for the amount of remaining components of TP, TN, COD, and SS.
- Table 2 the amount of each drug added was set so that M 3+ was the same for each drug.
- the test results are shown in Table 2.
- TS is an abbreviation for total evaporation residue (total solids), and here indicates the amount of sludge as solids.
- the metal salt flocculant of the present invention had the best sludge settling property (SV value) at a smaller amount than polyaluminum chloride or polyferric sulfate. . Particularly when paying attention to the SV 10 value, there was a significant difference in the initial sedimentation rate, which indicates that the drug has excellent immediate efficacy. Since the use of the metal salt flocculant of the present invention greatly improves the solid-liquid separability of treated water, it can be used in all types of water treatment equipment for the purpose of flocculation (e.g. flocculation tanks, biological reaction tanks, gravity concentration tanks, etc.). Available.
- flocculation tanks e.g. flocculation tanks, biological reaction tanks, gravity concentration tanks, etc.
- the metal salt flocculant of the present invention was able to remove more TP, TN, COD, and SS from supernatant water with a smaller amount added than polyaluminum chloride or polyferric sulfate. . Therefore, by using the metal salt flocculant of the present invention, it is possible to efficiently remove and recover the above-mentioned components, and therefore, it is expected to be effective in countering eutrophication and improving water quality. [Example 3]
- the removal rate of hydrogen sulfide was in the order of polyaluminum chloride ⁇ metal salt flocculant of the present invention ⁇ polyferric sulfate.
- the immobilization of sulfur by iron ions greatly contributes to suppressing hydrogen sulfide, so the metal salt flocculant of the present invention exhibited a higher hydrogen sulfide suppressing effect than ordinary polyaluminum chloride. Therefore, the metal salt flocculant of the present invention can also be used as a deodorizer in water treatment. Possible usage examples include sewage treatment plants, wastewater treatment facilities, pumping stations, and mud pumping facilities. [Example 4]
- the dehydration properties were good in the order of polyaluminum chloride ⁇ polyferric sulfate ⁇ the metal salt flocculant of the present invention.
- the metal salt flocculant of the present invention With the metal salt flocculant of the present invention, the moisture content of the cake was reduced by 1.5 points compared to when no chemical was added.
- the metal salt flocculant of the present invention can also be used in a dehydrator for the purpose of reducing the water content of sludge, which ultimately leads to a reduction in sludge transportation and treatment costs. [Example 5]
- Example 2 Chromaticity reduction characteristic
- the polyaluminum chloride (25 mg/L) used in Example 2 was placed at the end of the biological reaction tank of the sewage treatment plant with the flow shown in Figure 1 (daily average inflow water amount: approximately 33,000 m 3 /day, standard activated sludge method).
- the metal salt flocculant (14 mg/L) of the present invention was continuously injected for one week.
- the drug was added into the liquid in a biological reaction tank using a diaphragm metering pump.
- the amount of the drug added was set so that the trivalent metal ion concentrations were equal, as described above.
- Overflow water was periodically sampled from the final settling tank located after the biological reaction tank, and its chromaticity was measured.
- Table 5 Here, the average value and minimum value of chromaticity are weekly average values.
- the agent of the present invention is expected to be used not only for sewage but also for wastewater such as clean water and gray water.
- the metal salt flocculant of the present invention could be injected using the same equipment as ordinary polyaluminum chloride. Additionally, since the amount of medicine used can be reduced, the frequency of transportation and reception by lorries will be reduced, which will lead to a reduction in required labor and personnel costs.
- polyaluminum chloride (PAC) is added as a flocculant before the final reaction tank in another series (step flow type two-stage nitrification-denitrification method with coagulant).
- PAC polyaluminum chloride
- a portion of the treated water undergoes sand filtration, ozone treatment, and chlorine disinfection, and is then reused as water for nearby parks.
- PAC and high-concentration iron-aluminum were added to a treatment facility (A system) using a step flow type two-stage nitrification-denitrification method using a flocculant.
- the drug was injected at the front stage of the final tank of the reaction tank, and PAC and high-concentration iron-aluminum were injected for two weeks each using a metering pump (addition rate Comparative Example 1 (PAC): 34 mg/L, Example 6 (high-concentration iron-aluminum) ): 17 mg/L).
- a treatment facility (B system) using a standard activated sludge method (simulated step inflow type two-stage nitrification and denitrification method) was selected as a blank.
- Activated sludge from the final reaction tanks of systems A and B and overflow water from the final settling tank were periodically sampled to evaluate sludge settling properties and water quality. The test was conducted from November 26, 2020 to December 17, 2020.
- the sludge capacity index (SVI) of the reaction tank is shown in Figure 3.
- SVI sludge capacity index
- the SVI of the A system was 150 to 300 mL/g during PAC injection and 100 to 200 mL/g during high concentration iron-aluminum injection.
- the settling properties of sludge were improved by the injection of flocculant, and it was thought that especially high-concentration iron-aluminum had a higher flocculation effect.
- Figure 4 shows the change in TP concentration in the final sedimentation tank overflow water.
- the TP concentration of system A was constant between 0.05 and 0.50 mg/L during the injection period of PAC and high concentration iron-aluminum.
- the addition rate of high-concentration iron-aluminum was approximately 50% of PAC, it was shown that the same phosphorus removal could be performed because the metal ion concentration was the same as that of PAC.
- E. bacteria, odor substance removal evaluation Table 6 shows the analysis results of the number of E. coli bacteria, residual chlorine concentration, and odor substance concentration (geosmin, 2-methylisoborneol) in the final sedimentation tank overflow water.
- the number of E. coli in system A was lower than that of the blank system B, and the removal rate was about 75 to 83% during PAC injection and about 90% during high concentration iron aluminum injection.
- the residual chlorine (free residual chlorine/combined residual chlorine) concentration is the same for both A and B systems, and the values are low, and it is considered that the concentration does not have disinfecting power. It is generally thought that some of the pathogenic microorganisms in sewage (E.
- E. coli, norovirus, cryptosporidium, etc. are adsorbed to sludge, become entangled in flocs, and are removed from the treated water as they coagulate and settle.
- the number of E. coli is also correlated with the SVI values of A and B systems, and since there is no chlorine component with disinfecting power in the treated water, it is thought that E. coli was removed from the treated water through coagulation and precipitation in this test. Furthermore, no E. coli was detected in the recycled water that had undergone sand filtration, ozone treatment, and chlorine disinfection. Since the concentration of odorants was low in both Type A and Type B, and there was no significant difference in the analytical values, no superior deodorizing effect was confirmed by the injection of the flocculant in this test.
- Table 7 shows the measurement results of the color and turbidity of the final settling tank overflow water.
- the chromaticity of system A was lower than that of system B, and it could be said that the clarity of the treated water was improved by the injection of the flocculant.
- the chromaticity at the time of high-concentration iron-aluminum injection was 10 degrees, and the chromaticity decreased to the standard value level (10 degrees or less) for hydrophilic water.
- the turbidity was approximately 2.0 regardless of the type of flocculant, and no major difference was observed in the analytical values of the A and B systems.
- Reclaimed sewage water can be used as (1) water for flushing, (2) water for sprinkling, (3) water for landscaping, and (4) water for hydrophilic purposes.
- the water quality standards include E. coli count, turbidity, pH, appearance, and chromaticity. , there is an odor. Based on these items, the degree of water quality improvement due to the use of flocculants was evaluated. In this test, the blank treated water was excluded from the evaluation because the turbidity and odor concentration were low. As mentioned above, injection of a flocculant is effective in reducing chromaticity, and this test showed that it improved to the standard value level. Regarding the number of E.
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Abstract
Selon l'invention, la teneur totale en ions aluminium et en ions fer dans 1 litre de cet agent d'agrégation de sels métalliques est de 5,7 mol ou moins, le rapport molaire (Cl/Fe) entre les ions chlore et les ions fer étant de 28 ou plus, le rapport molaire (SO4/Al2O3) entre les ions sulfate et les ions aluminium en termes d'oxyde d'aluminium étant de 0,15 ou moins, et le taux d'élimination de coliformes étant de 83 % ou plus. Grâce au mélange de polysulfate ferrique et de polychlorure d'aluminium et à leur utilisation en combinaison, cet agent d'agrégation de sel métallique présente une stabilité de stockage supérieure et une performance d'agrégation supérieure comparativement au cas où le polysulfate ferrique et le polychlorure d'aluminium sont utilisés individuellement, et cet agent d'agrégation de sels métalliques peut également être appliqué à une large gamme de déchets liquides de traitement ayant diverses caractéristiques. Cet agent d'agrégation de sels métalliques possède également une action d'élimination de coliformes.
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KR (1) | KR102592806B1 (fr) |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH10272304A (ja) * | 1997-03-31 | 1998-10-13 | Takenobu Horiguchi | 無機電解凝集剤 |
JP2013031838A (ja) * | 2011-06-29 | 2013-02-14 | Sanyo Chem Ind Ltd | 有機/無機ハイブリッド高分子凝集剤 |
CN112390321A (zh) * | 2020-11-16 | 2021-02-23 | 神美科技有限公司 | 一种污水处理用除磷剂及其制备方法 |
JP2022055836A (ja) * | 2020-09-29 | 2022-04-08 | 日鉄鉱業株式会社 | 金属塩凝集剤 |
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JPH01180210A (ja) | 1988-01-13 | 1989-07-18 | Nittetsu Mining Co Ltd | 含鉄廃塩酸を利用した凝集剤の製造法 |
JP3524246B2 (ja) | 1995-11-15 | 2004-05-10 | 多木化学株式会社 | 高塩基性塩化アルミニウム溶液の製造方法 |
JP2000070609A (ja) | 1998-09-01 | 2000-03-07 | Asahi Kagaku Kogyo Co Ltd | 高濃度凝集剤 |
KR20190082682A (ko) * | 2019-04-03 | 2019-07-10 | 삼구화학공업 주식회사 | 하·폐수 및 슬러지 처리용 응결제 조성물 |
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- 2022-06-13 WO PCT/JP2022/023668 patent/WO2023181430A1/fr unknown
- 2022-06-13 KR KR1020227033526A patent/KR102592806B1/ko active IP Right Grant
- 2022-06-23 TW TW111123468A patent/TW202337831A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10272304A (ja) * | 1997-03-31 | 1998-10-13 | Takenobu Horiguchi | 無機電解凝集剤 |
JP2013031838A (ja) * | 2011-06-29 | 2013-02-14 | Sanyo Chem Ind Ltd | 有機/無機ハイブリッド高分子凝集剤 |
JP2022055836A (ja) * | 2020-09-29 | 2022-04-08 | 日鉄鉱業株式会社 | 金属塩凝集剤 |
CN112390321A (zh) * | 2020-11-16 | 2021-02-23 | 神美科技有限公司 | 一种污水处理用除磷剂及其制备方法 |
Non-Patent Citations (2)
Title |
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KOMAI: "Study of Water Treatment and Wastewater Recycling Using High-Concentration Iron-Aluminum Flocculant", PROCEEDINGS OF 58TH MEETING OF JAPAN WATER WORKS ASSOCIATION, vol. 58, 30 June 2021 (2021-06-30), pages 25 - 27, XP009549326 * |
TOSHIMA: "Performance Evaluation of High-Concentration Iron-Aluminum Flocculant", PROCEEDINGS OF 57TH MEETING OF JAPAN WATER WORKS ASSOCIATION, vol. 57, 22 July 2020 (2020-07-22), pages 40 - 42, XP009552909 * |
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TW202337831A (zh) | 2023-10-01 |
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