WO2008096988A1 - Chemical reagent for the purpose of simultaneous treatment of n, p and microalgae for prevention eutrophication of water bodies - Google Patents
Chemical reagent for the purpose of simultaneous treatment of n, p and microalgae for prevention eutrophication of water bodies Download PDFInfo
- Publication number
- WO2008096988A1 WO2008096988A1 PCT/KR2008/000647 KR2008000647W WO2008096988A1 WO 2008096988 A1 WO2008096988 A1 WO 2008096988A1 KR 2008000647 W KR2008000647 W KR 2008000647W WO 2008096988 A1 WO2008096988 A1 WO 2008096988A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- agent
- lanthanum
- rare
- earth metal
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000012851 eutrophication Methods 0.000 title claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 title description 2
- 230000002265 prevention Effects 0.000 title description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 56
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010457 zeolite Substances 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 48
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052773 Promethium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000012258 stirred mixture Substances 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 abstract description 29
- 241000192710 Microcystis aeruginosa Species 0.000 abstract description 5
- -1 (Lu) Chemical compound 0.000 description 26
- 235000015097 nutrients Nutrition 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229940037003 alum Drugs 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 235000016709 nutrition Nutrition 0.000 description 4
- 230000035764 nutrition Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000004941 influx Effects 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 235000019640 taste Nutrition 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000252230 Ctenopharyngodon idella 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
- 206010012289 Dementia Diseases 0.000 description 1
- 241000252234 Hypophthalmichthys nobilis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000276707 Tilapia Species 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000003619 algicide Substances 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 241000902900 cellular organisms Species 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
-
- 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
- C02F2101/105—Phosphorus compounds
-
- 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
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Definitions
- the present invention relates to an agent for simultaneously treating nitrogen (N) and phosphorus (P) that enables simultaneous removal of N and P which cause eu- trophication of water bodies (lakes, marshes, rivers and dams) by using an agent prepared by mixing zeolite and a rare-earth metal or by using another agent prepared by a mixture of zeolite and a rare-earth metal added by a small amount of an additive (surfactant) or flocculant.
- the agent also has high treatment efficiency even in the case that algae form water bloom.
- the present invention relates to a preparation method of the agent.
- a fundamental measure for controlling algae in raw water is adjustment of a nutrition level of water. That is, it is most important to reduce the nutrition level of water from a eutrophic state to a state below a mesotrophic state.
- One method that can be used is to restrict influx of nutrient salts such as N and P in the upstream of a river.
- N and P nutrient salts
- it requires high costs, and lots of time and labor, and therefore there is a limit in using this method for a current water resource management.
- Aeration may be carried out in a pond as a physical treatment method to circulate water in a still region of the pond, supply dissolved oxygen and maintain water temperature in a desired level.
- it is used as a preventive measure to reduce dominance of algae by accelerating death of algae due to proliferation of aerobic microorganisms.
- it can not remove nutrient salts (N, P) that are fundamental materials that cause eutrophication.
- a method of using an algicide and a method of precipitating by a flocculant are mainly used as a chemical treatment method.
- Copper sulfate has been used as one of chemical treatment methods since 1904. It has been most frequently used to kill algae for about 90 years and is widely used now in many countries including the United States of America. However, it is known that use of copper sulfate causes various and serious side effects. Efficacy of copper sulfate lasts for 7 to 10 days, algae cluster is formed again after this period and copper sulfate must be used repetitively and continuously. Long -term use of copper sulfate causes distortion of organism cluster in water bodies. For example, it causes decrease in an existing amount of zooplankton, and thereby consumption of phytoplankton decreases remarkably.
- Aluminum sulfate is mainly used for inactivating P in a wastewater treatment process and water purification process, and is extensively used because it is cheap.
- Aluminum-based flocculants have a high precipitation speed that helps removal of suspended solids, and the applicable range of pH is narrow (pH 5.5-8.5). After passage of a long period (longer than 65 days), re-dissolution of P occurs on the surface of sediment. pH may become remarkably low in a certain local area of a lake because agitation for mixing is not enough in the lake.
- Aluminum has a significant influence on invertebrate animals and is reported to have an indirect influence on dementia such as Alzheimer's disease.
- a method of precipitating P on the bottom of lakes and marshes by combining P with aluminum, iron and calcium salt using aluminum, iron salt and calcium salt is used in the Republic of Korea among the chemical treatment methods described in the above.
- this method has a problem that re-dissolution of P occurs after precipitation.
- the present invention is provided to solve the above problems.
- the present invention provides an agent for simultaneously treating N, P and microalgae to convert nutrient salts into a form that can not be used by organisms by using an agent prepared by mixing a rare-earth metal and zeolite as an inactivation agent of nutrient salts (P, N) in water bodies to simultaneously treat P and N in rivers, lakes and dams, to remove nutrient salts from a production layer or restrict circulation of nutrient salts that have a potential to be used, and to prevent dissolution of nutrient salts (P, N) from a deposit layer; and a preparation method thereof.
- the present provides an agent for simultaneously treating N, P and microalgae to prevent eutrophication of water bodies, that is prepared by mixing 98.00 ⁇ 99.99wt% of zeolite and 0.01 ⁇ 2.00wt% of a rare-earth metal, or by mixing 93.00 ⁇ 99.98wt% of zeolite, 0.01 ⁇ 2.00wt% of a rare-earth metal and 0.01 ⁇ 5.00wt% of an additive or flocculant.
- the rare-earth metal according to the present invention is at least one selected from the group consisting of lanthanum (La), cerium (Ce), zirconium (Zr), praseodymium (Pr), neodymium (Nd), promethium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium, (Lu), yttrium (Y) and scandium (Sc).
- La lanthanum
- Ce cerium
- Zr zirconium
- Pr praseodymium
- Nd neodymium
- promethium Pr
- Sm samarium
- Eu europium
- Gd gadolinium
- Tb terbium
- Dy dysprosium
- La removes P from water bodies, prevents dissolution of P in sediment, and forms a very stable lanthanum phosphate (LaPO -nH O) by reacting large anionic particles with particles such as orthophosphate ions (PO ) in water bodies.
- LaPO -nH O very stable lanthanum phosphate
- Alum Al (SO ) -14H O
- Alum is described in relation to lanthanum ions.
- Alum is
- AlPO formed by removing P with alum is regarded as a material that is hardly dissolved. However, it is sensitive to pH, and P is dissolved when pH is below 5.5 and above 8.5.
- Lanthanum phosphate (LaPO ), which is different from alum having the above described problems, formed according to the present invention is a stable and hardly dissolved material having a solubility product constant (Ksp)of 10 ⁇ 10 in a wide range of pH 4 - 11.
- Zeolite has a function of physical absorption and of substitution of cations, and establishes rapid fixation of heavy metals and ammonium ions (NH + ) in water.
- Zeolite is a three-dimensional inorganic polymer having a typical skeleton in which silicon (Si) atom and aluminum (Al) atom are each bonded through 4 oxygen atom bridges. Zeolite has a negative electric charge because Al atom is bonded to 4 oxygen atoms, and various cations (M + ) exist to compensate for the negative electric charge.
- Zeolite has generally uniform micropores and various micropores having a size of 3
- the surface area of a micropore in zeolite is generally 1000 m /g and such a wide surface area has an advantage that active sites may be distributed in a wide range.
- Cations in micropores of zeolite can easily be exchanged by various other metals and organic cations in water solution.
- Calcium (Ca + ) ions and magnesium (Mg + ) ions in water are exchanged by sodium (Na + ) ions by using the above described property, and thereby converting hard water into soft water.
- Na + sodium
- lanthanum (La + ) 0.01 ⁇ 2.00wt% of lanthanum (La + ) is used with respect to the total weight of the mixture. If a mixing ratio of lanthanum is below 0.0 lwt %, excessive input of a mixture of lanthanum (La + ) and zeolite is required to remove P in water bodies that are eutrophic and results in a large amount of deposit. If a mixing ratio of lanthanum is above 2.00wt%, a mixture of lanthanum (La + ) and zeolite loses competitiveness in price, and it is preferable to use 0.01 ⁇ 2.00wt% of lanthanum.
- [37] 98.00 ⁇ 99.99wt% of zeolite is used with respect to the total weight of mixture. If a mixing ratio of zeolite is below 98.00wt%, long reaction time is required to simultaneously remove N and P, and precipitation speed of small suspended solids decreases. If a mixing ratio of zeolite is above 99.99wt%, a mixture of lanthanum (La + ) and zeolite can not be applied for removal of P in water bodies, and it is preferable to use 93.00 ⁇ 99.99wt% of zeolite.
- zeolite which is used as a binder of lanthanum, may be replaced by an inorganic material having a precipitation property, for example clay minerals such as smectite, goethite, silica mineral and bentonite.
- Zeolite is a supporter of lanthanum (La + ) ions and a mixing ratio of zeolite may be adjusted between 93.00 ⁇ 99.98wt% depending on the amount of lanthanum, additive and flocculant.
- a mixing ratio of zeolite may be adjusted between 93.00 ⁇ 99.98wt% depending on the amount of lanthanum, additive and flocculant.
- Technical features of a mixture of lanthanum (La + ) and zeolite added by a small amount of an additive or flocculant are described.
- An agent for simultaneously treating N, P and microalgae comprises 0.01 ⁇
- the additive is one selected from a surfactant and isopropanol. If the additive is a surfactant, the surfactant acts as a pore forming agent and helps to increase surface area. It is preferable that the surfactant is used in the amount of 0.01 ⁇ 2.00% with respect to the total weight of the agent, and lanthanum is uniformly absorbed to zeolite by distributing lanthanum widely. If the additive is isopropanol, isopropanol forms aerogel and ester bonds are induced by adding acetic acid.
- the flocculant is at least one selected from inorganic electrolyte and organic high polymer compound.
- the inorganic electrolyte is at least one selected from the group consisting of calcium hydroxide, alum, aluminum chloride, iron sulfate (III) and iron sulfate (II), and floe is formed by making electric potential on surfaces of particles in liquor near zero and removing electrical repulsive force between particles.
- the organic high polymer compound is at least one selected from starches, poly- acrylamides and derivatives thereof.
- the starches coagulate by increase or decrease of colloidal phenomena.
- the polyacrylamides and derivatives thereof attract particles by bridge actions of molecules absorbed to particles.
- an agent for simultaneously treating N, P and microalgae is prepared by mixing lanthanum ions and zeolite as follows. 98.00 ⁇ 99.99wt% of zeolite and 0.01 ⁇ 2.00wt% of 0.5 - 1% water solution of lanthanum are poured into an agitator and stirred for mixing for 1 - 48 hours, a stirred mixture thereof is separated by a centrifugal separator at 10,000 ⁇ 20,000 rpm for 5 - 10 minutes, supernatant thereof after centrifugal separation is separately stored for reuse, particles separated by the centrifugal separator are dried at a room temperature for 24 hours and are hardened at 105 - 200 0 C at 1 - 3 hours, the hardened particles are input to the supernatant, namely 0.5 - 1% lanthanum water solution, and a series of processes of agitation, centrifugal separation, drying and hardening is repeated 3 times under the same conditions as those described in the above.
- another agent for simultaneously treating N, P and microalgae is prepared by mixing lanthanum ions and zeolite added by an additive or flocculant as follows. Isopropanol and acetic acid are added to a surfactant such as polyoxyethyene sorbitan monooleate and lanthanum ions to make a sol state (colloid that has a continuous liquid phase in which a solid is suspended in a liquid with fluidity) in which the surfactant and lanthanum ions exist,
- a surfactant such as polyoxyethyene sorbitan monooleate and lanthanum ions
- a mixture of the lanthanum ions and surfactant in a sol state is coated on zeolite which is a supporter.
- zeolite and the mixture of the lanthanum ions and surfactant in a sol state are stirred together for 1 - 48 hours, and separated centrifugally at 10,000 - 20,000 rpm for 5 - 10 minutes.
- Supernatant thereof is stored for reuse, particles separated centrifugally are dried in a room temperature for 20 ⁇ 30 hours, and the dried particles are hardened at 105 ⁇ 200 0 C for 1 ⁇ 3 hours.
- Drying in a room temperature is used to maintain supercritical dried state of absorbed lanthanum in a sol state and hydrophile property of the surfactant, and to completely remove moisture that is adhered to the formed particles, and the dried particles are hardened at 105 ⁇ 200 0 C for 1 ⁇ 3hours after drying at a room temperature to adjust strength of the prepared agent.
- an agent according the present invention is prepared by mixing zeolite with lanthanum ions, or by adding an additive or flocculant to a mixture of lanthanum ions and zeolite for a synergy effect and uniform dispersion.
- Zeolite used as a supporter of lanthanum ions does not remove large anionic particles. However zeolite has an excellent absorption ability of organic materials and excellent selective absorption ability of NH 4 + ions, which is ion exchange ability that
- Ig of zeolite can absorb 5.56 mg of NH + -N.
- precipitation speed is increased by increase in the specific gravity of floe, and P and suspended solids such as microalgae may be precipitated together.
- an agent for simultaneously treating N, P and microalgae according to the present invention can simultaneously remove N and P that can induce eutrophication in water bodies (lakes, marshes and dam).
- High treatment efficiency may be expected even in the case of water bloom of algae because it has excellent absorption ability due to zeolite and acts as a flocculant, and suspended solids of dead algae may be removed by precipitating them.
- An agent according to the present invention provides an environment friendly agent that accelerates precipitation speed and thereby maximizing the treatment efficiency in a short period, treated N and P do not dissolve again under any change of environment conditions (sediment), and finally formed materials (deposit) are not environmentally toxic.
- Figure 1 is a cross-sectional view schematically showing an agent for simultaneously treating N, P and microalgae according to the present invention
- Figure 2 is a graph showing an EDX (Energy Dispersive X-ray) analysis result for an agent for simultaneously treating N, P and microalgae according to Example 4 of the present invention
- Figure 3 is a graph showing an amount of N and P simultaneously removed by a mixed compound of La, zeolite and flocculant according to the present invention.
- An agent for simultaneously treating N, P and microalgae according to the present invention is prepared by mixing 2.00 g of lanthanum ions (La + ), which is a rare-earth metal, and 98.00 g of zeolite. [71] Example 2
- An agent for simultaneously treating N, P and microalgae according to the present invention is prepared by mixing 0.01 g of lanthanum ions (La + ), which is a rare-earth metal, 99.98 g of zeolite and 0.01 g of polyoxyethyene sorbitan monooleate which is a surfactant.
- La + lanthanum ions
- An agent for simultaneously treating N, P and microalgae according to the present invention is prepared by mixing 2.00 g of lanthanum ions (La + ), which is a rare-earth metal, 96.00 g of zeolite and 2.00 g of aluminum chloride. [75] [76] Preparation method of an Agent for simultaneously treating nitrogen (N). phosphorus (P). and microalgae
- An agent for simultaneously treating N, P and microalgae according to the present invention is prepared as follows. 98.00 g of zeolite is put into 2 g of 1% water solution of lanthanum, a mixture thereof is mixed for 5 hours by an agitator and is separated centrifugally at 10,000 rpm for 5 minutes, supernatant thereof is separately stored for reuse, and particles separated by centrifugal separation are dried at a room temperature for 24 hours and are hardened at 105 0 C for lhour.
- the hardened particles are added to the separately stored supernatant, namely 1% water solution of lanthanum, and processes of stirring, separation and drying are repeated three times under the same conditions as those of the above processes to complete the preparation of the agent for simultaneously treating N, P and microalgae.
- Figure 1 schematically shows an agent for simultaneously treating N, P and microalgae
- Figure 2 shows an EDX (Energy Dispersive X-ray) analysis result for an agent for simultaneously treating N, P and microalgae
- Figure 3 shows an amount of N and P simultaneously removed by a mixed compound of lanthanum, zeolite and flocculant.
- an agent for simultaneously treating N, P and microalgae is an agent (1) formed by utilizing lanthanum ions (La + ) to insolubilize P and zeolite to insolubilize N.
- La + lanthanum ions
- Nutrient salts (P, N) in water bodies may be simultaneously removed with only a small amount of the agent (1).
- N is removed by zeolite (10)
- P is removed by lanthanum ions (30)
- N, P and microalgae are removed simultaneously by a synergy effect of increasing precipitation speed of microalgae due to increase in the specific gravity of the agent formed by mixing.
- the agent (1) according to the present invention is prepared considering selective absorption, exchange reaction and physicochemical precipitation, it has less influence on ecosystem of water bodies, effective treatment of nutrient salts (N, P) and high precipitation speed can be expected even when a small amount of it is used, the size of finally formed materials (deposit) is small as it is within lmm, re- dissolution of nutrient salts (N, P) may be prevented under any change of environmental conditions because it contains lanthanum phosphate(LaPO nH O)and zeolite that are natural minerals and is a stable material which is hardly soluble, and nutrient salts (N, P) in sediment may be expected to be removed.
- LaPO nH O lanthanum phosphate
- Figure 2 shows an Energy Dispersive X-ray (EDX) analysis result for an agent for simultaneously treating N, P and microalgae according to Example 4 of the present invention. Composition of the agent is shown in Table 1.
- Figure 3 is a graph showing an amount of nutrient salts (N, P) simultaneously removed by the agent (1).
Abstract
An agent for simultaneously treating nitrogen (N) and phosphorus (P) is disclosed which enables simultaneous removal of N and P that cause eutrophication of water bodies (lakes, marshes, rivers and dams) by using an agent prepared by mixing zeolite and a rare-earth metal or by using another agent prepared by a mixture of zeolite and a rare-earth metal added by a small amount of an additive (surfactant) or flocculant. The agent has high treatment efficiency even in the case that algae form water bloom. A preparation method of the agent is also disclosed.
Description
Description
CHEMICAL REAGENT FOR THE PURPOSE OF SIMULTANEOUS TREATMENT OF N, P AND MICRO ALGAE FOR PREVENTION EUTROPHICATION OF WATER BODIES
Technical Field
[1] The present invention relates to an agent for simultaneously treating nitrogen (N) and phosphorus (P) that enables simultaneous removal of N and P which cause eu- trophication of water bodies (lakes, marshes, rivers and dams) by using an agent prepared by mixing zeolite and a rare-earth metal or by using another agent prepared by a mixture of zeolite and a rare-earth metal added by a small amount of an additive (surfactant) or flocculant. The agent also has high treatment efficiency even in the case that algae form water bloom. Also, the present invention relates to a preparation method of the agent.
[2]
Background Art
[3] Eutrophication of water bodies causes numerous damages caused by algae such as water bloom. Typical damages are loss of value as a source of a municipal water supply system, hindrance to water purification treatment, deformation of tourist attractions, unpleasant tastes and odors, and generation of toxic materials.
[4] In the Republic of Korea, the amount of P fluxing into rivers generally starts to increase from April every year due to rise of water temperature and start of an agricultural activity, reaches the maximum value which is almost twice higher than the average value during July and August, and P precipitates on the bottom of the rivers when temperatures of the rivers decrease. P rises up from the bottom of the rivers next year and contaminates the rivers.
[5] Growth of algae due to eutrophication contaminates water when the algae grow rapidly; dead algae are deposited as time passes; the deposited algae are decayed on the bottom of a lake, and discharge P into water in the lake; and P rises from the bottom of the lake when temperature of water rises and causes permanent eutrophication.
[6] A fundamental measure for controlling algae in raw water is adjustment of a nutrition level of water. That is, it is most important to reduce the nutrition level of water from a eutrophic state to a state below a mesotrophic state. One method that can be used is to restrict influx of nutrient salts such as N and P in the upstream of a river. However, it requires high costs, and lots of time and labor, and therefore there is a limit in using this method for a current water resource management.
[7] Other measures for controlling algae in raw water (measures that can be taken in a
lake) may be classified as a chemical treatment, biological treatment and physical treatment, and a combination of them is generally used considering the current situation of the lake.
[8] Only one method of utilizing large grass-eating fishes such as a grass carp, silver carp and tilapia is reported as a method of biological control for algae and it is almost not used in the world.
[9] Aeration may be carried out in a pond as a physical treatment method to circulate water in a still region of the pond, supply dissolved oxygen and maintain water temperature in a desired level. However, it is used as a preventive measure to reduce dominance of algae by accelerating death of algae due to proliferation of aerobic microorganisms. However, it can not remove nutrient salts (N, P) that are fundamental materials that cause eutrophication.
[10] A method of using an algicide and a method of precipitating by a flocculant are mainly used as a chemical treatment method.
[11] Copper sulfate has been used as one of chemical treatment methods since 1904. It has been most frequently used to kill algae for about 90 years and is widely used now in many countries including the United States of America. However, it is known that use of copper sulfate causes various and serious side effects. Efficacy of copper sulfate lasts for 7 to 10 days, algae cluster is formed again after this period and copper sulfate must be used repetitively and continuously. Long -term use of copper sulfate causes distortion of organism cluster in water bodies. For example, it causes decrease in an existing amount of zooplankton, and thereby consumption of phytoplankton decreases remarkably. Accordingly dominant species are changed from green algae and diatom to violet algae in species composition of the algae cluster and therefore more unfavorable situation for water quality control is established. Copper is accumulated in deposit, hurts various biota such as fishes, and recirculation of organic materials and nutrient salts in water bodies are accompanied inevitably. Copper sulfate is not used frequently as a method for removing algae because of the above described reasons.
[12] Removal of algae by using lime (calcium carbonate or calcium hydroxide) is performed by forming and precipitating floe without destruction or oxidation of algae. Use of lime provides an additional effect that concentration of N and P in water is reduced. Precipitation of algae without destruction of cells of the algae has a decisive advantage that organic materials such as various metabolic materials in cells and toxic materials such as materials having unpleasant tastes and odors and microcystin are not dissolved into water around them. Deposited dead algae and nutrient salts are also coated by lime and it is expected that re-dissolution thereof may be restricted to some extent. However, use of lime has a disadvantage that pH of water bodies is raised and microfloc floats (Precipitation speed is low). Dominant degree of violet algae is high in
alkaline water and thereby more unfavorable situation for water quality control is established.
[13] Aluminum sulfate is mainly used for inactivating P in a wastewater treatment process and water purification process, and is extensively used because it is cheap. Aluminum-based flocculants have a high precipitation speed that helps removal of suspended solids, and the applicable range of pH is narrow (pH 5.5-8.5). After passage of a long period (longer than 65 days), re-dissolution of P occurs on the surface of sediment. pH may become remarkably low in a certain local area of a lake because agitation for mixing is not enough in the lake. Aluminum has a significant influence on invertebrate animals and is reported to have an indirect influence on dementia such as Alzheimer's disease.
[14] Potassium permanganate (KMnO ), chlorine-based chemicals and herbicides have problems similar to those of copper sulfate.
[15] A method of precipitating P on the bottom of lakes and marshes by combining P with aluminum, iron and calcium salt using aluminum, iron salt and calcium salt is used in the Republic of Korea among the chemical treatment methods described in the above. However, this method has a problem that re-dissolution of P occurs after precipitation.
[16] P was regarded as a main limiting factor that causes eutrophication till now and much effort has been made to treat P. However, simultaneous removal of N and P is required depending on a nutrition level of water bodies (Criterion for deciding eutrophication level: TN in the case of TN/TP> 7, TP in the case of TN/TP < 16, and a factor having a high nutrition level in the case of TN/TP = 7 - 16 are regarded as a criterion).
[17]
Disclosure of Invention Technical Problem
[18] The present invention is provided to solve the above problems. The present invention provides an agent for simultaneously treating N, P and microalgae to convert nutrient salts into a form that can not be used by organisms by using an agent prepared by mixing a rare-earth metal and zeolite as an inactivation agent of nutrient salts (P, N) in water bodies to simultaneously treat P and N in rivers, lakes and dams, to remove nutrient salts from a production layer or restrict circulation of nutrient salts that have a potential to be used, and to prevent dissolution of nutrient salts (P, N) from a deposit layer; and a preparation method thereof.
[19]
Technical Solution
[20] To solve the above problems, the present provides an agent for simultaneously treating N, P and microalgae to prevent eutrophication of water bodies, that is prepared by mixing 98.00 ~ 99.99wt% of zeolite and 0.01 ~ 2.00wt% of a rare-earth metal, or by mixing 93.00 ~ 99.98wt% of zeolite, 0.01 ~ 2.00wt% of a rare-earth metal and 0.01 ~ 5.00wt% of an additive or flocculant.
[21] The rare-earth metal according to the present invention is at least one selected from the group consisting of lanthanum (La), cerium (Ce), zirconium (Zr), praseodymium (Pr), neodymium (Nd), promethium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium, (Lu), yttrium (Y) and scandium (Sc).
[22] Technical features of an agent for simultaneously treating N, P and microalgae are described in detail based on lanthanum (La) which is one of the rare-earth metals according to the present invention.
[23] Lanthanum (La) is used for inactivation of P.
[24] La removes P from water bodies, prevents dissolution of P in sediment, and forms a very stable lanthanum phosphate (LaPO -nH O) by reacting large anionic particles with particles such as orthophosphate ions (PO ) in water bodies.
[25] Treatment efficiency above 90% can be obtained by using only a small amount of lanthanum ions (La +) because lanthanum ion (La +) reacts with orthophosphate ion (PO 4 ) in the molar ratio of 1 : 1 even under various conditions of water bodies. Related reaction formula is described as follows. [26] [Reaction formula 1] [27] La3+ + PO 4 3" > LaPO 4
[28] Alum (Al (SO ) -14H O) is described in relation to lanthanum ions. Alum is
2 4 3 2 generally used because it is cheap. When alum is used, P reacts with aluminum (Al) theoretically in the molar ratio of 1 : 1. However, a large amount of flocculant (high than the molar ratio of 1:2) is required during actual treatment depending on characteristics of water bodies (alkalinity).
[29] AlPO formed by removing P with alum is regarded as a material that is hardly dissolved. However, it is sensitive to pH, and P is dissolved when pH is below 5.5 and above 8.5.
[30] Lanthanum phosphate (LaPO ), which is different from alum having the above described problems, formed according to the present invention is a stable and hardly dissolved material having a solubility product constant (Ksp)of 10 ~ 10 in a wide range of pH 4 - 11.
[31] Zeolite has a function of physical absorption and of substitution of cations, and establishes rapid fixation of heavy metals and ammonium ions (NH +) in water.
[32] Zeolite is a three-dimensional inorganic polymer having a typical skeleton in which
silicon (Si) atom and aluminum (Al) atom are each bonded through 4 oxygen atom bridges. Zeolite has a negative electric charge because Al atom is bonded to 4 oxygen atoms, and various cations (M+) exist to compensate for the negative electric charge.
[33] Zeolite has generally uniform micropores and various micropores having a size of 3
~ 20 (10-10 m). The surface area of a micropore in zeolite is generally 1000 m /g and such a wide surface area has an advantage that active sites may be distributed in a wide range.
[34] Cations in micropores of zeolite can easily be exchanged by various other metals and organic cations in water solution. Calcium (Ca +) ions and magnesium (Mg +) ions in water are exchanged by sodium (Na+) ions by using the above described property, and thereby converting hard water into soft water. One of significant characteristics of a method for removing ammonia using zeolite is that removal ratio is high when temperature is below 150C.
[35] Technical features of a mixture of lanthanum (La +) and zeolite that is used as an agent for simultaneously treating N, P and microalgae are described.
[36] 0.01 ~ 2.00wt% of lanthanum (La +) is used with respect to the total weight of the mixture. If a mixing ratio of lanthanum is below 0.0 lwt %, excessive input of a mixture of lanthanum (La +) and zeolite is required to remove P in water bodies that are eutrophic and results in a large amount of deposit. If a mixing ratio of lanthanum is above 2.00wt%, a mixture of lanthanum (La +) and zeolite loses competitiveness in price, and it is preferable to use 0.01 ~ 2.00wt% of lanthanum.
[37] 98.00 ~ 99.99wt% of zeolite is used with respect to the total weight of mixture. If a mixing ratio of zeolite is below 98.00wt%, long reaction time is required to simultaneously remove N and P, and precipitation speed of small suspended solids decreases. If a mixing ratio of zeolite is above 99.99wt%, a mixture of lanthanum (La + ) and zeolite can not be applied for removal of P in water bodies, and it is preferable to use 93.00 ~ 99.99wt% of zeolite.
[38] Additionally, zeolite, which is used as a binder of lanthanum, may be replaced by an inorganic material having a precipitation property, for example clay minerals such as smectite, goethite, silica mineral and bentonite.
[39] Zeolite is a supporter of lanthanum (La +) ions and a mixing ratio of zeolite may be adjusted between 93.00 ~ 99.98wt% depending on the amount of lanthanum, additive and flocculant. Technical features of a mixture of lanthanum (La +) and zeolite added by a small amount of an additive or flocculant are described.
[40] An agent for simultaneously treating N, P and microalgae comprises 0.01 ~
2.00wt% of lanthanum (La3+), 93.00 ~ 99.98wt% of zeolite, and 0.01 ~ 5.00wt% of an additive (surfactant) or flocculant.
[41] The additive is one selected from a surfactant and isopropanol. If the additive is a
surfactant, the surfactant acts as a pore forming agent and helps to increase surface area. It is preferable that the surfactant is used in the amount of 0.01 ~ 2.00% with respect to the total weight of the agent, and lanthanum is uniformly absorbed to zeolite by distributing lanthanum widely. If the additive is isopropanol, isopropanol forms aerogel and ester bonds are induced by adding acetic acid.
[42] The flocculant is at least one selected from inorganic electrolyte and organic high polymer compound. The inorganic electrolyte is at least one selected from the group consisting of calcium hydroxide, alum, aluminum chloride, iron sulfate (III) and iron sulfate (II), and floe is formed by making electric potential on surfaces of particles in liquor near zero and removing electrical repulsive force between particles.
[43] The organic high polymer compound is at least one selected from starches, poly- acrylamides and derivatives thereof. The starches coagulate by increase or decrease of colloidal phenomena. The polyacrylamides and derivatives thereof attract particles by bridge actions of molecules absorbed to particles.
[44] Referring to the above description, a preparation method of an agent for simultaneously treating N, P and microalgae according to the present invention is described.
[45] Firstly, an agent for simultaneously treating N, P and microalgae is prepared by mixing lanthanum ions and zeolite as follows. 98.00 ~ 99.99wt% of zeolite and 0.01 ~ 2.00wt% of 0.5 - 1% water solution of lanthanum are poured into an agitator and stirred for mixing for 1 - 48 hours, a stirred mixture thereof is separated by a centrifugal separator at 10,000 ~ 20,000 rpm for 5 - 10 minutes, supernatant thereof after centrifugal separation is separately stored for reuse, particles separated by the centrifugal separator are dried at a room temperature for 24 hours and are hardened at 105 - 2000C at 1 - 3 hours, the hardened particles are input to the supernatant, namely 0.5 - 1% lanthanum water solution, and a series of processes of agitation, centrifugal separation, drying and hardening is repeated 3 times under the same conditions as those described in the above.
[46] Secondly, another agent for simultaneously treating N, P and microalgae is prepared by mixing lanthanum ions and zeolite added by an additive or flocculant as follows. Isopropanol and acetic acid are added to a surfactant such as polyoxyethyene sorbitan monooleate and lanthanum ions to make a sol state (colloid that has a continuous liquid phase in which a solid is suspended in a liquid with fluidity) in which the surfactant and lanthanum ions exist,
[47] A mixture of the lanthanum ions and surfactant in a sol state is coated on zeolite which is a supporter. To coat a mixture of the lanthanum ions and surfactant in a sol state on zeolite, zeolite and the mixture of the lanthanum ions and surfactant in a sol state are stirred together for 1 - 48 hours, and separated centrifugally at 10,000 - 20,000 rpm for 5 - 10 minutes.
[48] Supernatant thereof is stored for reuse, particles separated centrifugally are dried in a room temperature for 20 ~ 30 hours, and the dried particles are hardened at 105 ~ 2000C for 1 ~ 3 hours.
[49] Drying in a room temperature is used to maintain supercritical dried state of absorbed lanthanum in a sol state and hydrophile property of the surfactant, and to completely remove moisture that is adhered to the formed particles, and the dried particles are hardened at 105 ~ 2000C for 1 ~ 3hours after drying at a room temperature to adjust strength of the prepared agent.
[50] As described in the above, an agent according the present invention is prepared by mixing zeolite with lanthanum ions, or by adding an additive or flocculant to a mixture of lanthanum ions and zeolite for a synergy effect and uniform dispersion.
[51] Lanthanum ions (La +) in water bodies react with orthophosphate (PO ) in a molar ratio of 1:1 to form chemically very stable lanthanum phosphate (LaPO -nH O) having
94 S 98 1 a solubility product constant (Ksp) of 10 ~ 10" , P in which is not dissolved again. [52] Zeolite used as a supporter of lanthanum ions does not remove large anionic particles. However zeolite has an excellent absorption ability of organic materials and excellent selective absorption ability of NH 4 + ions, which is ion exchange ability that
Ig of zeolite can absorb 5.56 mg of NH +-N. When zeolite is used together with aluminum and calcium, precipitation speed is increased by increase in the specific gravity of floe, and P and suspended solids such as microalgae may be precipitated together.
Advantageous Effects
[53] As described in the above, an agent for simultaneously treating N, P and microalgae according to the present invention can simultaneously remove N and P that can induce eutrophication in water bodies (lakes, marshes and dam). High treatment efficiency may be expected even in the case of water bloom of algae because it has excellent absorption ability due to zeolite and acts as a flocculant, and suspended solids of dead algae may be removed by precipitating them.
[54] An agent according to the present invention provides an environment friendly agent that accelerates precipitation speed and thereby maximizing the treatment efficiency in a short period, treated N and P do not dissolve again under any change of environment conditions (sediment), and finally formed materials (deposit) are not environmentally toxic.
[55]
Brief Description of the Drawings
[56] The features and advantages of the present invention will be more apparent from the following detailed description in conjunction with the accompanying drawings, in
which:
[57] Figure 1 is a cross-sectional view schematically showing an agent for simultaneously treating N, P and microalgae according to the present invention; [58] Figure 2 is a graph showing an EDX (Energy Dispersive X-ray) analysis result for an agent for simultaneously treating N, P and microalgae according to Example 4 of the present invention; and [59] Figure 3 is a graph showing an amount of N and P simultaneously removed by a mixed compound of La, zeolite and flocculant according to the present invention. [60] <Brief Description of Symbols in the Drawings>
[61] 1: agent
[62] 10: zeolite
[63] 20: flocculant
[64] 30: lanthanum ion
[65]
Best Mode for Carrying Out the Invention [66] Technical features of the present invention are described in detail with reference to exemplary embodiments. Although exemplary embodiments of the present invention have been described in detail hereinafter, it should be understood that many variations and modifications of the basic inventive concepts herein taught will still fall within the spirit and scope of the present invention. [67]
[68] Agent for simultaneously treating nitrogen (N). phosphorus (P). and microalgae
[69] Example 1
[70] An agent for simultaneously treating N, P and microalgae according to the present invention is prepared by mixing 2.00 g of lanthanum ions (La +), which is a rare-earth metal, and 98.00 g of zeolite. [71] Example 2
[72] An agent for simultaneously treating N, P and microalgae according to the present invention is prepared by mixing 0.01 g of lanthanum ions (La +), which is a rare-earth metal, 99.98 g of zeolite and 0.01 g of polyoxyethyene sorbitan monooleate which is a surfactant.
[73] Example 3
[74] An agent for simultaneously treating N, P and microalgae according to the present invention is prepared by mixing 2.00 g of lanthanum ions (La +), which is a rare-earth metal, 96.00 g of zeolite and 2.00 g of aluminum chloride. [75] [76] Preparation method of an Agent for simultaneously treating nitrogen (N).
phosphorus (P). and microalgae
[77] Example 4
[78] An agent for simultaneously treating N, P and microalgae according to the present invention is prepared as follows. 98.00 g of zeolite is put into 2 g of 1% water solution of lanthanum, a mixture thereof is mixed for 5 hours by an agitator and is separated centrifugally at 10,000 rpm for 5 minutes, supernatant thereof is separately stored for reuse, and particles separated by centrifugal separation are dried at a room temperature for 24 hours and are hardened at 1050C for lhour.
[79] The hardened particles are added to the separately stored supernatant, namely 1% water solution of lanthanum, and processes of stirring, separation and drying are repeated three times under the same conditions as those of the above processes to complete the preparation of the agent for simultaneously treating N, P and microalgae.
[80]
Mode for the Invention
[81] Technical features of the present invention are described hereafter in more detail with reference to drawings.
[82] Figure 1 schematically shows an agent for simultaneously treating N, P and microalgae, Figure 2 shows an EDX (Energy Dispersive X-ray) analysis result for an agent for simultaneously treating N, P and microalgae, and Figure 3 shows an amount of N and P simultaneously removed by a mixed compound of lanthanum, zeolite and flocculant.
[83] As shown in Figure 1, an agent for simultaneously treating N, P and microalgae is an agent (1) formed by utilizing lanthanum ions (La +) to insolubilize P and zeolite to insolubilize N.
[84] Nutrient salts (P, N) in water bodies may be simultaneously removed with only a small amount of the agent (1).
[85] N is removed by zeolite (10), P is removed by lanthanum ions (30), and N, P and microalgae are removed simultaneously by a synergy effect of increasing precipitation speed of microalgae due to increase in the specific gravity of the agent formed by mixing.
[86] Turnover phenomena occur in water bodies (lakes, marshes and dams) in spring and autumn in the Republic of Korea, and water bodies are turbid for a long time due to the influx of deposited materials when it rains heavily. Water bloom of algae occurs due to the excessive influx of nutrient salts (N, P) during July and August. Algae die and float in water in early autumn. Yellow earth has been used to precipitate dead algae which float in water, and has a disadvantage that precipitation speed of it is slow because it can not act as a flocculant (20). However, the agent (1) according to the present
invention accelerates precipitation speed because it induces physicochemical precipitation due to the specific gravity of zeolite and has a property of a flocculant.
[87] Additionally, because the agent (1) according to the present invention is prepared considering selective absorption, exchange reaction and physicochemical precipitation, it has less influence on ecosystem of water bodies, effective treatment of nutrient salts (N, P) and high precipitation speed can be expected even when a small amount of it is used, the size of finally formed materials (deposit) is small as it is within lmm, re- dissolution of nutrient salts (N, P) may be prevented under any change of environmental conditions because it contains lanthanum phosphate(LaPO nH O)and zeolite that are natural minerals and is a stable material which is hardly soluble, and nutrient salts (N, P) in sediment may be expected to be removed.
[88] Figure 2 shows an Energy Dispersive X-ray (EDX) analysis result for an agent for simultaneously treating N, P and microalgae according to Example 4 of the present invention. Composition of the agent is shown in Table 1.
[89] Table 1 EDX analysis of agent of Example 4
[90] [91] Figure 3 is a graph showing an amount of nutrient salts (N, P) simultaneously removed by the agent (1).
[92] 1 g of zeolite and lanthanum ions (La +) are injected to synthesized wastewater (NH +- N: 5mg, PO : 2.5mg) by changing the injected amount of lanthanum ions (La +). It is observed that, as the injected amount of lanthanum ions (La +) increases, removal efficiency of P increases, and removal efficiency of ammoniac N is about 40%.
[93] [94]
Claims
[1] An agent for simultaneously treating nitrogen (N) and phosphorus (P) to prevent eutrophication of water bodies prepared by mixing 98.00 ~ 99.99wt% of zeolite and 0.01 ~ 2.00wt% of a rare-earth metal, wherein the rare-earth metal is at least one selected from the group consisting of lanthanum (La), cerium (Ce), zirconium (Zr), praseodymium (Pr), neodymium (Nd), promethium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc).
[2] An agent for simultaneously treating nitrogen (N) and phosphorus (P) to prevent eutrophication of water bodies prepared by mixing 93.00 ~ 99.98wt% of zeolite, 0.01 ~ 2.00wt% of a rare-earth metal, and 0.01 ~ 5.00wt% of an additive or flocculant, wherein the rare-earth metal is at least one selected from the group consisting of lanthanum (La), cerium (Ce), zirconium (Zr), praseodymium (Pr), neodymium (Nd), promethium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc); the additive is one of a surfactant and isopropanol; and the flocculant is at least one selected from the group consisting of aluminum chloride, iron sulfate (III), iron sulfate (II), starches, polyacrylamides and derivatives thereof.
[3] A preparation method of an agent for simultaneously treating nitrogen (N) and phosphorus (P) to prevent eutrophication of water bodies comprising: pouring 98.00 ~ 99.99 wt% of zeolite and 0.01 ~ 2.00wt% of 0.5 ~ 1% water solution of at least one rare-earth metal selected from the group consisting of lanthanum (La), cerium (Ce), zirconium (Zr), praseodymium (Pr), neodymium (Nd), promethium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc) into an agitator, and stirring a mixture thereof for 1 - 48 hours; separating centrifugally the stirred mixture at 10,000 ~ 20,000 rpm for 5 ~ 10 minutes; storing separately supernatant thereof after centrifugal separation for reuse, drying particles separated centrifugally at a room temperature for 24 hours, and hardening the dried particles at 105 ~ 2000C for 1 ~ 3 hours; and pouring the hardened particles into the supernatant and a series of processes of
stirring, centrifugal separation, drying and hardening is repeated three times under the same conditions as those of the above processes.
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| KR10-2007-0011797 | 2007-02-05 | ||
| KR1020070011797A KR100848605B1 (en) | 2007-02-05 | 2007-02-05 | Chemical reagent for the purpose of simultaneous treatment of n, p and microalgae for prevention eutrophication of water bodies |
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| WO2008096988A1 true WO2008096988A1 (en) | 2008-08-14 |
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| CN102399045A (en) * | 2010-09-13 | 2012-04-04 | 清华大学 | Composite medicament for fixing nitrogen and phosphorous in riverbed sludge, and preparation and application method thereof |
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| CN102399045A (en) * | 2010-09-13 | 2012-04-04 | 清华大学 | Composite medicament for fixing nitrogen and phosphorous in riverbed sludge, and preparation and application method thereof |
| CN103553194A (en) * | 2013-07-31 | 2014-02-05 | 乔占印 | Rear-earth poly aluminum ferric sulfate and preparation method thereof |
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| WO2019104941A1 (en) * | 2017-11-29 | 2019-06-06 | 环境保护部南京环境科学研究所 | Highly effective in situ treatment method for endogenous pollution in sludge |
| US11339074B2 (en) | 2017-11-29 | 2022-05-24 | Nanjing Institute Of Environmental Sciences, Ministry Of Ecology And Environment | Highly effective in situ treatment method for endogenous pollution in sludge |
| CN108083398A (en) * | 2017-12-07 | 2018-05-29 | 重庆精创联合环保工程有限公司 | The processing method of industrial wastewater |
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