JP5831914B2 - Water treatment method - Google Patents
Water treatment method Download PDFInfo
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- JP5831914B2 JP5831914B2 JP2013231988A JP2013231988A JP5831914B2 JP 5831914 B2 JP5831914 B2 JP 5831914B2 JP 2013231988 A JP2013231988 A JP 2013231988A JP 2013231988 A JP2013231988 A JP 2013231988A JP 5831914 B2 JP5831914 B2 JP 5831914B2
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- fluorine
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- 238000011282 treatment Methods 0.000 title claims description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 123
- 229910001868 water Inorganic materials 0.000 title claims description 123
- 238000000034 method Methods 0.000 title claims description 79
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 78
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 78
- 229910052796 boron Inorganic materials 0.000 claims description 78
- 239000002351 wastewater Substances 0.000 claims description 77
- 229910052731 fluorine Inorganic materials 0.000 claims description 53
- 239000011737 fluorine Substances 0.000 claims description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 49
- 239000000292 calcium oxide Substances 0.000 claims description 39
- 235000012255 calcium oxide Nutrition 0.000 claims description 39
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 27
- 239000000920 calcium hydroxide Substances 0.000 claims description 27
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 27
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 25
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 14
- 239000011669 selenium Substances 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- 150000002506 iron compounds Chemical class 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 21
- 230000000694 effects Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003546 flue gas Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 7
- 229910052785 arsenic Inorganic materials 0.000 description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- -1 fluorine ions Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100399296 Mus musculus Lime1 gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000339 iron disulfide Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Description
本発明は、塩化物イオン等の共存する排水、あるいはホウ素・フッ素の共存する排水中のホウ素、フッ素等の効率的除去を行うための水処理剤、及びこれらの水処理剤を用いた水処理方法に関する。 The present invention relates to a water treatment agent for efficiently removing boron, fluorine and the like in wastewater coexisting with chloride ions or the like, or wastewater coexisting with boron and fluorine, and water treatment using these water treatment agents. Regarding the method.
ホウ素・フッ素は、工業原料、下水、廃棄物等に含まれるとともに、自然界にも多く存在する。最近の環境省の調査では、製造事業場のうちホウ素化合物を使用する事業場は19%、フッ素化合物を使用する事業場は22%となっており、これらを用いる製造事業場は非常に多い。 Boron and fluorine are contained in industrial raw materials, sewage, waste, etc., and are also present in nature. According to a recent survey by the Ministry of the Environment, 19% of manufacturing establishments use boron compounds and 22% use fluorine compounds, and there are very many manufacturing establishments using these.
経済産業省、環境省が作成した平成18年度PRTR資料によると、公共水域への有害物質の排出量は、ホウ素及びその化合物、フッ化水素及びその水溶液塩、マンガン及びその化合物、亜鉛の水溶性化合物などの順となっている。また、公共水域に排出される対象化学物質合計排出量100,500t/年のうち、ホウ素及びその化合物は29%、さらにフッ素化合物及びその水溶塩は26%と上位の2種を占めている。従って、ホウ素、フッ素の新規で有効な排水処理技術を確立することは社会的に大いに意義がある。 According to the 2006 PRTR data prepared by the Ministry of Economy, Trade and Industry and the Ministry of the Environment, the amount of harmful substances released into public water bodies is boron and its compounds, hydrogen fluoride and its aqueous salts, manganese and its compounds, and the water solubility of zinc. It is in order of compounds. In addition, boron and its compounds account for 29%, and fluorine compounds and their water salts account for 26% of the total amount of target chemical substances discharged into public waters of 100,500t / year. Therefore, establishing a new and effective wastewater treatment technology for boron and fluorine has great social significance.
一方、ホウ素・フッ素等の排水規制については、平成11年に、WHO飲用水質ガイドラインや水道水水質基準等を参考に、環境基準が設定された。これを受けて、平成13年には新たなホウ素・フッ素等に関する排水基準として、ホウ素及びその化合物:10mg/L以下、フッ素及びその化合物:8mg/L以下の一律排水基準が設定された。 On the other hand, environmental regulations were established in 1999 with regard to regulations on drainage of boron, fluorine, etc., referring to WHO drinking water quality guidelines and tap water quality standards. Accordingly, in 2001, new drainage standards for boron and fluorine, etc. were set as uniform drainage standards for boron and its compounds: 10 mg / L or less and fluorine and its compounds: 8 mg / L or less.
しかしながら、実際の運用においては、経済的な処理方法が確立されていないため、技術的課題を有する業種については、3年の期限で暫定排水基準を設定し、さちに、26業種については、結果として平成19年7月まで暫定措置の延長がなされた。また、平成19年7月以降も、一部の業界においては暫定排水基準値の強化や暫定排水基準値のまま延長し運用が行われている。以上に述べた背景により、ホウ素フッ素の水処理を効率的に行う技術を確立することは、極めて社会的意義が大きいことである。 However, in the actual operation, the economic treatment method has not been established, so for industries with technical issues, provisional drainage standards were set with a three-year deadline. As a result, provisional measures were extended until July 2007. Since July 2007, in some industries, provisional drainage standard values have been strengthened and provisional drainage standard values have been extended for operation. Based on the background described above, it is extremely socially significant to establish a technique for efficiently performing water treatment of boron fluorine.
石炭火力発電所における排煙脱硫排水等は、石炭由来のホウ素、フッ素、ヒ素、セレン、六価クロムなどを含有する。なかでもホウ素の濃度レベルは数十〜数百mg/Lとなっており、排出量は最も多い。一般的な排煙脱硫排水には塩化物イオンが2,000〜8,000mg/L、硫酸イオンが3,000〜8,000mg/L含まれる。また、フッ素イオンは10〜50mg/L含まれ、そのために以下に述べるように排水処理が困難となる。 The flue gas desulfurization drainage in a coal-fired power plant contains boron, fluorine, arsenic, selenium, hexavalent chromium, etc. derived from coal. Among them, the concentration level of boron is several tens to several hundreds mg / L, and the discharge amount is the largest. General flue gas desulfurization waste water contains 2,000 to 8,000 mg / L of chloride ions and 3,000 to 8,000 mg / L of sulfate ions. Moreover, 10-50 mg / L of fluorine ions are contained, which makes it difficult to treat waste water as described below.
一方、最近では中国やインドの工業化に伴う石炭の消費量が増加し、これにより石炭価格の高騰が生じ、有害物質の含有量が多い石炭を使用する傾向となってきている。これにより、排煙脱硫排水に含まれるホウ素、フッ素、セレン等の濃度上昇は避けられず、これを効率的に、経済的に処理する技術の開発が求められている。 On the other hand, recently, the consumption of coal accompanying the industrialization of China and India has increased, which has led to a surge in coal prices and the tendency to use coal with a high content of harmful substances. As a result, an increase in the concentration of boron, fluorine, selenium, etc. contained in the flue gas desulfurization wastewater is unavoidable, and development of a technique for efficiently and economically treating this is required.
ホウ素の排水処理を行う既存技術としては、例えば、特許文献1では塩化物イオンを多く含むホウ素の水処理方法としてイオン交換樹脂を用い、これを再生して用いる方法が記載されている。これは通常の凝集分離法では塩化物が多い排水のホウ素を処理する効率が悪いことによる。また、特許文献2では、カルシウム塩とアルミニウム塩を用いた多段処理によるホウ素水処理方法が開示されている。これは1回の凝集分離処理のみでは処理効率が悪いため、この改善を行うために考案された方法である。 As an existing technique for performing wastewater treatment of boron, for example, Patent Document 1 describes a method of regenerating and using an ion exchange resin as a water treatment method for boron containing a large amount of chloride ions. This is because the efficiency of treating boron in wastewater containing a large amount of chloride is poor in the ordinary coagulation separation method. Patent Document 2 discloses a boron water treatment method by multistage treatment using calcium salt and aluminum salt. This is a method devised for making this improvement because the processing efficiency is poor only by one aggregation separation process.
特許文献3では硫酸アルミニウムと消石灰を用いた最適なホウ素水処理剤の調製方法などについて記載し、特許文献4ではカルシウム、アルミニウムイオンにより析出物を形成しホウ素を除去後、蒸留濃縮を組み合わせて行うホウ素の水処理方法について開示が行われている。また、文献5にはアルカリ土類金属とアルミニウム塩を加えて3工程に処理を分割し処理効率を高める方法などが提案されている。 Patent Document 3 describes an optimal method for preparing a boron water treatment agent using aluminum sulfate and slaked lime, and Patent Document 4 forms precipitates by removing calcium and aluminum ions, removes boron, and then combines distillation and concentration. Disclosed is a method for water treatment of boron. Further, Document 5 proposes a method of increasing the processing efficiency by adding alkaline earth metal and aluminum salt to divide the processing into three steps.
特許文献6においては、フッ素含有水をアルミニウム含有水と共に安定的に効率的に凝集処理を行う方法について示されている。 Patent Document 6 discloses a method for stably and efficiently agglomerating fluorine-containing water together with aluminum-containing water.
上記のように、これまでホウ素、フッ素の水処理方法として種々の関連技術が考案されてきたが、経済性の観点から、現在行われている処理方法は「硫酸バンド法」とよばれる消石灰と硫酸アルミニウムを用いた水処理方法とこれを多段処理やスラッジの返送プロセスなどと組合せることで効率化を図る方法が主流となっている。 As described above, various related technologies have been devised so far as water treatment methods for boron and fluorine. However, from the viewpoint of economy, the currently used treatment method is slaked lime called “sulfuric acid band method”. The mainstream is a water treatment method using aluminum sulfate and a method for improving efficiency by combining this with a multi-stage treatment, a sludge return process, and the like.
製造業における排水、廃棄物処分場の排水などには一般的に、塩化物イオンや硫酸イオンが高濃度で共存することが多い。しかしながら、前記の消石灰と硫酸アルミニウムによる水処理方法では、硫酸イオンによる阻害はほとんどないが、排水中に塩化物イオン等が含まれると、この影響で処理効果が大きく低下する問題点があった。また、ハイドロタルサイトなどの陰イオン吸着剤を用いる方法では、排水中に硫酸イオンや、塩化物イオンなどが共存する場合は、これらも吸着してしまうため、本来の優れた水処理効果を発揮することができない。従って、前記のように共存イオンが存在する排水処理では、現状では、ホウ素選択性が比較的高いイオン交換樹脂を用いる方法を行う以外にないが、この処理コストは非常に高価である。 In general, chloride ions and sulfate ions often coexist at a high concentration in wastewater from manufacturing industries, wastewater from waste disposal sites, and the like. However, in the water treatment method using slaked lime and aluminum sulfate, there is almost no inhibition by sulfate ions. However, if chloride ions or the like are contained in the waste water, there is a problem that the treatment effect is greatly reduced due to this influence. In addition, in the method using an anion adsorbent such as hydrotalcite, if sulfate ions or chloride ions coexist in the wastewater, they are also adsorbed, so that the original excellent water treatment effect is exhibited. Can not do it. Therefore, in the wastewater treatment in which coexisting ions exist as described above, at present, there is no other way but to perform a method using an ion exchange resin having a relatively high boron selectivity, but this treatment cost is very expensive.
また、ホウ素とフッ素が共存する排水においては、フッ素の選択性がホウ素より大きいため、ホウ素を低濃度まで除去することが困難となる問題点がある。このように、共存イオンの伴う排水中のホウ素処理については、以上の理由により未だ経済的な処理技術が確立させるに至っていない。 In addition, in wastewater in which boron and fluorine coexist, the selectivity of fluorine is larger than that of boron, so that it is difficult to remove boron to a low concentration. Thus, an economical treatment technique has not yet been established for the treatment of boron in wastewater accompanied by coexisting ions for the above reasons.
すなわち、本発明は、塩化物イオンが排水中に高濃度に含まれる排水やホウ素、フッ素の共存する排水においても、ホウ素、フッ素等の処理を行うための経済的かつ効果的な水処理剤及び水処理方法を提供することを目的とする。また、ホウ素、フッ素の排水処理は大企業のみならず、中小の様々な製造業やその他の産業でも課題となっており、シンプルで安価な処理装置を用いた水処理方法を提供することを目的とする。 That is, the present invention provides an economical and effective water treatment agent for treating boron, fluorine, etc. even in wastewater containing chloride ions in high concentration in wastewater and wastewater in which boron and fluorine coexist. An object is to provide a water treatment method. In addition, wastewater treatment of boron and fluorine is a problem not only in large companies but also in various small and medium-sized manufacturing industries and other industries. The purpose is to provide a water treatment method using a simple and inexpensive treatment device. And
本発明の水処理方法は、ホウ素、フッ素の両成分を含有する排水に、アルミニウムとカルシウムのモル比が1:5〜1:22の範囲になるように配合された硫酸アルミニウムと生石灰からなる水処理剤を添加し、ホウ素とフッ素を同時に除去してホウ素を10mg/L以下、かつ、フッ素を8mg/L以下とすることを特徴とする。 The water treatment method of the present invention is water comprising aluminum sulfate and quicklime mixed in a waste water containing both boron and fluorine components so that the molar ratio of aluminum to calcium is in the range of 1: 5 to 1:22. A treatment agent is added, and boron and fluorine are simultaneously removed to make boron 10 mg / L or less and fluorine 8 mg / L or less .
また、上記において、さらに消石灰を添加することを特徴とする。 In the above, slaked lime is further added.
また、上記において、さらに鉄化合物を添加し、セレンを除去することを特徴とする。 In the above, an iron compound is further added to remove selenium.
また、上記において、生石灰及び消石灰を粉末として排水に添加することを特徴とする。 Moreover, in the above, quick lime and slaked lime are added to waste water as powder.
また、上記において、生石灰及び消石灰の含有量が20質量%以下のスラリーを排水に添加することを特徴とする。 Moreover, in the above, the slurry whose content of quicklime and slaked lime is 20 mass% or less is added to waste water.
本発明の水処理剤及び水処理方法は、最も安価なアルカリ原料である生石灰、消石灰と硫酸アルミニウム、鉄化合物を用いるものである。本発明の水処理剤、水処理方法は排水中の塩化物イオンや硫酸イオンによる処理効果への阻害は少ない。本発明の水処理剤を排水に添加し混合攪拌を行うことで、従来技術では処理が困難であった塩化物イオンを含む排水や、あるいはホウ素、フッ素が共存する排水中のホウ素、フッ素処理を効率的に、経済的に行うことができる。また、この水処理剤はリン酸の除去等にも好適に用いることができる。 The water treatment agent and water treatment method of the present invention use quick lime, slaked lime, aluminum sulfate, and an iron compound, which are the least expensive alkali raw materials. In the water treatment agent and water treatment method of the present invention, there are few obstacles to the treatment effect by chloride ions or sulfate ions in the waste water. By adding the water treatment agent of the present invention to the wastewater and mixing and stirring, wastewater containing chloride ions, which has been difficult to treat with the prior art, or boron and fluorine treatment in wastewater in which boron and fluorine coexist are treated. It can be done efficiently and economically. Moreover, this water treatment agent can be used suitably also for the removal of phosphoric acid, etc.
前記、水処理剤に鉄化合物を混合して用いる場合は、排水中のホウ素、フッ素の処理に加え、セレン、ヒ素、六価クロム、鉛、カドミウム、水銀、銅、亜鉛、モリブデン、ニッケル、アンチモン等の有害イオンの除去を効率よく行うことが可能である。本発明では、このような特徴を生かしてフッ素やホウ素を併せて含む排煙脱硫排水や、フッ素と前記の有害物質等を共存する工場排水などの処理、地下水、土壌浸出水等の処理についても、確実に、効率よく行うことができる。 When mixing iron compounds with the water treatment agent, in addition to treating boron and fluorine in the wastewater, selenium, arsenic, hexavalent chromium, lead, cadmium, mercury, copper, zinc, molybdenum, nickel, antimony It is possible to efficiently remove harmful ions such as. In the present invention, by utilizing such characteristics, flue gas desulfurization drainage containing fluorine and boron together, factory drainage coexisting fluorine and the above-mentioned harmful substances, etc., groundwater, soil leachate treatment, etc. It can be done reliably and efficiently.
以下、本発明の水処理剤、水処理方法について詳細に説明する。 Hereinafter, the water treatment agent and the water treatment method of the present invention will be described in detail.
本発明の水処理剤は硫酸アルミニウムと安価なアルカリ原料である生石灰粉末とを用いる事を特徴とする。また、これに消石灰粉末を含有させても良く、さらに鉄化合物を含有させてもよい。 The water treatment agent of the present invention is characterized by using aluminum sulfate and quicklime powder which is an inexpensive alkali raw material. Further, this may contain slaked lime powder, and may further contain an iron compound.
本発明の水処理方法は前記水処理剤成分である生石灰、消石灰粉末を粉体のまま排水に添加する方法を特徴とする。あるいは、生石灰、消石灰粉末を濃度20質量%以下のスラリーとして排水に添加することを特徴とする。 The water treatment method of the present invention is characterized in that quick lime and slaked lime powder, which are the water treatment agent components, are added to waste water as powder. Alternatively, quick lime or slaked lime powder is added to the wastewater as a slurry having a concentration of 20% by mass or less.
本発明の水処理剤及び水処理方法は、上記によりホウ素、フッ素を含有する排水を効率よく処理することができ、また、これは塩化物イオンを高濃度に含んでいても大きな阻害を受けることはない。また、ホウ素、フッ素が共存する排水中でも、ホウ素、フッ素の両者を低濃度まで効率よく処理することが可能である。 The water treatment agent and water treatment method of the present invention can efficiently treat wastewater containing boron and fluorine as described above, and this is greatly hindered even when chloride ions are contained at a high concentration. There is no. Further, even in wastewater in which boron and fluorine coexist, both boron and fluorine can be efficiently treated to a low concentration.
本発明の水処理剤に鉄化合物を含有させる場合は、ホウ素、フッ素のほかにセレン、六価クロム、ヒ素、鉛、水銀、カドミウム、銅、亜鉛、モリブデン、ニッケル、アンチモンなどの処理も行うことができる。 When the water treatment agent of the present invention contains an iron compound, in addition to boron and fluorine, selenium, hexavalent chromium, arsenic, lead, mercury, cadmium, copper, zinc, molybdenum, nickel, antimony, etc. should also be treated. Can do.
本発明の水処理剤には硫酸アルミニウムを用いるが、これは粉末状でも、液状でも良い。このほか、アルミニウム原料として、塩化アルミニウム、ポリ塩化アルミニウム(PAC)、カリミョウバンなど、さらにはメタカオリン等のアルミニウム含有鉱物粉末などを硫酸アルミニウムと組み合わせて用いることが挙げることができるが、いずれもホウ素、フッ素を処理する場合の効率は低下する。 Although aluminum sulfate is used for the water treatment agent of the present invention, it may be powdery or liquid. In addition, as an aluminum raw material, aluminum chloride, polyaluminum chloride (PAC), potassium alum, etc., and further, aluminum-containing mineral powders such as metakaolin can be used in combination with aluminum sulfate. The efficiency when treating fluorine is reduced.
本発明の水処理剤として用いる生石灰は天然鉱物である石灰石(炭酸カルシウム)を900℃以上で焼成し、粒度調整を行ったものである。また、この生石灰に水を加えて水和反応を生じさせたものが消石灰となる。 The quicklime used as the water treatment agent of the present invention is obtained by calcining limestone (calcium carbonate), which is a natural mineral, at 900 ° C. or higher and adjusting the particle size. Moreover, what added water to this quicklime and produced the hydration reaction turns into slaked lime.
生石灰の一般的な工業製品としては、最大粒径百mm〜数十μm粒径の製品があるが、本発明の水処理には粒径0.5mm以下の物を用いることが望ましい。また、経済性の許す限り、細かい粒径であることが好ましい。 As a general industrial product of quicklime, there is a product having a maximum particle size of 100 mm to several tens of μm, but it is desirable to use a product having a particle size of 0.5 mm or less for the water treatment of the present invention. In addition, it is preferable that the particle diameter is as small as economic efficiency allows.
また、本発明の水処理剤は消石灰を含有させて用いることができる。この消石灰の粒径につては粒径0.6mm以下のものを用いることが好ましい。 Moreover, the water treatment agent of this invention can be made to contain slaked lime. It is preferable to use a slaked lime having a particle size of 0.6 mm or less.
前記のように、アルミニウム化合物、カルシウム化合物を組み合わせたホウ素、フッ素の水処理方法は従来から行われているが、これまでに生石灰を用いた技術は行われていない。これは生石灰が消石灰の前駆物質としてのみ認識されていること、水処理方法においては液状やスラリー化して排水に水処理剤を添加することが一般的であるが、これが困難であること、さらには生石灰は水と反応して強熱を発生するため保管管理が不良であると火災等の危険性がある物質であることなどが、原因であると思われる。 As described above, the water treatment method for boron and fluorine combined with an aluminum compound and a calcium compound has been conventionally performed, but no technique using quick lime has been performed so far. This is because quick lime is recognized only as a precursor of slaked lime, and in the water treatment method, it is common to add a water treatment agent to the wastewater in a liquid or slurry state, but this is difficult, It seems that quick lime reacts with water and generates a high temperature, so if the storage management is poor, it is a dangerous substance such as a fire.
しかしながら、本発明では、生石灰を利用することにより、以下に述べるように塩化物イオン共存下でも、ホウ素やフッ素を有効に処理することができることを見いだした。また、本水処理剤はフッ素イオン共存下でも低濃度までホウ素を処理することができる。これは、生石灰の活性が高いため、効率よくアルミン酸カルシウム化合物を形成するため、優れた水処理効果が生ずるものであると考えられる。また、本発明の水処理方法は、反応により生じる沈殿による固液分離のスピードも早く、水処理時間を短縮し、設備を小容量とすることができるなどの利点も挙げられる。 However, the present invention has found that by using quicklime, boron and fluorine can be effectively treated even in the presence of chloride ions as described below. Further, the present water treatment agent can treat boron to a low concentration even in the presence of fluorine ions. This is considered to be because the quick lime activity is high, and the calcium aluminate compound is efficiently formed, so that an excellent water treatment effect is produced. In addition, the water treatment method of the present invention has advantages such that the speed of solid-liquid separation due to precipitation caused by the reaction is fast, the water treatment time is shortened, and the equipment can be reduced in capacity.
本水処理剤においては、生石灰と消石灰を混合して使用することができる。これにより、保管時の危険性を低減することができる。実施に示すように生石灰原料の20〜30質量%を消石灰に置き換えても処理効果に大きな低下は生じず、塩化物イオンの共存する排水等の処理等に用いることができる。 In this water treatment agent, quick lime and slaked lime can be mixed and used. Thereby, the danger at the time of storage can be reduced. Even if 20-30 mass% of quicklime raw materials are replaced with slaked lime as shown in practice, the treatment effect is not greatly reduced, and can be used for treatment of waste water and the like in which chloride ions coexist.
本発明の水処理において、優れた水処理効果を得るためには、生石灰を粉末のまま排水に添加する方法が好ましい。また、濃度20質量%以下のスラリーとして添加することができる。これに対して消石灰を用いる従来の水処理法においては30%程度のスラリーとして使用する方法が一般的である。 In the water treatment of the present invention, in order to obtain an excellent water treatment effect, a method of adding quick lime as powder to waste water is preferable. Moreover, it can add as a slurry of a density | concentration of 20 mass% or less. On the other hand, in the conventional water treatment method using slaked lime, a method of using it as a slurry of about 30% is common.
本発明の水処理剤を構成するもう1種の原料である硫酸アルミニウムは含水粉末品あるいは液状品であるため、生石灰とは事前に混合せず別々に排水に添加を行わねばなない。添加する手順は硫酸アルミニウムを排水中に溶解させてから生石灰等を添加する方法が好ましいが、ほぼ同時に添加しても効果が低下することはない。なお、硫酸アルミニウムには、無水の粉末もあるが、これは水に溶解しにくいため好ましくない。 Since aluminum sulfate, which is another raw material constituting the water treatment agent of the present invention, is a water-containing powder product or a liquid product, it must be added separately to the wastewater without being mixed with quicklime. The method of adding aluminum sulfate is preferably a method of adding quicklime after dissolving aluminum sulfate in the waste water, but the effect is not lowered even if it is added almost simultaneously. In addition, although aluminum sulfate also has an anhydrous powder, this is not preferable because it is difficult to dissolve in water.
本発明の水処理剤を用いて、全体処理時間を30分程度でホウ素の水処理を行う場合には、排水のpHや共存イオン、本水処理剤添加量にもよるが、通常の場合は硫酸アルミニウム:生石灰の重量比を概ね1:2〜1:8の範囲に調整することが好ましい。また、これはAl:Caのモル比が、1:5〜1:22の範囲となり、これまでの先行技術で検討されてきた組成のバランスとはかなり異なるものとなる。 When the water treatment of the present invention is used to treat boron with an overall treatment time of about 30 minutes, it depends on the pH of the wastewater, the coexisting ions, and the amount of the water treatment agent added. It is preferable to adjust the weight ratio of aluminum sulfate: quick lime to a range of approximately 1: 2 to 1: 8. In addition, the molar ratio of Al: Ca is in the range of 1: 5 to 1:22, which is considerably different from the compositional balance studied in the prior art.
また、フッ素の処理を行うときは、前記より硫酸アルミニウム添加割合を増加させ、前記のpH範囲となるように配合を行う。 Moreover, when performing a process of fluorine, it mix | blends so that the addition rate of aluminum sulfate may be increased from the above and it may become the said pH range.
本発明の水処理剤には、さらに鉄化合物を加えて用いることができる。鉄化合物としては硫化鉄鉱粉末、硫酸鉄(II、III)、塩化鉄(II、III)、水酸化鉄(II、III)、酸化鉄(II、III)、四三酸化鉄、鉄粉などが挙げられる。 An iron compound can be further added to the water treatment agent of the present invention. Iron compounds include iron sulfide ore powder, iron sulfate (II, III), iron chloride (II, III), iron hydroxide (II, III), iron oxide (II, III), iron trioxide, iron powder, etc. Can be mentioned.
硫化鉄鉱としては二硫化鉄、黄鉄鉱、白鉄鉱、磁硫鉄鉱を用いることができ、これらは、水処理剤の反応活性を高めるため、1.0mm以下、好ましくは0.2mm以下に粉砕して使用することが好ましい。また、硫化鉄の純度は高いほど水処理効果は高く、80%以上の純度をもつものが好ましい。 Iron sulfide, pyrite, pyrite, pyrrhotite, and pyrrhotite can be used as the iron sulfide ore, and these are used by pulverizing to 1.0 mm or less, preferably 0.2 mm or less in order to increase the reaction activity of the water treatment agent. It is preferable to do. Further, the higher the purity of iron sulfide, the higher the water treatment effect, and those having a purity of 80% or more are preferred.
硫化鉄鉱粉末を加えることで、ホウ素、フッ素の処理に加えて、排水中の鉛、水銀、カドミウム、亜鉛、銅やその他の重金属類、六価クロム、セレン、ヒ素、アンチモンなどの水処理を行うことができる。また、石炭火力発電所の排煙脱硫排水中のホウ素、フッ素とともにセレン、水銀などの有害イオンの除去を行うことができる。また、排煙脱硫排水と同種の排水として石炭火力発電所等における貯炭場の排水、石炭灰埋め立て処分場の浸出水等が挙げられる。 By adding iron sulfide powder, water treatment of lead, mercury, cadmium, zinc, copper and other heavy metals, hexavalent chromium, selenium, arsenic, antimony, etc. in wastewater is performed in addition to treatment of boron and fluorine. be able to. In addition, harmful ions such as selenium and mercury can be removed together with boron and fluorine in the flue gas desulfurization effluent of a coal-fired power plant. In addition, wastewater of the same type as flue gas desulfurization wastewater includes wastewater from coal storage in coal-fired power plants and leachate from landfills for coal ash.
硫化鉄鉱の硫黄成分はヒ素、セレンなどと交換する性質をもち、この性質により、これらの成分を除去することができる。また、硫酸アルミニウム由来の硫酸イオンは、硫化鉄鉱表面に作用し、硫化鉄鉱の酸化分解を促進する機能をもっており、これにより比較的短時間に優れた水処理効果を得ることができる。 The sulfur component of the pyrite has the property of exchanging with arsenic, selenium, etc., and these components can be removed by this property. Moreover, the sulfate ion derived from aluminum sulfate acts on the iron sulfide ore surface and has a function of promoting the oxidative decomposition of the iron sulfide ore, whereby an excellent water treatment effect can be obtained in a relatively short time.
また、本発明の水処理剤に硫酸鉄(II、III)、塩化鉄(II、III)、水酸化鉄(II、III)、酸化鉄(II、III)、四三酸化鉄、鉄粉などの鉄化合物を加えることにより、ホウ素、フッ素の処理に加えて、ヒ素、六価クロム、セレン、アンチモンなどの処理をホウ素、フッ素の処理と同時に行うことができる。 Further, the water treatment agent of the present invention includes iron sulfate (II, III), iron chloride (II, III), iron hydroxide (II, III), iron oxide (II, III), iron trioxide, iron powder, etc. In addition to the treatment of boron and fluorine, the treatment of arsenic, hexavalent chromium, selenium, antimony and the like can be performed simultaneously with the treatment of boron and fluorine.
上記の各物質の処理方法においては、特にヒ素を処理する場合はpH10以下とし、また、セレン、アンチモンの処理を行うためにはpHを10以上とする事が好ましい。 In the above-described methods for treating each substance, the pH is preferably 10 or less when treating arsenic, and the pH is preferably 10 or more for treating selenium and antimony.
上記の鉄化合物は排水中に粉末として添加しても良いが、液体またはスラリーとして添加することが好ましい。 The iron compound may be added as powder to the waste water, but it is preferably added as a liquid or slurry.
本発明の水処理剤には、pH調整剤、副原料として、さらアルカリ、アルカリ土類金属元素含有原料を含有させることができる。アルカリ、アルカリ土類金属元素含有原料としては、水酸化ナトリウム、硫酸ナトリウム、消石灰、焼石膏、石灰石粉末、軽焼マグネシウム、硫酸マグネシウム、焼成ドロマイトからなる群のうち少なくとも1種を用いることができる。 The water treatment agent of the present invention may further contain alkali and alkaline earth metal element-containing raw materials as pH adjusters and auxiliary raw materials. As the alkali or alkaline earth metal element-containing raw material, at least one selected from the group consisting of sodium hydroxide, sodium sulfate, slaked lime, calcined gypsum, limestone powder, light calcined magnesium, magnesium sulfate and calcined dolomite can be used.
また、本発明の水処理剤においては、ポリアクリル酸系等の高分子凝集剤を組み合わせて用いてもよい。高分子凝集剤の併用により、ホウ素除去率を数パーセント向上させることができ、また水処理効果の安定性を高めることができる。 Further, in the water treatment agent of the present invention, a polymer flocculant such as polyacrylic acid may be used in combination. By using the polymer flocculant in combination, the boron removal rate can be improved by several percent, and the stability of the water treatment effect can be enhanced.
本発明の水処理剤は、前記の原料を用いたいわゆる凝集分離法タイプの水処理方法である。凝集分離法を用いた水処理方法は、通常、下のプロセスにより行われる。また、最近の設備では沈殿プロセスの替わりに膜分離プロセスを組み合わせることが行われている。膜分離方式を組み合わせる場合にはプラント設置面積を大きく減少できるメリットがある。 The water treatment agent of the present invention is a so-called coagulation separation type water treatment method using the above-mentioned raw materials. The water treatment method using the coagulation separation method is usually performed by the following process. In recent facilities, a membrane separation process is combined in place of the precipitation process. When the membrane separation method is combined, there is an advantage that the plant installation area can be greatly reduced.
(1)[反応プロセス]水処理剤を排水に添加し、均一に混合し化学反応を生じさせる反応プロセス。ここでは、回転速度100rpm〜300rpm程度で攪拌を行う。必要な場合はここでpH調整剤を添加する。 (1) [Reaction process] A reaction process in which a water treatment agent is added to waste water and mixed uniformly to cause a chemical reaction. Here, stirring is performed at a rotation speed of about 100 rpm to 300 rpm. If necessary, a pH adjuster is added here.
(2)[凝集プロセス]排水中にコロイドを形成し、これにホウ素、フッ素を固定する凝集プロセス。この段階では通常の硫酸アルミニウムを用いる方法では生じたコロイドのフロックを壊さないよう30〜50rpmの緩速で攪拌を行う。 (2) [Agglomeration process] An agglomeration process in which colloids are formed in the waste water, and boron and fluorine are fixed thereto. At this stage, stirring is carried out at a slow speed of 30 to 50 rpm so as not to break the colloidal floc generated by the usual method using aluminum sulfate.
(3)[沈殿プロセス(固液分離プロセス)]排水の攪拌を静止しコロイドを沈下させ、固液分離を行う沈殿プロセス。有害イオンはコロイドに固定されているため、この作用により排水中から分離される。沈殿はこの後、脱水機などで処理される。 (3) [Precipitation process (solid-liquid separation process)] A precipitation process in which the stirring of the waste water is stopped and the colloid is allowed to settle to perform solid-liquid separation. Since harmful ions are fixed to the colloid, they are separated from the waste water by this action. The precipitate is then processed with a dehydrator or the like.
(4)[pH調整プロセス]ここでは排水基準に適合するよう排水のpHを調整する。 (4) [pH adjustment process] Here, the pH of the waste water is adjusted to meet the waste water standard.
本発明の水処理方法において、優れた水処理効果を得るためには、(1)のプロセスにおいて生石灰、消石灰を粉末のまま排水に添加することが好ましい。また、生石灰、消石灰を20%以下、好ましくは15%以下のスラリーとして排水に添加することもできる。 In the water treatment method of the present invention, in order to obtain an excellent water treatment effect, it is preferable to add quick lime and slaked lime to the wastewater as powder in the process (1). Quick lime and slaked lime can be added to the wastewater as a slurry of 20% or less, preferably 15% or less.
生石灰を水中に添加すると発熱し水温が大きく上昇する。例えば、粒度が粒径0.5mm以下の生石灰粉末を水に対して30質量%添加した場合には、約60℃の温度上昇が生じ、夏期には沸点近くの温度となり、実際の処理に適用するためには様々な問題が生ずると思われる。このため、本発明では20質量%以下、好ましくは15質量%以下のスラリーとして排水に添加することが好ましい。 When quicklime is added to water, it generates heat and the water temperature rises greatly. For example, when quick lime powder having a particle size of 0.5 mm or less is added in an amount of 30% by mass with respect to water, the temperature rises by about 60 ° C. and becomes a temperature near the boiling point in the summer, and is applied to actual treatment. Various problems are likely to occur. For this reason, in this invention, it is preferable to add to a wastewater as a slurry of 20 mass% or less, preferably 15 mass% or less.
また、塩化物イオン等が共存する排水を処理する場合では、生石灰等をスラリーとして使用する方法においては、スラリーを調製後、可能な限り速やかに排水に添加することが好ましい。この一例として、塩化物イオン5000mg/L、ホウ素濃度500mg/Lの水処理に於いて、生石灰粉末を10質量%スラリーとして排水に添加した試験結果では、スラリー調製直後に排水に添加した場合は。粉末として添加する場合とホウ素処理能力は同一であるが、5分後に添加した場合は9%、30分後に添加した場合は46%ホウ素除去効率が低下する結果を得た。 Moreover, when processing the waste_water | drain with which chloride ion etc. coexist, in the method of using quicklime etc. as a slurry, it is preferable to add to a waste_water | drain as soon as possible after preparing a slurry. As an example of this, in the water treatment of chloride ion 5000 mg / L and boron concentration 500 mg / L, in the test result of adding quick lime powder as a 10% by mass slurry to the wastewater, when added to the wastewater immediately after slurry preparation. The boron treatment ability is the same as when added as a powder, but the boron removal efficiency is reduced by 9% when added after 5 minutes and 46% when added after 30 minutes.
また、本発明において硫酸アルミニウムは通常の水処理方法で行われているように、液状で添加してもよいし、また粉末として排水に添加をしてもよい。 Further, in the present invention, aluminum sulfate may be added in a liquid state as in a normal water treatment method, or may be added as a powder to waste water.
次に、本発明の水処理剤を用いた水処理においては、(2)の凝集プロセスにおける攪拌速度を前記の2〜3倍以上の回転速度である80rpm以上とすることが好ましく、100rpm以上で行うことがより好ましい。この理由は明らかになっていないが、本発明の水処理法においては、比較的密度の高い沈殿物が形成され、前記の攪拌速度では、固形分がうまく攪拌されないためだと思われる。 Next, in the water treatment using the water treatment agent of the present invention, the stirring speed in the aggregation process of (2) is preferably 80 rpm or more, which is a rotational speed of 2 to 3 times or more, and is 100 rpm or more. More preferably. The reason for this is not clear, but in the water treatment method of the present invention, it is considered that a precipitate with a relatively high density is formed, and the solid content is not stirred well at the above stirring speed.
本発明の水処理剤を用いて、ホウ素を含む水処理を行う場合は、排水のpHを9.0〜13.0の範囲にコントロールすることが好ましく、特にホウ素の濃度が高い場合は10.5〜12.5の範囲とすることがより好ましい。これはホウ素がpHと共に形態が変化することに起因しており、効率よく処理を行うためには前記の高アルカリとすることが好ましい。 When water treatment containing boron is performed using the water treatment agent of the present invention, it is preferable to control the pH of the waste water to a range of 9.0 to 13.0, particularly when the boron concentration is high. A range of 5 to 12.5 is more preferable. This is due to the fact that the form of boron changes with pH, and it is preferable to use the above-mentioned high alkali for efficient treatment.
次に本発明の水処理剤を用いて、フッ素を含む水処理を行う場合は排水のpHを5.0〜12.0の範囲とすることが好ましく、特にフッ素の濃度が高い場合は5.0〜9.0の範囲とすることがより好ましい。 Next, when water treatment containing fluorine is performed using the water treatment agent of the present invention, the pH of the waste water is preferably in the range of 5.0 to 12.0, particularly when the fluorine concentration is high. More preferably, it is in the range of 0 to 9.0.
ホウ素、フッ素の両者を含む排水は、それぞれの濃度にもよるがpH9.0〜12.0の範囲とすることが好ましい。また、どちらか、あるいは双方の濃度が高い場合は、先にpHを5.0〜9.0として最初のプロセスで先ずフッ素を処理し、次のステップで生石灰を追加しpH10.0〜12.5にまで上昇させ、ホウ素を処理する2プロセスを組み合わせて処理を行う方法などに適用することができる。 The waste water containing both boron and fluorine is preferably in the range of pH 9.0 to 12.0 depending on the respective concentrations. When either or both of the concentrations are high, the pH is first set to 5.0 to 9.0, and fluorine is first treated in the first process, and quick lime is added in the next step, and the pH is 10.0 to 12. The method can be applied to a method in which two processes for treating boron are combined and processed.
このpHのコントロールは、苛性ソーダや硫酸を用いても可能であるが、本発明の水処理剤の原料である硫酸アルミニウムと生石灰の添加量のバランスをコントロールするだけで、以下の実施例のように非常に効率よく処理を行うことができるため、この方法によることが好ましい。 This pH can be controlled by using caustic soda or sulfuric acid, but only by controlling the balance of the addition amount of aluminum sulfate and quicklime as the raw material of the water treatment agent of the present invention, as in the following examples. This method is preferable because processing can be performed very efficiently.
なお、本発明の水処理方法においては、水処理を多段に分割したり、処理水を循環して繰り返して行う方法やスラッジを返送し繰り返し水処理剤として利用する方法など、公知の水処理方法と組み合わせて実施することができる。 In the water treatment method of the present invention, known water treatment methods such as a method of dividing the water treatment into multiple stages, a method of repeatedly circulating the treated water, a method of returning sludge and repeatedly using it as a water treatment agent, etc. Can be implemented in combination.
本発明の水処理はこれまで述べてきたように、いわゆる凝集分離法に分類され、一般的にはシックナーやろ過処理により処理水と沈殿物を固液分離する方法を用いるが、前記の膜分離方式の処理等に適用することも可能である。 As described above, the water treatment of the present invention is classified as a so-called coagulation separation method, and generally uses a method of solid-liquid separation of treated water and precipitates by thickener or filtration treatment. It is also possible to apply to the processing of the method.
なお、本発明は上記の実施例に限定されるものでなく、本発明の要旨の範囲内において種々の変形実施が可能である。 In addition, this invention is not limited to said Example, A various deformation | transformation implementation is possible within the scope of the summary of this invention.
以下、具体例に基づき、さらに詳細に説明する。 Hereinafter, based on a specific example, it demonstrates in detail.
[模擬排水のホウ素水処理試験]
ホウ酸試薬、塩酸(濃度35〜36%)、水酸化ナトリウムを用いてホウ素濃度B:500mg/L、塩化物イオン濃度0〜10,000mg/Lの模擬排水を調整した。これに、表1に示す水処理剤を添加し、以下に記載する方法でホウ素水処理試験を実施した。
[Simulation wastewater boron water treatment test]
A simulated waste water having a boron concentration B of 500 mg / L and a chloride ion concentration of 0 to 10,000 mg / L was prepared using a boric acid reagent, hydrochloric acid (concentration 35 to 36%), and sodium hydroxide. The water treatment agent shown in Table 1 was added to this, and the boron water treatment test was implemented by the method described below.
(試験方法)
(1)試薬で調整したホウ素濃度500mg/Lの模擬排水を500mlビーカーに200ml分取し、所定配合の水処理剤を添加し、ホウ素等の水処理能力を評価する。
(Test method)
(1) 200 ml of simulated waste water with a boron concentration of 500 mg / L adjusted with a reagent is dispensed into a 500 ml beaker, a water treatment agent of a predetermined composition is added, and water treatment ability of boron or the like is evaluated.
(2)マグネティックスターラーを用いて回転速度300rpmで攪拌しながら2〜3種の水処理剤原料を粉末として同時に添加する。この時を試験開始とし、5分間溶液を撹拌する。ただし、実施例6においては、純水に生石灰粉末を10質量%投入しマグネティックスターラーで30秒攪拌してスラリーを調製し、調製後すぐに模擬排水に添加した。 (2) While stirring at a rotational speed of 300 rpm using a magnetic stirrer, two or three kinds of water treatment agent raw materials are simultaneously added as powder. At this time, the test is started and the solution is stirred for 5 minutes. However, in Example 6, 10% by mass of quicklime powder was added to pure water, stirred for 30 seconds with a magnetic stirrer to prepare a slurry, and added to the simulated waste water immediately after preparation.
(3)上記の作業の後、ジャーテスターにビーカーをセットし、回転速度を実施例1〜8においては100rpmに設定、比較例1〜5においては30rpmに設定し、さらに15分間撹拌を行う。その後、10分間溶液を静置し、沈殿を沈降させ固液分離を行う。(全体処理時間30分)
(4)吸引ろ過装置にろ紙(5C)をセットし、溶液を真空ろ過する。(pH測定)
(5)ろ液を使用し、ICPを用いてホウ素濃度を測定する。また、排水中に含有する場合はセレン濃度をICPにて測定、フッ素濃度をガラス電極で測定する。
(3) After the above operation, a beaker is set on the jar tester, the rotation speed is set to 100 rpm in Examples 1 to 8, and 30 rpm in Comparative Examples 1 to 5, and stirring is further performed for 15 minutes. Thereafter, the solution is allowed to stand for 10 minutes, the precipitate is allowed to settle, and solid-liquid separation is performed. (Total processing time 30 minutes)
(4) Set the filter paper (5C) on the suction filtration device, and vacuum filter the solution. (PH measurement)
(5) Using the filtrate, measure the boron concentration using ICP. Moreover, when it contains in waste_water | drain, a selenium density | concentration is measured by ICP and a fluorine concentration is measured by a glass electrode.
この試験結果は表2のとおりであった。 The test results are shown in Table 2.
本発明の水処理剤のホウ素処理結果を実施例1〜6に示した。本発明の水処理剤は、塩化物イオンが存在しないときは、下記の比較例1のいわゆる硫酸バンド法とよばれる方法よりも処理性能が低いが、塩化物イオン濃度が10,000mg/Lまで増加しても処理性能は全く低下をしない。また、生石灰の一部を消石灰と置き換えた実施例5では、処理効果が20%程度低下するが、比較例に比べて大きな処理性能を有する。さらにスラリーとして生石灰を添加した実施例6の試験結果では、ホウ素除去性能に低下は認められない。また、スラリーを調製したときの水温上昇は24℃であった。 The results of boron treatment of the water treatment agent of the present invention are shown in Examples 1-6. The water treatment agent of the present invention has lower treatment performance than the so-called sulfuric acid band method of Comparative Example 1 below when no chloride ions are present, but the chloride ion concentration is up to 10,000 mg / L. Even if it increases, processing performance does not decrease at all. Moreover, in Example 5 which replaced a part of quicklime with slaked lime, although a processing effect falls about 20%, it has a big processing performance compared with a comparative example. Furthermore, in the test results of Example 6 in which quick lime was added as a slurry, no decrease was observed in the boron removal performance. The water temperature rise when the slurry was prepared was 24 ° C.
一方、比較例1〜4に示した一般的手法である消石灰と硫酸アルミニウムを用いた試験結果は、塩化物イオンが存在しないときは処理効果が高く、水処理剤単位重量あたりのホウ素除去量は、17.5mg/kgと良好な処理性を示す。しかし、塩化物イオンの増加により処理性能が大きく低下し、10,000mg/L濃度では、ホウ素除去能力は本発明の水処理剤の1/3以下となる。 On the other hand, the test results using slaked lime and aluminum sulfate, which are general methods shown in Comparative Examples 1 to 4, have a high treatment effect when chloride ions are not present, and the boron removal amount per unit weight of the water treatment agent is 17.5 mg / kg and good processability. However, the treatment performance is greatly reduced due to an increase in chloride ions, and at a concentration of 10,000 mg / L, the boron removal ability becomes 1/3 or less of the water treatment agent of the present invention.
ここで、生石灰は上田石灰製造株式会社製、粒度−0.5mm、組成(CaO:94.8%、SiO2:0.7%、Al2O3:0.3%、Fe2O3:0.1%、MgO:0.9%、ig.loss:2.7%)、また、消石灰は上田石灰製造株式会社製、工業用特号、粒度−0.6mm、組成(CaO72.5質量%以上)のものを使用した。硫酸アルミニウムとしては、東信化学株式会社製、硫酸アルミニウム16水和物(Al2O3:16.0%)を使用した。また、塩酸は関東化学株式会社製の濃度35〜36%試薬を用いた。 Here, quicklime Ueda lime manufacturing Co., particle size -0.5 mm, the composition (CaO: 94.8%, SiO 2 : 0.7%, Al 2 O 3: 0.3%, Fe 2 O 3: 0.1%, MgO: 0.9%, ig.loss: 2.7%), and slaked lime manufactured by Ueda Lime Manufacturing Co., Ltd., industrial special number, particle size -0.6 mm, composition (CaO 72.5 mass) % Or more) was used. The aluminum sulfate, manufactured by Toshin Chemical Co., aluminum sulfate 16-hydrate was used (Al 2 O 3 16.0%) . Moreover, the concentration 35-36% reagent made from Kanto Chemical Co., Ltd. was used for hydrochloric acid.
[窯業における排水処理]
ここでは、ホウ素濃度95.1mg/L、フッ素濃度31.8mg/Lの窯業における排水の処理を検討する。排水中の両成分を一律排水基準値以下まで処理することが、水処理の目的である。(ホウ素:10mg/L以下、フッ素:8mg/L)この排水に以下の水処理剤を粉末として添加し、前記の方法で水処理試験を行った。
[Wastewater treatment in ceramics]
Here, wastewater treatment in a ceramic industry having a boron concentration of 95.1 mg / L and a fluorine concentration of 31.8 mg / L will be considered. The purpose of water treatment is to treat both components in the wastewater to a level equal to or lower than the wastewater standard value. (Boron: 10 mg / L or less, fluorine: 8 mg / L) The following water treatment agent was added as powder to this waste water, and a water treatment test was conducted by the above-described method.
この排水中に含まれる共存イオンなどの情報は次のとおりであった。 Information on the coexisting ions contained in this wastewater was as follows.
排水の組成等:Ca:31mg/L、Na:180mg/L、Al:11.3mg/L、Cl:117mg/L、pH:9.9
(実施例7)この排水に表1に記載した水処理剤を1.5質量%添加した。この結果は表3のとおりとなった。
Composition of drainage, etc .: Ca: 31 mg / L, Na: 180 mg / L, Al: 11.3 mg / L, Cl: 117 mg / L, pH: 9.9
(Example 7) The water treatment agent described in Table 1 was added to this waste water by 1.5% by mass. The results are shown in Table 3.
(比較例5)この排水に表1に記載した水処理剤を2.0質量%添加した。この結果は表3のとおりとなった。両方の処理において、溶液のpHは、原料の配合を変え、ほぼ同一の条件に調整した。 (Comparative Example 5) 2.0% by mass of the water treatment agent described in Table 1 was added to this waste water. The results are shown in Table 3. In both treatments, the pH of the solution was adjusted to almost the same conditions by changing the composition of the raw materials.
従来から行われている硫酸アルミニウム、消石灰による凝集沈殿方法では、フッ素共存の排水ではホウ素を低濃度まで低下させることは困難であると言われているが、本発明の水処理剤は、添加量1.5質量%で両成分が排水基準以下となり、ホウ素も低濃度まで除去されている。また、水処理剤単位重量あたりの除去量は、比較例に比べてホウ素処理で1.4倍、フッ素処理では2.0倍となっている。 It is said that it is difficult to reduce boron to a low concentration in wastewater coexisting with fluorine in the conventional method of coagulation and precipitation using aluminum sulfate and slaked lime. Both components are below the wastewater standard at 1.5% by mass, and boron is also removed to a low concentration. Moreover, the removal amount per unit weight of the water treatment agent is 1.4 times in the boron treatment and 2.0 times in the fluorine treatment as compared with the comparative example.
[排煙脱硫排水の処理]
ここでは、排煙脱硫排水の処理例を示す。石炭火力発電所から採取した脱硫排水にホウ酸試薬を添加し、ホウ素濃度をおよそ500mg/Lに調整を行った。調整後の排水の特性は以下のとおりであった。この排水に表1、実施例6に示した水処理剤を1.7質量%添加して、前記と同様の方法で水処理試験を実施した。この結果を表3に示す。
(排煙脱硫排水の特性)
・排水組成等:Ca:1210mg/l、Cl:3850mg/L、SO4:2510mg/L等、pH7.5
・有害イオン濃度:ホウ素濃度491mg/L(原水:185mg/L)、フッ素16.4mg/L、全セレン:0.55mg/L
表3、実施例8の結果に示すとおり本発明の水処理剤により、高濃度のホウ素を含有する排水を、全成分とも海域への排水基準以下まで極めて良好に処理することができた。また、この処理におけるホウ素の除去能力は20mg/gと極めて高い水準となった。(排水基準(海域):ホウ素:230mg/L、フッ素:15mg/L、全セレン:0.30mg/L)
ここで使用した二硫化鉄粉(黄鉄鉱粉)は、中国製粉砕品であり粒度100メッシュ以下、組成はFe:48.7質量%、S:45.9質量%、SiO2:4.1質量%の高純度なものである。また、生石灰、硫酸アルミニウムは前記と同じものを使用した。
[Treatment of flue gas desulfurization waste water]
Here, a processing example of flue gas desulfurization waste water is shown. A boric acid reagent was added to desulfurization effluent collected from a coal-fired power plant, and the boron concentration was adjusted to about 500 mg / L. The characteristics of the drainage after adjustment were as follows. To this waste water, 1.7% by mass of the water treatment agent shown in Table 1 and Example 6 was added, and a water treatment test was conducted in the same manner as described above. The results are shown in Table 3.
(Characteristics of flue gas desulfurization drainage)
-Wastewater composition, etc .: Ca: 1210 mg / l, Cl: 3850 mg / L, SO4: 2510 mg / L, etc., pH 7.5
Harmful ion concentration: Boron concentration 491 mg / L (raw water: 185 mg / L), fluorine 16.4 mg / L, total selenium: 0.55 mg / L
As shown in the results of Table 3 and Example 8, with the water treatment agent of the present invention, it was possible to treat wastewater containing high-concentration boron extremely well up to the standard for wastewater discharge to the sea area for all components. In addition, the boron removal ability in this treatment was as extremely high as 20 mg / g. (Effluent standard (sea area): Boron: 230 mg / L, Fluorine: 15 mg / L, Total selenium: 0.30 mg / L)
Here iron disulfide powder used (pyrite powder) is made in China a pulverized material particle size 100 mesh or less, the composition is Fe: 48.7 wt%, S: 45.9 wt%, SiO 2: 4.1 wt % Of high purity. Moreover, the same thing as the above was used for quicklime and aluminum sulfate.
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