JPH0315510B2 - - Google Patents
Info
- Publication number
- JPH0315510B2 JPH0315510B2 JP822983A JP822983A JPH0315510B2 JP H0315510 B2 JPH0315510 B2 JP H0315510B2 JP 822983 A JP822983 A JP 822983A JP 822983 A JP822983 A JP 822983A JP H0315510 B2 JPH0315510 B2 JP H0315510B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- fluorine
- water
- added
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 fluorine ions Chemical class 0.000 claims description 43
- 239000011737 fluorine Substances 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002506 iron compounds Chemical class 0.000 claims description 4
- 150000002604 lanthanum compounds Chemical class 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007788 liquid Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 229920002873 Polyethylenimine Polymers 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical group NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- DUAWRLXHCUAWMK-UHFFFAOYSA-N 2-iminiopropionate Chemical group CC(=[NH2+])C([O-])=O DUAWRLXHCUAWMK-UHFFFAOYSA-N 0.000 description 1
- TXPKUUXHNFRBPS-UHFFFAOYSA-N 3-(2-carboxyethylamino)propanoic acid Chemical group OC(=O)CCNCCC(O)=O TXPKUUXHNFRBPS-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical group NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical group OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 1
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical group [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940032950 ferric sulfate Drugs 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- NYVOYAFUSJONHU-UHFFFAOYSA-K trisodium;1,3,5-triazine-2,4,6-trithiolate Chemical compound [Na+].[Na+].[Na+].[S-]C1=NC([S-])=NC([S-])=N1 NYVOYAFUSJONHU-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Description
【発明の詳細な説明】
本発明は、水の処理方法に関するものであり、
さらに詳しくはフツ素イオンまたは、フツ素イオ
ンと重金属イオンを含有する水に、フツ素イオン
と錯化合物を形成する金属化合物として、鉄化合
物、アルミニウム化合物、ランタン化合物からな
る群より選ばれた少なくとも１種と金属と錯化合
物を形成するキレート性凝集剤とを添加し、フツ
素イオンまたは、フツ素イオンと金属イオンを水
に不溶性の錯化合物として分離除去する水の処理
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water treatment method,
More specifically, at least one metal compound selected from the group consisting of iron compounds, aluminum compounds, and lanthanum compounds is added to fluorine ions or water containing fluorine ions and heavy metal ions as a metal compound that forms a complex with fluorine ions. The present invention relates to a water treatment method in which fluorine ions or fluorine ions and metal ions are separated and removed as a water-insoluble complex compound by adding a chelating flocculant that forms a complex compound with a seed and a metal.
従来、水中のフツ素イオンを除去する方法とし
ては、水中に水酸化カルシウムまたは塩化カルシ
ウムなどのカルシウム塩を添加し、PHを６〜10に
調整して不溶性のフツ化カルシウムとして沈殿除
去する方法があるが、フツ化カルシウムの溶解度
や共存物質の影響などから、処理水中のフツ素イ
オンを低濃度まで除去することが出来ない。 Conventionally, the method for removing fluorine ions from water is to add calcium salts such as calcium hydroxide or calcium chloride to the water, adjust the pH to 6 to 10, and precipitate and remove it as insoluble calcium fluoride. However, due to the solubility of calcium fluoride and the effects of coexisting substances, it is not possible to remove fluoride ions from the treated water to a low concentration.
また、カルシウム塩による処理をした後、硫酸
アルミニウムなどのアルミニウム系の無機凝集剤
を併用し、フツ素イオンの除去を行なう方法もあ
るが、無機凝集剤の添加によるPHの制御が必要と
なるなどの欠点がある。 Another method is to use an aluminum-based inorganic flocculant such as aluminum sulfate after treatment with calcium salts to remove fluoride ions, but this requires the addition of an inorganic flocculant to control the pH. There are drawbacks.
また、陰イオン交換樹脂による除去方法では、
樹脂のアニオン交換順位が、OH-＞SO4 --＞
CrO4 --＞H2PO4 -＞Cl-……＞F-となつており、
フツ素イオンに対する選択性は極めて低く、共存
物の影響を受け易い。 In addition, in the removal method using anion exchange resin,
The anion exchange order of the resin is OH - > SO 4 -- >
CrO 4 -- ＞H 2 PO 4 - ＞Cl - ...＞F - ,
The selectivity for fluorine ions is extremely low and is easily influenced by coexisting substances.
さらにフツ素と錯化合物を形成する金属イオン
として鉄イオン、アルミニウムイオン、ランタン
イオンなどの少なくとも１種をキレート形成基に
吸着させた金属塩型キレート樹脂によりフツ素を
吸着除去する方法があるが、この処理方法は、除
去下限において優れているものの、他の処理方法
と比べて経済性の面でコストが高く、それを低下
させるために樹脂の再生を必要とするなどの欠点
がある。 Furthermore, there is a method of adsorbing and removing fluorine using a metal salt-type chelate resin in which at least one kind of metal ion, such as iron ion, aluminum ion, or lanthanum ion, which forms a complex compound with fluorine is adsorbed to a chelate-forming group. Although this treatment method is superior in terms of the lower limit of removal, it has drawbacks such as higher cost in terms of economy than other treatment methods and the need to regenerate the resin in order to lower the cost.
そこで、本発明者らは、以上の欠点を解決する
べく鋭意研究を行なつたところ、フツ素イオンを
含有する水にフツ素と錯化合物を形成する金属化
合物として、鉄化合物、アルミニウム化合物、ラ
ンタン化合物からなる群より選ばれた少なくも１
種の金属化合物および金属と錯化合物を形成する
キレート性凝集剤を添加することにより、フツ素
イオンを水に不溶性の錯化合物として分離除去で
きることを見い出した。 Therefore, the present inventors conducted intensive research to solve the above-mentioned drawbacks and found that iron compounds, aluminum compounds, and lanthanum are metal compounds that form complex compounds with fluorine in water containing fluorine ions. At least one selected from the group consisting of compounds
It has been discovered that by adding a chelating flocculant that forms a complex compound with a seed metal compound and the metal, fluorine ions can be separated and removed as a water-insoluble complex compound.
さらに、水中にフツ素イオンの他に重金属イオ
ンを含有した場合においても、フツ素イオンのみ
の場合と同様な処理方法でフツ素イオンを水に不
溶性の金属錯化合物として分離できることを見い
出した。しかも、共存していた重金属イオンはキ
レート性凝集剤によつて、水に不溶性の金属錯化
合物となり、フツ素イオンと同時に分離除去でき
る。本発明で除去することが出来る重金属として
Hg、Pb、Cd、Cu、Zn、Ni、Cr、As等が挙げら
れる。 Furthermore, we have discovered that even when water contains heavy metal ions in addition to fluoride ions, the fluoride ions can be separated as water-insoluble metal complex compounds using the same treatment method as when only fluorine ions are used. Moreover, the coexisting heavy metal ions become water-insoluble metal complex compounds by the chelating flocculant, and can be separated and removed at the same time as fluorine ions. Heavy metals that can be removed by the present invention
Examples include Hg, Pb, Cd, Cu, Zn, Ni, Cr, As, etc.
本発明において使用するフツ素イオンと錯化合
物を形成する金属としての鉄化合物、アルミニウ
ム化合物、ランタン化合物の例としては、鉄化合
物には、塩化第一鉄、塩化第二鉄、硫酸第一鉄、
硫酸第二鉄、硫酸鉄アンモニウム、硝酸第一鉄、
硝酸第二鉄等が挙げられる。 Examples of iron compounds, aluminum compounds, and lanthanum compounds as metals that form complex compounds with fluorine ions used in the present invention include ferrous chloride, ferric chloride, ferrous sulfate,
Ferric sulfate, ammonium ferrous sulfate, ferrous nitrate,
Examples include ferric nitrate.
アルミニウム化合物としては、塩化アルミニウ
ム、ポリ塩化アルミニウム、硫酸アルミニウム、
硫酸アルミニウムアンモニウム、硫酸アルミニウ
ムカリウム、硫酸アルミニウムナトリウム、硝酸
アルミニウム、酸化アルミニウム等が挙げられ
る。 Examples of aluminum compounds include aluminum chloride, polyaluminum chloride, aluminum sulfate,
Examples include ammonium aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, aluminum nitrate, and aluminum oxide.
ランタン化合物としては、塩化ランタン、硝酸
ランタン、酸化ランタンらが挙げられる。 Examples of lanthanum compounds include lanthanum chloride, lanthanum nitrate, and lanthanum oxide.
本発明におけるキレート性凝集剤とは、ポリア
ルキレンポリアミン類、ポリエチレンイミン類
（以下これらをポリアミン類と称す）及び、ポリ
アミン類並びにポリスチレン等に、キレート形成
基とし、アミノ酸基、イミノ酢酸基、イミノジ酢
酸基、イミノプロピオン酸基、イミノジプロピオ
ン酸基、アミノリン酸基、ジチオカルバミン酸
基、チオール基、チオ尿素基、ポリアミノ基、ア
ミドオキシム基などの少なくとも１種を導入した
もので、金属イオンと錯化合物を形成した後、水
に不溶性となる低分子量あるいは高分子量のキレ
ート性凝集剤である。 The chelating flocculant in the present invention refers to polyalkylene polyamines, polyethylene imines (hereinafter referred to as polyamines), polyamines, polystyrene, etc., with chelate-forming groups, amino acid groups, iminoacetic acid groups, iminodiacetic acid groups, etc. A complex compound with a metal ion, into which at least one type of group, iminopropionic acid group, iminodipropionic acid group, aminophosphoric acid group, dithiocarbamate group, thiol group, thiourea group, polyamino group, amidoxime group, etc., is introduced. It is a low molecular weight or high molecular weight chelating flocculant that becomes insoluble in water after forming.
ポリアミン類としては、エチレンジアミン、ジ
エチレントリアミン、トリエチレンテトラミン、
テトラエチレンペンタミン、ペンタエチレンヘキ
サミン等のポリアルキレンポリアミン類、及び分
子量300〜100000のポリエチレンイミン等が挙げ
られる。 Polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine,
Examples include polyalkylene polyamines such as tetraethylenepentamine and pentaethylenehexamine, and polyethyleneimine with a molecular weight of 300 to 100,000.
ポリスチレンには分子量1000〜100000のものが
用い得る。 Polystyrene having a molecular weight of 1,000 to 100,000 can be used.
ポリアミン類並びにポリスチレン等に導入する
キレート形成基の数は、導入される化合物１分子
中に少なくとも１ケ導入されていれば良い。 The number of chelate-forming groups to be introduced into polyamines, polystyrene, etc. may be such that at least one chelate-forming group is introduced into one molecule of the compound to be introduced.
また上記以外のキレート性凝集剤としてトリア
ジンにチオール基（Na塩）を導入したものが挙
げられる。そこに導入するチオール基の数は１〜
３ケである。 In addition, examples of chelating flocculants other than those mentioned above include those in which a thiol group (Na salt) is introduced into triazine. The number of thiol groups introduced therein is 1 to
There are 3.
本発明における金属化合物とキレート性凝集剤
の添加方法は、水に金属化合物を添加した後、キ
レート性凝集剤を添加するか、あるいはキレート
性凝集剤を添加した後、金属化合物を添加する
か、あるいは金属化合物とキレート性凝集剤を同
時に添加する、などが考えられる。この水溶液の
PHは２〜10好ましくは４〜８の範囲で処理すると
良い結果が得られる。 The method of adding the metal compound and the chelating flocculant in the present invention is to add the metal compound to water and then add the chelating flocculant, or add the chelating flocculant and then add the metal compound. Alternatively, it is possible to add a metal compound and a chelating flocculant at the same time. of this aqueous solution
Good results can be obtained when the pH is in the range of 2 to 10, preferably 4 to 8.
また、本発明により処理した後、固液分離する
場合、さらに高分子凝集剤を添加し、生成したブ
ロツクをさらに大きくし、沈降性を良くした後固
液分離することも可能である。 Further, when solid-liquid separation is performed after the treatment according to the present invention, it is also possible to further add a polymer flocculant to make the generated blocks larger and improve the sedimentation properties before solid-liquid separation.
本発明における、水中のフツ素イオンに対する
金属化合物の添加量は、目的とするフツ素イオン
処理濃度によつて左右されるが、水に含有してい
るフツ素イオンに対して、金属イオンとして等モ
ル以上の添加量、好ましくは金属イオンとして１
〜３倍モルの添加量になるよう金属化合物を添加
すると良い。さらにキレート性凝集剤の添加量
は、その凝集剤が低分子量の化合物の時にはその
分子量、またそれが繰返し単位を有する高分子化
合物の時にはその繰返し単位の分子量を、各々１
モルとして算出し、添加した金属イオンに対し
て、0.2〜５倍モル、好ましくは0.1〜２倍モルの
量を添加すると良い。 In the present invention, the amount of the metal compound added to the fluorine ions in water depends on the target fluorine ion treatment concentration, but the amount of metal compounds added to the fluorine ions in water is Addition amount of mol or more, preferably 1 as metal ion
It is preferable to add the metal compound in an amount of ~3 times the molar amount. Furthermore, the amount of the chelating flocculant to be added is based on the molecular weight of the flocculant when it is a low molecular weight compound, and the molecular weight of the repeating unit when it is a high molecular compound having repeating units.
Calculated as moles, the amount of the added metal ion is preferably 0.2 to 5 times, preferably 0.1 to 2 times, by mole.
また、水中にフツ素イオンの他の重金属イオン
を含有する場合には、金属化合物の添加量は上記
と同様で良いが、キレート性凝集剤の添加量は、
添加した金属イオンおよび水に含有する各種重金
属イオンのモル濃度を算出し、それらの総合計に
対して0.2〜５倍モル、好ましくは、0.5〜２倍モ
ルの量のキレート性凝集剤を添加すると良い。 In addition, when the water contains heavy metal ions other than fluoride ions, the amount of metal compound added may be the same as above, but the amount of chelating flocculant added is
Calculate the molar concentration of the added metal ions and various heavy metal ions contained in the water, and add the chelating flocculant in an amount of 0.2 to 5 times the mole, preferably 0.5 to 2 times the mole, relative to the total sum. good.
本発明の方法により、フツ素イオンを含有する
水を処理することにより、従来の無機系凝集剤の
みを使用した方法に比較して、フツ素イオンの除
去率が高くなると共に固液分離が容易に行い得
る。また、フツ素イオンの除去にキレート性樹脂
を用いた方法に比較して、除去率は同等である
が、コストが極めて低いと言うメリツトがある。
またフツ素イオンと重金属イオンを含有する水の
処理を行う際には、同時に除去することが出来
る。 By treating water containing fluoride ions using the method of the present invention, the removal rate of fluoride ions is higher and solid-liquid separation is easier than with conventional methods using only inorganic flocculants. can be done. Furthermore, compared to a method using a chelating resin to remove fluorine ions, this method has the same removal rate but has the advantage of being extremely low cost.
Furthermore, when treating water containing fluorine ions and heavy metal ions, they can be removed at the same time.
以下に本発明を実施例によつて説明する。 The present invention will be explained below by way of examples.
実施例 １
水道水にフツ素イオンを100ppm含有させた原
水（PH6.5）１を、１ビーカーに加え、さら
に0.2M硫酸バンド水溶液を50ml添加し、15分間
攪拌した。Example 1 Raw water (PH6.5) 1 containing 100 ppm of fluorine ions in tap water was added to 1 beaker, and 50 ml of 0.2 M band sulfate aqueous solution was added, followed by stirring for 15 minutes.
さらにキレート性凝集剤として10％ポリエチレ
ンイミン（分子量80000）水溶液を４ml添加し15
分間攪拌処理し水溶液は白濁した。次に苛性ソー
ダにて15分間PH７に調整後ろ紙で固液分離した。
ろ液の残存フツ素イオン濃度を測定したところ
1.5ppmであり、除去率は98.5％であつた。 Furthermore, 4 ml of 10% polyethyleneimine (molecular weight 80,000) aqueous solution was added as a chelating flocculant.
After stirring for a minute, the aqueous solution became cloudy. Next, the pH was adjusted to 7 with caustic soda for 15 minutes, and solid-liquid separation was performed using paper.
Measuring the residual fluorine ion concentration of the filtrate
It was 1.5 ppm, and the removal rate was 98.5%.
比較例 １
実施例−１と同様の原水１に0.2M硫酸バン
ド水溶液を50ml添加し15分間攪拌した。次に苛性
ソーダにてPH７に調整、ろ紙で固液分離した。ろ
液の残存フツ素イオン濃度を測定したところ
9.2ppmであり、除去率は90.8％で実施例−１の
98.5％におよばなかつた。Comparative Example 1 50 ml of 0.2M aqueous sulfuric acid solution was added to the same raw water 1 as in Example-1 and stirred for 15 minutes. Next, the pH was adjusted to 7 with caustic soda, and solid-liquid separation was performed using filter paper. Measuring the residual fluorine ion concentration of the filtrate
9.2 ppm, and the removal rate was 90.8%, which was the same as in Example-1.
It did not reach 98.5%.
実施例 ２
水道水にフツ素イオン100ppm、NaCl1％、お
よびNa2SO41％を含有させた原水１に、0.2M
塩化第二鉄水溶液を30ml添加し360分間攪拌した。
さらにポリエチレンイミン（分子量10000）酢酸
ナトリウム基を導入したキレート性凝集剤の５％
水溶液を10ml添加し、30分間攪拌処理した。次に
苛性ソーダにてPH６に30分間調整後、固液分離し
た。Example 2 0.2M was added to raw water 1, which is tap water containing 100ppm of fluorine ions, 1% of NaCl, and 1% of Na 2 SO 4
30 ml of ferric chloride aqueous solution was added and stirred for 360 minutes.
In addition, 5% of polyethyleneimine (molecular weight 10,000) chelating flocculant with sodium acetate group introduced.
10 ml of aqueous solution was added and stirred for 30 minutes. Next, after adjusting the pH to 6 with caustic soda for 30 minutes, solid-liquid separation was performed.
処理の残存フツ素イオン濃度を測定したところ
5.4ppmであり除去率は94.6％であつた。 Measurement of residual fluorine ion concentration after treatment
It was 5.4 ppm, and the removal rate was 94.6%.
実施例 ３
半導体製造メーカーから発生したフツ素イオン
53ppmを含有する実廃水１に希塩酸で溶解した
0.2M酸化ランタン水溶液を25ml添加し１時間攪
拌した。さらにポリエチレンイミン（分子量600）
にアミノリン酸ナトリウム基を導入したキレート
性凝集剤の５％水溶液を７ml添加し30分間攪拌処
理した。Example 3 Fluorine ions generated from a semiconductor manufacturer
Dissolved in real wastewater 1 containing 53ppm with dilute hydrochloric acid.
25 ml of 0.2M lanthanum oxide aqueous solution was added and stirred for 1 hour. Furthermore, polyethyleneimine (molecular weight 600)
7 ml of a 5% aqueous solution of a chelating flocculant into which a sodium aminophosphate group had been introduced was added and stirred for 30 minutes.
次に苛性ソーダにて15分間PH6.5に調整した後、
固液分離した。処理の残存フツ素イオン濃度を測
定したところ1.3ppmであり除去率は98.7％であ
つた。 Next, after adjusting the pH to 6.5 for 15 minutes with caustic soda,
Solid-liquid separation was performed. When the residual fluorine ion concentration after treatment was measured, it was 1.3 ppm, and the removal rate was 98.7%.
実施例 ４
水道水にフツ素イオン30ppmおよび水銀イオン
30ppmを含有させた原水１に10％ポリ塩化アル
ミニウム水溶液を30ml添加し30分間攪拌した。さ
らにキレート性凝集剤として５％トリメルカプト
−Ｓ−トリアジントリナトリウム塩水溶液を４ml
添加し１時間攪拌処理した後固液分離した。Example 4 30ppm of fluoride ions and mercury ions in tap water
30 ml of 10% polyaluminum chloride aqueous solution was added to raw water 1 containing 30 ppm and stirred for 30 minutes. Furthermore, 4 ml of 5% trimercapto-S-triazine trisodium salt aqueous solution was added as a chelating flocculant.
After adding and stirring for 1 hour, solid-liquid separation was performed.
処理液の残存フツ素イオンおよび水銀イオン濃
度を測定したところ、フツ素イオンは0.8ppm、
水銀イオンは0.03ppmで良好な結果が得られた。 When we measured the residual fluorine ion and mercury ion concentrations in the treatment solution, the fluorine ions were 0.8 ppm,
Good results were obtained for mercury ion at 0.03ppm.
実施例 ５
フツ素イオン10ppm、鉛イオン10ppm、塩化ナ
トリウム２％および硫酸ナトリウム２％の組成か
らなる原水10に10％硫酸バンド水溶液を100ml
添加し１時間攪拌した。さらにキレート性凝集剤
としてポリエチレンイミン（分子量20000）に、
アミドオキシム基（Na型）を導入したものの10
％水溶液を18ml添加し１時間攪拌処理した。Example 5 Add 100 ml of a 10% band sulfate aqueous solution to 100 mL of raw water with a composition of 10 ppm fluoride ions, 10 ppm lead ions, 2% sodium chloride, and 2% sodium sulfate.
and stirred for 1 hour. In addition, polyethyleneimine (molecular weight 20,000) is used as a chelating flocculant.
10 with introduced amidoxime group (Na type)
% aqueous solution was added and stirred for 1 hour.
次に苛性ソーダで30分間PH7.5に調整した後固
液分離した。処理液の残存フツ素イオン、鉛イオ
ン濃度を測定したところフツ素イオンは0.6ppm、
鉛イオンは0.1ppm以下で良好であつた。 Next, the pH was adjusted to 7.5 with caustic soda for 30 minutes, followed by solid-liquid separation. When we measured the residual fluorine ion and lead ion concentrations in the treatment solution, the fluorine ions were 0.6 ppm.
The lead ion content was good at 0.1 ppm or less.
実施例 ６
フツ素イオン、カドミウムイオン、鉛イオンお
よび銅イオンを各5ppm含有した原水１に５％
ポリ塩化アルミニウム水溶液を50ml添加し１時間
攪拌した。さらにキレート性凝集剤として、ポリ
スチレン（分子量5000）にイミノジ酢酸ナトリウ
ム基を導入したものの５％水溶液を10ml添加し、
１時間攪拌処理した。さらに水酸化カリウムでPH
７に30分間調整した後固液分離した。Example 6 5% in raw water 1 containing 5 ppm each of fluorine ions, cadmium ions, lead ions, and copper ions
50 ml of polyaluminum chloride aqueous solution was added and stirred for 1 hour. Furthermore, as a chelating flocculant, 10 ml of a 5% aqueous solution of sodium iminodiacetate group introduced into polystyrene (molecular weight 5000) was added.
The mixture was stirred for 1 hour. Furthermore, pH with potassium hydroxide
After adjusting the temperature to 7 for 30 minutes, solid-liquid separation was performed.
処理液の各種残存イオン濃度を測定したとこ
ろ、フツ素イオンは0.8ppm、カドミウムイオン
0.05ppm、鉛イオン0.2ppm、銅イオン0.1ppmで
良好な結果が得られた。 We measured the concentration of various residual ions in the treatment solution, and found that fluorine ions were 0.8 ppm and cadmium ions were 0.8 ppm.
Good results were obtained with 0.05ppm, lead ion 0.2ppm, and copper ion 0.1ppm.
実施例 ７
実施例−６に用いたと同じ原水１に、５％ポ
リ塩化アルミニウム水溶液を50ml添加し、１時間
攪拌したのち、これにテトラエチレンペンタミン
にジチオカルバミン酸基を導入して得られるキレ
ート性凝集剤の10％水溶液５mlを添加し、１時間
攪拌処理した。これに苛性ソーダで30分間PH７に
調整した後、固液分離した。Example 7 Add 50 ml of 5% polyaluminum chloride aqueous solution to the same raw water 1 used in Example 6, stir for 1 hour, and then introduce a dithiocarbamate group into tetraethylenepentamine to obtain chelating properties. 5 ml of a 10% aqueous flocculant solution was added and stirred for 1 hour. After adjusting the pH to 7 with caustic soda for 30 minutes, solid-liquid separation was performed.
処理液の各種残存イオン濃度を測定したとこ
ろ、フツ素イオン0.9ppm、カドミウムイオン
0.04ppm、鉛イオン0.2ppm、銅イオン0.2ppmで
あり、良好な結果が得られた。 When we measured the concentration of various residual ions in the treatment solution, we found 0.9 ppm of fluorine ions and 0.9 ppm of cadmium ions.
0.04ppm, lead ion 0.2ppm, copper ion 0.2ppm, and good results were obtained.
Claims (1)
オンを含有する水溶液に、フツ素と錯化合物を形
成する金属化合物として、鉄化合物、アルミニウ
ム化合物、ランタン化合物よりなる群より選ばれ
る少くとも一種と、金属と錯化合物を形成するキ
レート性凝集剤を添加し、フツ素イオンまたはフ
ツ素イオンと重金属イオンを水に、不溶性の錯化
合物として、分離除去することを特徴とする水の
処理方法。1. Into an aqueous solution containing fluorine ions or fluorine ions and heavy metal ions, at least one metal compound selected from the group consisting of iron compounds, aluminum compounds, and lanthanum compounds is added as a metal compound that forms a complex compound with fluorine. A method for treating water, which comprises adding a chelating flocculant that forms a complex compound, and separating and removing fluorine ions or fluorine ions and heavy metal ions as an insoluble complex compound in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP822983A JPS59132993A (en) | 1983-01-21 | 1983-01-21 | Water disposal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP822983A JPS59132993A (en) | 1983-01-21 | 1983-01-21 | Water disposal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59132993A JPS59132993A (en) | 1984-07-31 |
| JPH0315510B2 true JPH0315510B2 (en) | 1991-03-01 |
Family
ID=11687324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP822983A Granted JPS59132993A (en) | 1983-01-21 | 1983-01-21 | Water disposal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59132993A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851020A (en) * | 2019-02-13 | 2019-06-07 | 江西沃格光电股份有限公司 | Wastewater treatment agent, preparation method thereof, and wastewater treatment method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236548A (en) * | 1998-02-19 | 1999-08-31 | Miyoshi Oil & Fat Co Ltd | Metal collecting agent composition and metal collecting method |
| JP4811899B2 (en) * | 2001-11-30 | 2011-11-09 | 栗田工業株式会社 | Method for determining required addition amount of chelating heavy metal treating agent and method for controlling chemical injection |
| JP6776163B2 (en) * | 2017-03-24 | 2020-10-28 | 株式会社神戸製鋼所 | Purification agent and purification method |
-
1983
- 1983-01-21 JP JP822983A patent/JPS59132993A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851020A (en) * | 2019-02-13 | 2019-06-07 | 江西沃格光电股份有限公司 | Wastewater treatment agent, preparation method thereof, and wastewater treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59132993A (en) | 1984-07-31 |
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