KR20110039215A - Agent for purifying soil and/or underground water and purification method - Google Patents
Agent for purifying soil and/or underground water and purification method Download PDFInfo
- Publication number
- KR20110039215A KR20110039215A KR1020107028714A KR20107028714A KR20110039215A KR 20110039215 A KR20110039215 A KR 20110039215A KR 1020107028714 A KR1020107028714 A KR 1020107028714A KR 20107028714 A KR20107028714 A KR 20107028714A KR 20110039215 A KR20110039215 A KR 20110039215A
- Authority
- KR
- South Korea
- Prior art keywords
- citric acid
- soil
- weight
- hydrogen peroxide
- parts
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002689 soil Substances 0.000 title claims abstract description 66
- 238000000746 purification Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 title description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 377
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 243
- 239000012629 purifying agent Substances 0.000 claims abstract description 84
- 239000003673 groundwater Substances 0.000 claims abstract description 81
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 62
- 229910052742 iron Inorganic materials 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 239000002738 chelating agent Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- -1 transition metal salt Chemical class 0.000 claims description 15
- 239000006174 pH buffer Substances 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- 150000004973 alkali metal peroxides Chemical class 0.000 claims description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000011550 stock solution Substances 0.000 claims description 3
- 150000004974 alkaline earth metal peroxides Chemical class 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 5
- 239000007924 injection Substances 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 78
- 239000003054 catalyst Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000007935 neutral effect Effects 0.000 description 16
- 239000007800 oxidant agent Substances 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 14
- 235000002639 sodium chloride Nutrition 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 238000011109 contamination Methods 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 238000010828 elution Methods 0.000 description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- 239000000347 magnesium hydroxide Substances 0.000 description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000872 buffer Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 241000581652 Hagenia abyssinica Species 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 229960001367 tartaric acid Drugs 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 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
- 230000003139 buffering effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 235000014413 iron hydroxide Nutrition 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
- 231100000719 pollutant Toxicity 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QEHXDDFROMGLSP-VDBFCSKJSA-K trisodium;(2s)-2-[2-[[(1s)-1-carboxy-2-carboxylatoethyl]amino]ethylamino]butanedioate Chemical compound [Na+].[Na+].[Na+].OC(=O)C[C@@H](C([O-])=O)NCCN[C@H](C([O-])=O)CC([O-])=O QEHXDDFROMGLSP-VDBFCSKJSA-K 0.000 description 2
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 description 1
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 1
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 101100345345 Arabidopsis thaliana MGD1 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-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
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- HIYYTEDADQJCRN-UHFFFAOYSA-N acetic acid;2-aminoethanesulfonic acid Chemical compound CC(O)=O.CC(O)=O.NCCS(O)(=O)=O HIYYTEDADQJCRN-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940048879 dl tartaric acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 229940079889 pyrrolidonecarboxylic acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- OHOTVSOGTVKXEL-WJXVXWFNSA-K trisodium;(2s)-2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)[C@H](C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-WJXVXWFNSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C11D2111/10—
Abstract
유기 화합물로 오염된 토양 및/또는 지하수를, 주변 환경, 생태계 등에 영향을 주지 않고, 원위치에 있어서 정화하는 방법으로 간편하게 응용할 수 있으며, 게다가 주입 개소로부터 비교적 먼 개소까지의 광범위를 안전하고 효과적으로 정화하는 것이 가능한 정화제 및 당해 정화제에 의한 정화 방법을 제공하는 것을 과제로 하고, (A) 과산화수소를 100중량부, (B) 시트르산을 적어도 10중량부, 및 (C) 물을 (A) 과산화수소와 (B) 시트르산의 합계를 100중량부로 한 경우에 적어도 15중량부 함유하고, (D) 알칼리 화합물을 하기 수학식 1의 시트르산(B)의 프로톤수를 만족시키기 위해 첨가하는 것을 특징으로 하는 토양 및/또는 지하수의 정화제를 제공한다. 또한 (A) 내지 (D)를 토양 및/또는 지하수에 첨가하는 정화 방법을 제공한다.
수학식 1
시트르산(B)의 프로톤수=0.05×M 내지 0.80×M
상기 수학식 1에서,
M은 시트르산(B)의 몰수이다.Soil and / or groundwater contaminated with organic compounds can be easily applied by in-situ purification without affecting the surrounding environment, ecosystem, etc. In addition, it is possible to safely and effectively purify a wide range from injection sites to relatively remote sites. It is an object of the present invention to provide a purifying agent and a purifying method using the purifying agent, and (A) 100 parts by weight of hydrogen peroxide, (B) at least 10 parts by weight of citric acid, and (C) water (A) with hydrogen peroxide and (B ) Soil and / or characterized by containing at least 15 parts by weight when the total amount of citric acid is 100 parts by weight, and (D) an alkali compound is added to satisfy the proton number of citric acid (B) Provide groundwater purifiers. Also provided are methods of purification in which (A)-(D) are added to soil and / or groundwater.
Equation 1
Proton number of citric acid (B) = 0.05 × M to 0.80 × M
In Equation 1,
M is the number-of-moles of citric acid (B).
Description
본 발명은, 유기 화합물로 오염된 토양 및/또는 지하수의 정화제, 및 당해 정화제를 사용한 정화 방법에 관한 것이다.
The present invention relates to a purifier of soil and / or groundwater contaminated with organic compounds, and a purifying method using the purifier.
토양 및 지하수 중의 유기물 오염이 환경에 크게 영향을 주는 것이 밝혀져 여러 가지 규제가 정비되어 오는 동시에, 지금까지 축적, 방치되고 있었던 오염의 정화가 필요해지고 있다. 여기에서의 유기물이란, 주로 생물에 의한 분해가 곤란한 유기물을 말하고, 농약, 방부제, 석유 및 그 유분에 포함되는 방향족 화합물, 할로겐화 유기 화합물 등이 해당된다. It has been found that pollution of organic matter in soil and groundwater greatly affects the environment, and various regulations have been maintained. At the same time, it is necessary to purify the pollution that has been accumulated and left unattended. The organic substance herein refers to an organic substance which is difficult to be mainly degraded by living organisms, and corresponds to pesticides, preservatives, petroleum, aromatic compounds contained in the oil, and halogenated organic compounds.
이 유기물 오염에 대해, 물리적, 화학적, 생물적인 여러 가지 정화 방법이 시도되고 있다. 물리적인 정화 방법에서는, 오염 장소의 정화는 가능하지만, 제거된 오염 물질의 2차적인 처리가 필요해진다는 결점이 있다. 생물적인 정화 방법은 주변 환경에 영향이 적은 방법이기는 하지만, 고농도의 오염에 대해 적용이 어렵다고 하는 결점이 있다. 이들에 대해 화학적인 정화 방법은 대상 오염 물질을 분해하기 위해서, 2차적인 처리가 필요없고, 고농도의 오염에 대해서도, 적용이 가능하다고 하는 특징을 가진다. For this organic contamination, various physical, chemical and biological purification methods have been tried. In the physical purification method, it is possible to purify a contaminated site, but the disadvantage is that a secondary treatment of the removed pollutant is required. Although biological purification methods have less impact on the environment, they have the drawback that they are difficult to apply to high concentrations of pollution. On the other hand, the chemical purification method does not require secondary treatment in order to decompose the contaminants of interest, and has a feature that it is applicable to high concentrations of pollution.
과산화수소 등의 산화제와, 촉매로서의 철 이온을 공급 가능한 화합물(예: 황산제1철·7수화물 등)을 첨가함으로써, 하이드록실라디칼을 발생시키고, 이 라디칼과 유기물을 반응시킴으로써, 유기물을 산화 분해하는 펜톤법이 알려져 있다. 화학적인 정화 방법 중에서, 이 펜톤법을 응용하여, 유기 화합물로 오염된 토양을 정화하는 것이 시도되고 있다[참조: 특허 문헌 1].By adding an oxidizing agent such as hydrogen peroxide and a compound capable of supplying iron ions as a catalyst (for example, ferrous sulfate and hexahydrate), hydroxyl radicals are generated, and the radicals and organic substances are reacted to oxidatively decompose organic substances. Fenton method is known. Among the chemical purification methods, the Fenton method is applied to purify soil contaminated with organic compounds (Patent Document 1).
통상의 펜톤법에서는 최적 pH 범위는 3 내지 4이며, pH 범위가 중성 이상인 경우의 반응은, 촉매의 철 이온이 수산화물이 되어 침전되어 버려 거의 반응이 진행되지 않는다. 그러나, 이 pH 3 내지 4라고 하는 최적 pH 범위에서 토양 정화를 실시하는 경우에는, 토양 중의 중금속 성분의 용출에 의한 2차 오염의 발생이나 확대의 가능성이 있어 지하 구조물인 철골이나 지하 배관의 부식이 발생할 우려가 있다. 이 결점을 보완하기 위해서, 완충제를 사용하여 중성 부근의 일정 pH로 정화하는 것이 제안되어 있다. In the conventional Fenton method, the optimum pH range is 3 to 4, and the reaction in the case where the pH range is neutral or more causes the iron ions of the catalyst to precipitate out as a hydroxide and hardly progress the reaction. However, when the soil is purified in the optimum pH range of 3 to 4, there is a possibility of secondary contamination or expansion due to the elution of heavy metal components in the soil. It may occur. To compensate for this drawback, it has been proposed to purify to a constant pH near neutral using a buffer.
특허 문헌 2, 3에서는, 오염 유기물의 분해에 의한 pH의 저하를 방지하기 위해서, 산화제와 완충제의 첨가가 고안되어 있지만, 철 등의 촉매가 되는 금속 이온의 고 pH 범위에서의 침전을 방지하는 수단이 명기되어 있지 않고, 산화제의 종류나 정화 장소의 환경에 따라서는 철 등의 지하수에 포함되는 금속 성분의 침전에 의한 유로, 배관의 폐색이 발생하여 정화 작업에 문제가 생길 가능성이 있다. In Patent Documents 2 and 3, although addition of an oxidizing agent and a buffer is devised to prevent a drop in pH due to decomposition of contaminating organics, means for preventing precipitation in a high pH range of metal ions serving as a catalyst such as iron. Although not specified, depending on the type of the oxidizing agent and the environment of the purification site, clogging of the flow path and piping due to precipitation of metal components contained in the groundwater such as iron may cause problems in the purification operation.
또한, 철 등의 촉매가 되는 금속 이온의 침전을 방지하기 위해, 산화제와 함께 킬레이트제를 첨가하는 기술이 고안되어 있다. 특허 문헌 4에서는 주로 철의 침전을 방지할 목적으로 킬레이트제를 첨가하고 있지만, 사용 pH 범위가 산성측이기 때문에, 규정되어 있는 첨가 몰비의 범위는, 철에 대해 1/3 정도의 소량이며, 액의 pH 범위를 고려하면 중금속의 용출 등의 2차 오염을 일으킬 위험성이 남는다. 또한, 특허 문헌 5에서도, 킬레이트제와 산화제의 병용이 고안되어 있지만, 킬레이트제의 첨가는 철 등의 금속 이온의 침전을 방지할 목적뿐으로, 완충제 등에 의한 pH 저하를 방지하는 수단이 강구되어 있지 않으며, 액의 pH 범위를 고려하면 중금속의 용출 등의 2차 오염을 일으킬 가능성이 높다. Moreover, in order to prevent precipitation of the metal ion used as a catalyst, such as iron, the technique which adds a chelating agent with an oxidizing agent is devised. In patent document 4, although the chelating agent is added mainly for the purpose of preventing iron precipitation, since the use pH range is acidic side, the range of prescribed addition molar ratio is a small amount about 1/3 of iron, Considering the pH range of, there is a risk of secondary contamination such as elution of heavy metals. In addition, in Patent Document 5, a combination of a chelating agent and an oxidizing agent has been devised. However, the addition of a chelating agent is not only intended to prevent precipitation of metal ions such as iron, and means for preventing a decrease in pH due to a buffer or the like has not been devised. In consideration of the pH range of the liquid, there is a high possibility of causing secondary contamination such as elution of heavy metals.
이것에 대해, 중성 부근의 Fe 킬레이트를 첨가하는 수법도 고안되어 있다. 특허 문헌 6에서는 처음에 산화제를 주입하고, 그 후에 Fe 킬레이트를 주입하는 수법이 제안되어 있다. 그러나, 처음에 첨가한 산화제에 의한 pH 저하를 방지하는 수단이 강구되어 있지 않다. 바람직한 산화제로서 제시되어 있는 과산화수소에는 통상 인산계의 안정제가 첨가되어 있으며 pH는 1 내지 4이기 때문에, 작용장의 pH가 저하되어 중금속의 용출 등의 2차 오염을 일으킬 가능성이 높다. On the other hand, the method of adding the Fe chelate of neutral vicinity is also devised. In Patent Document 6, a method of injecting an oxidant at first and then injecting Fe chelate has been proposed. However, no means have been devised for preventing the pH from being lowered by the oxidant added at first. Hydrogen peroxide, which is suggested as a preferred oxidant, is usually added with a phosphoric acid stabilizer and has a pH of 1 to 4, so that the pH of the working field is lowered, which is likely to cause secondary contamination such as elution of heavy metals.
또한, 특허 문헌 6에는, 산화제와 중성 부근의 Fe 킬레이트를 함께 주입하는 수법도 제안되어 있다. 그러나, 산화제와 Fe 킬레이트를 함께 주입한 경우, 혼합과 동시에 산화제의 분해가 개시되어 주입 개소로부터 벗어난 장소에는 산화제가 도달하지 않는다고 하는 결점이 있었다. Patent Document 6 also proposes a method of injecting an oxidizing agent and Fe chelate in the vicinity of neutrality. However, when the oxidant and the Fe chelate are injected together, there is a drawback that decomposition of the oxidant is started at the same time as mixing and the oxidant does not reach the place away from the injection point.
특허 문헌 7에는 생분해성 킬레이트제를 pH 완충제와 함께 땅 속에 첨가하여, 땅 속의 철과 착체를 생성시킨 후에, 작용장의 pH를 5 내지 10으로 유지한 채 산화제를 첨가하는 방법이 개시되어 있다. 그러나, 이 방법에서도 바람직한 산화제로서 제시되어 있는 과산화수소가 촉매 존재하에 첨가되기 때문에, 주입 개소로부터 떨어진 장소에는 산화제가 도달하지 않는다라는 결점이 있었다. Patent Document 7 discloses a method in which a biodegradable chelating agent is added to the ground together with a pH buffer to produce iron and complexes in the ground, and then an oxidizing agent is added while maintaining the pH of the working field at 5 to 10. However, also in this method, since hydrogen peroxide, which is proposed as a preferred oxidant, is added in the presence of a catalyst, there is a drawback that the oxidant does not reach a place away from the injection point.
또한, 상기의 특허 문헌 2, 3, 5 내지 7에서는 모두 작용장의 pH를 제어하기 위해서 pH 완충제를 사용하고 있으며, 정화 사이트에 있어서 산화제, 촉매 용액과 함께 pH 완충제를 조합할 필요가 있다.
In addition, the above-mentioned patent documents 2, 3, 5-7 are all using a pH buffer in order to control the pH of a working field, and it is necessary to combine a pH buffer with an oxidizing agent and a catalyst solution in a purification site.
본 발명은, 상기한 바와 같은 종래 기술의 각종 문제점을 감안하여 제안된 것으로, 유기 화합물로 오염된 토양 및/또는 지하수를 주변 환경, 생태계 그 밖에 영향을 주지 않고, 원위치에 있어서 정화하는 방법에 간편하게 응용할 수 있고, 게다가 주입 개소로부터 비교적 먼 개소까지의 넓은 범위를 안전하고 효과적으로 정화 처리할 수 있고, 또한 고농도 오염에 대해서도 정화 처리가 가능한 토양 및/또는 지하수의 정화제, 및 당해 정화제를 사용한 토양 및/또는 지하수의 정화 방법의 제공을 목적으로 한다.
The present invention has been proposed in view of the various problems of the prior art as described above, and is a simple method for purifying soil and / or groundwater contaminated with organic compounds in situ without affecting the surrounding environment and ecosystem. Soil and / or ground water purifier which can be applied, and can safely and effectively purify a wide range from the injection point to a relatively distant point, and is also capable of purifying high concentration pollution, and the soil using the purifier and // Another object is to provide a method for the purification of groundwater.
본 발명자들은, 상기한 문제점을 해결하기 위해서 예의 연구를 실시한 결과, 과산화수소수, 시트르산, 물을 함유하고, 시트르산의 프로톤수가 조정된 수용액인 본 발명의 정화제는, (1) 토양 및/또는 지하수에 첨가해도 작용장의 pH의 변동이 적은 점, (2) 토양 및/또는 지하수에 첨가하기 전에 당해 정화제를 희석해도, 그 pH는 중성 부근이 되어 비교적 안전한 점, 및 (3) 작용장에서의 과산화수소의 안정성이 양호한 점을 밝혀내었다. 또한, 본 발명의 정화제를 원액으로, 또는 희석하여 유기물로 오염된 토양 및/또는 지하수에 첨가함으로써, pH 완충제의 별도 조제가 불필요하며, 중금속의 용출도 없고, 넓은 범위를 정화할 수 있는 것을 밝혀내고, 본 발명을 완성하기에 이르렀다.MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, the present inventors found that the purifying agent of this invention which is the aqueous solution which contains hydrogen peroxide water, citric acid, and water, and the proton number of citric acid was adjusted is (1) in soil and / or groundwater Even if it is added, the pH of the working field is small, (2) even if the purifying agent is diluted before adding to the soil and / or groundwater, the pH becomes neutral and relatively safe, and (3) of hydrogen peroxide in the working field. The stability was found to be good. In addition, it has been found that by adding or diluting the purifying agent of the present invention with a stock solution or by diluting it with soil and / or groundwater contaminated with organic matter, it is unnecessary to prepare a pH buffer, there is no elution of heavy metals, and it is possible to purify a wide range. It came out and completed this invention.
즉 본 발명은, 이하에 나타내는 토양 및/또는 지하수의 정화제, 및 토양 및/또는 지하수의 정화 방법에 관한 것이다. That is, this invention relates to the purification | cleaning agent of the soil and / or groundwater shown below, and the purification method of the soil and / or groundwater.
<1><1>
(A) 과산화수소를 100중량부, (A) 100 parts by weight of hydrogen peroxide,
(B) 시트르산을 적어도 10중량부, 및(B) at least 10 parts by weight of citric acid, and
(C) 물을 (A) 과산화수소와 (B) 시트르산의 합계를 100중량부로 한 경우에 적어도 15중량부 함유하고, (C) water is contained at least 15 parts by weight when the total amount of (A) hydrogen peroxide and (B) citric acid is 100 parts by weight,
(D) 알칼리 화합물을 하기 수학식 1의 시트르산(B)의 프로톤수를 만족시키기 위해 첨가하는 것을 특징으로 하는 토양 및/또는 지하수의 정화제.(D) An alkali compound is added to satisfy the proton number of citric acid (B) of the following formula (1), Soil and / or ground water purifier.
상기 수학식 1에서,In the above equation (1)
M은 시트르산(B)의 몰수이다.M is the number-of-moles of citric acid (B).
<2> <2>
상기 항목 <1>에 있어서, 과산화수소가 60중량% 이하인 과산화수소 수용액을 사용하는 토양 및/또는 지하수의 정화제.The soil and / or ground water purifier according to the above item <1>, which uses an aqueous hydrogen peroxide solution of 60% by weight or less.
<3> <3>
상기 항목 <1>에 있어서, 과산화수소가 30 내지 43중량%인 과산화수소 수용액을 사용하는 토양 및/또는 지하수의 정화제.The soil and / or ground water purifier according to the above <1>, wherein the hydrogen peroxide aqueous solution is 30 to 43 wt%.
<4> <4>
상기 항목 <1> 내지 <3> 중의 어느 한 항에 있어서, 알칼리 화합물이, 알칼리금속 수산화물, 알칼리금속 산화물, 알칼리금속 과산화물, 알칼리토금속 수산화물, 알칼리토금속 산화물, 알칼리토금속 과산화물, 암모니아, 아민, 수산화4급암모늄으로 이루어지는 그룹으로부터 선택되는 1종 이상의 화합물인 정화제.The alkali compound according to any one of items <1> to <3>, wherein the alkali compound is an alkali metal hydroxide, an alkali metal oxide, an alkali metal peroxide, an alkaline earth metal hydroxide, an alkaline earth metal oxide, an alkaline earth metal peroxide, ammonia, amine, or hydroxide 4 A purifying agent which is at least one compound selected from the group consisting of quaternary ammonium.
<5> <5>
유기 화합물로 오염된 토양 및/또는 지하수의 정화 방법으로서, A method of purifying soil and / or groundwater contaminated with organic compounds,
(A) 과산화수소를 100중량부, (A) 100 parts by weight of hydrogen peroxide,
(B) 시트르산을 적어도 10중량부, 및(B) at least 10 parts by weight of citric acid, and
(C) 물을 (A) 과산화수소와 (B) 시트르산의 합계를 100중량부로 한 경우에 적어도 15중량부 첨가하고, (C) water is added at least 15 parts by weight when the total amount of (A) hydrogen peroxide and (B) citric acid is 100 parts by weight,
(D) 알칼리 화합물을 하기 수학식 2의 시트르산(B)의 프로톤수를 만족시키기 위해서 첨가하는 것을 특징으로 하는 토양 및/또는 지하수의 정화 방법.(D) A method for purifying soil and / or groundwater, wherein an alkali compound is added to satisfy the proton number of citric acid (B) of the following formula (2).
상기 수학식 2에서,In Equation 2,
M은 시트르산(B)의 몰수이다.M is the number-of-moles of citric acid (B).
<6> <6>
상기 항목 <5>에 있어서, 알칼리 화합물이, 알칼리금속 수산화물, 알칼리금속 산화물, 알칼리금속 과산화물, 알칼리토금속 수산화물, 알칼리토금속 산화물, 알칼리토금속 과산화물, 암모니아, 아민, 수산화4급암모늄으로 이루어지는 그룹으로부터 선택되는 1종 이상의 화합물인 것을 특징으로 하는 토양 및/또는 지하수의 정화 방법.In the item <5>, the alkali compound is selected from the group consisting of alkali metal hydroxides, alkali metal oxides, alkali metal peroxides, alkaline earth metal hydroxides, alkaline earth metal oxides, alkaline earth metal peroxides, ammonia, amines and quaternary ammonium hydroxides. A method of purifying soil and / or groundwater, characterized in that at least one compound.
<7><7>
상기 항목 <5> 또는 <6> 중의 어느 한 항에 있어서, (A), (B), (C), 및 (D)를 미리 정화제로서 조제하고, 당해 정화제를 원액으로 또는 희석하여 첨가하는 토양 및/또는 지하수의 정화 방법.The soil according to any one of the above <5> or <6>, wherein (A), (B), (C), and (D) are prepared in advance as a purifying agent, and the purifying agent is added to the stock solution or diluted. And / or methods of purifying groundwater.
<8><8>
상기 항목 <5> 내지 <7> 중의 어느 한 항에 있어서, (A), (B), (C), 및 (D)의 첨가 후, 천이 금속 단체(單體), 천이 금속 산화물, 천이 금속염, 천이 금속 킬레이트로 이루어지는 그룹으로부터 선택되는 적어도 1종을 토양 및/또는 지하수에 첨가하는 것을 특징으로 하는 토양 및/또는 지하수의 정화 방법.The transition metal element, transition metal oxide, or transition metal salt according to any one of the items <5> to <7>, after the addition of (A), (B), (C), and (D). And at least one selected from the group consisting of transition metal chelates to the soil and / or groundwater.
<9> <9>
상기 항목 <8>에 있어서, 천이 금속이, 2가의 철 및/또는 3가의 철인 것을 특징으로 하는 토양 및/또는 지하수의 정화 방법.The method for purifying soil and / or ground water according to item <8>, wherein the transition metal is divalent iron and / or trivalent iron.
<10> <10>
상기 항목 <8> 또는 <9>에 있어서, 천이 금속 킬레이트가, 하기 화학식 3의 비스카르복시메틸아민계 킬레이트제로 이루어지는 것을 특징으로 하는 토양 및/또는 지하수의 정화 방법.The method for purifying soil and / or ground water according to item <8> or <9>, wherein the transition metal chelate is made of a biscarboxymethylamine chelating agent of the following general formula (3).
상기 화학식 3에서,In Chemical Formula 3,
R은 질소 원자를 포함하지 않는 유기기이고,R is an organic group containing no nitrogen atom,
X는 H 또는 알칼리금속이다.X is H or an alkali metal.
<11> <11>
상기 항목 <10>에 있어서, 상기 화학식 3에 있어서의 R이, -CH(CH3)COOX, -CH(COOH)C2H4COOX, -CH(COOX)CH2COOX, 또는 -C2H4SO3X(X는 H 또는 알칼리금속)인 토양 및/또는 지하수의 정화 방법.In the item <10>, R in the formula ( 3 ) is -CH (CH 3 ) COOX, -CH (COOH) C 2 H 4 COOX, -CH (COOX) CH 2 COOX, or -C 2 H 4 SO 3 X wherein X is H or an alkali metal.
<12> <12>
상기 항목 <8> 내지 <11> 중의 어느 한 항에 있어서, 천이 금속 단체, 천이 금속 산화물, 천이 금속염, 천이 금속 킬레이트로 이루어지는 그룹으로부터 선택되는 적어도 1종과 pH 완충제를 첨가하는 토양 및/또는 지하수의 정화 방법.The soil and / or ground water according to any one of the above <8> to <11>, wherein the pH and buffer are added to at least one selected from the group consisting of a transition metal element, a transition metal oxide, a transition metal salt, and a transition metal chelate. Purification method.
<13> <13>
상기 항목 <5> 내지 <12> 중의 어느 한 항에 있어서, 토양 및/또는 지하수를 원위치에 있어서 정화하는 것을 특징으로 하는 토양 및/또는 지하수의 정화 방법.The method for purifying soil and / or ground water according to any one of items <5> to <12>, wherein the soil and / or ground water is purified in situ.
<14><14>
상기 항목 <5> 내지 <13> 중의 어느 한 항에 있어서, 바이오레메디에이션 처리를 실시하는 토양 및/또는 지하수에, (A), (B), (C), 및 (D)를 첨가하는 것을 특징으로 하는, 토양 및/또는 지하수의 정화 방법.
The method according to any one of items <5> to <13>, wherein (A), (B), (C), and (D) are added to the soil and / or groundwater subjected to the bioremediation treatment. Characterized in that the soil and / or ground water purification method.
본 발명의 정화제에 의한 토양 및/또는 지하수의 정화 방법은 이하의 효과를 가진다. The method for purifying soil and / or ground water by the purifying agent of the present invention has the following effects.
(1) 중성 부근에 있어서 안정화된 과산화수소 수용액을 첨가하기 때문에, 중금속을 용출시키지 않고, 과산화수소를 주입 개소로부터 떨어진 장소에까지 도달시킬 수 있어 토양 및/또는 지하수의 정화 범위를 확대할 수 있다.(1) Since a stabilized aqueous hydrogen peroxide solution is added in the vicinity of neutral, hydrogen peroxide can be reached to a place away from the injection point without eluting heavy metals, and the range of purification of soil and / or ground water can be expanded.
(2) 중성 부근에 있어서 안정화된 과산화수소 수용액을 첨가하기 때문에, 정화로 연결되지 않는 과산화수소의 분해를 방지할 수 있어 과산화수소를 효율적으로 이용할 수 있다. (2) Since a stabilized aqueous hydrogen peroxide solution is added in the neutral vicinity, decomposition of hydrogen peroxide that is not linked to purification can be prevented, and hydrogen peroxide can be used efficiently.
(3) 토양 및/또는 지하수를 중성 부근으로 유지하면서, 철 등의 천이 금속 이온을 첨가하기 때문에, 중금속을 용출시키지 않고, 오염원인 유기 화합물을 분해할 수 있다.(3) Since transition metal ions such as iron are added while the soil and / or ground water are kept near neutral, organic compounds that are pollutants can be decomposed without eluting heavy metals.
(4) 미리 pH 완충제를 조합한 농후한 과산화수소 수용액을 제조할 수 있기 때문에, 정화 사이트에 있어서 조합 작업이 불필요하여 간편하게 사용할 수 있다. (4) Since the concentrated hydrogen peroxide aqueous solution which combined the pH buffer previously can be manufactured, a combination operation is unnecessary at a purification site and can be used simply.
따라서, 본 발명에 의하면, 유기 화합물로 오염된 토양 및/또는 지하수를 주변 환경, 생태계 그 밖에 영향을 주지 않고, 원위치에 있어서, 안전하고 효과적으로 정화하는 것이 가능하다.
Therefore, according to the present invention, the soil and / or groundwater contaminated with the organic compound can be safely and effectively purified in situ without affecting the surrounding environment, the ecosystem and the like.
본 발명에 있어서 정화 대상이 되는 토양 및/또는 지하수는, 유기물로 오염된 것이다. 당해 유기물로서는, 예를 들면 농약, 방부제, 석유 및 그 유분에 포함되는 방향족 화합물, 할로겐화 탄화수소 등을 들 수 있다. 석유 및 그 유분에 포함되는 방향족 화합물로서는 톨루엔, 벤젠 등을 들 수 있다. 유기염소 화합물로서는 트리클로로에틸렌(TCE), 테트라클로로에틸렌(PCE) 등을 들 수 있다. In the present invention, the soil and / or ground water to be purified is contaminated with organic matter. Examples of the organic substance include agrochemicals, preservatives, petroleum and aromatic compounds contained in the fraction thereof, halogenated hydrocarbons and the like. Toluene, benzene, etc. are mentioned as an aromatic compound contained in petroleum and its fraction. Trichloroethylene (TCE), tetrachloroethylene (PCE), etc. are mentioned as an organochlorine compound.
본 발명에 사용되는 과산화수소에는 특별히 제한은 없지만, 공업용 과산화수소 수용액을 사용하는 것이 바람직하다. Although there is no restriction | limiting in particular in hydrogen peroxide used for this invention, It is preferable to use the industrial hydrogen peroxide aqueous solution.
공업용 과산화수소 수용액 중의 과산화수소의 농도는 특별히 제한은 없지만, 60중량%보다 고농도의 과산화수소 수용액은 입수가 곤란하기 때문에, 60중량% 이하인 것이 바람직하다. 더욱 바람직한 것은, 위험물에 해당하지 않는 45중량% 이하의 과산화수소 수용액이며, 수송 비용의 관점에서 과산화수소 농도 3O중량% 이상의 과산화수소 수용액이다. The concentration of hydrogen peroxide in the aqueous hydrogen peroxide aqueous solution is not particularly limited, but it is preferable that the concentration of hydrogen peroxide solution higher in concentration than 60% by weight is 60% by weight or less. More preferred is an aqueous 45% by weight or less aqueous hydrogen peroxide solution which does not correspond to a dangerous substance, and an aqueous hydrogen peroxide solution having a hydrogen peroxide concentration of 30% by weight or more from the viewpoint of transportation cost.
본 발명의 정화제는, 과산화수소를 중성 조건하에서 안정화시키는 것 및 pH 완충제능을 부여하는 것을 목적으로, 시트르산을 함유한다. The purifying agent of the present invention contains citric acid for the purpose of stabilizing hydrogen peroxide under neutral conditions and imparting pH buffering capacity.
본 발명에 사용하는 시트르산은 공업용, 시약용, 식첨용, 약국방 중 어느 것이라도 사용 가능하다. 수용액, 수화물, 무수물 및 이들의 염이 사용 가능하다. 본 발명의 정화제에 있어서, 시트르산 농도의 하한은 정화 대상이 되는 토양 및/또는 지하수 중의 철의 양에 영향을 받지만, 과산화수소 100중량부에 대해, 적어도 10중량부를 함유한다. 시트르산이 10중량부 미만인 경우, 통상의 토양 및/또는 지하수 중에 있어서는 과산화수소의 안정성이 저하되어 정화 범위가 좁아진다. The citric acid used in the present invention can be used in any of industrial, reagent, food additives, and pharmacy room. Aqueous solutions, hydrates, anhydrides and salts thereof can be used. In the purifying agent of the present invention, the lower limit of the citric acid concentration is affected by the amount of iron in the soil and / or ground water to be purified, but contains at least 10 parts by weight based on 100 parts by weight of hydrogen peroxide. If the citric acid is less than 10 parts by weight, the stability of the hydrogen peroxide is lowered in the normal soil and / or groundwater, the purification range is narrowed.
시트르산의 보다 바람직한 배합량은, 과산화수소 100중량부에 대해 10 내지 50중량부이다. The more preferable compounding quantity of citric acid is 10-50 weight part with respect to 100 weight part of hydrogen peroxide.
본 발명의 정화제에는 또한, 안정화제로서, 시트르산 이외의 안정화제(예를 들면, 8-하이드록시퀴놀린, 1,10-페난트롤린, 벤조트리아졸, 요소, 제4급 암모늄염, 피롤리돈카복실산류, 지방족 아민, 니트로 화합물, 설파민산, 알코올류, 페놀류, 페닐글리콜에테르, 카복실산, 알코올아민, 아미노카복실산염, 알코올산, 살리실산, α-케토-카복실산에스테르, 알데히드-카복실산에스테르, 규산염, 타르타르산염, 탄탈, 지르코늄 및 니오브, 피트산, 아황산염, 유황계 안정화제, 공업용 과산화수소 수용액에 통상 첨가되는 인산계 안정화제 등)을, 필요에 따라 함유하고 있어도 된다. In the purifying agent of the present invention, a stabilizer other than citric acid (e.g., 8-hydroxyquinoline, 1,10-phenanthroline, benzotriazole, urea, quaternary ammonium salt, pyrrolidonecarboxylic acid) , Aliphatic amines, nitro compounds, sulfamic acids, alcohols, phenols, phenyl glycol ethers, carboxylic acids, alcohol amines, aminocarboxylic acids, alcoholic acids, salicylic acids, α-keto-carboxylic acid esters, aldehyde-carboxylic acid esters, silicates, tartarates , Tantalum, zirconium and niobium, phytic acid, sulfite, sulfur-based stabilizer, phosphoric acid-based stabilizer ordinarily added to an industrial aqueous hydrogen peroxide solution, and the like.
본 발명의 정화제는, 과산화수소와 시트르산의 합계 100중량부에 대해 적어도 15중량부의 물을 함유한다. 물의 함유량이 이것보다 적으면, 시트르산 및/또는 시트르산염이 석출되고, 정화제의 조성이 안정되지 않을 우려가 있다. 또한, 공업용 과산화수소 수용액을 사용하는 경우, 물의 함유량은, 이 공업용 과산화수소 수용액에 미리 포함되는 물도 포함하여 고려한다. 물의 보다 바람직한 함유량은 160 내지 2000중량부이다. The purifying agent of the present invention contains at least 15 parts by weight of water based on 100 parts by weight of the total of hydrogen peroxide and citric acid. If the content of water is less than this, citric acid and / or citrate may precipitate and the composition of the purifying agent may not be stable. In addition, when using the industrial hydrogen peroxide aqueous solution, content of water considers including the water previously contained in this industrial hydrogen peroxide aqueous solution. More preferable content of water is 160-2000 weight part.
본 발명의 정화제에는, 과산화수소와 시트르산과 물 이외에, 알칼리 화합물이 배합되어 있다. 알칼리 화합물은, 정화제에 포함되는 시트르산의 프로톤수를 조정하기 위해서 배합된다. 시트르산의 산기에 유래하는 수소 원자 및 수소 이온을 프로톤이라고 하고, 프로톤수는, 이들 시트르산의 산기에 유래하는 수소 원자 및 수소 이온의 합을 나타내는 수이다. 시트르산은 카르복실기를 3개 갖기 때문에, 정화제 중의 시트르산의 프로톤수는, 알칼리 화합물을 첨가하지 않을 경우, 이론적으로는 배합되는 시트르산의 몰수의 3배가 된다.In the purifying agent of the present invention, an alkali compound is blended in addition to hydrogen peroxide, citric acid and water. An alkali compound is mix | blended in order to adjust the proton number of citric acid contained in a purification agent. The hydrogen atom and hydrogen ion derived from the acidic radical of citric acid are called protons, and proton number is a number which shows the sum of the hydrogen atom and hydrogen ion derived from the acidic radical of these citric acid. Since citric acid has three carboxyl groups, the proton number of citric acid in a purification agent will theoretically be three times the number-of-moles of citric acid mix | blended, if an alkali compound is not added.
여기서, 정화제 중에 시트르산과 함께 알칼리 화합물을 배합하면, 당해 알칼리 화합물의 양이온과의 반응에 의해, 정화제 중의 시트르산의 카르복실기에 유래하는 수소 원자 및 수소 이온(프로톤)은 소비되며, 알칼리 화합물의 첨가량에 따라 감소된다. 즉, 본 발명의 정화제에 시트르산과 함께 알칼리 화합물을 첨가하면, 정화제 중의 시트르산의 프로톤수는, 알칼리 화합물의 첨가량에 따라서 저하된다. Here, when an alkali compound is combined with citric acid in a purifier, the hydrogen atom and hydrogen ion (proton) derived from the carboxyl group of the citric acid in a purifier are consumed by reaction with the cation of the said alkali compound, and according to the addition amount of an alkali compound Is reduced. That is, when an alkali compound is added together with citric acid to the purifying agent of this invention, the proton number of the citric acid in a purifying agent will fall according to the addition amount of an alkali compound.
상기한 바와 같이, 정화제 중의 시트르산의 프로톤수는, 알칼리 화합물을 첨가하지 않은 경우, 이론적으로는 배합되는 시트르산의 몰수의 3배가 되지만, 본 발명에서는, 이 정화제 중의 시트르산의 프로톤수를 이론값보다 적은 일정 범위로 하는 것이 중요하다. As described above, the proton number of citric acid in the purifying agent is theoretically three times the number of moles of citric acid to be formulated when the alkali compound is not added. However, in the present invention, the proton number of citric acid in the purifying agent is less than the theoretical value. It is important to have a range.
본 발명에서는, 정화제에 포함되는 시트르산의 프로톤수를, 알칼리 화합물에 의해, 수학식 1을 만족시키도록 조정한다. In the present invention, the proton number of citric acid contained in the purifying agent is adjusted to satisfy the formula (1) with an alkali compound.
수학식 1Equation 1
시트르산의 프로톤수=0.05×M 내지 0.80×MProton number of citric acid = 0.05 × M to 0.80 × M
상기 수학식 1에서,In the above equation (1)
M은 정화제에 배합되는 시트르산의 몰수이다.M is the number of moles of citric acid blended into the purifying agent.
본 발명의 수학식 1에 있어서의 정화제 중의 시트르산의 프로톤수는, 정화제 중에 함유되는 시트르산의 산기에 유래하는 수소 원자와 수소 이온의 합을 나타낸다. 본 발명에서는, 정화제로의 알칼리 화합물의 첨가량을 조정함으로써, 정화제 중의 시트르산의 프로톤수를, 수학식 1을 만족시키도록 조정할 수 있다. The proton number of citric acid in the purification | cleaning agent in Formula (1) of this invention shows the sum of the hydrogen atom and hydrogen ion derived from the acidic group of the citric acid contained in a purification agent. In this invention, the proton number of the citric acid in a purification agent can be adjusted so that Formula (1) may be satisfied by adjusting the addition amount of the alkali compound to a purification agent.
예를 들면, 시트르산의 몰수가 1몰인 경우, 수학식 1로부터 산출되는 시트르산의 프로톤수 범위는 0.05 내지 0.80이기 때문에, 알칼리 화합물로서 수산화나트륨 등의 1가 양이온의 알칼리금속 수산화물을 첨가할 때는, 하기 수학식으로 나타내는 대로 당해 알칼리 화합물을 2.20 내지 2.95몰 첨가함으로써, 최적의 시트르산의 프로톤수 범위로 할 수 있다. For example, when the number of moles of citric acid is 1 mol, the proton number range of citric acid calculated from Equation 1 is 0.05 to 0.80. Therefore, when an alkali metal hydroxide of a monovalent cation such as sodium hydroxide is added as an alkali compound, By adding 2.20-2.95 mol of the said alkali compounds as shown by a formula, it can be set as the optimal proton number range of a citric acid.
M×3-A1=M×(0.05 내지 0.80)M × 3-A 1 = M × (0.05 to 0.80)
A1=M×[3-(0.05 내지 0.80)]=M×[2.95 내지 2.20]A 1 = M × [3- (0.05 to 0.80)] = M × [2.95 to 2.20]
상기 식에서,Where
M은 배합되는 시트르산의 몰수이고,M is the number of moles of citric acid blended,
A1은 배합되는 1가 양이온의 알칼리 화합물의 몰수이다.A 1 is the number of moles of the alkali compound of the monovalent cation to be blended.
또한, 수산화마그네슘 등의 2가 양이온의 알칼리토금속 수산화물을 첨가할 때는, 하기 수학식으로 나타내는 대로 당해 알칼리 화합물을 1.10 내지 1.475몰 첨가함으로써, 최적의 시트르산의 프로톤수 범위로 할 수 있다. In addition, when adding alkaline-earth metal hydroxide of divalent cation, such as magnesium hydroxide, it can be set as the optimal proton number range of citric acid by adding 1.10-1.475 mol of the said alkali compound as shown by following formula.
M×3-A2×2=M×(0.05 내지 0.80)M x 3-A 2 x 2 = M x (0.05 to 0.80)
A2×2=M×[3-(0.05 내지 0.80)]A 2 x 2 = M x [3- (0.05 to 0.80)]
A2=M×[2.95 내지 2.20]÷2=M×[1.475 내지 1.10]A 2 = M × [2.95 to 2.20] ÷ 2 = M × [1.475 to 1.10]
상기 식에서,Where
M은 배합되는 시트르산의 몰수이고,M is the number of moles of citric acid blended,
A2는 배합되는 2가 양이온의 알칼리 화합물의 몰수이다.A 2 is the number of moles of the alkali compound of the divalent cation to be blended.
또한, 3가 이상의 양이온의 알칼리 화합물의 첨가량 범위도, 상기와 같이 구할 수 있다. 또한, 1가 양이온의 알칼리 화합물과 2가 양이온의 알칼리 화합물을 조합하는 것도 가능하다. 그 경우도, 시트르산의 프로톤수가 수학식 1에서 규정하는 범위 내가 되도록, 양자의 비율을 적절히 선택할 수 있다. Moreover, the addition amount range of the alkali compound of a trivalent or more cation can also be calculated | required as mentioned above. Moreover, it is also possible to combine the alkali compound of monovalent cation and the alkali compound of divalent cation. Also in that case, the ratio of both can be appropriately selected so that the proton number of citric acid falls within the range defined by the formula (1).
정화제에 포함되는 시트르산의 프로톤수가 수학식 1에 규정되는 범위보다 크면, 당해 정화제를 희석했을 때의 pH가 지나치게 낮아져 작업자의 위험성이 높아지거나, 사용 기기의 부식의 위험성이 높아지거나 한다. 또한, 토양 및/또는 지하수에 첨가하여 지하수에 희석되었을 때의 pH가 지나치게 낮아져 중금속의 용출을 초래하여 2차 오염의 위험성이 높아진다. 시트르산의 프로톤수가 수학식 1에 규정되는 범위보다 작으면, 당해 정화제를 희석했을 때의 pH 완충능이 약해져 과산화수소의 분해가 빨라질 우려나, 중금속이나 비소의 용출에 의한 2차 오염의 위험성이 높아질 우려가 있다. If the number of protons of citric acid contained in the purifying agent is larger than the range specified in Equation 1, the pH at the time of diluting the purifying agent is too low to increase the worker's risk or the risk of corrosion of the equipment used. In addition, when added to soil and / or groundwater and diluted in groundwater, the pH is too low, leading to elution of heavy metals, thereby increasing the risk of secondary contamination. If the number of protons of citric acid is smaller than the range specified in Equation 1, the pH buffering capacity when the purification agent is diluted becomes weak and the decomposition of hydrogen peroxide may be accelerated, or the risk of secondary contamination by elution of heavy metals or arsenic may be increased. have.
본 발명의 시트르산의 프로톤수의 조정에 사용하는 알칼리 화합물은, 그 수용액이 알카리성을 나타내는 화합물이며, 알칼리금속 수산화물, 알칼리금속 산화물, 알칼리금속 과산화물, 알칼리토금속 수산화물, 알칼리토금속 산화물, 알칼리토금속 과산화물, 암모니아, 아민, 수산화4급암모늄으로 이루어지는 그룹으로부터 선택되는 1종 이상의 화합물인 것이 바람직하다. The alkali compound used for the adjustment of the proton number of citric acid of this invention is a compound whose aqueous solution shows alkalinity, Alkali metal hydroxide, Alkali metal oxide, Alkali metal peroxide, Alkaline earth metal hydroxide, Alkaline earth metal oxide, Alkaline earth metal peroxide, Ammonia , At least one compound selected from the group consisting of amines and quaternary ammonium hydroxides.
알칼리금속 수산화물로서는, 수산화나트륨, 수산화칼륨, 수산화리튬이 바람직하다. 알칼리금속 산화물로서는, 산화나트륨, 산화칼륨, 산화리튬이 바람직하다. 알칼리금속 과산화물로서는, 과산화나트륨, 과산화칼륨, 과산화리튬이 바람직하다. As alkali metal hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. As an alkali metal oxide, sodium oxide, potassium oxide, and lithium oxide are preferable. As an alkali metal peroxide, sodium peroxide, potassium peroxide, and lithium peroxide are preferable.
알칼리토금속 수산화물로서는, 수산화마그네슘, 수산화칼슘이 바람직하다. 알칼리토금속 산화물로서는, 산화마그네슘, 산화칼슘이 바람직하다. 알칼리토금속 과산화물로서는, 과산화마그네슘, 과산화칼슘이 바람직하다. As alkaline earth metal hydroxide, magnesium hydroxide and calcium hydroxide are preferable. As alkaline earth metal oxide, magnesium oxide and calcium oxide are preferable. As alkaline earth metal peroxide, magnesium peroxide and calcium peroxide are preferable.
아민으로서는, 메틸아민, 디메틸아민, 트리메틸아민, 에틸아민, 디에틸아민, 트리에틸아민, 프로필아민, 이소프로필아민, 디이소프로필아민, 2급-부틸아민, t-부틸아민이 바람직하다. 수산화4급암모늄으로서는, 수산화테트라메틸암모늄이 바람직하다. 특히 바람직하게는, 수산화나트륨, 수산화칼륨, 수산화마그네슘, 및 암모니아로부터 선택되는 1종 이상의 화합물이다. As the amine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, secondary-butylamine and t-butylamine are preferable. As quaternary ammonium hydroxide, tetramethylammonium hydroxide is preferable. Especially preferably, it is at least one compound selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide, and ammonia.
본 발명의 정화제는 상기의 수학식 1을 만족시키도록 조제되는 한, 중성염을 함유해도 좋다. 중성염으로서는, 강산과 강염기의 중화에 의해 생기는 정염이 바람직하고, 예를 들면 염화나트륨, 염화칼륨, 염화마그네슘, 염화칼슘, 황산나트륨, 황산칼륨, 황산마그네슘, 질산나트륨, 질산칼륨, 등을 들 수 있다. The purifying agent of the present invention may contain a neutral salt so long as it is formulated to satisfy the above formula (1). As neutral salts, the salt formed by neutralization of a strong acid and a strong base is preferable, For example, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, sodium nitrate, potassium nitrate, etc. are mentioned.
본 발명의 정화제를 조제하기 위한 장치에 특별히 제한은 없으며, 널리 일반적으로 사용되는 교반기 장착 혼합조를 사용할 수 있다. 혼합조의 재질은, 스테인리스 등의 과산화수소 내성이 있는 것이면 양호하다. There is no restriction | limiting in particular in the apparatus for preparing the purifying agent of this invention, The mixing tank with agitator which is widely used generally can be used. The material of a mixing tank should just be a thing with hydrogen peroxide tolerance, such as stainless steel.
본 발명의 정화제를 조제하는 순서에 제한은 없지만, 과산화수소 수용액에 시트르산 및/또는 시트르산염을 더하고, 계속해서 수산화나트륨 수용액을 첨가하는 방법 등이 채용 가능하다. 또한, 본 발명의 정화제는 미리 조합하여 정화 사이트로 수송해도 되고, 정화 사이트에서 조합해도 된다.Although there is no restriction | limiting in the order which prepares the purification | cleaning agent of this invention, The method etc. which add citric acid and / or citrate to aqueous hydrogen peroxide solution, and then add aqueous sodium hydroxide solution etc. are employable. In addition, the purification | cleaning agent of this invention may be combined previously, and may be transported to a purification site, or may be combined at a purification site.
본 발명의 토양 및/또는 지하수의 정화 방법으로서는, 본 발명의 정화제를 그대로, 또는 희석하여 토양 및/또는 지하수에 첨가한다. 또한, 토양 및/또는 지하수 중에 있어서, 시트르산의 프로톤수가 수학식 1을 만족시키도록, 각 성분을 따로 따로 토양 및/또는 지하수에 첨가하여, 유기 화합물로 오염된 토양 및/또는 지하수를 정화할 수도 있다. 정화제의 첨가 방법에는 특별히 제한은 없으며, 주입, 압입, 분사, 교반, 자연 확산, 침투 등이 사용 가능하다. 또한, 첨가 위치와 상이한 위치에서 흡인, 감압을 실시함으로써, 첨가의 속도, 또는 방향을 제어할 수도 있다. As a method for purifying soil and / or ground water of the present invention, the purifying agent of the present invention is added to the soil and / or ground water as it is or after dilution. In addition, in the soil and / or groundwater, each component may be separately added to the soil and / or groundwater so that the proton number of citric acid satisfies Equation 1 to purify the soil and / or groundwater contaminated with the organic compound. have. There is no restriction | limiting in particular in the addition method of a purifying agent, Injecting, indenting, spraying, stirring, natural diffusion, infiltration, etc. can be used. Moreover, the speed | rate or direction of addition can also be controlled by performing suction and pressure_reduction | reduced_pressure at the position different from an addition position.
본 발명의 정화제를 희석하여 사용하는 경우는, 임의의 농도로 희석하여 사용할 수 있다. 희석제로서는 물이 바람직하지만, pH 완충제를 포함하는 수용액의 사용도 가능하다. When diluting and using the purifying agent of this invention, it can dilute to arbitrary concentration and can be used. Water is preferred as the diluent, but the use of an aqueous solution containing a pH buffer is also possible.
본 발명의 정화제를 토양 및/또는 지하수에 첨가할 때의 pH는 5 내지 8이 바람직하고, 더욱 바람직하게는 5.5 내지 7이다. pH가 낮은 정화제를 토양 및/또는 지하수에 첨가하면 중금속의 용출을 초래하여 2차 오염의 위험성이 높아지고, 지하 구조물인 철골이나 지하 배관의 부식이 생길 우려가 있다. 또한, 하수도법의 기준값에 나타내는 바와 같이, 배수의 pH가 5 이하이면 지하 구조물을 손상시킬 우려가 있다고 한다. 이 관점에서도 정화제의 pH는 5 이상인 것이 바람직하다. pH가 낮은 경우는, 희석제에 의해 pH 조정한 후 사용하는 것이 바람직하다. The pH at the time of adding the purifying agent of the present invention to the soil and / or ground water is preferably 5 to 8, more preferably 5.5 to 7. If a low pH purifier is added to the soil and / or groundwater, the leaching of heavy metals increases the risk of secondary contamination, and there is a risk of corrosion of steel structures or underground pipes, which are underground structures. Moreover, as shown by the reference value of the sewerage method, when the pH of wastewater is 5 or less, there exists a possibility that it may damage an underground structure. Also from this point of view, the pH of the purifying agent is preferably 5 or more. When pH is low, it is preferable to use, after adjusting pH with a diluent.
본 발명의 정화제를 사용하여, 토양 및/또는 지하수를 정화하는 경우, 천이 금속 등의 촉매를 병용하여, 보다 신속하게 정화를 진행시키는 것도 가능하다. 정화제를 첨가한 후에 촉매를 첨가하면 되는데, 오염이 고농도인 경우는 정화제와 촉매를 교대로 첨가하는 형태가 바람직하다. When the soil and / or ground water is purified using the purifying agent of the present invention, it is also possible to use a catalyst such as a transition metal in combination to further advance the purification. What is necessary is just to add a catalyst after adding a purifier, but when contamination is high concentration, the form which adds a purifier and a catalyst alternately is preferable.
상기 촉매는, 천이 금속 단체, 천이 금속 산화물, 천이 금속염, 천이 금속 킬레이트로 이루어지는 그룹으로부터 선택되는 적어도 1종의 천이 금속 화합물이며, 천이 금속으로서는, 2가의 철 및/또는 3가의 철인 것이 바람직하다. 더욱 바람직하게는 황산철, 염화철, 산화철, 질산철, 황화철, 수산화철, 옥시수산화철, 철 킬레이트 등이 사용 가능하며, 특히 바람직하게는 철 킬레이트이다. The catalyst is at least one transition metal compound selected from the group consisting of a transition metal element, a transition metal oxide, a transition metal salt, and a transition metal chelate, and the transition metal is preferably divalent iron and / or trivalent iron. More preferably, iron sulfate, iron chloride, iron oxide, iron nitrate, iron sulfide, iron hydroxide, iron oxyhydroxide, iron chelate and the like can be used, and particularly preferably iron chelate.
상기 촉매의 형태는, 특별히 제한을 받는 것이 아니지만, 수용액, 현탁액, 분체, 에어로졸이 사용 가능하고, 취급이 간편한 점에서 수용액이 바람직하다.Although the form of the said catalyst is not specifically limited, An aqueous solution, suspension, powder, an aerosol can be used, and aqueous solution is preferable at the point which is easy to handle.
상기 킬레이트를 조제하기 위한 킬레이트제는, 특별히 제한을 받는 것이 아니지만, 환경 부하의 관점에서 생분해성의 것을 선택하는 것이 바람직하다. 예를 들면, 하기 화학식 3의 비스카르복시메틸아민계 킬레이트제를 사용할 수 있다. Although the chelating agent for preparing said chelate is not specifically limited, It is preferable to select a biodegradable thing from a viewpoint of environmental load. For example, the biscarboxymethylamine chelating agent of the following general formula (3) can be used.
화학식 3Formula 3
상기 화학식 3에서,In Chemical Formula 3,
R은 질소 원자를 포함하지 않는 유기기이고,R is an organic group containing no nitrogen atom,
X는 H 또는 알칼리금속이다.X is H or an alkali metal.
상기 X의 알칼리금속으로서는, 나트륨(Na), 칼륨(K) 등을 들 수 있다. 바람직하게는, R은 질소 원자를 포함하지 않는 탄소수 1 내지 10, 보다 바람직하게는 탄소수 1 내지 4의 유기기를 나타낸다. 보다 바람직하게는, R은 질소 원자를 포함하지 않는 유기기로서, -COOX 및 -SO3X로 이루어지는 그룹으로부터 선택되는 적어도 하나를 포함하는 것을 의미한다. 더욱 바람직하게는, R은 질소 원자를 포함하지 않는 탄소수 1 내지 4의 유기기로서, -COOX 및 -SO3X로 이루어지는 그룹으로부터 선택되는 적어도 하나를 포함하는 것을 나타낸다. Examples of the alkali metal of X include sodium (Na), potassium (K) and the like. Preferably, R represents an organic group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, which does not contain a nitrogen atom. More preferably, R is an organic group that does not contain a nitrogen atom and means that it contains at least one selected from the group consisting of -COOX and -SO 3 X. More preferably, R represents an organic group having 1 to 4 carbon atoms that does not contain a nitrogen atom, and includes at least one selected from the group consisting of -COOX and -SO 3 X.
상기 화학식 3의 비스카르복시메틸아민계 생분해성 킬레이트제 중, 특히 바람직한 것은, 화학식 3 중의 R이 -CH(CH3)COOX, -CH(COOX)C2H4COOX, -CH(COOX)CH2COOX, 또는 -C2H4SO3X(X는 H 또는 알칼리금속)을 나타내는 것이다. Among the biscarboxymethylamine-based biodegradable chelating agents of Formula 3, R is preferably -CH (CH 3 ) COOX, -CH (COOX) C 2 H 4 COOX, -CH (COOX) CH 2 COOX, or —C 2 H 4 SO 3 X (X is H or an alkali metal).
이러한 비스카르복시메틸아민계 생분해성 킬레이트제의 예로서, 메틸글리신2아세트산, 글루탐산2아세트산, 아스파라긴산2아세트산, 2-아미노에탄설폰산2아세트산, 및 이들의 나트륨염 등을 들 수 있다. Examples of such biscarboxymethylamine biodegradable chelating agents include methylglycine diacetic acid, glutamic acid diacetic acid, aspartic acid diacetic acid, 2-aminoethanesulfonic acid diacetic acid, and sodium salts thereof.
킬레이트제의 첨가가 부족하면 수산화철의 침전을 일으키고, 과잉으로 첨가하면 정화를 저해하기 때문에, 철 이온 1몰에 대해 킬레이트제 0.5 내지 4.0배의 몰비로 사용하는 것이 바람직하다. 특히 철 이온 1몰에 대해 킬레이트제 1.0 내지 2.0배의 몰비가 킬레이트제의 첨가 효과가 높아 바람직하다. 촉매 수용액의 킬레이트제 농도로서는 50 내지 20000mg/L이 바람직하다. Insufficient addition of a chelating agent causes precipitation of iron hydroxide, and excessive addition inhibits purification, so it is preferable to use a molar ratio of 0.5 to 4.0 times the chelating agent per mole of iron ions. In particular, the molar ratio of the chelating agent 1.0 to 2.0 times per mole of iron ions is preferable because the effect of adding the chelating agent is high. As a chelating agent concentration of aqueous catalyst solution, 50-20000 mg / L is preferable.
상기 촉매는 토양 및/또는 지하수의 pH 변동을 제어하기 위해서 pH 완충제와 함께 사용하는 것이 바람직하다. pH 완충제로서는, 탄산계가 바람직하다. 탄산계 완충제로서는, 탄산나트륨, 탄산칼륨, 탄산칼슘, 탄산마그네슘, 탄산수소나트륨, 탄산수소칼륨 등을 사용할 수 있다. 이 중, 비용이나 용해도, pH의 관점에서는 탄산수소나트륨을 단독으로 사용하거나, 또는 탄산수소나트륨과 탄산나트륨을 병용하는 것이 바람직하다. pH 완충제로서, 붕산 또는 인산을 사용하는 것은 붕산 또는 인산에 의한 지하수의 오염을 초래할 우려가 있고, 아세트산은 펜톤 반응을 방해할 우려가 있기 때문에, 바람직하지 못하다. 정화 대상의 pH가 5 내지 10의 범위이면, pH의 저하가 생겨도, 반드시 pH 완충제의 첨가는 필요하지 않지만, 정화 기간단축을 위해서는 pH 완충제를 첨가하여 pH 7 내지 9로 제어하는 것이 바람직하다. The catalyst is preferably used with a pH buffer to control the pH variation of the soil and / or groundwater. As the pH buffer, a carbonic acid system is preferable. As the carbonic acid-based buffer, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like can be used. Among them, from the viewpoint of cost, solubility, and pH, it is preferable to use sodium hydrogencarbonate alone or to use sodium hydrogencarbonate and sodium carbonate together. The use of boric acid or phosphoric acid as the pH buffer is undesirable because it may cause contamination of groundwater by boric acid or phosphoric acid, and acetic acid may interfere with the Fenton reaction. If the pH of the purification target is in the range of 5 to 10, even if the pH decreases, the addition of the pH buffer is not necessarily required, but for shortening the purification period, it is preferable to control the pH to 7 to 9 by adding a pH buffer.
본 발명은, 원위치 정화 및/또는 장외에서의 2차 처리에도 응용 가능하다. 또한, 본 발명의 정화제를 산소원 및/또는 영양원으로서 사용함으로써, 바이오레메디에이션 처리를 실시하는 토양 및/또는 지하수의 정화 처리에 이용하는 것도 가능하다.
The present invention is also applicable to in-situ purification and / or secondary treatment outside the intestine. In addition, by using the purifying agent of the present invention as an oxygen source and / or a nutrient source, it is also possible to use it for the purification process of soil and / or groundwater subjected to bioremediation treatment.
실시예Example
다음에 실시예를 나타내고, 본 발명을 더욱 구체적으로 설명한다. 단 본 발명은 이하의 실시예에 의해 제한되는 것이 아니다. 한편, 과산화수소의 농도는 과망간산칼륨 적정법에 의해 구하였다. Next, an Example is shown and this invention is demonstrated further more concretely. However, the present invention is not limited by the following examples. In addition, the concentration of hydrogen peroxide was calculated | required by the potassium permanganate titrimetric method.
<실시예 1>≪ Example 1 >
순수(純水)에 FeSO4·7H2O[참조: 와코쥰야쿠 가부시키가이샤 제조 특급 시약]를 용해시켜서, 모의 지하수를 조제하였다. 35중량% 과산화수소 수용액[참조: 미쓰비시가스가가쿠 가부시키가이샤 제조 공업용]에, 과산화수소 100중량부에 대해 20중량부의 시트르산(무수)[참조: 코소우가가쿠야쿠힌 가부시키가이샤 제조 특급 시약], 염기와 시트르산의 몰비를 수산화나트륨/시트르산=2.85/1(몰비)로 한 수산화나트륨[참조: 와코쥰야쿠 가부시키가이샤 제조 특급 시약], 및 순수(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대해 568중량부)를 가하여 용해시켜서 정화제(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 함유 수량 723중량부)를 조제하였다. 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여, 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 1에 기재한다.
FeSO 4 .7H 2 O (reference: Wako Pure Chemical Industries, Ltd. special reagent) was dissolved in pure water to prepare simulated ground water. 20 parts by weight of citric acid (anhydrous) (refer to Koso Kagaku Chemical Co., Ltd. special reagent manufactured by Kosuga Chemical Co., Ltd.), base and Sodium hydroxide [refer to Wako Pure Chemical Industries, Ltd. express reagent] whose molar ratio of citric acid was made into sodium hydroxide / citric acid = 2.85 / 1 (molar ratio), and pure water (568 weight part with respect to a total of 100 weight part of addition amounts of hydrogen peroxide and a citric acid). Parts) were added to dissolve to prepare a purifying agent (containing 723 parts by weight of water with respect to 100 parts by weight of the total amount of hydrogen peroxide and citric acid added). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 1.
<비교예 1>Comparative Example 1
실시예 1의 시트르산(무수) 대신에, DL-타르타르산[참조: 칸토가가쿠 가부시키가이샤 제조 특급 시약]을 사용하고, 염기와 타르타르산의 몰비를, 수산화나트륨/타르타르산=1.95/1로 한 것 이외에는 실시예 1과 같이 정화제를 조제하였다. 단, 순수의 추가 첨가량은, 과산화수소와 시트르산의 첨가량의 합계 100중량부에 대해 567중량부이며, 조정후의 정화제 중의 함유 수량은 722중량부였다. 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 1에 기재한다.
Instead of citric acid (anhydrous) of Example 1, DL-tartaric acid (Ref. Kantogaku Co., Ltd. special reagent) was used, except that the molar ratio of the base and tartaric acid was set to sodium hydroxide / tartaric acid = 1.95 / 1. Purifying agent was prepared in the same manner as in Example 1. However, the addition amount of pure water was 567 weight part with respect to a total of 100 weight part of the addition amount of hydrogen peroxide and a citric acid, and the water content in the purification | cleaning agent after adjustment was 722 weight part. The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 1.
<비교예 2>Comparative Example 2
실시예 1의 시트르산(무수) 대신에, DL-말산[참조: 칸토가가쿠 가부시키가이샤 제조 특급 시약]을 사용하고, 염기와 말산의 몰비를, 수산화나트륨/말산=1.95/1로 한 것 이외에는 실시예 1과 같이 정화제를 조제하였다. 단, 순수의 추가 첨가량은, 과산화수소와 시트르산의 첨가량의 합계 100중량부에 대해 565중량부이며, 조정후의 정화제 중의 함유 수량은 720중량부였다. 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 1에 기재한다.Instead of citric acid (anhydrous) of Example 1, DL-malic acid (Ref. Kanto Chemical Co., Ltd. special reagent) was used, except that the molar ratio of base to malic acid was set to sodium hydroxide / malic acid = 1.95 / 1. Purifying agent was prepared in the same manner as in Example 1. However, the addition amount of pure water was 565 weight part with respect to a total of 100 weight part of the addition amount of hydrogen peroxide and a citric acid, and the water content in the purification agent after adjustment was 720 weight part. The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 1.
실시예 1의 결과로부터, 중성 부근에 있어서 시트르산이 과산화수소를 안정화하는 것이 나타났다. 이것에 대해, 비교예 1 및 비교예 2의 결과로부터, 중성 부근에 있어서 타르타르산 및 말산은 과산화수소를 안정화할 수 없는 것이 나타났다.
From the result of Example 1, citric acid stabilized hydrogen peroxide in neutral vicinity. On the other hand, from the result of the comparative example 1 and the comparative example 2, it showed that tartaric acid and malic acid cannot stabilize hydrogen peroxide in neutral vicinity.
<비교예 3>Comparative Example 3
염기와 시트르산의 몰비를, 수산화나트륨/시트르산=3.00/1로 한 것 이외에는, 실시예 1과 동일한 조건으로 정화제(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 568중량부, 정화제 중의 함유 수량은 723중량부)를 조제하고, 과산화수소의 안정성을 비교하였다. 그 결과를 표 2에 기재한다.Except for setting the molar ratio of base and citric acid to sodium hydroxide / citric acid = 3.00 / 1, the amount of pure water added to the purifying agent (100 parts by weight of the total amount of hydrogen peroxide and citric acid added) was 568 parts by weight, 723 parts by weight of the amount of water contained in the purifying agent was prepared to compare the stability of hydrogen peroxide. The results are shown in Table 2.
실시예 1의 결과로부터, 본원 발명의 시트르산의 프로톤수를 만족시키도록 알칼리 화합물에 의해 조정한 경우에는, 과산화수소가 안정화되어 있는 것이 나타났다. 이것에 대해, 비교예 3의 결과로부터, 본원 발명의 시트르산의 프로톤수를 만족시키지 않는 경우에는, 과산화수소가 안정화되어 있지 않는 것이 나타났다.
The result of Example 1 showed that hydrogen peroxide was stabilized when it adjusted with the alkali compound so that the proton number of the citric acid of this invention may be satisfied. On the other hand, from the result of the comparative example 3, when the proton number of the citric acid of this invention is not satisfied, it turned out that hydrogen peroxide is not stabilized.
<실시예 2 내지 5><Examples 2 to 5>
35중량% 과산화수소 수용액[참조: 미쓰비시가스가가쿠 가부시키가이샤 제조 공업용]에, 과산화수소 100중량부에 대해 20중량부의 시트르산(무수)[참조: 코소우가가쿠야쿠힌 가부시키가이샤 제조 특급 시약], 수산화나트륨, 및 순수를 첨가하고 용해시켜 정화제를 조제하였다. 정화제에 있어서의 염기와 시트르산의 몰비는, 수산화나트륨/시트르산=2.95/1 내지 2.20/1로 하였다. 추가 첨가한 순수량 및 정화제 중의 함유 수량은, 표 3에 기재한 대로이다. 조제한 정화제의 pH를 표 3에 기재한다.
20 parts by weight of citric acid (anhydrous) [refer to Koso Kagaku Chemical Co., Ltd. special reagent manufactured by Koso Kagaku Chemical Co., Ltd.], sodium hydroxide in an aqueous solution of 35% by weight of hydrogen peroxide [Ref. , And pure water were added and dissolved to prepare a purifying agent. The molar ratio of the base and citric acid in the purifying agent was sodium hydroxide / citric acid = 2.95 / 1 to 2.20 / 1. The amount of pure water added and the amount of water contained in the purifying agent are as shown in Table 3. The pH of the prepared purification agent is shown in Table 3.
<비교예 4><Comparative Example 4>
염기와 시트르산의 몰비를, 수산화나트륨/시트르산=2.10/1으로 한 것 이외에는, 실시예 2 내지 5와 같이 하여 정화제를 조제하였다. 추가 첨가한 순수량 및 정화제 중의 함유 수량은, 표 3에 기재한 대로이다. 조제한 정화제의 pH를 표 3에 기재한다.Purifying agents were prepared in the same manner as in Examples 2 to 5, except that the molar ratio of the base to citric acid was set to sodium hydroxide / citric acid = 2.10 / 1. The amount of pure water added and the amount of water contained in the purifying agent are as shown in Table 3. The pH of the prepared purification agent is shown in Table 3.
실시예 2 내지 5 및 비교예 4의 결과로부터, 시트르산의 프로톤수가 본원 발명의 범위를 만족시키는 경우에는, 정화제의 pH가 5.0 이상이 되어, 정화제의 pH로서 적합한 것이 나타났다.
From the results of Examples 2 to 5 and Comparative Example 4, when the proton number of citric acid satisfied the scope of the present invention, the pH of the purifying agent was 5.0 or more, indicating that the pH of the purifying agent was suitable.
<실시예 6><Example 6>
순수에 FeSO4·7H2O[참조: 와코쥰야쿠 가부시키가이샤 제조 특급 시약]을 용해시켜서 모의 지하수를 조제하였다. 35중량% 과산화수소 수용액[참조: 미쓰비시가스가가쿠 가부시키가이샤 제조 공업용]에, 과산화수소 100중량부에 대해 100중량부의 시트르산(무수)[참조: 코소우가가쿠야쿠힌 가부시키가이샤 제조 특급 시약], 염기와 시트르산의 몰비를 수산화나트륨/시트르산=2.85/1(몰비)로 한 수산화나트륨, 및 순수(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대해 278중량부)를 첨가하고 용해시켜 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 함유 수량은 370중량부).A simulated groundwater was prepared by dissolving FeSO 4 .7H 2 O (Ref .: Wako Pure Chemical Industries, Ltd. special reagent) in pure water. 100 parts by weight of citric acid (anhydrous) (refer to Koso Kagaku Chemical Co., Ltd. special reagent manufactured by Koso Kagaku Chemical Co., Ltd.), base and 35% by weight aqueous hydrogen peroxide solution [refer to Mitsubishi Gas Chemical Co., Ltd. industry]. Sodium hydroxide having a molar ratio of citric acid to sodium hydroxide / citric acid = 2.85 / 1 (molar ratio) and pure water (278 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added) were added and dissolved to prepare a purifying agent (hydrogen peroxide). Content of the total amount of the addition amount of the citric acid and 100 parts by weight of 370 parts by weight).
과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 7><Example 7>
실시예 6의 시트르산의 함유량을, 과산화수소 100중량부에 대해 50중량부의 시트르산으로 한 것 이외에는, 실시예 6과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 433중량부, 정화제 중의 함유 수량은 559중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
Purifying agent was prepared in the same manner as in Example 6 except that the content of citric acid in Example 6 was 50 parts by weight of citric acid per 100 parts by weight of hydrogen peroxide (addition of pure water to 100 parts by weight of the total amount of hydrogen peroxide and citric acid added). The addition amount is 433 parts by weight, and the amount of water contained in the purifying agent is 559 parts by weight). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 8><Example 8>
실시예 6의 시트르산의 함유량을, 과산화수소 100중량부에 대해 20중량부의 시트르산으로 한 것 이외에는, 실시예 6과 같이 하여 정화제를 조정하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 569중량부, 정화제 중의 함유 수량은 723중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
The purifying agent was adjusted in the same manner as in Example 6 except that the content of citric acid in Example 6 was 20 parts by weight of citric acid per 100 parts by weight of hydrogen peroxide (addition of pure water to 100 parts by weight of the total amount of hydrogen peroxide and citric acid added). The amount of addition was 569 parts by weight, and the amount of water contained in the purifying agent was 723 parts by weight). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 9>Example 9
실시예 6의 시트르산의 함유량을, 과산화수소 100중량부에 대해 10중량부의 시트르산으로 한 것 이외에는, 실시예 6과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 636중량부, 정화제 중의 함유 수량은 804중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
A purifying agent was prepared in the same manner as in Example 6 except that the content of citric acid in Example 6 was 10 parts by weight of citric acid per 100 parts by weight of hydrogen peroxide (addition of pure water to 100 parts by weight of the total amount of hydrogen peroxide and citric acid added). The amount of addition was 636 parts by weight, and the amount of water contained in the purifying agent was 804 parts by weight). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<비교예 5>Comparative Example 5
실시예 6의 시트르산의 함유량을, 과산화수소 100중량부에 대해 5중량부의 시트르산으로 한 것 이외에는, 실시예 6과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 673중량부, 정화제 중의 함유 수량은 850중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
A purifying agent was prepared in the same manner as in Example 6 except that the content of citric acid in Example 6 was 5 parts by weight of citric acid per 100 parts by weight of hydrogen peroxide (addition of pure water to 100 parts by weight of the total amount of hydrogen peroxide and citric acid added). The addition amount is 673 parts by weight, and the amount of water contained in the purifying agent is 850 parts by weight). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<비교예 6>Comparative Example 6
실시예 6의 시트르산의 함유량을, 과산화수소 100중량부에 대해 2중량부의 시트르산으로 한 것 이외에는, 실시예 6과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 698중량부, 정화제 중의 함유 수량은 880중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다. A purifying agent was prepared in the same manner as in Example 6 except that the content of citric acid in Example 6 was 2 parts by weight of citric acid per 100 parts by weight of hydrogen peroxide (addition of pure water to 100 parts by weight of the total amount of hydrogen peroxide and citric acid added). The amount of addition was 698 parts by weight, and the amount of water contained in the purifying agent was 880 parts by weight). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 10><Example 10>
실시예 8의 수산화나트륨 대신에 수산화칼륨을 사용하고, 염기와 시트르산의 몰비를 수산화칼륨/시트르산=2.85/1(몰비)로 한 것 이외에는, 실시예 8과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 561중량부, 정화제 중의 함유 수량은 716중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
Purifying agent was prepared in the same manner as in Example 8 except that potassium hydroxide was used instead of sodium hydroxide of Example 8 and the molar ratio of base to citric acid was set to potassium hydroxide / citric acid = 2.85 / 1 (molar ratio) (hydrogen peroxide and citric acid). 561 parts by weight of pure water with respect to a total of 100 parts by weight of the total amount of added 716 parts by weight in the purifying agent). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 11><Example 11>
실시예 8의 수산화나트륨 대신에 수산화마그네슘을 사용하고, 수산화마그네슘/시트르산=1.425/1(몰비)로 한 것 이외에는, 실시예 8과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 567중량부, 정화제 중의 함유 수량은 722중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
A purification agent was prepared in the same manner as in Example 8 except that magnesium hydroxide was used instead of sodium hydroxide of Example 8 and magnesium hydroxide / citric acid = 1.425 / 1 (molar ratio) (total amount of 100% of the total amount of hydrogen peroxide and citric acid added). 567 parts by weight of the pure water to the parts, 722 parts by weight of water contained in the purifying agent). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 12><Example 12>
실시예 8의 수산화나트륨 대신에 암모니아를 사용하고, 암모니아/시트르산=2.85/1(몰비)로 한 것 이외에는, 실시예 8과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 568중량부, 정화제 중의 함유 수량은 723중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
A purification agent was prepared in the same manner as in Example 8 except that ammonia was used instead of sodium hydroxide of Example 8 and ammonia / citric acid was 2.85 / 1 (molar ratio) (to 100 parts by weight of the total amount of hydrogen peroxide and citric acid added). 568 parts by weight of the pure water was added thereto, and the amount of water contained in the purifier was 723 parts by weight). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 13>Example 13
실시예 8의 수산화나트륨 대신에 수산화나트륨 및 암모니아를 사용하고, 수산화나트륨/암모니아/시트르산=1.425/1.425/1(몰비)으로 한 것 이외에는, 실시예 8과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 572중량부, 정화제 중의 함유 수량은 727중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다.
Purifying agent was prepared in the same manner as in Example 8 except that sodium hydroxide and ammonia were used instead of sodium hydroxide of Example 8 and sodium hydroxide / ammonia / citric acid = 1.425 / 1.425 / 1 (molar ratio) (hydrogen peroxide and citric acid). 572 parts by weight of pure water relative to a total of 100 parts by weight of the total amount of added water, and the amount of water contained in the purifying agent was 727 parts by weight). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
<실시예 14><Example 14>
실시예 8의 수산화나트륨 대신 수산화나트륨 및 수산화마그네슘을 사용하고, 수산화나트륨/수산화마그네슘/시트르산=1.425/0.713/1(몰비)이라고 한 것 이외에는, 실시예 8과 같이 하여 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 570중량부, 정화제 중의 함유 수량은 725중량부). 과산화수소 농도 1.0중량%, Fe 이온 농도 25mg/kg이 되도록 모의 지하수 및 정화제를 혼합하여 삼각 플라스크에 넣고, 50℃ 항온 수조 중에 24시간 동안 정치시켰다. 정치 전후의 과산화수소 농도로부터, 과산화수소의 안정성을 비교하였다. 그 결과를 표 4에 기재한다. A purification agent was prepared in the same manner as in Example 8 except that sodium hydroxide and magnesium hydroxide were used instead of sodium hydroxide of Example 8, and sodium hydroxide / magnesium hydroxide / citric acid = 1.425 / 0.713 / 1 (molar ratio). (570 parts by weight of the pure water added to 100 parts by weight of the total amount of citric acid added) and 725 parts by weight of the water contained in the purifying agent). The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0 wt% and the Fe ion concentration was 25 mg / kg, and the mixture was placed in a Erlenmeyer flask and allowed to stand for 24 hours in a 50 ° C constant temperature water bath. From the hydrogen peroxide concentration before and after standing, the stability of hydrogen peroxide was compared. The results are shown in Table 4.
실시예 6 내지 14의 결과로부터, 정화제에 10중량부 이상의 시트르산을 함유하는 경우에는, 과산화수소 잔존율이 높고, 과산화수소가 안정화되어 있는 것이 나타났다. 한편, 비교예 5 및 비교예 6의 결과로부터, 정화제의 시트르산이 10중량부 미만인 경우에는, 과산화수소 잔존율이 현저하게 저하되어 과산화수소가 안정화되어 있지 않고, 또한 철의 침전이 확인되었다. 이상의 결과로부터, 시트르산을 적어도 10중량부 함유하는 중성 부근의 정화제가, 과산화수소를 안정화할 수 있는 정화제로서 적합한 것이 나타났다.
From the results of Examples 6 to 14, it was found that when the purifying agent contains 10 parts by weight or more of citric acid, the hydrogen peroxide residual ratio is high and the hydrogen peroxide is stabilized. On the other hand, from the results of Comparative Example 5 and Comparative Example 6, when the citric acid of the purifying agent is less than 10 parts by weight, the hydrogen peroxide residual rate is remarkably lowered, hydrogen peroxide is not stabilized, and iron precipitation was confirmed. From the above result, it was shown that the purification | purification agent in neutral vicinity containing at least 10 weight part of citric acid is suitable as a purification | purification agent which can stabilize hydrogen peroxide.
<실시예 15 내지 16><Examples 15 to 16>
수산화나트륨과 시트르산의 몰비를 수산화나트륨/시트르산=2.85/1로 하고, 중성염으로서 염화나트륨 또는 황산칼륨을 첨가한 것 이외에는, 실시예 8과 같이 하여 정화제를 조제하고, 과산화수소의 안정성을 비교하였다. 중성염과 시트르산의 몰비는, 실시예 15에서는 염화나트륨/시트르산=0.5/1로 하고, 실시예 16에서는 황산칼륨/시트르산=0.25/1로 하였다. 또한, 실시예 15에서는 과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 566중량부, 정화제 중의 함유 수량은 721중량부이며, 실시예 16에서는 과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 565중량부, 정화제 중의 함유 수량은 720중량부였다. 그 결과를 표 5에 기재한다.The molar ratio of sodium hydroxide and citric acid was set to sodium hydroxide / citric acid = 2.85 / 1, and the purification agent was prepared like Example 8 except having added sodium chloride or potassium sulfate as a neutral salt, and the stability of hydrogen peroxide was compared. The molar ratio of neutral salt and citric acid was set to sodium chloride / citric acid = 0.5 / 1 in Example 15, and potassium sulfate / citric acid = 0.25 / 1 in Example 16. In Example 15, the total amount of the pure water added to the total of 100 parts by weight of the hydrogen peroxide and the citric acid added was 566 parts by weight, and the amount of water contained in the purifying agent was 721 parts by weight. In Example 16, the total amount of the added amounts of the hydrogen peroxide and the citric acid was 100% by weight. The amount of pure water added to the part was 565 parts by weight, and the amount of water contained in the purifying agent was 720 parts by weight. The results are shown in Table 5.
실시예 15 및 16으로부터, 정화제가 중성염을 함유하고 있는 경우도, 과산화수소가 안정화되어 있는 것이 나타났다.
Examples 15 and 16 show that hydrogen peroxide is stabilized even when the purifying agent contains a neutral salt.
<실시예 17 내지 20><Examples 17 to 20>
과산화수소 농도는 6.55중량%, 시트르산 농도는 0.655중량%, 수산화나트륨 농도는 0.389중량%의 정화제를 조제하였다(과산화수소와 시트르산의 첨가량의 합계 100중량부에 대한 순수의 추가 첨가량은 1117중량부, 정화제 중의 함유 수량은 1286중량부). 또한, Fe 화합물을 순수에 용해시켜서 철 이온 농도가 0.2O중량%인 촉매 수용액을 조제하였다. 촉매 수용액의 조제는, 실시예 17에서는 FeSO4·7H2O[참조: 와코쥰야쿠 가부시키가이샤 제조 특급 시약]을 순수에 용해시켜서 조제하고, 실시예 18에서는 FeSO4·7H2O 0.116g, 0.5M 황산 0.209g, 및 BASF재팬 가부시키가이샤 제조의 40중량% 메틸글리신2아세트산3나트륨염(MGDA, 상품명 「Trilon M(등록상표)」) 0.220g을 순수에 용해시켜서 조제하고, 실시예 19에서는 FeSO4·7H2O 0.127g, 및 나카베키레스트 가부시키가이샤 제조의 (S,S)-에틸렌디아민디석신산3나트륨염(EDDS, 상품명 「키레스트 EDDS-35」) 0.459g을 순수에 용해시켜서 조제하고, 실시예 20에서는 FeSO4·7H2O 0.130g, 및 50중량% 글루콘산 수용액 0.183g을 순수에 용해시켜서 조제하였다. 6.55 wt% of hydrogen peroxide, 0.655 wt% of citric acid, and 0.389 wt% of sodium hydroxide were prepared (additional amount of pure water was 1117 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and Water content of 1286 parts by weight). In addition, the Fe compound was dissolved in pure water to prepare an aqueous catalyst solution having an iron ion concentration of 0.2O% by weight. In Example 17, FeSO 4 .7H 2 O (Reference: Wako Pure Chemical Industries, Ltd. special reagent) was dissolved in pure water to prepare a catalyst aqueous solution. In Example 18, 0.116 g of FeSO 4 .7H 2 O, 0.209 g of 0.5 M sulfuric acid and 0.220 g of 40% by weight methylglycine diacetic acid trisodium salt (MGDA, trade name `` Trilon M '') manufactured by BASF Japan were prepared by dissolving in pure water, Example 19 0.127 g of FeSO 4 · 7H 2 O and 0.459 g of (S, S) -ethylenediaminedisuccinic acid trisodium salt (EDDS, trade name "Kyrest EDDS-35") manufactured by Nakabekirest Co., Ltd. are dissolved in pure water. In Example 20, 0.130 g of FeSO 4 · 7H 2 O and 0.183 g of a 50% by weight aqueous solution of gluconic acid were dissolved and prepared in pure water.
131mL의 바이알병에, 휘발성 유기 화합물로서 테트라클로로에틸렌(PCE)을 53.3mg/L의 농도로 용해시킨 모의 오염수 100mL, 정화제 1mL, 탄산수소나트륨/탄산나트륨의 조합에 의한 완충제(탄산수소나트륨 농도 18.7g/L, 탄산나트륨 농도0.10g/L) 10mL, 촉매 수용액 1mL, 순수 19mL을 넣은 후, 밀폐하여 실온에서 정화 시험을 실시하였다. 반응 개시로부터 한시간 경과후, 반응액을 헤드 스페이스·가스 크로마토그래프법에 의해 분석하고, PCE 분해능을 비교하였다. 그 결과를 표 6에 기재한다.In a 131 mL vial bottle, 100 mL of simulated contaminated water in which tetrachloroethylene (PCE) was dissolved at a concentration of 53.3 mg / L as a volatile organic compound, a buffer of 1 mL of a purifying agent, and a combination of sodium bicarbonate / sodium carbonate (sodium bicarbonate concentration 18.7) 10 mL of g / L, sodium carbonate concentration 0.10 g / L), 1 mL of catalyst aqueous solution, and 19 mL of pure water were added, and it sealed and performed the purification test at room temperature. After one hour from the start of the reaction, the reaction solution was analyzed by head space gas chromatography, and the PCE resolution was compared. The results are shown in Table 6.
실시예 17 내지 20으로부터, 철 촉매의 존재하에서 휘발성 유기 화합물의 분해가 진행되는 것이 나타났다. 또한, 실시예 18로부터, 비스카르복시메틸아민계 킬레이트제를 사용한 경우에 휘발성 유기 화합물의 분해가 크게 진행되는 것이 나타났다.
It was found from Examples 17 to 20 that decomposition of volatile organic compounds proceeds in the presence of an iron catalyst. Moreover, from Example 18, when the biscarboxymethylamine type chelating agent was used, it showed that decomposition | disassembly of a volatile organic compound greatly advances.
산업상의 이용분야Industrial use
본 발명에 의하면, 유기 화합물로 오염된 토양 및/또는 지하수를 주변 환경, 생태계 그 밖에 영향을 주지 않고, 원위치에 있어서, 안전하고 효과적으로 정화하는 것이 가능하다.
According to the present invention, the soil and / or groundwater contaminated with the organic compound can be safely and effectively purified in situ without affecting the surrounding environment, the ecosystem and others.
Claims (14)
(B) 시트르산을 적어도 10중량부 및
(C) 물을 (A) 과산화수소와 (B) 시트르산의 합계를 100중량부로 한 경우에 적어도 15중량부 함유하고,
(D) 알칼리 화합물을 하기 수학식 1의 시트르산(B)의 프로톤수를 만족시키기 위해서 첨가하는 것을 특징으로 하는 토양 및/또는 지하수의 정화제.
수학식 1
시트르산(B)의 프로톤수=0.05×M 내지 0.80×M
상기 수학식 1에서,
M은 시트르산(B)의 몰수이다.(A) 100 parts by weight of hydrogen peroxide,
(B) at least 10 parts by weight of citric acid and
(C) water is contained at least 15 parts by weight when the total amount of (A) hydrogen peroxide and (B) citric acid is 100 parts by weight,
(D) The alkaline compound is added to satisfy the proton number of citric acid (B) of the following formula (1), Soil and / or groundwater purifier.
Equation 1
Proton number of citric acid (B) = 0.05 × M to 0.80 × M
In Equation 1,
M is the number-of-moles of citric acid (B).
(A) 과산화수소를 100중량부,
(B) 시트르산을 적어도 10중량부 및
(C) 물을 (A) 과산화수소와 (B) 시트르산의 합계를 100중량부로 한 경우에 적어도 15중량부 첨가하고,
(D) 알칼리 화합물을 하기 수학식 2의 시트르산(B)의 프로톤수를 만족시키기 위해 첨가하는 것을 특징으로 하는 토양 및/또는 지하수의 정화 방법.
수학식 2
시트르산(B)의 프로톤수=0.05×M 내지 0.80×M
상기 수학식 2에서,
M은 시트르산(B)의 몰수이다.A method of purifying soil and / or groundwater contaminated with organic compounds,
(A) 100 parts by weight of hydrogen peroxide,
(B) at least 10 parts by weight of citric acid and
(C) water is added at least 15 parts by weight when the total amount of (A) hydrogen peroxide and (B) citric acid is 100 parts by weight,
(D) A method for purifying soil and / or groundwater, wherein an alkali compound is added to satisfy the proton number of citric acid (B) of the following formula (2).
Equation 2
Proton number of citric acid (B) = 0.05 × M to 0.80 × M
In Equation 2,
M is the number-of-moles of citric acid (B).
화학식 3
상기 화학식 3에서,
R은 질소 원자를 포함하지 않는 유기기이고,
X는 H 또는 알칼리금속이다.The method for purifying soil and / or groundwater according to claim 8 or 9, wherein the transition metal chelate is composed of a biscarboxymethylamine chelating agent of the following general formula (3).
Formula 3
In Chemical Formula 3,
R is an organic group containing no nitrogen atom,
X is H or an alkali metal.
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| CN103464455B (en) * | 2013-09-11 | 2015-05-13 | 中科华南（厦门）环保有限公司 | Method for carrying out chemical oxidation repair on organic contaminated soil by compounding potassium permanganate (KMnO4) and hydrogen peroxide (H2O2) |
| CN103482751A (en) * | 2013-10-14 | 2014-01-01 | 河海大学 | Application of biodegradable chelating agent EDDS (Ethylenediaminedisuccinic Acid) to treatment on non-degradable organic wastewater |
| CN106794494B (en) * | 2014-05-04 | 2021-07-02 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Remediation of contaminated soil |
| CN104178177B (en) * | 2014-08-12 | 2017-07-28 | 上田环境修复股份有限公司 | A kind of macromolecule chromium stabilizer and preparation method thereof and its application |
| CN104692515A (en) * | 2015-02-04 | 2015-06-10 | 华东理工大学 | Method for removing chloro-olefin in water through strengthening activating calcium peroxide |
| CN104889152B (en) * | 2015-06-04 | 2017-06-23 | 西安建筑科技大学 | A kind of degradation selectivity method rich in organic soil petrochina pollutant |
| CN106337028A (en) * | 2015-07-17 | 2017-01-18 | 上海海洋大学 | Cleaning agent, and preparation method and application thereof |
| CN105565466A (en) * | 2016-03-02 | 2016-05-11 | 清泽环境发展（北京）有限公司 | Efficient environment-friendly Fenton's reagent and method thereof for oxidizing and treating nitrobenzene |
| JP6817899B2 (en) * | 2016-06-10 | 2021-01-20 | 宇部マテリアルズ株式会社 | Oxygen sustained release agent, its manufacturing method and oxygen supply method |
| CN105906073A (en) * | 2016-06-29 | 2016-08-31 | 江苏艾特克环境工程设计研究院有限公司 | Oxidant for treating chemical wastewater and preparation method thereof |
| CN106799396B (en) * | 2017-03-01 | 2022-04-08 | 北京建工环境修复股份有限公司 | High-pressure rotary spraying and shallow layer stirring combined in-situ remediation method for soil and underground water |
| CN107442565A (en) * | 2017-09-30 | 2017-12-08 | 青岛农业大学 | A kind of method and device of in-situ immobilization polycyclic aromatic hydrocarbon polluted farmland soil |
| CN107470338A (en) * | 2017-09-30 | 2017-12-15 | 青岛农业大学 | The in-situ remediation method and system of plasticiser and heavy metal lead pollution agricultural land soil |
| CN107617635A (en) * | 2017-09-30 | 2018-01-23 | 青岛农业大学 | The class Fenton restorative procedure in situ and system of phthalic acid ester and As polluted soil |
| CN107413840A (en) * | 2017-09-30 | 2017-12-01 | 青岛农业大学 | The in-situ remediation method and system of heavy metal cadmium and polycyclic aromatic hydrocarbon polluted farmland soil |
| CN107470339A (en) * | 2017-09-30 | 2017-12-15 | 青岛农业大学 | The method and system of polycyclic aromatic hydrocarbon pollution is repaired in class Fenton and microorganism combination |
| CN109351768A (en) * | 2018-11-14 | 2019-02-19 | 中国石油大学(华东) | A kind of method of chemical oxidation and chemical leaching renovation of heavy metal polluted soil with combined |
| CN110961451B (en) * | 2019-12-30 | 2021-07-23 | 上海交通大学 | Soil remediation material for oxidative degradation of organic pollutants and soil remediation method |
| CN111760899B (en) * | 2020-06-22 | 2021-08-24 | 南京农业大学 | Feeding improvement method for repairing toxic organic contaminated soil through oxidant compounding oxidation |
| CN113072235A (en) * | 2021-04-22 | 2021-07-06 | 广东瑞星环境科技有限公司 | Method for treating polyvinyl alcohol swelling wastewater generated in polarizer production |
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| JP2000301172A (en) * | 1999-04-15 | 2000-10-31 | Kurita Water Ind Ltd | Method for cleaning soil and/or ground water |
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