WO2016017821A1 - オゾン水およびその製造方法 - Google Patents
オゾン水およびその製造方法 Download PDFInfo
- Publication number
- WO2016017821A1 WO2016017821A1 PCT/JP2015/071896 JP2015071896W WO2016017821A1 WO 2016017821 A1 WO2016017821 A1 WO 2016017821A1 JP 2015071896 W JP2015071896 W JP 2015071896W WO 2016017821 A1 WO2016017821 A1 WO 2016017821A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ozone
- water
- iron
- microbubbles
- ozone water
- Prior art date
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 171
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 25
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- PLKYGPRDCKGEJH-UHFFFAOYSA-N azane;2-hydroxypropane-1,2,3-tricarboxylic acid;iron Chemical compound N.[Fe].OC(=O)CC(O)(C(O)=O)CC(O)=O PLKYGPRDCKGEJH-UHFFFAOYSA-N 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 241000124008 Mammalia Species 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims description 6
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 4
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001877 deodorizing effect Effects 0.000 claims description 4
- 229940095100 fulvic acid Drugs 0.000 claims description 4
- 239000002509 fulvic acid Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- KXFFQVUPQCREHA-UHFFFAOYSA-K sodium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [Na+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KXFFQVUPQCREHA-UHFFFAOYSA-K 0.000 claims description 4
- 230000005514 two-phase flow Effects 0.000 claims description 4
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 claims description 3
- 229920002307 Dextran Polymers 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 231100000460 acute oral toxicity Toxicity 0.000 claims description 3
- MDXRFOWKIZPNTA-UHFFFAOYSA-L butanedioate;iron(2+) Chemical compound [Fe+2].[O-]C(=O)CCC([O-])=O MDXRFOWKIZPNTA-UHFFFAOYSA-L 0.000 claims description 3
- 238000011978 dissolution method Methods 0.000 claims description 3
- 239000011640 ferrous citrate Substances 0.000 claims description 3
- 235000019850 ferrous citrate Nutrition 0.000 claims description 3
- 239000004222 ferrous gluconate Substances 0.000 claims description 3
- 235000013924 ferrous gluconate Nutrition 0.000 claims description 3
- 229960001645 ferrous gluconate Drugs 0.000 claims description 3
- 229960001604 ferrous succinate Drugs 0.000 claims description 3
- 150000003278 haem Chemical class 0.000 claims description 3
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 claims description 3
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 3
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- HWVFSIHLBZDKFK-DFWYDOINSA-M sodium (4S)-4-amino-5-(dicarboxymethoxy)-5-oxopentanoate Chemical compound N[C@@H](CCC(=O)[O-])C(=O)OC(C(=O)O)C(=O)O.[Na+] HWVFSIHLBZDKFK-DFWYDOINSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- 229940009662 edetate Drugs 0.000 claims description 2
- 239000011706 ferric diphosphate Substances 0.000 claims description 2
- 235000007144 ferric diphosphate Nutrition 0.000 claims description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims description 2
- 229940036404 ferric pyrophosphate Drugs 0.000 claims description 2
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- KWJPTZSGVFKSDH-UHFFFAOYSA-N 1-(3-nitrophenyl)piperazine;dihydrochloride Chemical compound Cl.Cl.[O-][N+](=O)C1=CC=CC(N2CCNCC2)=C1 KWJPTZSGVFKSDH-UHFFFAOYSA-N 0.000 claims 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims 1
- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 claims 1
- 229960001459 ferrous ascorbate Drugs 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 10
- 239000007789 gas Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000002101 nanobubble Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BKJXSPNFVILSSW-UHFFFAOYSA-N n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine;iron Chemical compound [Fe].NCCNCCNCCN BKJXSPNFVILSSW-UHFFFAOYSA-N 0.000 description 2
- ZEYKLMDPUOVUCR-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 ZEYKLMDPUOVUCR-UHFFFAOYSA-N 0.000 description 1
- RCGKRBKRENYEFF-UHFFFAOYSA-K C(C)(=O)[O-].[Fe+2].NCCNCCN.[Na+].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Fe+2].NCCNCCN.[Na+].C(C)(=O)[O-].C(C)(=O)[O-] RCGKRBKRENYEFF-UHFFFAOYSA-K 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 231100000694 OECD Guidelines for the Testing of Chemicals Toxicity 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 241001354013 Salmonella enterica subsp. enterica serovar Enteritidis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QKWNIOMGXBERHJ-RXSVEWSESA-N azane;(2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound N.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O QKWNIOMGXBERHJ-RXSVEWSESA-N 0.000 description 1
- GLMQHZPGHAPYIO-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [NH4+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O GLMQHZPGHAPYIO-UHFFFAOYSA-L 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ZRZYLFPZOSSVFG-UHFFFAOYSA-N pentaazanium;pentaacetate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ZRZYLFPZOSSVFG-UHFFFAOYSA-N 0.000 description 1
- OOTLZFANIDERRE-UHFFFAOYSA-K sodium butanedioic acid 2-hydroxypropane-1,2,3-tricarboxylate iron(2+) Chemical compound [Na+].[Fe+2].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CCC(=O)O)(=O)O OOTLZFANIDERRE-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 1
- SRFKWQSWMOPVQK-UHFFFAOYSA-K sodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(2+) Chemical compound [Na+].[Fe+2].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O SRFKWQSWMOPVQK-UHFFFAOYSA-K 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
- A61L2/183—Ozone dissolved in a liquid
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/231—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids by bubbling
- B01F23/23105—Arrangement or manipulation of the gas bubbling devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
- B01F23/2373—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media for obtaining fine bubbles, i.e. bubbles with a size below 100 µm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/10—Mixing by creating a vortex flow, e.g. by tangential introduction of flow components
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
- A61L2209/20—Method-related aspects
- A61L2209/21—Use of chemical compounds for treating air or the like
- A61L2209/212—Use of ozone, e.g. generated by UV radiation or electrical discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/48—Mixing water in water-taps with other ingredients, e.g. air, detergents or disinfectants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
- B01F23/2376—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media characterised by the gas being introduced
- B01F23/23761—Aerating, i.e. introducing oxygen containing gas in liquids
- B01F23/237613—Ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/784—Diffusers or nozzles for ozonation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Definitions
- ozone Since ozone has an oxidizing action, a bactericidal action, a deodorizing action, etc., it is expected to be used in various fields, but since it is a gas, it is not versatile as it is. Therefore, in order to effectively use ozone, for example, it is necessary to dissolve ozone in water and use it as ozone water. However, ozone basically has a low solubility in water and has a short half-life when dissolved in water. For this reason, at present, ozone is used by dissolving ozone gas in water by a method such as bubbling at the site of use.
- Patent Document 1 proposes a method for ensuring storage over a long period of time. However, further improvement in the storage stability of ozone water is required at the site where ozone is used.
- an object of the present invention is to provide ozone water having improved storage stability and a method for producing the same.
- the present inventor has dissolved ozone in a predetermined amount of organic iron compound and inorganic salt in water in which ozone microbubbles have been generated using ozone gas at a predetermined concentration. It has been found that the storage stability of water can be improved.
- the ozone water of the present invention made based on the above knowledge is, as described in claim 1, 0.1 ⁇ M to 1 mM in water in which ozone microbubbles are generated using ozone gas having a concentration of 1 to 300 g / Nm 3.
- the organic iron compound and 1 to 300 mM inorganic salt are dissolved.
- the ozone water according to claim 2 is the ozone water according to claim 1, wherein the organic iron compound is ammonium iron citrate, iron fulvic acid, iron acetate, heme iron, dextran iron, diethylenetriamine sodium iron acetate, diethylenetriamine.
- the ozone water according to claim 3 is the ozone water according to claim 1, wherein the inorganic salt is at least one selected from the group consisting of sodium chloride, potassium chloride, magnesium chloride, and magnesium sulfate.
- the inorganic salt is at least one selected from the group consisting of sodium chloride, potassium chloride, magnesium chloride, and magnesium sulfate.
- ozone microbubbles are generated using a microbubble generator capable of generating microbubbles having a particle size of 5 to 50 ⁇ m. Is called.
- the ozone water according to claim 5 is the ozone water according to claim 4, wherein the microbubble generator is a microbubble generator of a two-phase flow swirling method or a pressure dissolution method.
- the ozone water according to claim 6 is the water in which ozone microbubbles are generated by dissolving the organic iron compound and the inorganic salt in the water in which ozone microbubbles are generated. This is carried out after 20 minutes or more have elapsed since the oxidation-reduction potential has increased and reached at least +600 mV.
- the ozone water according to claim 7 is the ozone water according to claim 1, wherein the ozone half-life is 3 days when stored in a sealed container under atmospheric pressure at a temperature of 40 ° C. That's it.
- the ozone water according to claim 8 is the ozone water according to claim 1 after the ozone water is filled in a sealed container under atmospheric pressure and frozen and stored at a temperature of -20 ° C for one month or more. When naturally thawed at room temperature (25 ° C.), it recovers to ozone water before freezing.
- the ozone water according to claim 9 is the ozone water according to claim 1, wherein the ozone water is not irritating to the skin of the mammal, does not show oral acute toxicity to the mammal, has a bactericidal effect and is effective. Has an odor effect.
- 0.1 ⁇ M to 1 mM organic iron is added to water in which ozone microbubbles are generated using ozone gas having a concentration of 1 to 300 g / Nm 3.
- ozone gas having a concentration of 1 to 300 g / Nm 3.
- the method for producing ozone water according to claim 11 is the method for producing ozone water according to claim 10, wherein the generation of ozone microbubbles is a microbubble capable of generating microbubbles having a particle size of 5 to 50 ⁇ m. Use a generator.
- the method for producing ozone water according to claim 12 is the method for producing ozone water according to claim 10, wherein the dissolution of the organic iron compound and the inorganic salt in the water in which the ozone microbubbles are generated This is performed after 20 minutes or more have elapsed since the oxidation-reduction potential of the water in which the water is generated rises and reaches at least +600 mV.
- ozone water having improved storage stability and a method for producing the same can be provided.
- the ozone water of the present invention is obtained by dissolving 0.1 ⁇ M to 1 mM organic iron compound and 1 to 300 mM inorganic salt in water in which ozone microbubbles are generated using ozone gas having a concentration of 1 to 300 g / Nm 3. Become.
- the production of ozone water of the present invention begins with preparing water in which ozone microbubbles are generated.
- the method for generating ozone microbubbles in water may be a publicly known method, and can generate microbubbles having a particle size of 5 to 50 ⁇ m. Can be used.
- ozone is included inside the microbubbles by using a rotor or the like to forcibly generate a vortex with a radius of 10 cm or less and obstacles such as walls and fluids with different relative velocities.
- the desired ozone microbubbles can be generated by applying the gas-liquid mixture containing the gas to disperse the gas components acquired in the vortex along with the disappearance of the vortex.
- the ozone contained in the microbubbles is dissolved in water under a high pressure of 2 atm or higher, and then released from the supersaturated condition of the dissolved gas generated by opening it to atmospheric pressure.
- Ozone microbubbles can be generated.
- a large number of vortices with a radius of 1 mm or less are generated at the pressure release site using water flow and obstacles, and a large amount of gas phase nuclei (bubble nuclei due to water molecular fluctuation in the central region of the vortex ), And by diffusing gas components in water toward these bubble nuclei along with the supersaturation condition to grow the bubble nuclei, a large amount of desired ozone microbubbles can be generated.
- the ozone microbubbles generated by these methods have a particle size of 50 ⁇ m or less, and a particle size peak at 10 to 15 ⁇ m when measured with a laser light blocking liquid particle counter (for example, LiQuilaz-E20 manufactured by SPM).
- the number of microbubbles in the peak region is 1000 / mL or more (see JP 2000-51107 A, JP 2003-265938 A, etc. if necessary).
- the ozone gas used to generate ozone microbubbles in water is prepared, for example, to a concentration of 1 to 300 g / Nm 3 using a commercially available oxygen source ozone generator.
- ozone gas having a concentration of less than 1 g / Nm 3 When ozone gas having a concentration of less than 1 g / Nm 3 is used, a large amount of ozone microbubbles cannot be efficiently generated in water. On the other hand, it is difficult to prepare ozone gas having a concentration exceeding 300 g / Nm 3 .
- the ozone gas may contain oxygen, nitrogen, etc. in addition to ozone.
- an organic iron compound and an inorganic salt are dissolved in water in which ozone microbubbles are generated.
- the organic iron compounds include ammonium iron citrate, iron fulvic acid, iron acetate, heme iron, dextran iron, sodium diethylenetriaminepentaacetate, ammonium diethylenetriaminepentaacetate, sodium iron ethylenediaminetetraacetate, ammonium ammonium ethylenediaminetetraacetate , Iron triethylenetetraamine, sodium dicarboxymethyl glutamate, ferrous citrate, sodium iron citrate, iron oxalate, ferrous succinate, sodium iron citrate succinate, ferrous pyrophosphate, pyrophosphate Water-soluble compounds such as ferric iron, iron lactate, ferrous gluconate, ferrous formate, ferric formate, potassium ferric oxalate, ferrous ammonium ascorbate, ferric sodium edetate Can be mentioned.
- the dissolved amount of the organic iron compound is 0.1 ⁇ M to 1 mM. If the dissolution amount is less than 0.1 ⁇ M, the effect due to dissolution may not be sufficiently obtained. On the other hand, even if it exceeds 1 mM, the improvement of the effect due to dissolution cannot be expected, and only the cost is increased. There is a risk that iron hydroxide may be generated and precipitated.
- the dissolved amount of the organic iron compound is desirably 1 to 100 ⁇ M.
- the microbubbles After dissolving the inorganic salt in the water in which ozone microbubbles are generated, the microbubbles are reduced and then stably exist as nanobubbles having a particle size of, for example, 10 to 500 nm.
- the inorganic acid include water-soluble compounds such as sodium chloride, potassium chloride, magnesium chloride, magnesium sulfate.
- the dissolved amount of the inorganic salt is 1 to 300 mM. If the dissolution amount is less than 1 mM, the effect due to dissolution may not be sufficiently obtained. On the other hand, even if it exceeds 300 mM, the improvement of the effect due to dissolution cannot be expected and the cost may be increased. There is.
- the dissolved amount of the inorganic salt is desirably 10 to 100 mM.
- Dissolution of a predetermined amount of an organic iron compound and an inorganic salt in water that has generated ozone microbubbles causes the redox potential of the water to increase from the initial +300 to 500 mV by at least +600 mV by continuing to generate ozone microbubbles. It is desirable to carry out after 20 minutes or more have passed since reaching the above in terms of effectively improving the storage stability of ozone water (the rise in oxidation-reduction potential reaches a plateau at about +1000 mV).
- ozone is converted into microbubbles for at least 5 minutes, preferably at least 30 minutes, more preferably at least 1 hour. It is desirable to continue to supply at a point where the storage stability of ozone water can be effectively improved.
- the dissolution order of the predetermined amount of the organic iron compound and the inorganic salt in the water in which the ozone microbubbles are generated is not particularly limited, and may be dissolved simultaneously or stepwise.
- the pH of water in which ozone microbubbles in which a predetermined amount of an organic iron compound and an inorganic salt are dissolved is desirably 3 to 10, and more desirably 5 to 9. If the acidity is too strong or the alkalinity is too strong, destabilization of microbubbles and nanobubbles will occur, and in addition to the generation and disappearance of hydroxyl radicals, the generated iron radicals will decompose the organic iron compound. This is because the storage stability of ozone water may not be improved.
- the pH may be adjusted as appropriate using hydrochloric acid or sodium hydroxide.
- ozone is present stably in water at a concentration of 1 to 50 mg / L, for example, and its half-life is, for example, that in a sealed container under atmospheric pressure at a temperature of 40 ° C. 3 days or more when stored.
- the ozone water of the present invention is, for example, filled in a sealed container under atmospheric pressure and stored frozen at -20 ° C for one month or more and then naturally thawed at room temperature (25 ° C). Restores to ozone water.
- the organic iron compound contributes to the stability of ozone in water, but the iron ions contained in the organic iron compound are caused by the oxidation of ozone supplied to water in the form of microbubbles.
- the present inventor believes that the nanobubbles are stabilized by being held.
- the ozone water of the present invention can be used for various applications known as ozone water applications.
- the ozone water of the present invention is not irritating to the skin of mammals, exhibits no oral acute toxicity to mammals, and exhibits bactericidal and deodorizing effects.
- Example 1 Ozone microbubbles are generated in distilled water using a commercially available two-phase flow swirl microbubble generator that can generate microbubbles with a particle size of 5 to 50 ⁇ m (aqua air small bubble generator). I let you. Ozone gas prepared at a concentration of about 30 g / Nm 3 using a commercially available oxygen source ozone generator is supplied to the microbubble generator at about 100 mL / min, so that the ozone concentration in water is about 5 mg / L. did.
- Example 2 Ozone microbubbles are generated in distilled water using a commercially available pressure dissolution type microbubble generator (A-02, manufactured by Resource Development Laboratories) that can generate microbubbles with a particle size of 5-50 ⁇ m.
- A-02 pressure dissolution type microbubble generator
- Ozone gas prepared at a concentration of about 20 g / Nm 3 using a commercially available oxygen source ozone generator is supplied to the microbubble generator at about 100 mL / min, so that the ozone concentration in water is about 5 mg / L. did.
- Example 3 The ozone water of the present invention was produced in the same manner as in Example 1 except that iron fulvic acid was dissolved instead of ammonium iron citrate.
- Example 4 The ozone half-life of the ozone water of the present invention produced in Example 1 was examined when stored in a plastic bottle as a sealed container under atmospheric pressure when stored under a temperature condition of 40 ° C. for 3 days or more. (More than half of ozone remained when 3 days passed).
- Example 5 The ozone water of the present invention produced in Example 1 was filled in a PET bottle as an airtight container under atmospheric pressure, and frozen at -20 ° C for 1 month or more and then at room temperature (25 ° C). When it thawed naturally, it was restored to ozone water before freezing (the ozone concentration was the same as that before freezing even after thawing after freezing for 1 month).
- Example 6 The ozone water of the present invention produced in Example 1 was allowed to stand in a dark place at room temperature for 1 week, and then a spin trap agent DMPO (5,5-dimethyl-1-pyrroline N-oxide) was added.
- DMPO electron spin resonance
- ESR electron spin resonance
- Example 7 When the skin water irritation test using the rabbit according to OECD Guidelines for the Testing of Chemicals 404 was conducted using the ozone water of the present invention produced in Example 1 as a specimen, no irritation was observed.
- Example 8 When the ozone water of the present invention produced in Example 1 was orally administered to rats at a dose of 20 mg / kg for 14 days, no acute toxicity was observed.
- Example 9 When the bactericidal effect of the ozone water of the present invention produced in Example 1 on the pathogenic bacterium Salmonella enteritidis was examined, an excellent bactericidal effect was observed.
- Example 10 When an appropriate amount of the ozone water of the present invention produced in Example 1 was sprayed on cutting waste (industrial waste) of a plastic bottle that gives off a bad smell in summer, an excellent deodorizing effect was exhibited.
- Example 11 By continuing to generate ozone microbubbles in distilled water, when 1 hour has passed since the redox potential of water reached +600 mV, Example 1 except that iron ammonium citrate and sodium chloride were dissolved. Similarly, when the ozone water of the present invention was produced, the ozone half-life was extended as compared with the ozone water of the present invention produced in Example 1.
- Comparative Example 1 Ozone water produced in the same manner as in Example 1 except that the supply of ozone is performed by bubbling using a general air diffuser, is filled in a PET bottle as a sealed container under atmospheric pressure, and the temperature is 40 ° C. When stored under the conditions, the ozone concentration almost disappeared when one day passed from the start of the experiment.
- Comparative Example 2 Ozone water produced in the same manner as in Example 1 except that ammonium iron citrate was not dissolved was filled into a PET bottle as a sealed container under atmospheric pressure and stored under a temperature condition of 40 ° C. When 3 hours passed, the ozone concentration almost disappeared.
- the present invention has industrial applicability in that it can provide ozone water having improved storage stability and a method for producing the same.
Abstract
Description
そこで本発明者は、オゾン水の欠点である保存性の短さを劇的に改善させる方法として、オゾンのナノサイズの気泡(オゾンナノバブル)を利用することにより、オゾンが有する作用を維持させつつ長期に亘る保存性を確保する方法を特許文献1において提案している。しかしながら、オゾンの使用現場では、オゾン水の保存安定性のさらなる向上が求められている。
また、請求項2記載のオゾン水は、請求項1記載のオゾン水において、有機鉄化合物が、クエン酸鉄アンモニウム、フルボ酸鉄、酢酸鉄、ヘム鉄、デキストラン鉄、ジエチレントリアミン五酢酸鉄ナトリウム、ジエチレントリアミン五酢酸鉄アンモニウム、エチレンジアミン四酢酸鉄ナトリウム、エチレンジアミン四酢酸鉄アンモニウム、トリエチレンテトラアミン鉄、ジカルボキシメチルグルタミン酸鉄ナトリウム、クエン酸第一鉄、クエン酸鉄ナトリウム、シュウ酸鉄、コハク酸第一鉄、コハク酸クエン酸鉄ナトリウム、ピロリン酸第一鉄、ピロリン酸第二鉄、乳酸鉄、グルコン酸第一鉄、ギ酸第一鉄、ギ酸第二鉄、シュウ酸カリウム第二鉄アンモニウム、アスコルビン酸第一鉄、エデト酸ナトリウム第二鉄からなる群から選択される少なくとも1種である。
また、請求項3記載のオゾン水は、請求項1記載のオゾン水において、無機塩が、塩化ナトリウム、塩化カリウム、塩化マグネシウム、硫酸マグネシウムからなる群から選択される少なくとも1種類以上である。
また、請求項4記載のオゾン水は、請求項1記載のオゾン水において、オゾンマイクロバブルの発生が、粒径が5~50μmのマイクロバブルを発生させることができる微小気泡発生装置を用いて行われる。
また、請求項5記載のオゾン水は、請求項4記載のオゾン水において、微小気泡発生装置が、二相流旋回方式または加圧溶解方式の微小気泡発生装置である。
また、請求項6記載のオゾン水は、請求項1記載のオゾン水において、オゾンマイクロバブルを発生させた水への、有機鉄化合物と無機塩の溶解が、オゾンマイクロバブルを発生させた水の酸化還元電位が上昇して少なくとも+600mVに到達してから20分間以上が経過した後に行われる。
また、請求項7記載のオゾン水は、請求項1記載のオゾン水において、オゾンの半減期が、大気圧下で密閉容器に充填したものを40℃の温度条件下において保存した場合に3日間以上である。
また、請求項8記載のオゾン水は、請求項1記載のオゾン水において、オゾン水が、大気圧下で密閉容器に充填して-20℃の温度条件下において1ヶ月間以上凍結保存した後に常温(25℃)で自然解凍した場合、凍結前のオゾン水に回復する。
また、請求項9記載のオゾン水は、請求項1記載のオゾン水において、オゾン水が、哺乳動物の皮膚に対する刺激性がなく、哺乳動物に対して経口急性毒性を示さず、殺菌効果と消臭効果を有する。
また、本発明のオゾン水の製造方法は、請求項10記載の通り、濃度が1~300g/Nm3のオゾンガスを用いてオゾンマイクロバブルを発生させた水に、0.1μM~1mMの有機鉄化合物と1~300mMの無機塩を溶解することによる。
また、請求項11記載のオゾン水の製造方法は、請求項10記載のオゾン水の製造方法において、オゾンマイクロバブルの発生を、粒径が5~50μmのマイクロバブルを発生させることができる微小気泡発生装置を用いて行う。
また、請求項12記載のオゾン水の製造方法は、請求項10記載のオゾン水の製造方法において、オゾンマイクロバブルを発生させた水への、有機鉄化合物と無機塩の溶解を、オゾンマイクロバブルを発生させた水の酸化還元電位が上昇して少なくとも+600mVに到達してから20分間以上が経過した後に行う。
主に粒径が5~50μmのマイクロバブルを発生させることができる市販の二相流旋回方式のマイクロバブル発生装置(アクアエアー社製小型気泡発生装置)を用いて蒸留水中にオゾンマイクロバブルを発生させた。オゾンガスは、市販の酸素源オゾン発生装置を用いて約30g/Nm3の濃度で調製したものをマイクロバブル発生装置に約100mL/分で供給し、水中のオゾン濃度が約5mg/Lになるようした。オゾンマイクロバブルを発生させ続けることで、水の酸化還元電位が当初の約+500mVから連続的に上昇することを確認した後、+600mVに到達してから30分間が経過した時点で、有機鉄化合物として10μMのクエン酸鉄アンモニウムと無機塩として50mMの塩化ナトリウムを溶解し、水酸化ナトリウムを用いてpHを8に調整した。その後、さらに1時間オゾンマイクロバブルを発生し続けた。こうして製造した本発明のオゾン水のオゾン濃度をKI法によって測定すると5mg/Lであった。5Lの本発明のオゾン水を製造するのに要した時間は約2時間であった。
主に粒径が5~50μmのマイクロバブルを発生させることができる市販の加圧溶解方式のマイクロバブル発生装置(資源開発研究所社製A-02)を用いて蒸留水中にオゾンマイクロバブルを発生させた。オゾンガスは、市販の酸素源オゾン発生装置を用いて約20g/Nm3の濃度で調製したものをマイクロバブル発生装置に約100mL/分で供給し、水中のオゾン濃度が約5mg/Lになるようした。オゾンマイクロバブルを発生させ続けることで、水の酸化還元電位が当初の約+500mVから連続的に上昇することを確認した後、+600mVに到達してから20分間が経過した時点で、有機鉄化合物として10μMのクエン酸鉄アンモニウムと無機塩として50mMの硫酸マグネシウムを溶解し、水酸化ナトリウムを用いてpHを8に調整した。その後、さらに1時間オゾンマイクロバブルを発生し続けた。こうして製造した本発明のオゾン水のオゾン濃度をKI法によって測定すると4mg/Lであった。5Lの本発明のオゾン水を製造するのに要した時間は約1時間であった。
クエン酸鉄アンモニウムのかわりにフルボ酸鉄を溶解すること以外は実施例1と同様にして本発明のオゾン水を製造した。
実施例1で製造した本発明のオゾン水のオゾンの半減期を、大気圧下で密閉容器としてペットボトルに充填したものを40℃の温度条件下において保存した場合において調べたところ、3日間以上であった(3日間が経過した時点で半分以上のオゾンが残存)。
実施例1で製造した本発明のオゾン水のオゾンを、大気圧下で密閉容器としてペットボトルに充填して-20℃の温度条件下において1ヶ月間以上凍結保存した後に常温(25℃)で自然解凍したところ、凍結前のオゾン水に回復した(1ヶ月間凍結保存した後に解凍してもオゾン濃度は凍結前と同じ)。
実施例1で製造した本発明のオゾン水を、室温条件で暗所に1週間放置した後、スピントラップ剤であるDMPO(5,5-ジメチル-1-ピロリン N-オキサイド)を添加し、さらに塩酸を添加してpH2の強酸条件下で電子スピン共鳴(ESR)スペクトルを測定したところ、スピンアダクトであるDMPO-OHのスペクトル(水酸基ラジカルの発生を意味するスペクトル)を観測することができた。
実施例1で製造した本発明のオゾン水を検体として、OECD Guidelines for the Testing of Chemicals 404に準拠するウサギを用いた皮膚一次刺激性試験を行ったところ、刺激性は認められなかった。
実施例1で製造した本発明のオゾン水を、ラットに20mg/kgの投与量で14日間経口投与したところ、急性毒性は認められなかった。
実施例1で製造した本発明のオゾン水の、病原性細菌サルモネラ・エンテリティディスに対する殺菌効果を調べたところ、優れた殺菌効果が認められた。
夏場に異臭を発するペットボトルの裁断くず(産業廃棄物)に、適量の実施例1で製造した本発明のオゾン水を噴霧したところ、優れた消臭効果を発揮した。
蒸留水中にオゾンマイクロバブルを発生させ続けることで、水の酸化還元電位が+600mVに到達してから1時間が経過した時点で、クエン酸鉄アンモニウムと塩化ナトリウムを溶解すること以外は実施例1と同様にして本発明のオゾン水を製造したところ、実施例1で製造した本発明のオゾン水と比較してオゾンの半減期の延長が認められた。
オゾンの供給を、一般的な散気管を用いたバブリングによって行うことに以外は実施例1と同様にして製造したオゾン水を、大気圧下で密閉容器としてペットボトルに充填し、40℃の温度条件下において保存したところ、実験開始から1日間が経過した時点でオゾン濃度はほぼ皆無となった。
クエン酸鉄アンモニウムを溶解しないこと以外は実施例1と同様にして製造したオゾン水を、大気圧下で密閉容器としてペットボトルに充填し、40℃の温度条件下において保存したところ、実験開始から3時間が経過した時点でオゾン濃度はほぼ皆無となった。
Claims (12)
- 濃度が1~300g/Nm3のオゾンガスを用いてオゾンマイクロバブルを発生させた水に、0.1μM~1mMの有機鉄化合物と1~300mMの無機塩を溶解させてなるオゾン水。
- 有機鉄化合物が、クエン酸鉄アンモニウム、フルボ酸鉄、酢酸鉄、ヘム鉄、デキストラン鉄、ジエチレントリアミン五酢酸鉄ナトリウム、ジエチレントリアミン五酢酸鉄アンモニウム、エチレンジアミン四酢酸鉄ナトリウム、エチレンジアミン四酢酸鉄アンモニウム、トリエチレンテトラアミン鉄、ジカルボキシメチルグルタミン酸鉄ナトリウム、クエン酸第一鉄、クエン酸鉄ナトリウム、シュウ酸鉄、コハク酸第一鉄、コハク酸クエン酸鉄ナトリウム、ピロリン酸第一鉄、ピロリン酸第二鉄、乳酸鉄、グルコン酸第一鉄、ギ酸第一鉄、ギ酸第二鉄、シュウ酸カリウム第二鉄アンモニウム、アスコルビン酸第一鉄、エデト酸ナトリウム第二鉄からなる群から選択される少なくとも1種である請求項1記載のオゾン水。
- 無機塩が、塩化ナトリウム、塩化カリウム、塩化マグネシウム、硫酸マグネシウムからなる群から選択される少なくとも1種類以上である請求項1記載のオゾン水。
- オゾンマイクロバブルの発生が、粒径が5~50μmのマイクロバブルを発生させることができる微小気泡発生装置を用いて行われる請求項1記載のオゾン水。
- 微小気泡発生装置が、二相流旋回方式または加圧溶解方式の微小気泡発生装置である請求項4記載のオゾン水。
- オゾンマイクロバブルを発生させた水への、有機鉄化合物と無機塩の溶解が、オゾンマイクロバブルを発生させた水の酸化還元電位が上昇して少なくとも+600mVに到達してから20分間以上が経過した後に行われる請求項1記載のオゾン水。
- オゾンの半減期が、大気圧下で密閉容器に充填したものを40℃の温度条件下において保存した場合に3日間以上である請求項1記載のオゾン水。
- オゾン水が、大気圧下で密閉容器に充填して-20℃の温度条件下において1ヶ月間以上凍結保存した後に常温(25℃)で自然解凍した場合、凍結前のオゾン水に回復する請求項1記載のオゾン水。
- オゾン水が、哺乳動物の皮膚に対する刺激性がなく、哺乳動物に対して経口急性毒性を示さず、殺菌効果と消臭効果を有する請求項1記載のオゾン水。
- 濃度が1~300g/Nm3のオゾンガスを用いてオゾンマイクロバブルを発生させた水に、0.1μM~1mMの有機鉄化合物と1~300mMの無機塩を溶解することによるオゾン水の製造方法。
- オゾンマイクロバブルの発生を、粒径が5~50μmのマイクロバブルを発生させることができる微小気泡発生装置を用いて行う請求項10記載のオゾン水の製造方法。
- オゾンマイクロバブルを発生させた水への、有機鉄化合物と無機塩の溶解を、オゾンマイクロバブルを発生させた水の酸化還元電位が上昇して少なくとも+600mVに到達してから20分間以上が経過した後に行う請求項10記載のオゾン水の製造方法。
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JP2016538474A JP6341581B2 (ja) | 2014-08-01 | 2015-08-01 | オゾン水の製造方法 |
EP15827201.3A EP3176131A4 (en) | 2014-08-01 | 2015-08-01 | Ozone water and method for producing same |
CN201580040683.6A CN106573805A (zh) | 2014-08-01 | 2015-08-01 | 臭氧水及其制造方法 |
US15/500,290 US10351451B2 (en) | 2014-08-01 | 2015-08-01 | Ozone water and method for producing the same |
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