US20050089805A1 - Material and method for treating photographic effluents - Google Patents
Material and method for treating photographic effluents Download PDFInfo
- Publication number
- US20050089805A1 US20050089805A1 US10/624,761 US62476103A US2005089805A1 US 20050089805 A1 US20050089805 A1 US 20050089805A1 US 62476103 A US62476103 A US 62476103A US 2005089805 A1 US2005089805 A1 US 2005089805A1
- Authority
- US
- United States
- Prior art keywords
- aqueous solution
- oxidizing material
- material according
- imogolite
- organisms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000001590 oxidative effect Effects 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 230000001580 bacterial effect Effects 0.000 claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 244000005700 microbiome Species 0.000 claims abstract description 21
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 19
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000000084 colloidal system Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000011133 lead Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000005406 washing Methods 0.000 description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 22
- 238000012545 processing Methods 0.000 description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 17
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 16
- QYYMDNHUJFIDDQ-UHFFFAOYSA-N 5-chloro-2-methyl-1,2-thiazol-3-one;2-methyl-1,2-thiazol-3-one Chemical compound CN1SC=CC1=O.CN1SC(Cl)=CC1=O QYYMDNHUJFIDDQ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- -1 silver ions Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 238000005251 capillar electrophoresis Methods 0.000 description 2
- 238000005515 capillary zone electrophoresis Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- PKTZMZDDMQHVIC-UHFFFAOYSA-N 3-chloro-1,2-thiazole 1-oxide Chemical compound ClC=1C=CS(=O)N=1 PKTZMZDDMQHVIC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical group CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZEFUPIGIKKXZQI-UHFFFAOYSA-N CC1=CC(=O)N(C)S1 Chemical compound CC1=CC(=O)N(C)S1 ZEFUPIGIKKXZQI-UHFFFAOYSA-N 0.000 description 1
- 238000005079 FT-Raman Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- PMYZNOFDGBIUON-UHFFFAOYSA-M S(=S)(=O)([O-])O.S(=O)(O)O.[Na+] Chemical compound S(=S)(=O)([O-])O.S(=O)(O)O.[Na+] PMYZNOFDGBIUON-UHFFFAOYSA-M 0.000 description 1
- 230000002353 algacidal effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000000721 bacterilogical effect Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012476 oxidizable substance Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/395—Regeneration of photographic processing agents other than developers; Replenishers therefor
- G03C5/3952—Chemical, mechanical or thermal methods, e.g. oxidation, precipitation, centrifugation
-
- 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
- A61L2/0005—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts
- A61L2/0082—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts using chemical substances
-
- 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
- A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
- A61L2/238—Metals or alloys, e.g. oligodynamic metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
- C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/40—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture or use of photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Definitions
- the present invention relates to a method for preparing an oxidizing material, to the oxidizing material thus prepared, and to a method for treating effluents, and in particular to method for treating photographic effluents.
- the processing of photographic products comprises a development step and a de-silvering step.
- the de-silvering step comprises the bleaching of the photographic product, which consists in converting metallic silver into silver ions, followed by fixing, which consists in eliminating the silver ions contained in the photographic product.
- the photographic processing steps can also include wash and stabilizing baths.
- Photographic products are generally developed automatically and as quickly as possible.
- the product passes through each of the baths described above.
- non-negligible quantities of chemicals are carried over from one tank to the next, either by the photographic product itself or by the drive belts that convey the photographic product.
- These chemicals build up in the processing baths and thereby reduce their efficacy.
- wash baths are intercalated between successive processing baths. In particular, after passage through a fixing or bleaching-fixing bath, the film passes through several wash baths before it enters the stabilizing bath.
- wash baths that come after the fixing step contain many substances such as sulfites, thiosulfates and (or) ammonium salts used in the fixing baths, the sulfites and thiosulfates possibly deriving also from the developer.
- wash baths cannot be discarded directly into the sewers and must be treated first to eliminate inorganic salts such as sulfites, thiosulfates, ammonium, and other organic by-products that raise the COD of the baths and are particularly harmful to the environment.
- micro-organisms in particular in pre-baths, stabilizing baths and wash baths commonly occurs, worsening when the quantities of water consumed are reduced.
- the growth of micro-organisms such as molds and yeasts, if not controlled, causes the formation of sludge that clog the plant, degrade the processing bath, and so impair the quality of photographic image.
- the presence of micro-organisms, especially bacteria causes a biofilm to form on the walls of the processing tanks and on the film drive rollers and wheels, so that the machinery has to be shut down for cleaning.
- control agents to prevent or limit bacterial growth in processing baths is common practice.
- certain bacterial growth control agents are very sensitive to the presence of sulfites and thiosulfates found in washing water and are broken down before they can fully act. To compensate for this breakdown, excess quantities are used relative to the exact amount required. In this case the water discharged into the environment contains large quantities of bacterial growth control agents, which causes problems in wastewater treatment plants that exploit the action of micro-organisms for effluent treatment.
- the present invention provides a method for preparing a material that allows to minimize the occurrence and growth of micro-organisms in processing water in order thereby to reduce the quantities of control agents that have to be used.
- the present invention provides also a material that rids processing water of pollutant by-products so as to obtain effluents that comply with regulatory requirements.
- the present invention provides also a material to rid processing water of pollutant by-products that generate unwanted reactions with bacterial growth control agents, in order thereby to extend the life of said agents.
- the present invention relates to a method for preparing an oxidizing material comprising the step of (i) dispersing in colloidal form a metal or a metal compound in an aqueous solution of an inorganic aluminosilicate polymer, said aluminosilicate being able to form an inorganic gel, and said metal or metal compound being able to cause the oxidation of oxidizable compounds and (or) micro-organisms to be eliminated, and the step of (ii) adding a base to cause said aluminosilicate to gel.
- the present invention also concerns a material obtainable by the method described above, as well as its use to oxidize, in the presence of water, oxidizable compounds and (or) micro-organisms to be eliminated.
- the invention also concerns a method for treating an aqueous solution liable to contain oxidizable compounds to be eliminated and (or) to harbor micro-organisms, as well as a device for carrying out said method.
- the method comprises contacting the aqueous solution with said oxidizing material. It is especially efficient for the treatment of photographic baths, in particular wash baths after the fixing step, because it rids such baths of micro-organisms and oxidizable chemical by-products.
- the “micro-organisms to be eliminated” are in particular algae, fungi, bacteria and yeasts.
- the “oxidizable chemicals to be eliminated” are in particular inorganic or organic by-products considered as pollutants either with regard to aqueous the solution to be treated or in a general way with regard to the environment, for example sulfite and ammonium ions, surfactants, etc.
- FIG. 1 is a plot of optical density as a function of time for a solution processed with materials according to the invention and comparative materials.
- an aqueous solution of an inorganic aluminosilicate polymer is used that is liable to form an inorganic gel in certain conditions, for example when the pH of the medium is increased.
- imogolite is used as aluminosilicate polymer.
- Imogolite is an aluminosilicate polymer that occurs in the form of fibers, including in solution, and an essential characteristic of which is that it forms a gel at a pH of about 8 and above. In this way physical gels are obtained in an aqueous phase.
- Imogolite fibers comprise active hydroxyl groups on their outer surface. Imogolite occurs naturally in an impure form. It was first described by Wada in J.
- Imogolite can be synthesized with different degrees of purity by different methods.
- a method for obtaining a highly pure imogolite gel is described in patent U.S. Pat. No. 5,888,711.
- the metal used in the present invention can be any of the following: silver, zinc, copper, iron, titanium, lead or nickel.
- a metal compound when used, said compound contains one of the metals listed above.
- monodisperse silver in powder form may be used, in which most of the particles are of diameter equal to or smaller than 10 microns, said silver producing a colloid when dispersed in the aqueous solution of imogolite.
- the silver can be mixed with other metals such as copper.
- Silver nitrate can also be used.
- Zinc can also be used in the form of zinc powder or zinc nitrate. All these metal compounds are commercially available and are distributed, for example, by the Alfa Aesar company.
- the metals or metal compounds are preferably used in the form of powders that are able to form colloids when they are dispersed in the imogolite. They can also be used in the form of a colloidal solution.
- the pH of the solution must be below the gelling threshold of the imogolite, for example below about 5, so that the addition of the colloidal metal solution does not cause the immediate gelling of the imogolite, which would prevent the metal particles from homogenizing properly in the imogolite solution.
- the initial metal or metal compound content is preferably in the range of 5 to 10% by weight relative to the [Al+Si] content of the imogolite.
- the material according to the invention is obtained by dispersing the metal or metal compound in the aqueous solution of imogolite at ambient temperature, while stirring the solution adequately so as to obtain a homogeneous dispersion of metal particles in colloidal form, and then adding a base to the reaction mixture, for example NH 4 OH, NaOH or KOH, so as to raise the pH to cause the aluminosilicate to gel.
- a base for example NH 4 OH, NaOH or KOH
- An imogolite gel is thereby obtained in which metal particles are evenly dispersed, do not agglomerate, and remain dispersed in the imogolite matrix.
- the material obtained by the method of the invention displays oxidizing properties. These oxidizing properties are demonstrated in the following way: when the material of the invention is placed at ambient temperature in the presence of cyclohexene dissolved in methanol, the conversion of cyclohexene into cyclohexanol can be observed by Fourier-transform Raman spectroscopy. The oxidation takes place more readily with heating.
- the metal particles dispersed in the imogolite present an appropriate configuration to allow a local micro-electrolysis of water that generates active oxygen, which combines immediately with water to form hydrogen peroxide in situ.
- the material according to the invention is a gel that allows hydrogen peroxide to be generated in situ, and in which it accumulates. The gel then slowly desorbs the hydrogen peroxide in the aqueous solution to be treated. The hydrogen peroxide, which is unstable, combines immediately with an oxidizable substance and degrades it.
- active agents other than the colloidal metal or metal compound are dispersed in the aqueous solution of imogolite, these active agents being chosen so as not to react with the said metal or metal compound.
- the active agents can be bacterial growth control agents, which are defined as organic compounds displaying pesticidal, algicidal, fungicidal or bactericidal properties. Some bacterial growth control agents are very sensitive to the presence of sodium sulfite or thiosulfate, but only weakly sensitive to oxidation.
- bacterial growth control agents A large number of bacterial growth control agents are known. From their general knowledge, those skilled in the art can easily select one or more suitable bacterial growth control agents. However, these agents must not form a covalent bond with the matrix of imogolite gel, because they would then be trapped in the matrix.
- the bacterial growth control agents that are useful for the invention are, for example, thiazole derivatives such as isothiazolones, azole derivatives such as benzotriazoles, benzimidazoles, or sulfamide-type agents such as sulfanilamide.
- hydrophilic isothiazolones such as 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one and hydrophobic isothiazolones such as 2-octyl-4-isothiazolin-3-one.
- the mixture of hydrophilic and hydrophobic bacterial growth agents is introduced in the oxidizing material of the invention by simple dispersion in the aqueous solution of imogolite before it has gelled.
- an alkylalkoxysilane of formula RSiR 1 x (OR 2 ) 3-x wherein R is an alkyl group containing an —SH or —S(—CH 2 ) n —S— function with n between 0 and 4, R 1 and R are independently a methyl or ethyl group and x is 0 or 1, is hydrolyzed before the imogolite has been made to gel.
- a preferred alkylalkoxysilane is 3-mercaptopropyltrimethoxysilane.
- inventions of the method for preparing the oxidizing material of the invention can be combined in such a way as to obtain a material in which the imogolite matrix comprises grafted sulfur-containing molecules and contains a metal or metal compound dispersed as a colloid, and a bacterial growth control agent.
- the oxidizing material described above is placed in contact with the said aqueous solution containing the oxidizable chemicals and (or) the micro-organisms to be eliminated.
- the oxidizing material of the invention must be permeated by the aqueous solution to be treated, for example an aqueous effluent.
- the material according to the invention can either be placed directly in the solution to be treated or be placed in a container that is permeable to the solution to be treated. It can, for example, be placed in a dialysis bag or in a closed bag made of filter paper or non-woven fabric.
- the oxidizing properties of the material of the invention make it possible to eliminate all the micro-organisms that may be present in the effluent, none of which is able to survive in such an oxidizing medium. This makes it possible to reduce the quantity of bacterial growth control agents.
- the material of the invention can be used in a very broad domain of application, effectively killing, for example, algae, fungi, bacteria and yeasts.
- the oxidizing material of the invention can be used in any application in which the bacteriological quality of water has to be controlled.
- the oxidizing material can be used in the photographic sector, or in the maintenance of industrial cooling water, etc.
- the oxidizing material can be advantageously used in a photographic treatment machine conventionally comprising a developing bath, a bleaching bath, a fixing bath and one or more wash baths.
- the oxidizing material of the invention can be used for any of these baths, preferably for the treatment of a wash bath obtained after the fixing step.
- the oxidizing properties of the material of the invention make it possible to eliminate the oxidizable chemical by-products present in the effluent.
- certain inorganic salts are readily oxidized, such as sulfites and ammonium ions that occur in large amounts in wash baths.
- certain organic by-products are oxidized, such as surfactants, emulsion thickening agents, etc. As a result, the COD of the effluent will be strongly reduced.
- the effluents treated using the material of the invention are rid of by-products that may be banned by various regulations.
- the material of the invention by affording an in situ oxidation, offers the advantage that hydrogen peroxide solutions do not have to be handled or tanks of oxidizing solution managed.
- the method of the invention extends the life of such bacterial growth control agents that are sensitive to sulfites and thiosulfates.
- the bacterial growth control agents are protected as long as they remain in the imogolite gel matrix. When they diffuse into the effluent to exert their action they are generally destroyed by sulfites and thiosulfates before they can take effect.
- the sulfites and thiosulfates present in the effluent are oxidized and broken down before they can destroy the control agents, the concentrations of which in the effluent to be treated therefore remain sufficient. This is particularly useful when the bacterial growth control agent is a curative agent with very high water-solubility designed to massively attack the cells of micro-organisms.
- the material of the invention also contains, on the surface of the imogolite fibers, organic radicals with a sulfur function, ionic silver present in the medium is eliminated in addition to the oxidizable chemicals.
- Another embodiment of the method of the invention consists in placing the effluent to be treated successively in contact with the oxidizing material of the invention and with a composite material comprising a matrix of imogolite gel in which are dispersed bacterial growth control agents such as those described above and (or) with an inorganic imogolite polymer in fiber form containing at least at the surface of the fibers an organic radical with an —SH or —S(—CH 2 ) n —S— function with n between 0 and 4.
- the oxidizing material of the invention is placed in contact with the effluent to be treated, or placed in a first dialysis bag, and the composite material for the bacterial growth control or the imogolite comprising grafted sulfur-containing molecules is placed in a second dialysis bag, both bags being placed in a treatment apparatus through which flows the aqueous solution to be treated.
- the dialysis bags can be arranged so that the treatment by the oxidizing material of the invention is carried out first.
- the method of the invention can also combine all three treatments, each of the materials, the oxidizing material, the bacterial growth control material and the sulfur-containing material, being placed in separate bags.
- oxidizing material of the invention together with a composite material made up of a matrix of imogolite gel comprising grafted sulfur-containing molecules, and containing a bacterial growth control agent dispersed in the matrix.
- a composite material made up of a matrix of imogolite gel comprising grafted sulfur-containing molecules, and containing a bacterial growth control agent dispersed in the matrix.
- the aluminosilicate of this example was prepared using teachings from patent U.S. Pat. No. 5,888,711.
- the gel was collected and redissolved in 5 ml of a mixture of 1M HCl and 2M acetic acid. The volume was made up to 2 liters with water. The resulting solution contained 30 mmoles of Al, 16.6 mmoles of Si, 5 mmoles of HCl and 10 mmoles of acetic acid. This solution was stored at 5° C.
- This solution was then diluted with de-ionized water to obtain an Al concentration of 10 mmoles/l.
- the diluted solution was heated for 5 days at 96° C. and then filtered through an ultrafiltration membrane with a separating power of 10,000 daltons (membrane manufactured by AMICON).
- a clear solution was obtained containing Al and Si in the Al:Si ratio 1.8 and with a [Al+Si] content equal to 3 g/l.
- the oxidizing material according to the invention was prepared by dispersing in colloidal form, 20 mg of silver in 200 ml of imogolite prepared according to paragraph A at ambient temperature and at a pH of 4.
- the silver powders used to make the colloid are referenced ⁇ 635 mesh and ⁇ 500 mesh and present a very large number of particles of diameter less than or equal to 10 microns. Such powders are commercialized by the Alfa Aesar company.
- Example 1 To demonstrate the oxidizing properties of the materials obtained in Example 1, 5 g of one of these materials was placed in contact with 20 ml of cyclohexene dissolved in 80 ml of methanol, and the disappearance of the cyclohexene, readily converted into cyclohexanol by any efficient oxidizing agent, was followed (Examples 2-11). The same experiment was carried out with hydrogen peroxide alone, and with zeolite (Examples 12-13). When no imogolite was present in the test the volume of imogolite was replaced by an equivalent volume of water so as to retain a constant volume.
- Table I shows that hydrogen peroxide is a weak oxidizing agent, being very difficult to activate. In addition, with zeolite, no oxidation of the cyclohexene was observed.
- the imogolite gels containing colloidal silver were particularly efficacious oxidizing agents.
- the imogolite gels containing colloidal zinc, lead or nickel were also oxidizing materials.
- Kathon LX® aqueous solution containing 13.7% by weight of isothiazolones of formula:
- Kathon LX® is highly sensitive to the presence of sodium sulfite or thiosulfate. 2 ml of Kathon LX® was mixed with 1 ml of methanol with magnetic stirring. To this mixture was added 100 ml of a 2 g/l solution of imogolite prepared according to Example 1-A. The addition of the mixture of Kathon LX® to the imogolite was carried out with slow mechanical stirring at ambient temperature. Ammonia was then added (0.4 ml). As soon as the gel mass appeared the stirring was stopped.
- a sulfite solution was also prepared containing 20% by weight of an equimolar sodium sulfite-thiosulfate mixture.
- polyester bag containing the bacterial growth control agent was placed in 400 ml of the sulfite solution, and then 10 g of an oxidizing material prepared according to Example 1-B was added to the sulfite solution. The mixture was stirred (Examples 14-16).
- the solution was analyzed by UV spectroscopy.
- the optical density measured against time was characteristic of the quantity of bacterial growth control agent present in the solution.
- a wavelength of 274 nm is characteristic of Kathon LX®.
- Table II shows that in the control sample (solution of sulfites+Kathon LX®) the optical density and therefore the concentration of Kathon LX® were strongly reduced after 48 hours. Likewise, with zeolite and imogolite gel plus hydrogen peroxide the concentration of Kathon LX® tended to fall with time. In contrast, with the oxidizing materials of the invention there was first a fall in the concentration of Kathon LX®, followed by a marked increase after 48 h. This can be explained by the initial degradation of the Kathon LX® by the sulfites in the sulfite solution, so reducing its concentration. In parallel, the sulfites are oxidized by the oxidizing material of the invention and disappear from the solution.
- the imogolite gel+Ag of the invention was particularly efficient in extending the life of the Kathon LX® in the sulfite solution.
- T-Mat G® radiographic films supplied by Eastman Kodak were processed in a KODAK X-OMAT® machine, model 5000 RA set for the operating conditions of the KODAK X-OMAT® process described in “Service Bulletin No 30, Health Imaging Products” published by Eastman Kodak Company.
- These processing lines have a single washing tank placed after the fixing step. The rate of water replenishment in the washing tank was limited to 1 l/min.
- This washing tank is equipped with an overflow that allows to keep a constant volume in the tank.
- the tank was also equipped with an outlet connected by piping to a treatment device according to the invention in which a polyester foam bag was placed, containing 1 kg of the imogolite gel+colloidal silver material made according to Example 1.
- the treatment device was connected to a pump to send the treated washing water back into the washing bath.
- the washing water contained, in particular, ammonium ions to be eliminated, and flowed continuously through the treatment tank. By flowing through the oxidizing material of the invention, these ammonium ions were oxidized. The washing water thus treated was then sent back into the processing tank.
- the 1-liter sample of the treated washing water was analyzed by capillary electrophoresis (CZE, capillary zone electrophoresis) to determine the concentration of NH 4 + and SO 3 2 ⁇ ions.
- CZE capillary electrophoresis
- Time t 0 corresponds to the first sampling. Before each sampling procedure the bath was seasoned by processing 100 T-Mat G® film plates. TABLE IV Untreated washing water Concentration in mg/l Species t 0 NH 4 + 57.90 SO 3 2 ⁇ 10.00
- Example 20 The experiment of Example 20 was repeated using, for the KODAK X-OMAT® processing of T-Mat G® films, a KODAK X-OMAT® model 480 RA machine.
- the water replenishment rate for the washing tank was 3.8 l/min.
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Abstract
The present invention relates to a material and a method for treating of photographic effluents in order to eliminate micro-organisms and pollutant by-products so as to control bacterial growth and thereby obtain effluents that comply with regulatory requirements. The method for preparing an oxidizing material according to the invention comprises the dispersion in colloidal form of a metal or metal compound in an aqueous solution of an inorganic aluminosilicate polymer, said aluminosilicate being able to form an inorganic gel, and said metal or metal compound being able to cause the oxidation of oxidizable products and (or) micro-organisms to be eliminated, followed by the addition of a base to cause said aluminosilicate to gel. The metal is preferably silver in a powder form that is able to form a colloid when it is dispersed. The oxidizing material of the invention is efficient especially for the treatment of photographic baths, in particular wash baths placed after the fixing step.
Description
- The present invention relates to a method for preparing an oxidizing material, to the oxidizing material thus prepared, and to a method for treating effluents, and in particular to method for treating photographic effluents.
- Many manufacturing or processing methods produce effluents that cannot be released directly into the sewers because of their composition. One example is that of the photographic industry, in which exposed films and papers pass successively through several processing baths that produce effluents rich in chemicals. Such processing methods for photographic films are well known (see, for example, Chimie et Physique Photographiques, Pierre Glafkides, Vol. 2, Cap. XL, pages 947-967).
- Conventionally, the processing of photographic products comprises a development step and a de-silvering step. The de-silvering step comprises the bleaching of the photographic product, which consists in converting metallic silver into silver ions, followed by fixing, which consists in eliminating the silver ions contained in the photographic product. Conventionally, the photographic processing steps can also include wash and stabilizing baths.
- Photographic products are generally developed automatically and as quickly as possible. During processing, the product passes through each of the baths described above. When the photographic product passes through the successive baths, non-negligible quantities of chemicals are carried over from one tank to the next, either by the photographic product itself or by the drive belts that convey the photographic product. These chemicals build up in the processing baths and thereby reduce their efficacy. The faster the photographic products are processed, the worse is the pollution of baths by the carry-over of chemicals. To counter this pollution, wash baths are intercalated between successive processing baths. In particular, after passage through a fixing or bleaching-fixing bath, the film passes through several wash baths before it enters the stabilizing bath.
- The wash baths that come after the fixing step contain many substances such as sulfites, thiosulfates and (or) ammonium salts used in the fixing baths, the sulfites and thiosulfates possibly deriving also from the developer. These wash baths cannot be discarded directly into the sewers and must be treated first to eliminate inorganic salts such as sulfites, thiosulfates, ammonium, and other organic by-products that raise the COD of the baths and are particularly harmful to the environment.
- In addition, because the development process takes place in an aqueous phase, the growth of micro-organisms, in particular in pre-baths, stabilizing baths and wash baths commonly occurs, worsening when the quantities of water consumed are reduced. The growth of micro-organisms such as molds and yeasts, if not controlled, causes the formation of sludge that clog the plant, degrade the processing bath, and so impair the quality of photographic image. Also, the presence of micro-organisms, especially bacteria, causes a biofilm to form on the walls of the processing tanks and on the film drive rollers and wheels, so that the machinery has to be shut down for cleaning.
- The use of control agents to prevent or limit bacterial growth in processing baths is common practice. Unfortunately, certain bacterial growth control agents are very sensitive to the presence of sulfites and thiosulfates found in washing water and are broken down before they can fully act. To compensate for this breakdown, excess quantities are used relative to the exact amount required. In this case the water discharged into the environment contains large quantities of bacterial growth control agents, which causes problems in wastewater treatment plants that exploit the action of micro-organisms for effluent treatment.
- The present invention provides a method for preparing a material that allows to minimize the occurrence and growth of micro-organisms in processing water in order thereby to reduce the quantities of control agents that have to be used.
- The present invention provides also a material that rids processing water of pollutant by-products so as to obtain effluents that comply with regulatory requirements.
- The present invention provides also a material to rid processing water of pollutant by-products that generate unwanted reactions with bacterial growth control agents, in order thereby to extend the life of said agents.
- The present invention relates to a method for preparing an oxidizing material comprising the step of (i) dispersing in colloidal form a metal or a metal compound in an aqueous solution of an inorganic aluminosilicate polymer, said aluminosilicate being able to form an inorganic gel, and said metal or metal compound being able to cause the oxidation of oxidizable compounds and (or) micro-organisms to be eliminated, and the step of (ii) adding a base to cause said aluminosilicate to gel.
- The present invention also concerns a material obtainable by the method described above, as well as its use to oxidize, in the presence of water, oxidizable compounds and (or) micro-organisms to be eliminated.
- The invention also concerns a method for treating an aqueous solution liable to contain oxidizable compounds to be eliminated and (or) to harbor micro-organisms, as well as a device for carrying out said method. The method comprises contacting the aqueous solution with said oxidizing material. It is especially efficient for the treatment of photographic baths, in particular wash baths after the fixing step, because it rids such baths of micro-organisms and oxidizable chemical by-products. The “micro-organisms to be eliminated” are in particular algae, fungi, bacteria and yeasts. The “oxidizable chemicals to be eliminated” are in particular inorganic or organic by-products considered as pollutants either with regard to aqueous the solution to be treated or in a general way with regard to the environment, for example sulfite and ammonium ions, surfactants, etc.
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FIG. 1 is a plot of optical density as a function of time for a solution processed with materials according to the invention and comparative materials. - In the method of the invention for preparing an oxidizing material, an aqueous solution of an inorganic aluminosilicate polymer is used that is liable to form an inorganic gel in certain conditions, for example when the pH of the medium is increased. In a preferred embodiment imogolite is used as aluminosilicate polymer. Imogolite is an aluminosilicate polymer that occurs in the form of fibers, including in solution, and an essential characteristic of which is that it forms a gel at a pH of about 8 and above. In this way physical gels are obtained in an aqueous phase. Imogolite fibers comprise active hydroxyl groups on their outer surface. Imogolite occurs naturally in an impure form. It was first described by Wada in J. Soil Sci. 1979, 30(2), 347-355. Imogolite can be synthesized with different degrees of purity by different methods. A method for obtaining a highly pure imogolite gel is described in patent U.S. Pat. No. 5,888,711.
- The metal used in the present invention can be any of the following: silver, zinc, copper, iron, titanium, lead or nickel. When a metal compound is used, said compound contains one of the metals listed above. Preferably, monodisperse silver in powder form may be used, in which most of the particles are of diameter equal to or smaller than 10 microns, said silver producing a colloid when dispersed in the aqueous solution of imogolite. The silver can be mixed with other metals such as copper. Silver nitrate can also be used. Zinc can also be used in the form of zinc powder or zinc nitrate. All these metal compounds are commercially available and are distributed, for example, by the Alfa Aesar company.
- In the scope of the invention the metals or metal compounds are preferably used in the form of powders that are able to form colloids when they are dispersed in the imogolite. They can also be used in the form of a colloidal solution. However, the pH of the solution must be below the gelling threshold of the imogolite, for example below about 5, so that the addition of the colloidal metal solution does not cause the immediate gelling of the imogolite, which would prevent the metal particles from homogenizing properly in the imogolite solution.
- The initial metal or metal compound content is preferably in the range of 5 to 10% by weight relative to the [Al+Si] content of the imogolite.
- The material according to the invention is obtained by dispersing the metal or metal compound in the aqueous solution of imogolite at ambient temperature, while stirring the solution adequately so as to obtain a homogeneous dispersion of metal particles in colloidal form, and then adding a base to the reaction mixture, for example NH4OH, NaOH or KOH, so as to raise the pH to cause the aluminosilicate to gel.
- An imogolite gel is thereby obtained in which metal particles are evenly dispersed, do not agglomerate, and remain dispersed in the imogolite matrix.
- The material obtained by the method of the invention displays oxidizing properties. These oxidizing properties are demonstrated in the following way: when the material of the invention is placed at ambient temperature in the presence of cyclohexene dissolved in methanol, the conversion of cyclohexene into cyclohexanol can be observed by Fourier-transform Raman spectroscopy. The oxidation takes place more readily with heating.
- It can be hypothesized that the metal particles dispersed in the imogolite present an appropriate configuration to allow a local micro-electrolysis of water that generates active oxygen, which combines immediately with water to form hydrogen peroxide in situ. According to this hypothesis, the material according to the invention is a gel that allows hydrogen peroxide to be generated in situ, and in which it accumulates. The gel then slowly desorbs the hydrogen peroxide in the aqueous solution to be treated. The hydrogen peroxide, which is unstable, combines immediately with an oxidizable substance and degrades it. This hypothesis in no way limits the claims made for the present invention.
- According to one embodiment of the method for preparing the oxidizing material according to the invention, active agents other than the colloidal metal or metal compound are dispersed in the aqueous solution of imogolite, these active agents being chosen so as not to react with the said metal or metal compound. For example, the active agents can be bacterial growth control agents, which are defined as organic compounds displaying pesticidal, algicidal, fungicidal or bactericidal properties. Some bacterial growth control agents are very sensitive to the presence of sodium sulfite or thiosulfate, but only weakly sensitive to oxidation.
- A large number of bacterial growth control agents are known. From their general knowledge, those skilled in the art can easily select one or more suitable bacterial growth control agents. However, these agents must not form a covalent bond with the matrix of imogolite gel, because they would then be trapped in the matrix. The bacterial growth control agents that are useful for the invention are, for example, thiazole derivatives such as isothiazolones, azole derivatives such as benzotriazoles, benzimidazoles, or sulfamide-type agents such as sulfanilamide. It is preferable to use a mixture of hydrophilic isothiazolones such as 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one and hydrophobic isothiazolones such as 2-octyl-4-isothiazolin-3-one. The mixture of hydrophilic and hydrophobic bacterial growth agents is introduced in the oxidizing material of the invention by simple dispersion in the aqueous solution of imogolite before it has gelled.
- According to another embodiment of the method for preparing the oxidizing material of the invention, an alkylalkoxysilane of formula RSiR1 x(OR2)3-x, wherein R is an alkyl group containing an —SH or —S(—CH2)n—S— function with n between 0 and 4, R1 and R are independently a methyl or ethyl group and x is 0 or 1, is hydrolyzed before the imogolite has been made to gel. A preferred alkylalkoxysilane is 3-mercaptopropyltrimethoxysilane. This process and the material obtained are described in patent U.S. Pat. No. 6,179,898. It makes it possible to graft onto the surface of the imogolite fibers an organic radical with —SH or —S(—CH2)n—S— function with n between 0 and 4. These sulfur-containing molecules are able to capture the silver present in ionic form in the aqueous solutions to be treated.
- These embodiments of the method for preparing the oxidizing material of the invention can be combined in such a way as to obtain a material in which the imogolite matrix comprises grafted sulfur-containing molecules and contains a metal or metal compound dispersed as a colloid, and a bacterial growth control agent.
- In the method for treating an aqueous solution according to the invention the oxidizing material described above is placed in contact with the said aqueous solution containing the oxidizable chemicals and (or) the micro-organisms to be eliminated. To be active the oxidizing material of the invention must be permeated by the aqueous solution to be treated, for example an aqueous effluent. The material according to the invention can either be placed directly in the solution to be treated or be placed in a container that is permeable to the solution to be treated. It can, for example, be placed in a dialysis bag or in a closed bag made of filter paper or non-woven fabric.
- The oxidizing properties of the material of the invention make it possible to eliminate all the micro-organisms that may be present in the effluent, none of which is able to survive in such an oxidizing medium. This makes it possible to reduce the quantity of bacterial growth control agents. The material of the invention can be used in a very broad domain of application, effectively killing, for example, algae, fungi, bacteria and yeasts. The oxidizing material of the invention can be used in any application in which the bacteriological quality of water has to be controlled.
- For example, the oxidizing material can be used in the photographic sector, or in the maintenance of industrial cooling water, etc.
- The oxidizing material can be advantageously used in a photographic treatment machine conventionally comprising a developing bath, a bleaching bath, a fixing bath and one or more wash baths. The oxidizing material of the invention can be used for any of these baths, preferably for the treatment of a wash bath obtained after the fixing step.
- In addition, the oxidizing properties of the material of the invention make it possible to eliminate the oxidizable chemical by-products present in the effluent. Thus certain inorganic salts are readily oxidized, such as sulfites and ammonium ions that occur in large amounts in wash baths. Likewise, certain organic by-products are oxidized, such as surfactants, emulsion thickening agents, etc. As a result, the COD of the effluent will be strongly reduced.
- Consequently the effluents treated using the material of the invention are rid of by-products that may be banned by various regulations. In addition, the material of the invention, by affording an in situ oxidation, offers the advantage that hydrogen peroxide solutions do not have to be handled or tanks of oxidizing solution managed.
- When the material of the invention also includes bacterial growth control agents dispersed in the imogolite matrix, the method of the invention extends the life of such bacterial growth control agents that are sensitive to sulfites and thiosulfates. The bacterial growth control agents are protected as long as they remain in the imogolite gel matrix. When they diffuse into the effluent to exert their action they are generally destroyed by sulfites and thiosulfates before they can take effect. With the material of the invention the sulfites and thiosulfates present in the effluent are oxidized and broken down before they can destroy the control agents, the concentrations of which in the effluent to be treated therefore remain sufficient. This is particularly useful when the bacterial growth control agent is a curative agent with very high water-solubility designed to massively attack the cells of micro-organisms.
- When the material of the invention also contains, on the surface of the imogolite fibers, organic radicals with a sulfur function, ionic silver present in the medium is eliminated in addition to the oxidizable chemicals. Another embodiment of the method of the invention consists in placing the effluent to be treated successively in contact with the oxidizing material of the invention and with a composite material comprising a matrix of imogolite gel in which are dispersed bacterial growth control agents such as those described above and (or) with an inorganic imogolite polymer in fiber form containing at least at the surface of the fibers an organic radical with an —SH or —S(—CH2)n—S— function with n between 0 and 4.
- This method offers the same advantages as those described above. In this case the oxidizing material of the invention is placed in contact with the effluent to be treated, or placed in a first dialysis bag, and the composite material for the bacterial growth control or the imogolite comprising grafted sulfur-containing molecules is placed in a second dialysis bag, both bags being placed in a treatment apparatus through which flows the aqueous solution to be treated. The dialysis bags can be arranged so that the treatment by the oxidizing material of the invention is carried out first. The method of the invention can also combine all three treatments, each of the materials, the oxidizing material, the bacterial growth control material and the sulfur-containing material, being placed in separate bags. It is also possible to use the oxidizing material of the invention together with a composite material made up of a matrix of imogolite gel comprising grafted sulfur-containing molecules, and containing a bacterial growth control agent dispersed in the matrix. Such a composite material is described in the Patent application EP-A-937 393.
- The following examples illustrate the present invention in detail.
- A) Preparation of an Aqueous Solution of Imogolite.
- The aluminosilicate of this example was prepared using teachings from patent U.S. Pat. No. 5,888,711.
- To 1,000 ml of de-ionized water were added 16.7 mmoles of tetraethylorthosilicate Si(OC2H5)4. The reaction mixture was stirred at ambient temperature for one hour, and then to the solution was added 31.2 moles of AlCl3.6H2O dissolved in 1,000 ml of pure water. The mixture was stirred for 20 minutes and the pH was adjusted to 4.5 with 1M NaOH. The solution became cloudy. When the solution became transparent again, 1M NaOH was added until the pH reached 6.8. A white gel was obtained, which was centrifuged for 20 minutes at 2,000 r.p.m. The gel was collected and redissolved in 5 ml of a mixture of 1M HCl and 2M acetic acid. The volume was made up to 2 liters with water. The resulting solution contained 30 mmoles of Al, 16.6 mmoles of Si, 5 mmoles of HCl and 10 mmoles of acetic acid. This solution was stored at 5° C.
- This solution was then diluted with de-ionized water to obtain an Al concentration of 10 mmoles/l. The diluted solution was heated for 5 days at 96° C. and then filtered through an ultrafiltration membrane with a separating power of 10,000 daltons (membrane manufactured by AMICON). A clear solution was obtained containing Al and Si in the Al:Si ratio 1.8 and with a [Al+Si] content equal to 3 g/l.
- B) Preparation of the Oxidizing Materials
- The oxidizing material according to the invention was prepared by dispersing in colloidal form, 20 mg of silver in 200 ml of imogolite prepared according to paragraph A at ambient temperature and at a pH of 4. The silver powders used to make the colloid are referenced −635 mesh and −500 mesh and present a very large number of particles of diameter less than or equal to 10 microns. Such powders are commercialized by the Alfa Aesar company.
- To cause the imogolite to gel 10 ml of NH4OH (15.5M) was then added.
- Other materials according to the invention were prepared in a similar way using other metals or metal compounds indicated in Table I (Examples 2-11).
- To demonstrate the oxidizing properties of the materials obtained in Example 1, 5 g of one of these materials was placed in contact with 20 ml of cyclohexene dissolved in 80 ml of methanol, and the disappearance of the cyclohexene, readily converted into cyclohexanol by any efficient oxidizing agent, was followed (Examples 2-11). The same experiment was carried out with hydrogen peroxide alone, and with zeolite (Examples 12-13). When no imogolite was present in the test the volume of imogolite was replaced by an equivalent volume of water so as to retain a constant volume.
- The oxidation of the cyclohexene was followed by FT (Fourier transform) Raman spectroscopy by measuring the percentage of cyclohexene converted to cyclohexanol after 48 hours. The tests were carried out at ambient temperature.
- The results are set out in Table I.
TABLE I Cyclohexene oxidized Examples after 48 h (%) 1 (inv) Imogolite gel + Ag 79 2(inv) Imogolite gel + Ag(NO3) 34 3 (inv) Imogolite gel + Ag-Cu 14 4 (inv) Imogolite gel + Cu(NO3)2 34 5 (inv) Imogolite gel + Zn 40 6 (inv) Imogolite gel + Zn(NO3)2 18 7 (inv) Imogolite gel + Pb 35 8 (inv) Imogolite gel + Pb(NO3)2 37 9 (inv) Imogolite gel + Ni 36 10 (inv) Imogolite gel + Fe 28 11 (inv) Imogolite gel + TiO2 31 12 (comp) Zeolite 2 13 (comp) H2O2 3 - Table I shows that hydrogen peroxide is a weak oxidizing agent, being very difficult to activate. In addition, with zeolite, no oxidation of the cyclohexene was observed.
- In contrast, the imogolite gels containing colloidal silver were particularly efficacious oxidizing agents. The imogolite gels containing colloidal zinc, lead or nickel were also oxidizing materials.
- An imogolite gel containing Kathon LX®, a mixture of hydrophilic bacterial growth control agents that is completely soluble in water, supplied by Rohm & Haas, was prepared using the following operating procedure.
-
-
- where the chloroisothiazolone:isothiazolone ratio is 3:1.
- Kathon LX® is highly sensitive to the presence of sodium sulfite or thiosulfate. 2 ml of Kathon LX® was mixed with 1 ml of methanol with magnetic stirring. To this mixture was added 100 ml of a 2 g/l solution of imogolite prepared according to Example 1-A. The addition of the mixture of Kathon LX® to the imogolite was carried out with slow mechanical stirring at ambient temperature. Ammonia was then added (0.4 ml). As soon as the gel mass appeared the stirring was stopped.
- 10 g of the imogolite-Kathon LX® gel thus obtained was placed in a permeable polyester bag.
- A sulfite solution was also prepared containing 20% by weight of an equimolar sodium sulfite-thiosulfate mixture.
- The polyester bag containing the bacterial growth control agent was placed in 400 ml of the sulfite solution, and then 10 g of an oxidizing material prepared according to Example 1-B was added to the sulfite solution. The mixture was stirred (Examples 14-16).
- The same experiment was carried out with the oxidizing material of the invention replaced by an imogolite gel, an imogolite gel plus hydrogen peroxide, and zeolite (Examples 17-19).
- The solution was analyzed by UV spectroscopy. The optical density measured against time was characteristic of the quantity of bacterial growth control agent present in the solution. A wavelength of 274 nm is characteristic of Kathon LX®.
- The results are set out in Table II below and are illustrated by
FIG. 1 .TABLE II Optical density of Kathon LX ® in the presence of sulfites Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Imogolite Imogolite Imogolite Imogolite Imogolite Ex. 19 Time gel + Ag—Cu gel + Ag gel + Zn(NO3)2 gel gel + H2O2 Zeolite (hours) Control (inv) (inv) (inv) (comp) (comp) (comp) 1 17.2 15.1 22.8 26.3 8.52 25.2 20.1 2 13.4 32 41.1 27.4 45 11.4 26 24 20.5 24.8 33.2 22 22.6 23.8 22.1 48 9.6 38.5 41.9 34.8 34.6 20.8 20.6 - Table II shows that in the control sample (solution of sulfites+Kathon LX®) the optical density and therefore the concentration of Kathon LX® were strongly reduced after 48 hours. Likewise, with zeolite and imogolite gel plus hydrogen peroxide the concentration of Kathon LX® tended to fall with time. In contrast, with the oxidizing materials of the invention there was first a fall in the concentration of Kathon LX®, followed by a marked increase after 48 h. This can be explained by the initial degradation of the Kathon LX® by the sulfites in the sulfite solution, so reducing its concentration. In parallel, the sulfites are oxidized by the oxidizing material of the invention and disappear from the solution. Once the sulfites have been destroyed in this way the Kathon LX® diffusing into the solution is no longer degraded and so its concentration rises. The imogolite gel+Ag of the invention was particularly efficient in extending the life of the Kathon LX® in the sulfite solution.
- T-Mat G® radiographic films supplied by Eastman Kodak were processed in a KODAK X-OMAT® machine, model 5000 RA set for the operating conditions of the KODAK X-OMAT® process described in “
Service Bulletin No 30, Health Imaging Products” published by Eastman Kodak Company. These processing lines have a single washing tank placed after the fixing step. The rate of water replenishment in the washing tank was limited to 1 l/min. This washing tank is equipped with an overflow that allows to keep a constant volume in the tank. The tank was also equipped with an outlet connected by piping to a treatment device according to the invention in which a polyester foam bag was placed, containing 1 kg of the imogolite gel+colloidal silver material made according to Example 1. The treatment device was connected to a pump to send the treated washing water back into the washing bath. The washing water contained, in particular, ammonium ions to be eliminated, and flowed continuously through the treatment tank. By flowing through the oxidizing material of the invention, these ammonium ions were oxidized. The washing water thus treated was then sent back into the processing tank. - To analyze the composition of the treated washing water various samples were taken at the overflow outlet. The washing water sampling procedure was carried out in such a way that the conditions most representative of the average operation of the processing machine were modeled. For this purpose ten T-Mat G® radiographic films of
size 35×43 cm were used. Three of them were exposed to light and were completely fogged. At time zero a first unexposed film was introduced into the machine. At time 3 minutes a second unexposed film was introduced. 1 liter of washing water from the overflow of the washing tank was then sampled. Attime 6 minutes an exposed film was introduced, and so on until the last film. The unexposed films were thus introduced attimes 9, 12, 18, 21 and 27 minutes, and the exposed films attimes 15 and 24 minutes. - The sampling of 1 liter of washing water at the overflow outlet was repeated at
time 15 minutes during the development of the second exposed film, and again at time 27 minutes, during that of the last unexposed film. The three samples of washing water were pooled, and a 1-liter sample of the resulting mixture was taken. - The 1-liter sample of the treated washing water was analyzed by capillary electrophoresis (CZE, capillary zone electrophoresis) to determine the concentration of NH4 + and SO3 2− ions.
- The experiment was repeated but without treatment of the washing water by the material of the invention.
- The results obtained are set out respectively in Tables III and IV below.
TABLE III Treated washing water Concentration in mg/l Species t0 t0 + 5 days NH4 + 40.30 3.90 SO3 2− 0.00 0.00 - Time t0 corresponds to the first sampling. Before each sampling procedure the bath was seasoned by processing 100 T-Mat G® film plates.
TABLE IV Untreated washing water Concentration in mg/l Species t0 NH4 + 57.90 SO3 2− 10.00 - The above results show that the concentration of ammonium ions in the washing water decreased markedly when this washing water was treated with the oxidizing material of the invention. Also, the treated washing water no longer contained any sulfites. After treatment the washing water was compliant with regulations concerning the environment and was fit to be discharged into the sewers. In contrast, the untreated washing water contained high concentrations of ammonium ions owing to the low rate of replenishment of the water in the washing tank.
- The experiment of Example 20 was repeated using, for the KODAK X-OMAT® processing of T-Mat G® films, a KODAK X-OMAT® model 480 RA machine. The water replenishment rate for the washing tank was 3.8 l/min.
- The concentration of ammonium ions was measured in 1-liter samples taken as described in Example 20, after several processing runs over several days. The results are set out in Table V below.
TABLE V Treated washing water Concentration in mg/l Species t0 t0 + 9 days t0 + 14 days NH4 + 13.20 3.90 3.30 - When the washing water was not treated the concentration of NH4 + ions measured remained greater than or equal to 6.90 mg/l.
- The results show that the oxidizing material of the invention allows to reduce the concentration of ammonium ions in washing water significantly and lastingly. This can be explained, according to the hypothesis stated above, by the fact that the hydrogen peroxide generated in situ in the gel, in which it accumulates, is then desorbed slowly into the washing waters that flow continuously through the treatment device.
Claims (14)
1.-6. (canceled)
7. An oxidizing material obtainable by a method for preparing said oxidizing material comprising the step of (i) dispersing in colloidal form a metal or metal compound in an aqueous solution of an inorganic aluminosilicate polymer, said aluminosilicate being able to form an inorganic gel, and said metal or metal compound being able to cause the oxidation of oxidizable products and (or) micro-organisms to be eliminated, and the step of (ii) adding a base to cause said aluminosilicate to gel.
8. The oxidizing material according to claim 7 , wherein said metal is selected from among the metals silver, zinc, copper, iron, titanium, lead or nickel, and wherein the metal compound contains at least one of said metals.
9. The oxidizing material according to claim 8 , wherein the metal is silver in powder form of which most of the particles are of diameter less than or equal to 10 microns, and able to form a colloid when dispersed in said aqueous solution of aluminosilicate.
10. The oxidizing material according to claim 7 , wherein said inorganic aluminosilicate polymer is imogolite.
11. The oxidizing material according to claim 7 , further comprising a bacterial growth control agent dispersed in the aluminosilicate polymer.
12. The oxidizing material according to claim 7 , further comprising on the surface of the aluminosilicate polymer at least an organic radical having a —SH or —S(—CH2)n—S— function with n between 0 and 4.
13. The use of the material according to claim 7 to oxidize oxidizable chemicals and (or) micro-organisms to be eliminated.
14. A method for treating an aqueous solution liable to contain oxidizable chemicals to be eliminated and (or) to harbor micro-organisms, that involves placing said aqueous solution in contact with the oxidizing material according to claim 7 , and placing said aqueous solution in contact with an inorganic aluminosilicate polymer in fiber form in which a bacterial growth control agent is dispersed.
15. A method for treating an aqueous solution liable to contain silver in ionic form and oxidizable chemicals to be eliminated and (or) to harbor micro-organisms, that involves placing said solution in contact with the oxidizing material according to claim 7 , and placing said aqueous solution in contact with an inorganic imogolite polymer in fiber form comprising at least on the surface of the fibers an organic radical containing an —SH or —S(—CH2)n—S—function with n between 0 and 4.
16. A method for treating an aqueous solution liable to contain silver in ionic form and oxidizable chemicals to be eliminated and (or) to harbor micro-organisms, that involves placing said aqueous solution in contact with the oxidizing material according to claim 12 .
17. The method according to any of claims 14 to 16 for the treatment of a photographic bath.
18. The method according to claim 17 , wherein the photographic bath is a wash bath.
19. A device for the treatment of an aqueous solution liable to contain oxidizable chemicals to be eliminated and (or) to harbor micro-organisms, comprising a support that is permeable to said aqueous solution and in which is placed the oxidizing material according to claim 7.
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US10/624,761 US20050089805A1 (en) | 2001-06-11 | 2003-07-22 | Material and method for treating photographic effluents |
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FR0107566A FR2825696B1 (en) | 2001-06-11 | 2001-06-11 | MATERIAL AND METHOD FOR THE TREATMENT OF PHOTOGRAPHIC EFFLUENTS |
US10/159,680 US6620397B2 (en) | 2001-06-11 | 2002-05-31 | Material and method for treating photographic effluents |
US10/624,761 US20050089805A1 (en) | 2001-06-11 | 2003-07-22 | Material and method for treating photographic effluents |
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EP (1) | EP1267208B1 (en) |
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US10416176B2 (en) | 2013-12-13 | 2019-09-17 | Ventana Medical Systems, Inc. | Staining reagents and other liquids for histological processing of biological specimens and associated technology |
US10656168B2 (en) | 2013-12-13 | 2020-05-19 | Ventana Medical Systems, Inc. | Automated processing systems and methods of thermally processing microscope slides |
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FR2825696B1 (en) * | 2001-06-11 | 2004-06-11 | Eastman Kodak Co | MATERIAL AND METHOD FOR THE TREATMENT OF PHOTOGRAPHIC EFFLUENTS |
FR2889649A1 (en) * | 2005-08-11 | 2007-02-16 | Eastman Kodak Co | Use of a dispersion of silver in imogolite and/or allophane matrix as antiseptic agent for the manufacture of bandages |
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US5882624A (en) * | 1997-01-29 | 1999-03-16 | Englehard Corporation | ETS-14 crystalline titanium silicate molecular sieves, manufacture and use thereof |
-
2001
- 2001-06-11 FR FR0107566A patent/FR2825696B1/en not_active Expired - Fee Related
-
2002
- 2002-05-17 DE DE60208515T patent/DE60208515T2/en not_active Expired - Lifetime
- 2002-05-17 EP EP02356093A patent/EP1267208B1/en not_active Expired - Lifetime
- 2002-05-31 US US10/159,680 patent/US6620397B2/en not_active Expired - Fee Related
- 2002-06-10 JP JP2002168715A patent/JP2003033655A/en active Pending
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2003
- 2003-07-22 US US10/624,761 patent/US20050089805A1/en not_active Abandoned
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US3373109A (en) * | 1963-10-29 | 1968-03-12 | Mobil Oil Corp | Crystalline aluminosilicate catalyst |
US3373110A (en) * | 1966-04-14 | 1968-03-12 | Mobil Oil Corp | Process for the preparation of platinum metal containing aluminosilicates |
US5888711A (en) * | 1994-10-31 | 1999-03-30 | Eastman Kodak Company | Polymeric conductive alumino-silicate material, element comprising said material, and process for preparing it |
US6179898B1 (en) * | 1998-02-23 | 2001-01-30 | Eastman Kodak Company | Aluminosilicate organic-inorganic polymer |
US6440308B1 (en) * | 1998-02-23 | 2002-08-27 | Eastman Kodak Company | Method for treating a photographic processing bath |
US6555008B1 (en) * | 1999-09-06 | 2003-04-29 | Eastman Kodak Company | Method to extract silver from a photographic developer |
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US10416176B2 (en) | 2013-12-13 | 2019-09-17 | Ventana Medical Systems, Inc. | Staining reagents and other liquids for histological processing of biological specimens and associated technology |
US10656168B2 (en) | 2013-12-13 | 2020-05-19 | Ventana Medical Systems, Inc. | Automated processing systems and methods of thermally processing microscope slides |
US11567091B2 (en) | 2013-12-13 | 2023-01-31 | Ventana Medical Systems, Inc. | Automated processing systems and methods of thermally processing microscope slides |
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US6620397B2 (en) | 2003-09-16 |
JP2003033655A (en) | 2003-02-04 |
US20030077547A1 (en) | 2003-04-24 |
FR2825696A1 (en) | 2002-12-13 |
DE60208515D1 (en) | 2006-03-30 |
EP1267208A1 (en) | 2002-12-18 |
DE60208515T2 (en) | 2006-08-24 |
FR2825696B1 (en) | 2004-06-11 |
EP1267208B1 (en) | 2006-01-04 |
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