US3634088A - Regeneration of blix solutions used in photographic processing - Google Patents
Regeneration of blix solutions used in photographic processing Download PDFInfo
- Publication number
- US3634088A US3634088A US8026A US3634088DA US3634088A US 3634088 A US3634088 A US 3634088A US 8026 A US8026 A US 8026A US 3634088D A US3634088D A US 3634088DA US 3634088 A US3634088 A US 3634088A
- Authority
- US
- United States
- Prior art keywords
- solution
- silver
- blix
- oxygen
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000012545 processing Methods 0.000 title abstract description 16
- 230000008929 regeneration Effects 0.000 title description 7
- 238000011069 regeneration method Methods 0.000 title description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 46
- 239000004332 silver Substances 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 13
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 44
- 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 10
- 229910052946 acanthite Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229940056910 silver sulfide Drugs 0.000 claims description 4
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 37
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 239000007844 bleaching agent Substances 0.000 abstract description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000004061 bleaching Methods 0.000 abstract description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 69
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000005273 aeration Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- -1 silver halide Chemical class 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 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 5
- 239000010959 steel Substances 0.000 description 5
- 210000002268 wool Anatomy 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical class SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-N 0.000 description 1
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 1
- TZMVSJNOQJXJMO-UHFFFAOYSA-N 2-[1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1(CC(O)=O)CC(O)=O TZMVSJNOQJXJMO-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 1
- ZIUZDRMIXJKUNY-UHFFFAOYSA-N 3-[2-carboxyethyl(ethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC)CCC(O)=O ZIUZDRMIXJKUNY-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Definitions
- Removal of silver from the solution can be effected by addition of a chemical precipitant, by metallic replacement, or by electrolytic recovery and the necessary contact with oxygen after silver removal can be accomplished by aerating the solution.
- Treatment of spent bleach-fix solutions in this manner will essentially restore their original bleaching and fixing capabilities and thereby permit their reuse in photographic processing.
- This invention relates in general to photographic processing and in particular to the use of bleach-fix solutions. More specifically, this invention relates to treatment of spent bleach-fix solutions to substantially restore their original bleaching and fixing capabilities so as to permit their reuse.
- Combined bleaches and fixes commonly referred to as blixes, have been known for many years. They are used in processing silver halide photographic materials to simultaneously accomplish the steps of bleaching and fixing and thereby eliminate one step in the conventional processing procedure.
- the essential components of a blix solution are the bleaching agent, i.e. an agent which oxidizes the metallic silver in the silver image to a soluble form, and the fixing agent, i.e., an agent which dissolves the underdeveloped silver halide and the silver salts formed by the action of the bleaching agent.
- blixes While a large number of different blix formulations are known to the art, of particular importance because of their stability and the excellent results obtained therewith are blixes in which the bleaching agent is a ferric salt of an aminopolycarboxylic acid and the fixing agent is a thiosulfate.
- Blixes comprising a thiosulfate and a ferric salt of an aminopolycarboxylic acid are relatively costly and their commercial use has been hampered by this fact, especially in view of the further fact that heretofore they could be used only once and then had to be discarded.
- the methods employed are not useful for treatment of the aforesaid blix solutions.
- ferricyanide bleach solutions can be regenerated by treatment with bromine, as is described in US. Pat. No. 2,515,930, or by treatment with reagents capable of releasing bromine in aqueous solution, as are described in US. Pat. Nos.
- blix solutions in which a thiosulfate serves as the fixing agent and a ferric salt of an aminopolycarboxylic acid as the bleaching agent are regenerated by a method which essentially restores their original bleaching and fixing capabilities and thereby permits their reuse.
- the method comprises reduction of the concentration of silver in the solution to a low level, as hereinafter described, and mixing of oxygen with the solution in a sufficient amount, as hereinafter described, to convert substan tially all ferrous ion in the solution to ferric ion.
- Appropriate additions of minor amounts of chemicals to restore the solution to its exact original composition are also made, as needed.
- Blix solutions to which the method of this invention is applicable are solutions comprising a water-soluble thiosulfate which serves as the fixing agent.
- thiosulfates which are useful for this purpose include ammonium thiosulfate and alkali metal thiosulfates such as sodium thiosulfate and potassium thiosulfate.
- aminopolycarboxylic acids Use of ferric salts of aminopolycarboxylic acids as bleaching agents in blix formulations is also well known.
- aminopolycarboxylic acids are the following:
- the ferric salts of aminopolycarboxylic acids utilized in the practice of this invention may be salts in which all cations are the ferric ion or salts in which one or more of the carboxyl groups have formed a salt with a cation other than iron, e.g. with ammonia or with an alkali metal ion.
- An example of such a salt is sodium ferric ethylenediamine tetraacetate.
- the blix may also contain a nonchelated salt of an aminopolycarboxylic acid, e.g. the tetra sodium salt of ethylenediamine tetraacetic acid, in addition to the ferric salt.
- the blixes will usually also include other addenda known to the art to be useful for incorporation in blix formulations.
- they may include an additional silver halide solvent such as a water-soluble thiocyanate, e.g. ammonium thiocyanate, sodium thiocyanate or potassium thiocyanate, as well as such compounds as ammonium bromide, alkali metal bromides, amines, sulfites, mercaptotriazoles, etc.
- the concentration of thiosulfate in the blix solution is typically from about 5 to about 200 grams per liter and the concentration of the ferric salt of an aminopolycarboxylic acid is typically from about 5 to about 200 per grams per liter.
- any of the methods which are known to the art for recovering silver from a fixing solution can be utilized in accordance with this invention to reduce the concentration of silver ion in the blix to the desired level.
- these methods are of three types, namely, precipitation of the silver by addition of a chemical agent which forms an insoluble silver salt, metallic replacement in which the solution is brought into contact with a metal which is more electropositive than silver and thereby serves to replace the dissolved silver, and electrolytic recovery in which the silver is plated out on the cathode of an electrolytic cell.
- Electrolytic recovery should be carried out using a cell designed to operate with high agitation and high current density.
- the minimum current density needed to remove silver from the blix solution is higher than is required with a fixing solution while the tendency to formation of silver sulfide is less with the blix solution than with most fixing solutions so that use of high current densities is feasible.
- the concentration of silver in the blix solution should be reduced to a level of less than about one gram of silver per liter of solution and more preferably to a level of less than about 0.5 gram of silver per liter of solution.
- the spent blix solution subjected to regeneration may have a silver concentration of up to about 10 grams per liter, or more, but will most usually have a concentration of silver of about 2 to 3 grams per liter.
- the second step of the process of this invention is the step of mixing the blix solution, from which the silver has been removed by one of the methods discussed above, with oxygen in order to oxidize ferrous ion to ferric ion.
- oxygen in order to oxidize ferrous ion to ferric ion.
- At least 0.25 mole of oxygen per mole of ferrous ion in the solution Preferably, an amount of oxygen of at least about one mole per mole of ferrous ion is used. Any combination of oxygen flow rate and time which will permit adequate contact of the oxygen with the solution can be utilized. Of course, the amount of oxygen necessary will depend upon the composition of the blix being treated and the optimum amount of oxygen for a particular blix solution will depend upon the efficiency of the contacting procedure employed. Optimum amounts of oxygen in any particular instance may be readily determined by a few routine experiments.
- Mixing of oxygen with the blix solution can be carried out using batch, semicontinuous or continuous techniques, as desired.
- a portion of the blix solution can be continuously withdrawn from the processing machine and returned as a recycle stream after regeneration.
- pure oxygen can be employed to effect regeneration by the method of this invention, its use is not necessary and it will ordinarily be satisfactory to effect the oxidation by contacting the solution with air.
- oxidation could be carried out using any otherwise inert oxygen-containing gaseous mixture, e.g. a mixture of oxygen and nitrogen or a mixture of oxygen and argon. Aeration will ordinarily be the simplest, most convenient and most inexpensive procedure.
- the time required for aeration will depend upon such factors as the characteristics of the air distributor, the flow rate, the size and shape of the tank in which the blix solution is aerated, the method used for removing the silver and so forth. Typical times required for substantially complete oxidation of ferrous ion by aeration are from about to about 90 minutes.
- the silver should, under ordinary circumstances, be removed from the solution before contact of the solution with oxygen is effected since the common procedures for silver recovery, e.g. metallic replacement or electrolytic recovery, will at the same time as they effect removal of silver bring about reduction of ferric ion to ferrous ion and thus counteract the effect of the oxidation step.
- common procedures for silver recovery e.g. metallic replacement or electrolytic recovery
- the solution can be analyzed using well-known analytical techniques.
- Example 1 The blix employed in this example had the following composition:
- the blix employed in this example had the following composition:
- This blix was used in the same manner as described in example l and the seasoned blix overflow from the machine was passed through a single steel wool packed cartridge at a rate of 5 gallons per hour.
- the effluent from the cartridge was aerated for 1 hour using a -micron pore sintered stainless steel air sparger and an air flow rate of 40 cubic feet per hour.
- the aerated blix was then diluted by percent with water to aerated blix to be used as replenisher, the following chemical additions were made:
- Nl-LSCN 1 g./l. Na,EDTA 53 71 The pH of the blix was adjusted to 7.0 and it was used as replenisher in the process.
- the regenerated blix was found to 10 b 1 1' m1 1 11 r 11 bl d h hoo x soln.) 60 e on y s 1g y ess act1ve t an res 1x an no p otograp 1c NH,SCN s gJl. d1fferences were observed as a result of its use. Analysis of The pH of the blix was adjusted to 7.0 and it was used as seasoned blix from the process using fresh replenisher, of the replenisher in the process.
- a method of regenerating a used photographic bleach-fix solution to restore its bleaching and fixing capabilities and thereby permit its reuse in photographic processing the bleaching agent being a ferric salt of an aminopolycarboxylic acid and the fixing agent a thiosulfate and said solution containing silver ions as a result of its use in photographic processing and ferrous ions formed by reduction of said ferric salt, which method comprises the steps of: (a) first removing said silver ions from said solution by chemical precipitation, metallic replacement or electrolytic recovery; and (b) second mixing oxygen with said solution in an amount sufficient to convert said ferrous ions to ferric ions, whereby the oxidation potential of said solution is restored without destruction of said thiosulfate so as to permit reuse of said solution in photographic processing.
- ferric salt of an aminopolycarboxylic acid is a ferric salt of ethylenediaminetetraacetic acid.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US802670A | 1970-02-02 | 1970-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3634088A true US3634088A (en) | 1972-01-11 |
Family
ID=21729434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US8026A Expired - Lifetime US3634088A (en) | 1970-02-02 | 1970-02-02 | Regeneration of blix solutions used in photographic processing |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3634088A (OSRAM) |
| AU (1) | AU2489171A (OSRAM) |
| FR (1) | FR2079164B1 (OSRAM) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767401A (en) * | 1971-12-15 | 1973-10-23 | Minnesota Mining & Mfg | Regeneration of photographic bleach/fix baths |
| US3767572A (en) * | 1971-11-08 | 1973-10-23 | T Bober | Destruction of edta by alkaline chlorination |
| USB391509I5 (OSRAM) * | 1973-08-24 | 1975-01-28 | ||
| US3879203A (en) * | 1972-04-12 | 1975-04-22 | Agfa Gevaert Ag | Process for bleach-fixing color photographic silver halide material |
| US3907568A (en) * | 1971-10-22 | 1975-09-23 | Fuji Photo Film Co Ltd | Process for regenerating blixing solution for color photographic processing |
| US3931004A (en) * | 1972-04-21 | 1976-01-06 | Fuji Photo Film Co., Ltd. | Method of treating waste liquids from photographic processings |
| US3942984A (en) * | 1972-03-17 | 1976-03-09 | Agfa-Gevaert Aktiengesellschaft | Process for bleach-fixing chromogenically color photographic silver halide material |
| US4014764A (en) * | 1971-07-08 | 1977-03-29 | Agfa-Gevaert, A.G. | Process for desilvering used bleach fix baths |
| US4128464A (en) * | 1976-02-25 | 1978-12-05 | Fuji Photo Film Co., Ltd. | Process for regenerating bleaching-fixing solution |
| AP210A (en) * | 1989-10-12 | 1992-08-26 | Univ Alberta | Silver recovery from spent photographic solutions. |
| US5162106A (en) * | 1989-10-12 | 1992-11-10 | The Governors Of The University Of Alberta | Photographic fixer regeneration |
| US5716766A (en) * | 1995-05-18 | 1998-02-10 | Fuji Photo Film Co., Ltd. | Method and apparatus for the electrolytic treatment of bleach-fix baths, as well as an apparatus for processing photographic materials |
| US5858631A (en) * | 1996-11-25 | 1999-01-12 | Agfa Gevaert Aktiengesellschaft | Processing color photographic materials |
| EP1209520A1 (en) * | 2000-11-28 | 2002-05-29 | Eastman Kodak Company | Ferrous photographic bleach-fixing precursor compositions and methods for their use |
| EP1312980A1 (en) * | 2001-11-15 | 2003-05-21 | Eastman Kodak Company | Direct photographic bleach-fixing replenishment using ferrous bleach-fixing precursor composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB801106A (en) * | 1956-07-10 | 1958-09-10 | Ilford Ltd | Improvements in or relating to the regeneration of photographic processing baths |
| CA580359A (en) * | 1959-07-28 | E. West Lloyd | Regeneration of photographic silver bleach solutions |
-
1970
- 1970-02-02 US US8026A patent/US3634088A/en not_active Expired - Lifetime
-
1971
- 1971-01-29 FR FR717102938A patent/FR2079164B1/fr not_active Expired
- 1971-02-02 AU AU24891/71A patent/AU2489171A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA580359A (en) * | 1959-07-28 | E. West Lloyd | Regeneration of photographic silver bleach solutions | |
| GB801106A (en) * | 1956-07-10 | 1958-09-10 | Ilford Ltd | Improvements in or relating to the regeneration of photographic processing baths |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014764A (en) * | 1971-07-08 | 1977-03-29 | Agfa-Gevaert, A.G. | Process for desilvering used bleach fix baths |
| US3907568A (en) * | 1971-10-22 | 1975-09-23 | Fuji Photo Film Co Ltd | Process for regenerating blixing solution for color photographic processing |
| US3767572A (en) * | 1971-11-08 | 1973-10-23 | T Bober | Destruction of edta by alkaline chlorination |
| US3767401A (en) * | 1971-12-15 | 1973-10-23 | Minnesota Mining & Mfg | Regeneration of photographic bleach/fix baths |
| US3942984A (en) * | 1972-03-17 | 1976-03-09 | Agfa-Gevaert Aktiengesellschaft | Process for bleach-fixing chromogenically color photographic silver halide material |
| US3879203A (en) * | 1972-04-12 | 1975-04-22 | Agfa Gevaert Ag | Process for bleach-fixing color photographic silver halide material |
| US3931004A (en) * | 1972-04-21 | 1976-01-06 | Fuji Photo Film Co., Ltd. | Method of treating waste liquids from photographic processings |
| US3925175A (en) * | 1973-08-24 | 1975-12-09 | Minnesota Mining & Mfg | Electrodialysis of fixer containing solutions |
| USB391509I5 (OSRAM) * | 1973-08-24 | 1975-01-28 | ||
| US4128464A (en) * | 1976-02-25 | 1978-12-05 | Fuji Photo Film Co., Ltd. | Process for regenerating bleaching-fixing solution |
| AP210A (en) * | 1989-10-12 | 1992-08-26 | Univ Alberta | Silver recovery from spent photographic solutions. |
| US5162106A (en) * | 1989-10-12 | 1992-11-10 | The Governors Of The University Of Alberta | Photographic fixer regeneration |
| US5716766A (en) * | 1995-05-18 | 1998-02-10 | Fuji Photo Film Co., Ltd. | Method and apparatus for the electrolytic treatment of bleach-fix baths, as well as an apparatus for processing photographic materials |
| US5858631A (en) * | 1996-11-25 | 1999-01-12 | Agfa Gevaert Aktiengesellschaft | Processing color photographic materials |
| EP1209520A1 (en) * | 2000-11-28 | 2002-05-29 | Eastman Kodak Company | Ferrous photographic bleach-fixing precursor compositions and methods for their use |
| US6582893B2 (en) | 2000-11-28 | 2003-06-24 | Eastman Kodak Company | Ferrous photographic bleach-fixing precursor compositions and methods for their use |
| US20040185390A1 (en) * | 2000-11-28 | 2004-09-23 | Vincent Sheridan E. | Ferrous photographic bleach-fixing precursor compositions and methods for their use |
| EP1312980A1 (en) * | 2001-11-15 | 2003-05-21 | Eastman Kodak Company | Direct photographic bleach-fixing replenishment using ferrous bleach-fixing precursor composition |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2489171A (en) | 1972-08-03 |
| FR2079164A1 (OSRAM) | 1971-11-12 |
| FR2079164B1 (OSRAM) | 1973-06-08 |
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