US3907568A - Process for regenerating blixing solution for color photographic processing - Google Patents

Process for regenerating blixing solution for color photographic processing Download PDF

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Publication number
US3907568A
US3907568A US298712A US29871272A US3907568A US 3907568 A US3907568 A US 3907568A US 298712 A US298712 A US 298712A US 29871272 A US29871272 A US 29871272A US 3907568 A US3907568 A US 3907568A
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Prior art keywords
blixing
solution
amount
color photographic
silver
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Expired - Lifetime
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US298712A
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English (en)
Inventor
Kazuo Shirasu
Sachio Matsushita
Tadao Hatano
Haruhiko Iwano
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C5/3958—Replenishment processes or compositions, i.e. addition of useful photographic processing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/137—Cobalt complex containing

Definitions

  • the present invention relates generally to processing photographic materials. in particular. blixing color photographic light-sensitive materials. More particularly. the invention relates to regenerating a used blixing solution for reuse in color photographic processing.
  • the necessary components for a blixing solution are one or more bleaching agents which oxidize the metallic silver of a silver image and one or more fixing agents which dissolve both undeveloped silver halide and the silver halide formed by the oxidation of the developed silver by the bleaching agent.
  • Various formulations for blixing solutions have been known in the field of photography. but a blixing solution using a combination of a ferric salt of an aminopolycarboxylic acid as the blcachingagent and a thiosulfate as the fixing agent is most used because of its stability. high reaction rate and ease of handling.
  • a ferric salt of an aminopolycarboxylic acid as the blcachingagent
  • a thiosulfate as the fixing agent
  • a blixing composition comprising a thiosulfate and a ferric salt of an aminopolycarboxylic acid is comparatively expensive and further it must be discarded after use since no acceptable regeneration method therefor exists. disadvantages to the industrial utilization ofblixing solutions of this type.
  • a ferricyanide-containing bleaching solution may be regenerated by treatment with bromine as dcscribed in the specification of 15.5. Pat. No. 2.515.930; by treating with a bromine releasing reagent in an aqueous solution as described in the specification of U.S. Pat. No. 2.61 1.699 and the specification of U.S. Pat. No. 2.6] 1.700; or by treating with a water-soluble persulfate as described in the specification of U.S. Pat. No. 2.944.895.
  • a used fixing solution can be reused by re moving all or a part ofthe silver from the fixing solution and adding components to the fixing solution necessary to provide the original formulation.
  • Such a process is disclosed in the specifications of U.S. Pat. Nos. 1.446.405. 1.527.942. and 3.082.079.
  • the regeneration process is fora used blixing solution containing a ferric salt of aminopolycarboxylic acid as a bleaching agent and a thiosulfate as a fixing agent together with silver complex ions and ferrous ions in the blixing process. At least a part of the silver ions is removed from the blixing solution and oxygen is introduced into the blixing solution in an amount sufficient to convert the ferrous ions into ferric ions. whereby the oxidation potential of the blixing solution is recovered without losing the thiosulfate. and thus the blixing solution is brought into a reusable state.
  • a further fault in such a process is that since metallic iron is oxidized and dissolved in the solution. the concentration of iron ions varies during the repeated practice of the regeneration of the blixing solution and thus it is very troublesome to control at stable concentra tions iron ions in the blixing solution.
  • One object of this invention is. therefor. to provide a process for the regeneration ofa usedblixing solution which can be practiced in an economical. simple. and stable manner without being "accompanied by the aforesaid disadvantages of the prior art. 5
  • Another object of this invention is to provide a color photographic processing systemin which an expensive blixing solution can be repeatedly used in a simple manner.
  • Yet another object of this invention is to provide a color photographic processing system which gives no or less water contamination or pollution. problems caused by the used blixing solution.
  • the silver ion concentration in a blixing solution may be kept below a certain level by employing a fixing bath prior to the blixing process. whereby the greater part of the soluble silver salt is dissolved in the fixing bath to prevent a large accumulation of the silver salt or silver ion in the blixing bath during the subsequent blixing step. or alternatively by reducing the amount of silver salts incorporated in the photographic light-sensitive material. whereby the accumulation of an undesirable level of silver ions in the blixing bath at processing is prevented.
  • the amount of silver used in a silver halide photographic material is less than 2 g/m, the accumulation of silver ions to an extent which has a harmful influence on blixing can be prevented without fixing. More preferably, the amount is less than L6 glm and most preferably it is in the range of l.() l.5 g/m to insure long term operation.
  • ferrous ions are oxidized into ferric ions by intentionally introducing oxygen into the used blixing solution to convert the ferrous ions into ferric ions at the same time that the blixing solution is brought into contact with metallic iron to remove silver ions.
  • the coated amount of silver halide for normal silver halide photographic elements is 2.0 to about l0 g/m
  • the blixing solution to which the .process of this invention is applied is a solution containing a fixing agent diaminotetraacetic acid. ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethyleneglycol bis(aminoethylether)tetraacetic acid. diaminopropanol tetraacetic' acid. N-( Z-hydroxyethyl )ethylenediamine triacetic acid, cthyliminodopropionic acid, and the like.
  • Other bleaching agents useful in the present invention are disclosed in US. Pat. No. 3,582,322.
  • the ferric salt of an amino'poly carboxylic acid used in this invention may be a ferric salt wherein all of the cations are ferric ions or it may be a ferric salt where at least one carboxyl group is bonded to a cation other than an iron ion, such as ammonia or an alkali metal ion.
  • a prefered example of such a ferric salt is sodium ferric ethylene'diamine tetraacetic acid.
  • bleaching agents other than those listed may be used above.
  • a polyanimine cobalt complex salt such as tetramminecarbonate cobalttlll) nitrate, quinones. or a simple water-soluble iron salt, e.g., ferric chloride.
  • a nonchelated salt of an aminopolycarboxylic acid such as a tetrasodium salt of cthylenediamine tetraacetic acid may also be used.
  • the fixing agent and the bleaching agent indicated above are the necessary components for the blixing solution to be used in the process of this invention.
  • the blixing solution of this invention may further contain other additives generally known in this area of the art as additives for ordinary blixing solutions e.g.. the blixing solution may contain a water-soluble thiocyanate such as ammonium thiocyanate. sodium thiocyanate. or potassium thiocyanate. or a silver halide solvent such as ammonium bromide. an alkali metal bro mide, an amine, a sulfite. and mercaptazoles such as 2.5-dimercapto-thiadiazole and mercaptotriazole.
  • a water-soluble thiocyanate such as ammonium thiocyanate. sodium thiocyanate. or potassium thiocyanate.
  • a silver halide solvent such as ammonium bromide. an alkali metal bro mide, an amine,
  • the concentration ofthe thiosulfate in the blixing solution is generally about 5 to about 200 g/liter and the concentration of the ferric salt of the aminopolycarboxylic acid is generally about 5 to about 200 g/liter.
  • the blixing rate of the com pletely blackened portion of a silver halide color photographic material changes with a change in the silver ion concentration in the blixing solution as shown below:
  • the average silver ion Iconcentration'in the blixing solution at processing is at ,amost about 4 g/liter. which amount will not have a harmful influence on blixing processing.
  • the absolute amount of silver thus entering the fix both (and then the blix bath) is thus seen to be about 2.0 g/m of material processed.
  • the silver ions carried in washing water after blixing or the silver ions formed in the fixing bath employed prior to blixing can be easily recovered by known processes. cg. electrolysis.
  • the solution is diluted with water carried by the photographic materials being processed. and necessary chemicals are consumed and by-products are formed as a result of reac tion in the processing. Accordingly. chemicals are added to the blixing solution to compensate for deficient components. According to the process of this invention it is unnecessary to forcibly introduce oxygen into the blixing solution and thus the occurence of ex cessive oxidation is less. Therefore. the oxidation of sulfite as well as the accumulation of sulfate are lssened. which makes the control and maintenance of the concentration of the blixing solution easy. Further more. due to the lowered accumulation of by-products. it becomes unnecessary to dispose ofa part of the overflow solution in the regeneration step. and thus the blix ing solution can be regenerated completely or the total amount of the blixing solution can be regenerated and reused.
  • the amount of the deficient components to be added to the blixing solution depends upon the kind of photographic lightsensitive material. the kind of developing machine. and the developing conditions. but a stable processing is possible under each condition.
  • the color developing solution used in combination with the process of this invention can generally be se lected from any of those used in. color photographic processings known to the prior art. and is generally an aqueous alkaline solution of an aromatic primary amine color developing agent containing. preferably. benzyl alcohol.
  • aromatic primary amine color developing agents are phenylenediamine derivative such as N.N- diethyl-p-phenylenediamine sulfate and other known aromatic primary amine color developing agents such as 4-amino-N-ethyl-N-Bhydroxycthylaniline sulfate. 3-methyl-4-amino-N-ethyl-B- methanesulfoamideethylaniline sesquisulfate monohydrate.
  • the color developing solution can further contain a sulfite. an alkali metal carbonate. a bisulflte. a bromide. an iodide. an antifoggant. a developing accelerator. and a solvent such as diethylene glycol.
  • blixing is conducted after color development. and the techniques for reducing the silver amount to be blixed are applied.
  • the color photographic material thus processed may be processed. if necessary, in an image stabilization bath.
  • conventional subsidiary baths such as a washing bath. a stopping bath. a hardening bath. a post-processing bath. an aldehyde neutralizing bath. etc.. may be added. if desired. between the aforesaid fundamental steps according to the nature of the color photographic materials to be processed.
  • a black and white development as a matter of course. conducted prior to color development.
  • the color photographic light-sensitive materials to be procesed by the process of this invention contain in the silver halide emulsion layers at least one type of a four equivalent coupler or a two equivalent coupler.
  • Exemplary of four equivalent couplers as may be used in the present invention are those represented by the formula wherein R represents a substituted or unsubstituted alkyl group. a substituted or unsubstited aryl group. or a substituted or unsubstituted heterocyclic group and R' represents an alkyl group. a carbamyl group. at amino group, or an amide group. 1
  • 2-cyanoacetyl-5-(p-sec-amylbenzoylamino)cou marone 2-cyan oacetyleoumaron'e-5-( N-n-amyl-p-- amylsulfoanilide).
  • 2-cyanoacetylcoumarone-S-sulfone-N-nbutylanilide 2-cyanoacetylcoumarone-S-sulfone-N-nbutylanilide.
  • l-,8-naphthyl-3-amyl-5-pyrazolone l-p-nitrophenol-3-n-amyl-5-pyrazolone.
  • l-phenyl-3-acetylamino-5-pyrazolone 2-cyanoacetyl-5-(p-sec-amylbenzoylamino)cou marone.
  • yellow couplers examples of four equivalent couplers giving yellow dyes such as benzoylaeetoanilide typc dyes and pivaloylacetoanilide type dyes are the yellow couplers disclosed in the specifications of British Pat. No. L] l3.()38 and U.S.Pat. No. 3.337.344. Furthermore, the following yellow couplers may also be employed for the above purpose:
  • couplers are only exemplary of the four equivalent couplers which maybe incorporated in the silver halide emulsion layers of color photographic materials to be processed by the process of this invention. and the invention is not to be construed as limited thereto.
  • the process of this invention can be applied to processing silver salt color photographic materials in general. such as color negative films. color papers, color positive films. color reversal cinne films, and color reversal TV films.
  • Color developing solution Benzyl alcohol Dicthylene glycol Sodium hydroxide Sodium sull'ite Potassium bromide Sodium chloride
  • a complementary blixing solution was continuously replenished to the blixing solution tank at rate of900 ml for every I m'-' of color paper processed.
  • the starting complementary solution liters ofthe fresh blixing complementary solution shown described above was employed. By the replenishments.
  • the overflowed solution was stored in a collection ation. which was then replenished at the same rate as above.
  • composition of the first complementary solution was then the same as the fresh complementary solution as shown in the following table.
  • A The total iron salts of ethylenediamine tetra-acetic acid (as sodium t'errii: cthylcncdiamine ⁇ ctracetic acid monoliydratc).
  • the necessary components of the blix bath and the replenishing solution are the bleaching agent and the fixing agent. Other components are optional. l
  • the amounts of the bleaching agent and the fixing agent in the blixing bath have been heretofore de scribed (about 5 to about 200 g/liter for each).
  • the amount of these components in the replenishing solution is usually about 1.0 to about 1.6 times by weight the amount in the blixing bath. Obviously. it is preferred to at least return the blix bath to its original strength.
  • the volume of the replenishing solution added is generally from about 200 to about 1250 cc/m" of material processed. preferably 500 800 cc/m It will be clear to one skilled in the art, however. that values outside of the above ranges can be used if one is willing to suffer. some inefficiencies in the blixing or regeneration.
  • the overflow solution of the blixing solution was introduced into a cartridge filled with metallic iron wool.
  • the solution from the cartridges contained ferrous ions formed from the complete reduction of ferric ions.
  • the solution was introduced into an aeration tank equipped with an air sparger and air was blown into the solution for about one hour. By the aeration the ferrous ions were converted into ferric ions. the solution changing dark red. At the same time it was confirmed that the oxidation reduction potential of the solution had been recovered.
  • Deficient components make up components needed to regenerate the solution) such as disodium ethylenediamine tetraacetate dihydrate. sodium ammonium thiosulfate. sodium sulfite. sodium carbonate. and boric acid were added to the solution to provide a complementary solution. which was reused.
  • the process of the present invention is a simple, convenient and stable process which is not accompanied by such faults.
  • the process of the present invent-ion requires a stopfixing step in one embodiment, but the addition of such a step is a very slight disadvantage as compared to the above-mentioned various advantages of this invention. Furthermore. in the process of this invention. silver can be recovered in the stop fixing process and during water washing. andthus the'efficiency of silver salt recovery can be maintained at a high level.
  • EXAMPLE 2 A color negative film comprising a sensitive silver halide emulsion layer containing gelatin and silver iodobromide on a cellulose acetate film (coated silver amount of 9.2 g/m) was processed in a small automatic developing machine according to the process of this invention.
  • the processes employed in this example were as follows: v v
  • compositions of the processing baths used in the above processing steps were as follows: It
  • Hardening fixing bath Sodium hexametaphosphate l g Sodium sulfite 5 g Sodium thiosulfate I50 g Sodium acetate 20 g Acetic acid ti ml Potassium alum [5 g 7 Water to make one liter.
  • Blixing bath Sodium ferric ethylenediaminc tetraaeetic acid monohydratc 33 g Z-Sodium etliylenediamine tetraacctic dihydrate 2 g BUItIXlOH O 5 g Boric acid H) g Sodium sulfite 5 g 70% Aqueous ammonium thiosulfatc lfitl ml soln. 'l'hiourca 5 g pH adjusted to 6.0 Water to make one liter.
  • the amount of each component in the complementary solution for blixing was l.5 times the amount of each component in the flixing solution.
  • the fresh complementary solution 40 was used in only the first round. and thereafter a complementary solution prepared by adding the additives necessary for regeneration to the overflow solution was used.
  • the volume of the complementary solution per round was 20 liters. 4g
  • EXAMPLE 3 This example shows that the process of this invention can be applied directly, without conducting pre-fixing, to a light-sensitive material having a reduced amount of Amount per liter of over llow solution Additive for regeneration First complementary solution for regene ration (analytical When the process of this invention was continuously conducted using the afore-indicated baths. the reaction was finished in a definite period of time without any unusual influence on the qualities of the processed products and at a sufliciently high blixing rate.
  • the compositions at the l()th and l5th rounds of the operation were as shown below. illustrating that the amount of silver coated thereon. That is to say. developing processings the same as in Example l were conducted using color papers having coated silver amounts of L56 g/m and 3.12 glm respectively. in this case. however. fixing before blixing was omitted.
  • the initial blixing time was 75 seconds for the color paper having silver coated in an amount of 1.56 g/m which was increased about to 105 seconds at the th round.
  • blixing was finished in a definite period of time and good results were obtained.
  • the initial time required for finishing blixing was 90- 100 seconds, and further the blixing time increased rapidly while repeating the processing cycle, whereby blixing became insufficient.
  • the blixing rate for the color papers was high and the accumulation of silver salt in the blixing solution repeated regenerations was low, which makes the application of the process of this invention possible.
  • EXAMPLE 4 The same continuous regeneration process as in Example l was followed using a Noritsu-type Four-File Paper Automatic Developing Machine (made by Noritsu Koki K. K.) and commercially available CLP 8905-Type color paper (made by Fuji Photo Film Co.) for 2 months.
  • the developing machine was equipped with an air sparger in the blixing tank to assist the agita tion of the solution in the tank. and one second air bursts were made at a rate of once every 10 seconds.
  • maintaining the silver salt concentration expressed in terms of the amou nt ft if silver ions. at level less than about LOg/Iiter iri' the blixing solution and thereafter adding components to the used blixing solution to make up for those in the blixing processing without removing silver salt from the used blixing solution. thereby providing a composition at least equivalent to that of the blixing solution prior to use for blixing additional color photographic materials. wherein said maintaining is accomplished by subjecting the color photographic materials. after color development.
  • said blixing solution contains (a) at least one member from the group consisting of a ferric complex salt of an aminopolycarboxylic acid. a cobalt (lll) complex salt of a polyammine. a cobalt (lll) complex salt of nitrous acid. and a water-soluble ferric salt as a bleaching agent; and (b) a thiosulfate as at fixing agent.
  • the blixing solution comprises a bleaching agent and at fixing agent each present in an amount of from about 5 to about 200 g I of blixing solution. and components are added to the spent blixing solution so as to maintain these ranges during blixing,
  • step (a) repeating steps (b) to) while observing the condition recited in step (a). wherein said maintaining is accomplished by subjecting the color photographic materials after color development. to fixing prior to blixing to preliminarily remove a substantial portion oi soluble silver salt from the color photographic materials or wherein said maintaining of the amount ofsilver salt is obtained by reducing the amount of coated silver in the initial color photographic materials to below 2.()g/m 11.
  • the process ot'elaim 10 wherein the regenerated blixing solution returned to the blixing treatment contains from about 1.0 to about l.6 times an amount of 18 bleaching agent and fixing agent present in the blising bath. on a unit volume basis. and the regenerated blixing solution is returned to the blixing treatment in an amount of from about 200 to about 1250 ce/m'- otcolor photograpi'iic material subjected to the biixing treatment.
  • condition (a) is maintained by fixing prior to blixing.
  • condition (a) is maintained by processing a color photographic material without fixing. which color photographic material initially contained coated silver in an amount less than 2.0 g/m.

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US298712A 1971-10-22 1972-10-18 Process for regenerating blixing solution for color photographic processing Expired - Lifetime US3907568A (en)

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JP (1) JPS5633697B2 (enrdf_load_stackoverflow)
BE (1) BE790374A (enrdf_load_stackoverflow)
CA (1) CA991468A (enrdf_load_stackoverflow)
DE (1) DE2251908A1 (enrdf_load_stackoverflow)
FR (1) FR2156874B1 (enrdf_load_stackoverflow)
IT (1) IT966430B (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065313A (en) * 1976-06-11 1977-12-27 Eastman Kodak Company Bleach-fix regeneration monitoring method
US4128464A (en) * 1976-02-25 1978-12-05 Fuji Photo Film Co., Ltd. Process for regenerating bleaching-fixing solution
US4451132A (en) * 1981-12-17 1984-05-29 Fuji Photo Film Co., Ltd. Color photographic processing apparatus including a reverse osmosis apparatus
US4601975A (en) * 1983-12-23 1986-07-22 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide color photographic material
US5063142A (en) * 1989-05-22 1991-11-05 Fuji Photo Film Co., Ltd. Process for processing silver halide color photographic materials
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

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5438894B2 (enrdf_load_stackoverflow) * 1973-08-30 1979-11-24
JPS50145231A (enrdf_load_stackoverflow) * 1974-05-14 1975-11-21
JPS5335534A (en) * 1976-09-14 1978-04-03 Toppan Printing Co Ltd Method of regenerating and reusing fixer
JPS5577743A (en) * 1978-12-08 1980-06-11 Oriental Shashin Kogyo Kk Replenishing method of bleaching agent and fixing agent for color photographic processing
JPS57190950A (en) * 1981-05-20 1982-11-24 Konishiroku Photo Ind Co Ltd Plate making method for photosensitive flat printing sheet
JP2900180B2 (ja) * 1989-07-24 1999-06-02 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP3049869B2 (ja) * 1990-10-02 2000-06-05 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3241966A (en) * 1960-06-14 1966-03-22 Agfa Ag Bleach fixing of photographic silver images
US3620725A (en) * 1969-01-23 1971-11-16 Technology Inc Rapid photographic development system
US3634088A (en) * 1970-02-02 1972-01-11 Eastman Kodak Co Regeneration of blix solutions used in photographic processing
US3706561A (en) * 1970-03-23 1972-12-19 Eastman Kodak Co Compositions for making blixes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3241966A (en) * 1960-06-14 1966-03-22 Agfa Ag Bleach fixing of photographic silver images
US3620725A (en) * 1969-01-23 1971-11-16 Technology Inc Rapid photographic development system
US3634088A (en) * 1970-02-02 1972-01-11 Eastman Kodak Co Regeneration of blix solutions used in photographic processing
US3706561A (en) * 1970-03-23 1972-12-19 Eastman Kodak Co Compositions for making blixes

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128464A (en) * 1976-02-25 1978-12-05 Fuji Photo Film Co., Ltd. Process for regenerating bleaching-fixing solution
US4065313A (en) * 1976-06-11 1977-12-27 Eastman Kodak Company Bleach-fix regeneration monitoring method
US4451132A (en) * 1981-12-17 1984-05-29 Fuji Photo Film Co., Ltd. Color photographic processing apparatus including a reverse osmosis apparatus
US4601975A (en) * 1983-12-23 1986-07-22 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide color photographic material
US5063142A (en) * 1989-05-22 1991-11-05 Fuji Photo Film Co., Ltd. Process for processing silver halide color photographic materials
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

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IT966430B (it) 1974-02-11
JPS5633697B2 (enrdf_load_stackoverflow) 1981-08-05
FR2156874B1 (enrdf_load_stackoverflow) 1978-03-03
DE2251908A1 (de) 1973-04-26
JPS4849437A (enrdf_load_stackoverflow) 1973-07-12
FR2156874A1 (enrdf_load_stackoverflow) 1973-06-01
BE790374A (fr) 1973-02-15
CA991468A (en) 1976-06-22

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