US3869383A - Process for treating waste photographic processing solutions - Google Patents

Process for treating waste photographic processing solutions Download PDF

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Publication number
US3869383A
US3869383A US307265A US30726572A US3869383A US 3869383 A US3869383 A US 3869383A US 307265 A US307265 A US 307265A US 30726572 A US30726572 A US 30726572A US 3869383 A US3869383 A US 3869383A
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United States
Prior art keywords
solution
ferricyanide
ions
basic anion
exchange resin
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Expired - Lifetime
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US307265A
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English (en)
Inventor
Isao Shimamura
Haruhiko Iwano
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Filing date
Publication date
Priority claimed from JP46092115A external-priority patent/JPS5137704B2/ja
Priority claimed from JP47000634A external-priority patent/JPS4872959A/ja
Priority claimed from JP47022907A external-priority patent/JPS4891858A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to US05/505,877 priority Critical patent/US4043907A/en
Application granted granted Critical
Publication of US3869383A publication Critical patent/US3869383A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C5/3956—Microseparation techniques using membranes, e.g. reverse osmosis, ion exchange, resins, active charcoal
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • 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
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/903—Nitrogenous
    • Y10S210/904—-CN containing

Definitions

  • the present invention relates to a process for treating and regenerating waste solutions from photographic treatments. Particularly, the present invention relates to a process for treating waste solutions containing ferricyanide and/or ferrocyanide ions from photographic treatments.
  • a bleaching step is included in treatments for photographic materials.
  • Bleaching is a treatment whereby materials such as silver formed by development are returned to ionic form using an oxidizing agent, and is included in treatments for silver halide color photosensitive materials and silver dye bleaching photosensitive materials and reduction treatments for photographic materials used for printing.
  • ferricyanides such as potassium ferricyanide are used as the oxidizing agent in bleaching solutions.
  • potassium bichromate, iron chelates, quinones and copper salts are used as the oxidizing agent instead of the ferricyanides.
  • the ferricyanides' are the most preferred bleaching agents from the view point of oxidizingpower, ease of bleaching and their stability.
  • Such cyano compounds have a strong toxicity and if introduced into the environment exhibit a very harmful pollutant effect.
  • the electrodialysis method and the reverse osmosis method are effective for treating solutions of a low concentration such as rinsing or washing water, they have the fault that the'necessary equipment is expensive. This fault is especially encountered in treating solutions having a large quantity of water such as rinsing water, i.e., the cost of the equipment becomes very high because large apparatus is required. Further, the
  • ferricyanide ions and/or ferrocyanide ions are still carried in a washing bath, which is followed by a rinsing. Since the amount of the ferricyahave a very strong toxicity, it is necessary to remove the sodium hypochlorite are added to the waste solution followed by decomposition at high temperature. In the case of applying these methods to waste solutions from photographic treatments containing ferricyanide and /or ferrocyanide ions, very large heat sources are nec-. essary because of the large quantity of water involved.
  • theferricyanide ions will damage a combustion furnace because of their high oxidation ability. both a serious fault of the combustion or pyrolysis method.
  • ferrocyanide and/or ferricyanide ions may be effectively removed from solutions with greatly increased efficiencies using the free base form ofa weakly basic anion exchange resin in the presence of a compound having a buffering action at a pH of from 7 to 9.
  • anion-exchange resins strongly basic anion exchange resins'are commonly used.
  • ferricyanide ions and ferrocyanide ions are adsorbed strongly in the ion-exchange resins if ion-exchange of ferricyanide ions or ferrocyanide ions is carried out using strongly basic anion exchange resins (which contain the ammonium group), and consequently it is difficult to regenerate the anion exchange resin even by treating it with hydrochloric acid,
  • the ion-exchange ability of the regenerated ion exchange resins deteriorates greatly to only 10 to 40 wt percent of the ion-exchange ability of the fresh resin.
  • the ease of regeneration of the ionexchange resin is not substantially improved, though the ion-exchange capability toward ferricyanide and/or ferrocyanide ions does increases a little, and again the ion-exchanging capability of the regenerated resin reaches 10 40 percent that of the fresh resin.
  • the strongly basic anion-exchange resin was used in the presence of strong acids such as sulfuric acid or hydrochloric acid, or organic acids such as acetic acid or citric acid, the ion-exchanging capability of the strongly basic anion exchange resin to ferricyanide and/or ferrocyanide ions could not be substantially improved.
  • the lowering of the ionexchange ability of the weakly basic anion-exchange resins after regeneration is very small. usually less than 10 wt percent.
  • the weakly basic anion-exchange resins used in the present invention are preferably styrenedivinylbenzene copolymers, methacrylatedivinylbenzene copolymers and phenolformaldehyde polycondensates having primary. secondary or tertiary amino groups as the ion-exchange group.
  • Any weakly basic anion exchange resin can be used irrespective of the type of base part of the resins. the process of preparation, the degree of polymerization. structural shape or the method of preparation thereof, so long as it has at least a primary, secondary or tertiary amino group.
  • Typical available weakly basic anion exchange resins are Diaion WA-lO, WA-1 l, WA-20, WA-2l and WA-30 (produced by Mitsubishi Chemical Ind. Ltd.) Ambe'rlite IRA-45. IRA-93. lR-4B and lRP-SS (produced by Organo Co.) and DOWEX-44 (produced by Dow Chemical Co.). These materials are, of course. merely illustrative. In the following. the structural formulae of some of these materials arc shown.
  • resins which are more easy to regenerate are those having tertiary amino groups as the exchange group.
  • these resins the most preferred is Diaion WA-l0.
  • WA-IO has the highest adsorption per unit volume of resin for ferricyanide and ferrocyanide ions and can be regenerated most easily.
  • WA-ll is a second preferred choice. In these resins, the amount of ferricyanide and ferrocyanide ions adsorbed based on the volume of the resins is largest, and the resins are most easy to regenerate.
  • the weakly basic anion exchange resins there are free base type resins and salt type resins, and both types can be used in the process of the present invention.
  • the salt type resins in situ, can adsorb ferricyanide and ferrocyanide ions, but must be treated with an alkali and then an acid for the regeneration of the resins. The acid treatment is conducted to convert the resins to the salt type.
  • the free base type resins have, in situ. a lower ion exchange capability to l'ericyanide and ferrocyanide ions they have the same capability when they are used in the presence of a material having a buffering capacity at a pH of from 7 to 9.
  • the free base type resins need not be treated with an acid followed by an alkali treatment to regenerate them as with the salt type resins and they are commercially available, so they are generally used.
  • the resins of the present invention are not, however, limited to the free base type resins.
  • the amount of buffering compound present ranges from about 1/10 to about 10" molar times the sum of the moles of ferricyanide "and ferrocyanide ions present.
  • the buffering compounds can be added to the solution which is treated so that the buffering compound is present during Contact with the free base form of the weakly basic anion exchange resin.
  • Alkali materials are usually used to regenerate the resins exchanged by ferricyanide and/or t'errocyanide ions, typically in the form of an aqueous solution.
  • alkali acids or salts may be used.
  • alkali acids or salts
  • aqueous solutions ofalkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkali metal carbonates such as sodium carbonate and potassium carbonate or an aqueous ammonia solution, etc.
  • alkali metal carbonates such as sodium carbonate and potassium carbonate or an aqueous ammonia solution, etc.
  • salt type resins theyare sometimes regenerated by a strong acid such as hydrochloric acid or a strong acid salt such as sodium chloride.
  • boric acid, metaboric acid, sodium borate, potassium borate, ammonium borate, sodium metaborate or like water-soluble borates can be used.
  • Boric acid and/or such borates may be added to a ferricyanide and/or ferrocyanide ion-containing waste solution which has been used for photographic processing, or may be in cluded in the photographic processing solution such as a bleaching solution, bleach-fixing solution or reducer.
  • Boric acid and/or a water-soluble borate can be used in an amount ranging from about l/llI) to about 10" times the sum of the moles of ferricyanide and ferrocyanide ions contained in the waste solution used for photographic processing or photographic processing solution such as the bleaching solution, bleach-fixing solution, reducer, etc.
  • boric acid and/or a water soluble borate is used in an amount of from l/S to 10 times the sum of the moles of ferricyanide and/or ferrocyanide ions.
  • the range in terms of borate ions is about 10" to about 10' rnol per one liter of the waste solution.
  • the process of the present invention can be utilized for any waste solution containing ferricyanide and/or ferrocyanide ions.
  • Solutions containing a ferricyanide and alkali metal bromide are generally used as the bleaching solution for'silver halide color photosensitive materials and silver-dye bleaching type color photosensitive materials.
  • bleaching solutions contain a pH adjusting agent such as potassium hydroxide, glacial acetic acid, potassium dihydrogen phosphate, sodium acetate or sodium hydrogen sulfate and potassium alum.
  • ferrocyanide and ferricyanide ions are used in bleach-fixing baths in combination with a silver halide solvent such as thiosulfate, thiocyanate etc.
  • farmers reducer In the treatment of a photographic plate used for printing, a. farmers reducer is sometimes used in order to retouch the images after development. farmers reducer consists of a solution containing a ferricyanide such as potassium ferricyanide and sodium thiosulfate.
  • a ferricyanide such as potassium ferricyanide and sodium thiosulfate.
  • the rinsing or washing water used after treatment with such a bleaching solution, a bleach-fixing solution or a reducer etc. containing ferricyanide and/or ferrocyanide ions, or the waste solution containing ferricyanide and ferrocyanide ions brought into another bath, is passed through a layer of weakly basic anion exchange resin, by which the ferricyanide and/or ferrocyanide ions which are noxious components can be removed.
  • the ion-exchange process using-weakly basic anion exchange resins of the present invention exhibits its effect especially when treating waste solutions containing below 500 ppm total of ferricyanide ions and ferrocyanide ions (1,000 ppm for the borate ion embodiment), that is, a low concentrationwith which low economical efficiency is encountered if other methods are used. Accordingly, the process is particularly suitable for removing ferricyanideand/or ferrocyanide ions in the rinsing water after bleaching.
  • any method or apparatus may be used in the presen invention for contacting the waste solution containing ferricyanide and ferrocyanide ions with the weakly basic anion-exchange resin.
  • one forms a resin layer by packing the ion-exchange resin in a cylinder container and passing the waste solution downwardly through this resin layer.
  • the waste solution may also be passed up through the layer of resin.
  • the ferricyanide and/or ferrocyanide ions can be continuously removed.
  • the waste solution may be treated by adding the ion-exchange resin to stored waste solution using a batch treatment and then removing the resin by precipitating the same with stirring or by filtering. Howerver, it is generally preferred to use an ion-exchange resin layer because one advantage of this invention is that it may be practised continuously.
  • the aqueous alkali solution to be used for the regeneration may be brought into contact with the ionexchange resin in any manner.
  • the foregoing methods of contacting the waste solution used for photographic processing with the ion-exchange resin can be applied per se in the regeneration.
  • ferricyanide and/or ferrocyanide ions are removed from the ion-exchange resin, while a solution containing ferricyanide and/or ferrocyanide ions is eluted therefrom.
  • the waste solution from the regeneration contains ferricyanide and/or ferrocyanide ions at a concentration generally as high as l0,000 100,000 ppm, which corresponds to about 10 to about g of potassium ferricyanide per one liter of the regeneration solution. Since the waste solution from the regeneration is concentrated in ferricyanide and/or ferrocyanide ions, and
  • ferricyanide and/or ferrocyanide ions can easily be removed therefrom by the process of pyrolysis or precipitation with iron salts, etc., if desired.
  • the waste liquor from the anion exchange resin regeneration whichcontains ferricyanide ion and/or ferrocyawith acid and the thus regnerated solutioncan be reused as bleaching liquid.
  • the essential components to be added to the waste regeneration solution are the ferricyanide, e.g., potassium or sodium ferricyanide, and
  • the bromide can be added in an amount necessary for the bleaching solution.
  • the bleaching solution composition is varied by the purposes thereof, the composition can be decided by one skilled in the art.
  • the pH of the regeneration solution is usually adjusted to apH of fromabout 5 to about 9 by adding an acid. Adjustment is'usually necessary because the solu- I tion is at a higher pH due to alkali added for the regneration of the anion-exchange resin.
  • an oxidizing agent such as potassium persulfate to oxidize the ferrocyanide ion to tion is analyzed.
  • the waste liquor after the regeneration may be concentrated to separate, e.g., potassium ferricyanide and ferrocyanide, which can then be used to prepare the bleaching liquid.
  • inorganic anions other than ferricyanide and ferrocyanide ion are preferably not contained in the waste liquor from the regeneration.
  • the process of the present invention has the follow ing advantages.
  • the equipment is small and cost of the equipment is low as opposed to large and expensive apparatus as is required in the electrodialysis method and in the reverse osmosis method.
  • the ionexchange resin can be used repeatedly because it can be regenerated. Accordingly, this process is very economical.
  • the electrodialysis method, the reverse osmosis method and the combustion and pyrolysis methods require a large source-of energy such as electricity, a heavy oil, etc., and the energy cost for operating these processes is high.
  • the ionexchange process of the invention requires onlya small amount of chemicals as the regenerant, and the cost thereof is very low.
  • the processing is very simple, it does not require significant skills or large numbers of personnel. (5) Since a waste solution discharged fromthe resin by regenerating using the regenerant is concentrated so as to have 50 g/l. of ferricyanide and/or ferrocyanide, it can be treated easily by precipitation, etc. (6) The waste liquor obtained by the regeneration contains ferricyanide ion and/or ferrocyanide ion of high concentration so that it may be reused. e.g.. as a bleaching liquid, whereby the harmful ferricyanide ion and ferrocyanide ion are not discharged at all and the waste liquor is re-used very economically. 1
  • the process of the present invention can-be applied to treatmentsof color-negative photosensitive materials, color reversal photosensitive materials, color papers and color positives etc. using a silver halide, color treatments such as a silver-dye bleaching method and other treatments using ferricyanides.
  • the process can be applied irrespective ofthe concentration of ferricyanides. Accordingly, the process can by applied to all so lutions containing ferricyanide and/or ferrocyanide ions such as bleaching solutions, bleach-fixing solutions, reducing solutions and rinsing water formed therefrom. Further; the process can be applied to a ferricyanide bath which is used for other objects except for bleaching as shown in US. Pat. No. 3,189,452 and rinsing water used thereafter. Furthermore, the process.
  • developing apparatus such as a cinema type automatic developingapparatus, a hanger type'automatic developing apparatus, a roll type automatic developing apparatus or a belt conveyor type automatic developing apparatus.
  • the ability of the weakly basic anion exchange resins of the invention to remove ferricyanide and ferrocyanide ions is larger than that of the strongly basic anion exchange resin when fresh. and deterioration of the ability to remove ferricyanide and ferrocyanide ions of the weakly basic anion exchange resin is very low.
  • EXAMPLE 2' A waste solution after bleaching and rinsing discharged from a hanger-type automatic developing apparatus' was passed through an ion-exchange resin layer.
  • This ion-exchange resin layer was prepared by packing 2 liters ofa weakly basic anion exchange resin (WA-10) in a cylinder having a 112 cm inside diameter.
  • the composition of the bleaching solution was the same as in Example 1.
  • the rate of flow of the waste solution through the cylinder and resin was 8 l/min.
  • EXAMPLE 3 The following examples show the importance of using a buffering compound as heretofore described when the process of the present invention is practiced using the free base form of the weakly basic anion exchange resin.
  • boric acid, metaborioacid or water soluble borates it is most preferred to use boric acid, metaborioacid or water soluble borates.
  • the other buffering compounds as heretofore described can be used with success, as can other buffering compounds known to the art.
  • boric acid, metaboric acid or water soluble borates offer such excellent results, the use of such compounds will be illustrated in the following examples.
  • Farmer-s reducer having the following composition was diluted 2O times'with water and passed through the above-described ion-exchange resin-packed cylinders at a flow rate of 300 ml/min. The amount of diluted farmers reduced flowed therethrough when ferricyanide or ferrocyanide ion was eluted (processing capability) was measured. Composition of farmers reducer:
  • Solution A Prepared by adding water to 37.5- g of Red prussiate to make 500 ml. of solution.
  • Solution Bz Prepared by adding water to 480 g of Crystalline sodium thiosulfate to make 2 liters of solution.
  • the farmers reducerthus contains 30 ml of solution A and 120 ml of solution B per one liter of aqueous solution. In other 'words, 500/30 (or 2,000/120) liter of the farmers reducer contains 500 ml of solution A and 2 liter of solution B. As the waste solution, the farmers reducer is further diluted 20 times with water.
  • Ferricyanide or ferrocyanide ion was detected by adding a dilute sulfuric acid solution containing 3 percent ferrous sulfate and conducting spectrophotometry in the visible light region.
  • the ionexchange resin was taken out, transferred into a beaker containing'SOO m1 of an aqueous 4 percent sodium hydroxide solution and left for 30 min., withoccasional stirring, to regenerate the resin.
  • the ion-exchange resins were then washed with water, and again packed in their respective cylinders. Thereafter, a solution prepared by diluting the farmers reducer 20 times was passed through the cylinders in the same manner as before at a flow rate of 300 ml/min. The amount passed when ferricyanide or ferrocyanide ion was eluted (processing capability) was measured.
  • EXAMPLE 4 Exposed and developed photographic original printing plates as described in US. Pat. No. 3,345,175 were well wetted with water, immersed in the farmers reducer having the following composition and then washed with water. As the plates were treated with farmers reducer, the reducer was deteriorated, and it was replaced with a newFarmers reducer when it was deteriorated. The used farmers reducer and water were the waste solution.
  • First solution Water 200 ml Crystalline sodium thiosulfate 20 g Second solution Water 100 ml Red prussiate g centration offerricyanide and/or ferrocyanide ions contained in this farmers reducer waste solution varies (as described, the farmers reducer was replaced with a new farmers reducer when it deteriorated, and
  • Solution A Prepared by adding water to 37.5 g of Red prussiate to make 500 ml. of solution.
  • Solution B Prepared by adding water to a mixture of 480 g of crystalline sodium thiosulfate, g of boric acid, and '10 g of sodium metaborate, to make 2 liters of solution.
  • the iomexchang'e resin was regenerated in the same manner as in Example 1. Then, the above-described solution prepared by diluting the farmers solution 20 times was passed through the regenerated resin. The procedures of regeneration, passing diluted solution of farmers reducer through the cylinder, regeneration, passing diluted solution of farmers reducer, etc., were repeated, and the'results obtained are given in the following table.
  • EXAMPLE 7 300 ml of Weakly basic anion-exchange resintDiaion WA-l) were filled in a cylinder of a 4.5 cm inner diameter. A solution of bleaching liquid-having the following composition diluted with water to a 20-fold volume was passed at 300 ml/min through the resin cylinder. After passing 26 liters therethrough, ferricyanide ion began to discharge from the resin cylinder.
  • a process for treating a waste solution from a photographic treatment which'solution contains at least one of ferricyanide and ferrocyanide ions comprising contacting the waste solution having a pH of 7 to 9 with a weakly basic anion exchange resin in the free base form in the presence of a buffering compound added in an amount to maintain a buffering action at a pH of 7-9, thereby adsorbing said ions on said weakly basic anion exchange resin.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Removal Of Specific Substances (AREA)
US307265A 1971-11-17 1972-11-16 Process for treating waste photographic processing solutions Expired - Lifetime US3869383A (en)

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JP46092115A JPS5137704B2 (enrdf_load_stackoverflow) 1971-11-17 1971-11-17
JP47000634A JPS4872959A (enrdf_load_stackoverflow) 1971-12-30 1971-12-30
JP47022907A JPS4891858A (enrdf_load_stackoverflow) 1972-03-06 1972-03-06

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043907A (en) * 1971-11-17 1977-08-23 Fuji Photo Film Co., Ltd. Process for treating waste photographic processing solutions
US4115260A (en) * 1977-04-07 1978-09-19 Rohm And Haas Company Selective removal of iron cyanide anions from fluids containing thiocyanates
US4122007A (en) * 1975-04-30 1978-10-24 Catalysts & Chemicals Industries Co., Ltd. Reclaiming process for zeolite served for adsorbing ammoniacal nitrogen contained in sewage
US4267159A (en) * 1980-08-08 1981-05-12 Crane Co. Cyanide recovery
US4606827A (en) * 1983-06-03 1986-08-19 Konishiroku Photo Industry Co., Ltd. Method for separating and recovering color developing agent
US4618569A (en) * 1984-04-17 1986-10-21 Konishiroku Photo Industry Co., Ltd. Method for processing of silver halide color photographic material
US4632763A (en) * 1984-06-29 1986-12-30 Agfa Gevaert Aktiengesellschaft Process for treating photographic washing waters
WO1987000072A1 (en) * 1985-06-28 1987-01-15 Resource Technology Associates Method for recovery of cyanide from waste streams
US4680123A (en) * 1984-10-13 1987-07-14 Agfa Gevaert Aktiengesellschaft Regeneration of spent developers
US4985118A (en) * 1987-03-24 1991-01-15 Konica Corporation Method for treating photographic process waste liquor through concentration by evaporation
US5004522A (en) * 1986-12-03 1991-04-02 Konica Corporation Method of treating photographic process waste liquor through concentration by evaporation
US5011571A (en) * 1986-12-17 1991-04-30 Konica Corporation Method for treating photographic process waste liquor through concentration by evaporation and apparatus therefor
US5059514A (en) * 1987-12-25 1991-10-22 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic light-sensitive materials
US5260184A (en) * 1989-04-26 1993-11-09 Eastman Kodak Company Method of forming a photographic color image

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1307762C (en) * 1985-11-19 1992-09-22 Satoru Kuse Method for evaporation treatment of photographic processing waste solution and device therefor

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US2611699A (en) * 1949-12-30 1952-09-23 Gen Aniline & Film Corp Regeneration of exhausted silver bleaching solutions
US3001868A (en) * 1957-02-19 1961-09-26 Nat Res Dev Recovery of metals from cyanide solution by anion exchange
US3253920A (en) * 1955-06-14 1966-05-31 Eastman Kodak Co Rejuvenation of photographic developers using ion exchange resins
US3788983A (en) * 1972-01-26 1974-01-29 Rohm & Haas Selective separation of cyanide from waste streams by adsorption process

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CH473737A (de) * 1964-05-12 1969-06-15 Goetzelmann Ind Abwasser Verfahren zur Aufbereitung von schwermetallhaltigen Abwässern

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2611699A (en) * 1949-12-30 1952-09-23 Gen Aniline & Film Corp Regeneration of exhausted silver bleaching solutions
US3253920A (en) * 1955-06-14 1966-05-31 Eastman Kodak Co Rejuvenation of photographic developers using ion exchange resins
US3001868A (en) * 1957-02-19 1961-09-26 Nat Res Dev Recovery of metals from cyanide solution by anion exchange
US3788983A (en) * 1972-01-26 1974-01-29 Rohm & Haas Selective separation of cyanide from waste streams by adsorption process

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043907A (en) * 1971-11-17 1977-08-23 Fuji Photo Film Co., Ltd. Process for treating waste photographic processing solutions
US4122007A (en) * 1975-04-30 1978-10-24 Catalysts & Chemicals Industries Co., Ltd. Reclaiming process for zeolite served for adsorbing ammoniacal nitrogen contained in sewage
US4115260A (en) * 1977-04-07 1978-09-19 Rohm And Haas Company Selective removal of iron cyanide anions from fluids containing thiocyanates
US4267159A (en) * 1980-08-08 1981-05-12 Crane Co. Cyanide recovery
US4606827A (en) * 1983-06-03 1986-08-19 Konishiroku Photo Industry Co., Ltd. Method for separating and recovering color developing agent
US4618569A (en) * 1984-04-17 1986-10-21 Konishiroku Photo Industry Co., Ltd. Method for processing of silver halide color photographic material
US4632763A (en) * 1984-06-29 1986-12-30 Agfa Gevaert Aktiengesellschaft Process for treating photographic washing waters
US4680123A (en) * 1984-10-13 1987-07-14 Agfa Gevaert Aktiengesellschaft Regeneration of spent developers
WO1987000072A1 (en) * 1985-06-28 1987-01-15 Resource Technology Associates Method for recovery of cyanide from waste streams
US4708804A (en) * 1985-06-28 1987-11-24 Resource Technology Associates Method for recovery of cyanide from waste streams
AU575293B2 (en) * 1985-06-28 1988-07-21 Resource Technology Associates Method for recovery of cyanide from waste streams
US5004522A (en) * 1986-12-03 1991-04-02 Konica Corporation Method of treating photographic process waste liquor through concentration by evaporation
US5011571A (en) * 1986-12-17 1991-04-30 Konica Corporation Method for treating photographic process waste liquor through concentration by evaporation and apparatus therefor
US4985118A (en) * 1987-03-24 1991-01-15 Konica Corporation Method for treating photographic process waste liquor through concentration by evaporation
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Publication number Publication date
FR2160569A1 (enrdf_load_stackoverflow) 1973-06-29
FR2160569B1 (enrdf_load_stackoverflow) 1975-11-07

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