EP0837364B1 - Procédé de traitement et récupération de matériaux provenant de la production et le développement de films photographiques et radiographiques - Google Patents

Procédé de traitement et récupération de matériaux provenant de la production et le développement de films photographiques et radiographiques Download PDF

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Publication number
EP0837364B1
EP0837364B1 EP97830513A EP97830513A EP0837364B1 EP 0837364 B1 EP0837364 B1 EP 0837364B1 EP 97830513 A EP97830513 A EP 97830513A EP 97830513 A EP97830513 A EP 97830513A EP 0837364 B1 EP0837364 B1 EP 0837364B1
Authority
EP
European Patent Office
Prior art keywords
stage
silver
gelatin
recovery
solubilization
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
Application number
EP97830513A
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German (de)
English (en)
Other versions
EP0837364A1 (fr
Inventor
Marino Miciano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Serf Srl
Original Assignee
Serf Srl
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Filing date
Publication date
Application filed by Serf Srl filed Critical Serf Srl
Publication of EP0837364A1 publication Critical patent/EP0837364A1/fr
Application granted granted Critical
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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
    • G03C11/00—Auxiliary processes in photography
    • G03C11/24—Removing emulsion from waste photographic material; Recovery of photosensitive or other substances

Definitions

  • the present invention relates to a process for the treatment and recovery of materials from the production and development of photographic and x-ray films.
  • it relates to a process for the recovery, by means of chemical/physical treatments, of the materials of which photographic films and x-ray plates are made, more precisely the recovery of silver, polyester, which forms the base of the photo-x-ray film, and the animal gelatin which coats one or both surfaces of the aforementioned polyester base.
  • the present invention therefore belongs to the sector of industrial chemical processes designed to recover materials which, when recycled, are suitable for further use.
  • polyester and gelatin are currently discarded, this being an undoubted disadvantage from the economic (and environmental) viewpoint, considered that recycled polyester and gelatin have excellent possibilities for re-use.
  • the silver may be recovered using dry or wet systems.
  • the dry system envisages that the starting material, i.e.: photosensitive plates or films, be subjected to combustion.
  • the silver evaporates or remains as an unburned base body, which may then be gathered.
  • the polyester and gelatin are lost.
  • the wet system envisages the use of developing and fixing baths.
  • the fixing bath is used to extract the "superfluous" silver from the fixed silver.
  • the disclosed process comprises the step of (a) shredding or chopping the film material into strips or pieces of predetermined size; (b) bleaching the shredded or chopped film material in a bath of bleach solution to convert the metallic silver present to silver salts that remain on the film material; (c) performing a first stage washing operation in which the bleached film material is washed with first stage wash water; (d) thereafter performing a second stage washing operation in which the bleached film material is washed with a second stage alkaline wash liquid separate and different from and more alkaline than the first stage wash water; (e) fixing the washed film material in at least one bath of fixing solution to remove the silver salts into the fixing solution; (f) collecting and transporting away the film base material from which the silver salts have been removed; and (g) circulating the fixing solution through at least one electrolytic silver recovery unit where the silver is electrolytically deposited on a cathode
  • the object of the present invention is, therefore, to recover all of the material, that is to say, the silver, polyester and animal gelatin.
  • a further object is to effect the said recovery in a relatively simple, low cost manner.
  • the material to be treated consists of a base which is a polyester film, coated on one or both surfaces with a gelatin of animal origin, in which metallic silver or silver salt is dispersed.
  • the material normally arrives in bales of waste or sheets, not yet exposed, or in the form of x-ray plates in envelopes.
  • the first step which is manual, consists in undoing the bales and separating the plates from the paper.
  • the film is then shredded in a special machine and reduced to pieces whose size is 0.3 - 3 cm 2 . It is essential that the material be shredded, in order to allow the completion of the chemical reactions which must take place on both surfaces of the film. Larger dimensions would promote adhesion of the surfaces, preventing completion of the reactions and reducing the overall efficiency of the process. In particular, recovery of the silver would be compromised.
  • the material containing metallic silver is then subjected to a "bleaching" action, that is to say, oxidation of the metallic silver to ionic silver.
  • This action occurs in an aqueous bath, kept at ambient temperature (10 - 25 °C), containing: copper sulphate (to oxidise the silver); hydrogen peroxide (to re-oxidise the copper); sodium chloride (to provide a counter-ion to the silver ion).
  • the reaction occurs at pH 0.5 - 3. Lower pH values could cause the gelatin to be detached; whilst higher pH values would make the bleaching action less effective.
  • the treatment time varies from 3 to 15 minutes: lower times would be insufficient to complete the reaction; higher times could cause the gelatin to be detached.
  • copper as an oxidising agent is determined by process economy and final quality of the polyester recovered: other oxidising agents would be more difficult to remove and would, as a result, pollute the final product.
  • concentrations of the reagents copper sulphate 5 - 12 %; sodium chloride 5 - 15 %; hydrogen peroxide 0.1 - 1 %.
  • the material containing bleached silver that is to say, silver salt
  • a fixing bath containing sodium thiosulphate containing sodium thiosulphate.
  • the silver salt contained in the gelatin, and insoluble in water is solubilized by the presence of the thiosulphate.
  • the treatment time is 3 - 15 minutes at a temperature of 5 - 30 °C; the concentration of the sodium thiosulphate may vary from 50 to 200 g/l.
  • the fixing solution enriched with silver, is then sent to the electrolytic recuperator; once the silver has been deposited, the bath is put into circulation again.
  • the material - now consisting of polyester coated with gelatin - is sent to the gelatin removal tank, which consists of a bath containing sodium hydrate 5 - 25 % and is kept at 55 - 80 °C.
  • the gelatin solubilizing process occurs within 5 - 20 minutes.
  • the polyester is then sent to the washing, rinsing and centrifugation plant.
  • the product washing stages may be envisaged upstream of those operating stages which require unpolluted products from the operating stage upstream.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Photographic Processing Devices Using Wet Methods (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (9)

  1. Un procédé de traitement et récupération de matériaux provenant de la production et le développement de films photographiques et radiographiques, lesdits matériaux consistant essentiellement en une base de polyester recouverte, sur une ou les deux surfaces, d'une gélatine dans laquelle de l'argent métallique ou du sel d'argent est dispersé, ledit procédé comprenant :
    une première phase de broyage du matériau pour le réduire en morceaux de dimensions adéquates pour favoriser la pleine efficacité du procédé ;
    une deuxième phase d'oxydation de l'argent métallique en argent ionique ;
    une troisième phase de solubilisation du sel d'argent dans de l'eau ;
    une quatrième phase de récupération d'argent métallique par électrolyse,
    ledit procédé étant caractérisé en ce qu'il comprend également les phases suivantes :
    une cinquième phase de solubilisation de la gélatine dans un bain alcalin, consistant en un procédé de solubilisation de la gélatine dans un bain contenant de 5 à 25 % d'hydrate de sodium, maintenu à une température de 55 à 80 °C pendant une période de temps de 5 à 20 minutes ;
    une sixième phase de récupération de la gélatine du bain alcalin ;
    une septième phase de lavage, rinçage et séchage du polyester privé de l'argent et de la gélatine.
  2. Le procédé selon la revendication 1, caractérisé en ce qu'il prévoit une huitième phase consistant à sécher le polyester jusqu'à ce que l'humidité résiduelle soit comprise entre 0,1 et 3 %.
  3. Le procédé selon la revendication 1, caractérisé en ce que les dimensions des morceaux susmentionnés sont comprises entre 0,3 et 3 cm2.
  4. Le procédé selon la revendication 1, caractérisé en ce que ladite oxydation de l'argent métallique a lieu dans un bain aqueux contenant : du sulfate de cuivre pour l'oxydation de l'argent métallique ; du peroxyde d'hydrogène pour la réoxydation du cuivre, et du chlorure de sodium pour fournir un contre-ion au ion argent ; ladite oxydation ayant lieu selon les paramètres de réaction préétablis.
  5. Le procédé selon la revendication 4, caractérisé en ce que lesdits paramètres de réaction sont :
    concentration des réactifs :
    sulfate de cuivre : 5 - 12 %
    chlorure de sodium : 5 - 15 %
    peroxyde d'hydrogène : 0,1 - 1 %
    valeurs de pH comprises entre 0,5 et 3 ;
    durée du traitement comprise entre 3 et 15 minutes ;
    température comprise entre 5 et 30 °C.
  6. Le procédé selon la revendication 1, caractérisé en ce que ladite solubilisation du sel d'argent a lieu dans un bain aqueux contenant du thiosulfate de sodium, selon les paramètres de réaction préétablis.
  7. Le procédé selon la revendication 6, caractérisé en ce que lesdits paramètres de réaction sont :
    concentration du thiosulfate de sodium : 50 - 200 g/l ;
    valeurs de pH comprises entre 4,5 et 5,5 ;
    durée du traitement comprise entre 3 et 15 minutes ;
    température comprise entre 5 et 30 °C.
  8. Le procédé selon la revendication 1, caractérisé en ce que ladite solubilisation de la gélatine a lieu dans un bain aqueux contenant de l'hydrate de sodium, selon les paramètres de réaction préétablis.
  9. Le procédé selon la revendication 1, caractérisé en ce que ladite phase de lavage et de rinçage a lieu dans de l'eau, et ladite phase de séchage est effectuée par centrifugation.
EP97830513A 1996-10-15 1997-10-10 Procédé de traitement et récupération de matériaux provenant de la production et le développement de films photographiques et radiographiques Expired - Lifetime EP0837364B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT96BO000515A IT1286260B1 (it) 1996-10-15 1996-10-15 Processo per il trattamento ed il recupero di materiali provenienti dalla produzione e sviluppo di film fotografici e radiografici
ITBO960515 1996-10-15

Publications (2)

Publication Number Publication Date
EP0837364A1 EP0837364A1 (fr) 1998-04-22
EP0837364B1 true EP0837364B1 (fr) 2001-08-16

Family

ID=11341648

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97830513A Expired - Lifetime EP0837364B1 (fr) 1996-10-15 1997-10-10 Procédé de traitement et récupération de matériaux provenant de la production et le développement de films photographiques et radiographiques

Country Status (4)

Country Link
EP (1) EP0837364B1 (fr)
AT (1) ATE204387T1 (fr)
DE (1) DE69706115T2 (fr)
IT (1) IT1286260B1 (fr)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047435A (en) * 1958-11-10 1962-07-31 Eastman Kodak Co Recovery of polyester film base from terpolymer-subbed photographic film scrap
US3647422A (en) * 1970-07-13 1972-03-07 Horizons Research Inc Recovery of silver, polyester and amino acids from processed film
US3793168A (en) * 1971-01-18 1974-02-19 R Lilly Method of recovering silver
US3928253A (en) * 1972-05-10 1975-12-23 Horizons Inc Process for recovery of clean polyester materials
GB1432000A (en) * 1973-11-09 1976-04-14 Horizons Research Inc Recovery of materials from photographic film
SU611168A1 (ru) * 1976-05-31 1978-05-15 Государственный научно-исследовательский и проектно-конструкторский институт гидрометаллургии цветных металлов Способ переработки желатиновых галогенсеребр ных фотографических эмульсий
JPS541026A (en) * 1977-06-04 1979-01-06 Konishiroku Photo Ind Co Ltd Processing method for silver halide color photographic material
US4299676A (en) * 1980-01-31 1981-11-10 Photographic Silver Recovery Limited Recovery of silver from photographic film
GB8605278D0 (en) * 1986-03-04 1986-04-09 Fixersave Ltd Photographic processing
JPS62237447A (ja) * 1986-04-08 1987-10-17 Mitsubishi Paper Mills Ltd 一液型エツチングブリ−チ液
US4799954A (en) * 1987-02-13 1989-01-24 E. I. Du Pont De Nemours And Company Recovery of silver from photographic film with high shear and caustic
SU1681295A1 (ru) * 1989-02-22 1991-09-30 Казанский научно-исследовательский технологический и проектный институт химико-фотографической промышленности Производственного объединения "Тасма" Способ удалени эмульсионного и адгезионного желатиновых слоев с полиэтилентерефталатной подложки фотоматериалов
JP3149289B2 (ja) * 1993-03-24 2001-03-26 三菱製紙株式会社 画像形成材料及びそれを使用する画像形成方法

Also Published As

Publication number Publication date
DE69706115D1 (de) 2001-09-20
IT1286260B1 (it) 1998-07-08
DE69706115T2 (de) 2002-04-25
ITBO960515A0 (it) 1996-10-15
ITBO960515A1 (it) 1998-04-15
EP0837364A1 (fr) 1998-04-22
ATE204387T1 (de) 2001-09-15

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