EP0837364B1 - Verfahren zur Behandlung und Rückgewinnung von Materialien aus der Produktion und Entwicklung photographischer Filme und Röntgenfilme - Google Patents
Verfahren zur Behandlung und Rückgewinnung von Materialien aus der Produktion und Entwicklung photographischer Filme und Röntgenfilme Download PDFInfo
- 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
Links
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 Of Macromolecular Shaped Articles (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Claims (9)
- Verfahren zur Behandlung und Rückgewinnung von Materialien aus der Produktion und Entwicklung photographischer Filme und Röntgenfilme, wobei die genannten Materialien im wesentlichen aus einer Polyesterbasis bestehen, beschichtet auf einer oder beiden Oberflächen mit einer Gelatine, in welcher metallenes Silber oder Silbersalz dispergiert ist, enthaltend:eine erste Phase des Schnitzelns des Materials zu Stückchen mit solchen Abmessungen, die geeignet sind, die volle Wirksamkeit der genannten Verfahrens zu begünstigen;eine zweite Phase der Oxydation des metallenen Silbers zu ionischem Silber;eine dritte Phase zum Lösen des Silbersalzes in Wasser;eine vierte Phase der Rückgewinnung des metallenen Silbers mit Hilfe der Elektrolyse,eine fünfte Phase des Lösens der Gelatine in einem alkalinen Bad, bestehend aus einem Gelatinelösungsverfahren in einem Bad enthaltend Natriumhydrat zu 5 - 25% bei einer Temperatur zwischen 55 - 80°C und für eine Dauer von 5 - 20 Minuten;eine sechste Phase der Rückgewinnung der Gelatine aus dem alkalinen Bad;eine siebente Phase des Waschens, Spülens und Trocknens des Polyesters, von welchem das Silber und die Gelatine abgezogen wurde.
- Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass es eine achte Phase zum Trocknen des Polyesters vorsieht, bis die Restfeuchtigkeit zwischen 0.1 und 3% beträgt.
- Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass die Abmessungen der genannten Stückchen zwischen 0.3 und 3 cm2 betragen.
- Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass die genannte Oxydation des metallenen Silbers in einem wässrigen Bad erfolgt, das wie folgt enthält: Kupfervitriol zum Oxydieren des metallenen Silbers; Perhydrol zum Reoxydieren des Kupfers und Chlornatrium zum Erzeugen eines Gegenions zu dem Silberion; wobei die genannte Oxydation in Übereinstimmung mit den eingestellten Reaktionsparametern erfolgt.
- Verfahren nach Patentanspruch 4, dadurch gekennzeichnet, dass die Reaktionsparameter folgende sind:
Konzentrationen der Reaktionsmittel:Kupfervitriol 5 - 12%;Chlornatrium 5 - 15%;Perhydrol 0.1 - 1%;pH-Werte zwischen 0.5 und 3;Behandlungsdauer zwischen 3 und 15 Minuten;Temperatur zwischen 5 und 30°C. - Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass die genannte Lösung des Silbersalzes in einem wässrigen Bad erfolgt, welches Natriumthiosulfat enthält, immer in Übereinstimmung mit den eingestellten Reaktionsparametern.
- Verfahren nach Patentanspruch 6, dadurch gekennzeichnet, dass die Reaktionsparameter folgende sind:Konzentration des Natriumthiosulfats 50 - 200 g/l;pH-Werte zwischen 4.5 und 5.5;Behandlungsdauer zwischen 3 und 15 Minuten;Temperatur zwischen 5 und 30°C.
- Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass die genannte Lösung der Gelatine in einem wässrigen Bad erfolgt, enthaltend Natriumhydrat in Übereinstimmung mit den eingestellten Reaktionsparametern.
- Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass die genannte Wasch- und Spülphase in Wasser erfolgt und die Trockenphase durch Schleudern ausgeführt wird.
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 (de) | 1998-04-22 |
EP0837364B1 true EP0837364B1 (de) | 2001-08-16 |
Family
ID=11341648
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97830513A Expired - Lifetime EP0837364B1 (de) | 1996-10-15 | 1997-10-10 | Verfahren zur Behandlung und Rückgewinnung von Materialien aus der Produktion und Entwicklung photographischer Filme und Röntgenfilme |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0837364B1 (de) |
AT (1) | ATE204387T1 (de) |
DE (1) | DE69706115T2 (de) |
IT (1) | IT1286260B1 (de) |
Family Cites Families (13)
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 |
-
1996
- 1996-10-15 IT IT96BO000515A patent/IT1286260B1/it active IP Right Grant
-
1997
- 1997-10-10 DE DE69706115T patent/DE69706115T2/de not_active Expired - Fee Related
- 1997-10-10 AT AT97830513T patent/ATE204387T1/de active
- 1997-10-10 EP EP97830513A patent/EP0837364B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ITBO960515A0 (it) | 1996-10-15 |
ITBO960515A1 (it) | 1998-04-15 |
EP0837364A1 (de) | 1998-04-22 |
ATE204387T1 (de) | 2001-09-15 |
DE69706115D1 (de) | 2001-09-20 |
DE69706115T2 (de) | 2002-04-25 |
IT1286260B1 (it) | 1998-07-08 |
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