WO2003048858A1 - Procede destine a preparer une nouvelle matiere composite presentant une efficacite amelioree, et nouvelle matiere composite ainsi obtenue - Google Patents

Procede destine a preparer une nouvelle matiere composite presentant une efficacite amelioree, et nouvelle matiere composite ainsi obtenue Download PDF

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Publication number
WO2003048858A1
WO2003048858A1 PCT/EP2002/012910 EP0212910W WO03048858A1 WO 2003048858 A1 WO2003048858 A1 WO 2003048858A1 EP 0212910 W EP0212910 W EP 0212910W WO 03048858 A1 WO03048858 A1 WO 03048858A1
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WO
WIPO (PCT)
Prior art keywords
composite material
tin
ions
effluent
organic
Prior art date
Application number
PCT/EP2002/012910
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English (en)
Inventor
Didier Jean Martin
Olivier Jean Christian Poncelet
Danielle Marie Henriette Wettling
Original Assignee
Eastman Kodak Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Company filed Critical Eastman Kodak Company
Priority to EP02787720A priority Critical patent/EP1454188A1/fr
Priority to AU2002352047A priority patent/AU2002352047A1/en
Priority to JP2003549991A priority patent/JP2005511824A/ja
Publication of WO2003048858A1 publication Critical patent/WO2003048858A1/fr

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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

Definitions

  • the present invention relates to a method for preparing a new composite material with improved efficiency, and to said composite material and its use in effluent treatment methods, in particular for treating photographic effluents.
  • Photographic processing generally comprises several processing baths and one or more washing and/or stabilization baths.
  • the build-up of substances from the previous processing steps in the washing and/or stabilization baths is especially damaging not only to the stability of the developed photographic images and to the good resistance of the sensitometric characteristics, but also to the possibility of recycling these washing and stabilization baths, or releasing them into the sewers.
  • the washing and stabilization baths contain inorganic compounds, . such as iron, silver, thiosulfate, or sulfate ions or organic compounds that are, either substances used for the development, or products from the reaction of these substances during the development, or from the fixing or bleach-fix step.
  • the problem of the discharge of silver to the drains is especially important because of the new standards applicable to photographic processing methods that very clearly limit water consumption per square meter of developed films and that require a concentration of silver ions in the water discharged to the drains less than 1 ppm. By reducing the permitted volume of water, washing baths are obtained that are more concentrated in silver and are consequently more difficult to decontaminate.
  • the present invention provides a new material, its preparation method and a new treatment method for photographic effluent using said new material and that has still better efficiency than that described in US Patent US-
  • the present invention relates to a method for preparing a composite material, comprising the following steps: a) preparation of an organic-inorganic aluminosilicate polymer comprising at least on the surface an organic radical having an -SH or -S(-CH2) n -S- function, with n being between 0 and 4, and b) placing the organic-inorganic aluminosilicate polymer obtained in step a) in contact with an aqueous solution containing tin (II) ions.
  • step b) is performed in dynamic mode, the aqueous solution containing the tin (II) ions being mixed with stirring with said organic- inorganic aluminosilicate polymer.
  • the present invention also relates to a composite material obtainable by said method.
  • the present invention further relates to a method for treating an effluent containing ionic silver that comprises placing the effluent in contact with said composite material.
  • placing the effluent in contact with said composite material is performed in dynamic mode, the treatment method comprising the following steps: i) mixing with stirring the composite material with said effluent, ii) letting said mixture settle to obtain a supernatant, said obtained supernatant containing less ionic silver than the effluent, and iii) recovering said supernatant.
  • This treatment method further improves the efficiency of the treatment method described in U.S. Patent US-A-6,179,898, and substantially reduces the quantity of ionic silver present in an effluent.
  • the treatment method according to the present invention is especially efficient for the decontamination of photographic effluent, in particular for processing baths of silver halide photographic materials, for example washing baths, stabilization baths, fixing or bleaching baths containing ionic silver.
  • Figures 1 and 2 are diagrams showing two embodiments of the treatment method of the present invention applied to the treatment of a photographic processing bath.
  • the first step a) of the method of the invention for preparing the composite material consists in preparing an organic-inorganic aluminosilicate polymer comprising at least on the surface an organic radical having an -SH or - S(-CH2) n -S- function, with n being between 0 and 4.
  • a method for preparing such a polymer is described in U.S. Patent US-A-6,179,898 of the same applicant. This method comprises the hydrolysis of an alkylalkoxysilane with formula RSiR' x (OR 2 ) 3 .
  • R is an alkyl group including an SH or -S(- CH 2 ) n -S- function, with n being between 0 and 4, and R 1 and R 2 are independently a methyl or ethyl group, x is 0 or 1, in the presence of an inorganic aluminosilicate polymer comprising active hydroxyl groups on its surface.
  • Active hydroxyl groups are groups capable of reacting with alkylalkoxysilane.
  • the aluminosilicate polymer is preferably imogolite. Imogolite exists in impure form in the natural state; it was described for the first time by Wada in J. Soil Sci. 1979, 30(2), 347-355. Imogolite can be synthesized with various degrees of purity using different methods. A method for obtaining an imogolite gel with a high degree of purity is described in U.S. Patent US-A- 5,888,711.
  • the alkylalkoxysilanes can be mercaptoalkylalkoxysilanes with formula HS-(CH 2 ) m -SiR 1 x (OR 2 ) 3 . x wherein m is at least 1, R 1 , R 2 and x being as defined above. Preferably, m is from 1 to 4. For example, they include 3- mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- mercaptopropylmethyldimethoxysilane, (mercaptomethyl)methyldiethoxysilane, and (mercaptomethyl)dimethylethoxysilane.
  • Alkylalkoxysilanes comprising an organic radical having an -S-S- function like for example Bis[3(triethoxysilyl) propyl]tetrasulfite can be used. • Alkylalkoxysilanes having a crown ether organic radical containing the -S-S- or - S(-CH 2 ) n -S- function, n being from 1 to 4, can also be used.
  • the alkylalkoxysilane hydrolysis is implemented at a pH greater than 7.
  • a pH is obtained by the addition of a base in the reaction medium, for example NH 4 OH, NAOH, or KOH.
  • a pH greater than 7 enables the gelation of the imogolite.
  • aluminosilicate organic-inorganic polymer is prepared, it is placed in contact with a solution containing tin (II) ions, for example, an aqueous solution of tin (II) chloride.
  • a solution containing tin (II) ions for example, an aqueous solution of tin (II) chloride.
  • Any other aqueous solution in which tin (II) salts are soluble, such as SnBr 2 , SnSO 4 , and Sn(BF 4 ) 2 can also be used.
  • the concentration of tin (II) ions is preferably between 50 ppm and 900 ppm, and preferably between 50 ppm and 300 ppm.
  • step a) When the aluminosilicate organic- inorganic polymer prepared in step a) is an imogolite gel comprising sulfured functions, for example 100 g of said imogolite gel can be placed in contact with 100 ml of the solution of tin (II) ions.
  • step b) placing the aluminosilicate organic-inorganic polymer obtained in step a) in contact with the solution of tin (II) ions is performed in static mode. This means that the aluminosilicate organic-inorganic polymer obtained in step a) is put into a permeable bag, itself put in a device in which the solution of tin (II) ions flows, with no stirring.
  • step b) placing the aluminosilicate organic-inorganic polymer obtained in step a) in contact with the solution of tin (II) ions is performed in dynamic mode.
  • the solution of tin (II) ions is mixed using stirring with said aluminosilicate organic-inorganic polymer, by means for example of a magnetic stirrer.
  • the mixture After stirring, the mixture is left to settle and then the supernatant is removed by settling or filtration to keep only the composite material according to the invention, i.e. an aluminosilicate organic-inorganic polymer comprising sulfured functions and having trapped tin ions.
  • step b) substantially increases the quantity of tin ions trapped in the aluminosilicate organic-inorganic polymer obtained in step a).
  • a composite material is thus obtained that is implemented in a treatment method of an effluent containing ionic silver, said treatment method consisting in placing the composite material obtained according to the invention in contact with said effluent to be treated.
  • placing the composite material according to the invention in contact with the effluent to be treated is performed in static mode.
  • the composite material according to the invention is put into a vessel permeable to the effluent to be treated, for example a dialysis bag, a filter material or a non-woven material.
  • the treated effluent has a silver ion concentration less than the silver ion concentration of the effluent to be treated.
  • the treated effluent is recovered and can be recycled or discharged to the drains.
  • placing the composite material according to the invention in contact with the effluent to be treated is performed in dynamic mode.
  • the composite material according to the invention is mixed with the effluent to be treated with stirring, by means for example of a magnetic stirrer, and then said mixture is left to settle to obtain a supernatant, said supernatant obtained containing less ionic silver than the effluent to be treated, and to recover said supernatant.
  • the recovered supernatant contains a silver ion concentration less than the maximum permitted concentration and can be discharged directly to the drains or recycled.
  • the treatment method according to the invention can be implemented advantageously in a photographic processing method that comprises passing a silver halide photographic material through a series of processing baths in between which are inserted washing and/or stabilization baths, these baths being treated with the treatment method of the invention.
  • the treatment according to the invention significantly reduce the silver content of these baths, which can then be recycled as photographic baths or discharged to the drains without additional treatment.
  • FIG. 1 is a diagrammatic representation of the first alternative of the treatment method of the invention applied to the treatment of a washing bath of a silver halide photographic material processing method.
  • This Figure 1 represents a wash tank 12 containing a washing bath. The tank is fitted with a fresh bath or water inlet 21, a means of drainage 22 and a means of discharging by overflow 24.
  • This washing bath is sent by means of the pipe 14 into a treatment cartridge 16 containing one or more containers 18 that are permeable to the washing bath and contain the composite material according to the invention.
  • the obtained solution is sent back using a pump 20 into the tank 12 where it is used again for washing photographic materials.
  • FIG. 2 is a diagrammatic representation of the second alternative of the treatment method of the invention applied to the treatment of a washing bath of a silver halide photographic material processing method.
  • This Figure 2 represents a wash tank 12 containing a washing bath.
  • the tank is fitted with a fresh bath or water inlet 21, a means of drainage 22 and a means of discharging by overflow 24.
  • This washing bath is sent by the pipe 14 into a vessel 30 containing the composite material according to the invention 31.
  • the vessel 30 is fitted with a suitable magnetic stirrer 32, rotating at a speed preferably between 300 and 800 rotations per minute. Stirring can also be carried out using a submerged pump with a flow rate preferably between 0.5 and 1 liters per minute.
  • the stirring is maintained for sufficient time so that the recovered supernatant contains silver ions in a quantity less than the initial concentration. For example, this time is between one and four hours, and preferably, between two and three hours. Then the mixture is left to settle.
  • a supernatant 33 forms that is discharged using a valve 34 directly to the drains. The supernatant 33 can also be sent back using a pump into the tank 12 where it will be used again for washing photographic materials.
  • the composite material removed from the vessels 18 or the composite material 31 that is deposited at the bottom of the vessel 30 are recovered when their efficiency has decreased, especially when the sulfur sites are saturated with silver ions.
  • the silver and tin contained in the composite material can be easily recovered by calcination of said composite material.
  • the composite material is prepared according to the two following steps: a) Preparation of imogolite comprising sulfured functions:
  • This preparation was performed according to the method described in U.S. Patent US-A-6,179,898.
  • the aluminosilicate was prepared, i.e. the imogolite: 16.7 mmoles of tetraethylorthosilicate Si(OR) 4 were added to 1000 ml deionized water.
  • the reaction mixture was stirred at ambient temperature for one hour, then this solution was added to 31.2 mmoles of AlCl 3 ,6H 2 O in solution in 1000 ml pure water.
  • the mixture was stirred for 20 minutes, then the pH was adjusted to 4.5 with NaOH,lM.
  • the solution clouded. When the solution became transparent again, NaOH,lM was added to obtain pH 6.8.
  • a white gel was obtained that was centrif ⁇ ged for 20 minutes at 2000 rpm. This gel was collected and was put into solution with 5 ml of a mixture comprising HC1, 1M and acetic acid, 2M. The volume was made up to 2 1 with water. The solution contained 30 mmoles Al, 16.6 mmoles Si, 5 mmoles HC1 and 10 mmoles acetic acid. This solution was kept at 5°C.
  • This solution was then diluted with deionized water to obtain a concentration in Al of 10 mmoles/1.
  • the diluted solution was heated for five days at 96 °C, then filtered through an ultrafiltration membrane with a separation power of 10 000 daltons (membrane manufactured by AMICON).
  • a clear solution was obtained containing Al and Si in a ratio Al:Si of 1.8.
  • the imogolite comprising sulfured functions was prepared: A solution of 3-mercaptopropyltrimethoxysilane in anhydrous methanol (10 "3 mole in 2 ml methanol) containing some drops of NH 4 OH was added to 20 ml imogolite prepared according to the above method and containing 2.5 g/1 of (Al+Si). The solution gelled (pH>7) and hydrolyzed in time. During hydrolysis, the siloxane grafted onto the imogolite. In addition, an infrared spectrum of the material showed that the organic part was not affected by the grafting and thus remained available to trap silver.
  • step a) 100 g of imogolite comprising sulfured functions prepared according to step a) were put into a porous polyester bag, and the bag was put into a device in which an aqueous solution of tin II chloride flowed with a flow rate of 1 1/min.
  • the various tin II ion concentrations tested are given in Table I.
  • the contact period was three hours. Then, the bag was removed and the composite material according to the invention was recovered.
  • step b) To determine the quantity of tin trapped in the imogolite gel for each implementation mode of step b) and for each concentration of tin II ions in the aqueous solutions of tin II chloride tested, at different times in the treatment, the concentration of tin ions remaining in the tin chloride solution placed in contact with the imogolite comprising the sulfured functions was measured. The tin ion concentration was monitored by inductively-coupled plasma-atomic emission spectroscopy (ICP). When step b) was carried out using the dynamic mode, stirring was stopped at each measurement time and the mixture was left to settle to form a supernatant. A sample of this supernatant was taken to measure its tin ion concentration.
  • ICP inductively-coupled plasma-atomic emission spectroscopy
  • Tables I and II show that, whatever implementation mode of step b), static or dynamic, the imogolite gel comprising the sulfured functions trapped tin ions and that the percentage of trapped tin ions varied according to the concentration of tin II ions in the tin chloride solution placed in contact with the imogolite gel comprising the sulfured functions.
  • step b) of preparing the material according to the invention is performed in dynamic mode, one observes that the imogolite gel trapped practically all the tin ions placed in contact with it.
  • More thorough analysis of the supernatant recovered after three hours of contact according to the dynamic mode can determine the concentration of tin II ions compared with the total concentration of tin ions measured using ICP. For this, the concentration of tin II ions in the supernatant is measured by colorimetric titration.
  • Table III shows that in contact with the imogolite comprising the sulfured functions in the dynamic mode, the supernatant contains a very low quantity of Sn 4+ ions, and no longer contains Sn 2+ ions, the other tin ions having been trapped by the imogolite gel comprising the sulfured functions.
  • the treatment method is implemented according to the dynamic mode.
  • 10 g of the composite material according to the invention obtained by carrying out step b) according to the static mode as described above were mixed with 250 ml of an effluent containing 5 g/1 of silver nitrate for three hours by means of a magnetic stirrer rotating at 500 rpm. The stirring was maintained for three hours.
  • stirring was stopped, and the mixture obtained left to settle to form a supernatant.
  • a sample of this supernatant was taken and the silver ion concentration was monitored by inductively-coupled plasma-atomic emission spectroscopy (ICP).
  • ICP inductively-coupled plasma-atomic emission spectroscopy
  • Patent US-A-6,179,898 the silver ion concentration is monitored for 250 ml of a solution of silver nitrate (5 g/1) mixed with 10 g of imogolite comprising sulfured functions prepared according to step a) and which has not been placed in contact with an aqueous solution containing tin II ions according to step b) of the method according to the invention.
  • the composite material according to the invention After three hours of treatment, the composite material according to the invention, of which step b) has been performed in static mode, has trapped more silver than the imogolite comprising the sulfured functions that has not been placed in contact with the tin II ions.
  • the percentage of silver ions trapped varied according to the concentration of tin II ions in the tin chloride solution that has been placed in contact with the imogolite gel comprising the sulfured functions. For a concentration of tin II ions of 50 ppm, an improvement of 23 % on the silver ion removal method as described in the US Patent US-A-6,179,898 was achieved.
  • step b) The above example was repeated but using 10 g of the composite material according to the invention obtained by implementing step b) according to the dynamic mode as described above and mixed with 250 ml of an effluent containing 10 g/1 of silver nitrate for three hours by means of a magnetic stirrer rotating at 500 rpm. The stirring was maintained for three hours. At various times of the treatment, stirring was stopped, and the resulting mixture left to settle to form a supernatant. At each stop a sample of this supernatant was taken and the silver ion concentration was monitored by inductively-coupled plasma-atomic emission spectroscopy (ICP). From this is worked out the quantity of silver ions trapped by the imogolite gel comprising the sulfured functions.
  • ICP inductively-coupled plasma-atomic emission spectroscopy
  • the composite material according to the invention used in dynamic mode has trapped more silver than the imogolite comprising the sulfured functions that has not been placed in contact with the tin II ions.
  • the percentage of silver ions trapped varied according to the concentration of tin II ions in the tin chloride solution that has been mixed with the imogolite gel comprising the sulfured functions. For a concentration of tin II ions of 270 ppm, an improvement of 27% , after three hours of treatment, and 30% after 200 hours of treatment, on the silver ion removal method as described in the US Patent US-A-6,179,898 was achieved.
  • the tin concentration in the supernatant was also measured using ICP, in order to determine whether tin is released in the effluent from the imogolite gel comprising the sulfured functions. The measurements were made for each concentration of the solution of tin II chloride tested.
  • Table VI shows that the quantity of tin released from the imogolite gel comprising the sulfured functions is negligible. The measured concentrations are near to the detection threshold of ICP measurements.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

La présente invention concerne une nouvelle matière composite présentant une efficacité améliorée lors d'une utilisation dans des procédés de traitement d'effluents, et notamment dans le traitement d'effluents photographiques. On obtient cette matière composite par préparation d'un polymère organique-inorganique d'aluminosilicate comprenant au moins en surface un radical organique présentant une fonction SH ou S(-CH2)n-S-, n étant compris entre 0 et 4, et par mise en contact du polymère organique-inorganique d'aluminosilicate avec une solution aqueuse contenant des ions étain (II). La présente invention concerne également un procédé de traitement d'effluent consistant à mettre la matière composite susmentionnée en contact avec un effluent.
PCT/EP2002/012910 2001-12-03 2002-11-18 Procede destine a preparer une nouvelle matiere composite presentant une efficacite amelioree, et nouvelle matiere composite ainsi obtenue WO2003048858A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP02787720A EP1454188A1 (fr) 2001-12-03 2002-11-18 Procede destine a preparer une nouvelle matiere composite presentant une efficacite amelioree, et nouvelle matiere composite ainsi obtenue
AU2002352047A AU2002352047A1 (en) 2001-12-03 2002-11-18 Method for preparing a new composite material with improved efficiency and said new composite material
JP2003549991A JP2005511824A (ja) 2001-12-03 2002-11-18 効率の改良された新規複合材料の製造方法及びその新規複合材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR01/15566 2001-12-03
FR0115566A FR2832998B1 (fr) 2001-12-03 2001-12-03 Procede de preparation d'un nouveau materiau composite a efficacite amelioree et ledit nouveau materiau composite

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WO2003048858A1 true WO2003048858A1 (fr) 2003-06-12

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PCT/EP2002/012910 WO2003048858A1 (fr) 2001-12-03 2002-11-18 Procede destine a preparer une nouvelle matiere composite presentant une efficacite amelioree, et nouvelle matiere composite ainsi obtenue

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EP (1) EP1454188A1 (fr)
JP (1) JP2005511824A (fr)
AU (1) AU2002352047A1 (fr)
FR (1) FR2832998B1 (fr)
WO (1) WO2003048858A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2246705B1 (es) * 2004-05-28 2007-06-16 Universidad Politecnica De Valencia Metodo para la eliminacion de boro en medio acuoso.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444939A1 (fr) * 1990-02-28 1991-09-04 Hagiwara Research Corporation Composition antimicrobienne
EP0545503A1 (fr) * 1991-12-06 1993-06-09 ENIRICERCHE S.p.A. Procédé pour la décontamination d'effluents aqueux en métaux lourds
EP0937393A1 (fr) * 1998-02-23 1999-08-25 Eastman Kodak Company Matériau composite pour le traitement d'effluents photographiques
EP1132771A1 (fr) * 2000-03-07 2001-09-12 Eastman Kodak Company Méthode et dispositif pour le traítement d'un film photographique inversible couleur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444939A1 (fr) * 1990-02-28 1991-09-04 Hagiwara Research Corporation Composition antimicrobienne
EP0545503A1 (fr) * 1991-12-06 1993-06-09 ENIRICERCHE S.p.A. Procédé pour la décontamination d'effluents aqueux en métaux lourds
EP0937393A1 (fr) * 1998-02-23 1999-08-25 Eastman Kodak Company Matériau composite pour le traitement d'effluents photographiques
EP1132771A1 (fr) * 2000-03-07 2001-09-12 Eastman Kodak Company Méthode et dispositif pour le traítement d'un film photographique inversible couleur

Also Published As

Publication number Publication date
FR2832998B1 (fr) 2004-01-16
AU2002352047A1 (en) 2003-06-17
EP1454188A1 (fr) 2004-09-08
JP2005511824A (ja) 2005-04-28
FR2832998A1 (fr) 2003-06-06

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