JPH05119440A - Treatment of waste photographic liquid - Google Patents

Abstract

PURPOSE:To decrease a COD value, TOC value and ammonia nitrogen quantity at a high rate by subjecting a waste photographic liquid to wet process oxidation in the presence of a specific catalyst under the supply of oxygen, then subjecting the liquid to a biooxidation treatment by a biophase contg. ocean bacteria. CONSTITUTION:While the waste photographic liquid is kept at a temp. from 100 to 370 deg.C and at which the waste liquid maintains the liquid phase, the waste liquid is subjected to the wet process oxidation treatment in the presence of the catalyst deposited with at least one kind of iron, cobalt, manganese, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, gold, and tungsten, and water-in soluble or hardly soluble compds. of these metals under the supply of the gas contg. the oxygen of the quantity necessary for decomposing the ammonia and org. materials in the waste liquid (stage A). The treated water past the stage A is subjected to the biooxidation treatment by the biophase contg. the ocean bacteria in the state of contg. an inorg. salt at >=30g per 1 liter concn. (stage B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method for reducing the pollution load of a processing waste liquid of a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A photographic waste liquid produced by processing black and white and color silver halide photographic light-sensitive materials usually contains a large amount of silver ions eluted from the light-sensitive material for the purpose of recovering silver which is a valuable metal (silver-containing system). And other types (non-silver-containing system) are classified and recovered, and silver is recovered from the silver-containing system by a waste liquid treatment company. Generally, used processing effluents from bleaching processing and one-bath bleach-fixing processing in fixing processing and color light-sensitive material processing are classified as silver-containing, and used processing effluents from development processing are classified as non-silver-containing. Spent treatment effluents from washing treatment and stabilizing treatment are classified into either silver-containing system or non-silver-containing system depending on the concentration of silver ions contained therein.

Conventionally, as a processing method for reducing the pollution load such as COD (Chemical Oxygen Demand) of these photographic waste liquids, a chemical processing method (JP-A-53-12152, JP-B-57-37396, JP-A-61-241746), ion exchange method (JP-B-51-37704, JP-B-53-383, JP-B-53-43271, etc.), reverse osmosis method (JP-A-50-22463), Activated sludge method (Japanese Patent Publication No. 55-49559, Japanese Patent Publication No. 51-12943, etc.), electrolytic oxidation method (Japanese Patent Publication No. 48-84462, Japanese Patent Publication No. 49-119458, etc.) and the like are known. But,
Each of these methods has the following drawbacks.

The chemical treatment method is hydrogen peroxide, persulfate,
Processing methods by addition of perhalogen acid salts, chlorous acid and hypochlorous acid are known, but the processing efficiency is extremely poor for any photographic waste liquid having a high COD value, and an excessive amount of chemicals is always required. Will result in higher operating costs. Also, when using resins or membranes such as in the ion exchange method or reverse osmosis method, it is necessary to frequently replace the resins or membranes due to adsorption of substances that easily polymerize such as developing agents or dirt, resulting in high operating costs. Prone.

Although the activated sludge method requires low operating costs, it has little effect on materials with poor biodegradability.
Particularly, a chelating agent such as EDTA (ethylenediaminetetraacetic acid) contained in a large amount in the photographic waste liquid is hardly decomposed. Further, a waste liquid having a high salt concentration and a high organic matter concentration, such as a photographic waste liquid, needs to be significantly diluted, which poses a problem of increasing the scale of equipment.

In the electrolysis method, a large amount of electric current is required to treat a waste liquid having a high COD, the operating cost is high, the organic compound such as a developing agent is polymerized, and the electrode is contaminated. However, there is a problem in that a harmful gas such as hydrogen sulfide is generated when a lower sulfur compound such as is treated. Further, a treatment method called a Chimmerman method is known as a treatment method of wastewater containing a COD component at a relatively high concentration. This is a method of introducing air into a wastewater containing a COD component under high temperature and high pressure to oxidize and decompose the COD component by liquid phase oxidation, but the reaction rate is low,
Moreover, since ammonia in the waste water is hardly decomposed and remains, it has a problem that the waste water containing a very high concentration of COD component like a photographic waste liquid and containing a large amount of ammonia has insufficient treatment capacity. It was

Further, by carrying out this wet oxidation method in the presence of a catalyst, a method aimed at removing ammonia and improving the COD component treatment rate (Japanese Patent Laid-Open Nos. 53-20663 and 55-55).
-86584) has also been proposed. The photographic waste liquid contains a large amount of inorganic salts such as 30 g or more per liter, and if an attempt is made to process the salt while containing a large amount of these salts, the oxidation reaction is hindered by them. There is a problem that the reaction is hindered by bromide ions that are contained in a large amount of 1 g or more per liter, and organic matter remains in a normal treatment. Although the treatment time is improved by increasing the treatment time, the cost and There was a problem that the equipment would increase.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new method for effectively solving the above problems. That is, the first object of the present invention is to establish an effective and inexpensive means for detoxifying photographic waste liquid which is free from environmental pollution over both water quality and air.

A second object of the present invention is to provide a processing means for effectively reducing the COD value. Third of the present invention
The purpose of is to provide a means for decomposing ammonia, which is a major inducer of eutrophication development, into harmless nitrogen gas.

[0010]

As a result of various investigations, the present inventors have found that the object of the present invention can be effectively achieved by using the following means for photographic waste liquid. That is, in the present invention, a photographic waste liquid containing an organic substance and an inorganic substance and having an inorganic salt concentration of 30 g or more per liter and a bromide concentration of 1 g or more per liter is treated in the following order (A) and (B). Is a method for treating photographic waste liquid. (A) Iron, cobalt, manganese, nickel, ruthenium, rhodium, palladium, iridium, while maintaining the above-mentioned photographic waste liquid at a temperature of 100 to 370 ° C. and a pressure at which the waste liquid holds a liquid phase.
Decomposes ammonia, organic substances and inorganic substances in waste liquid in the presence of a catalyst body carrying at least one of platinum, copper, gold and tungsten and water-insoluble or sparingly soluble compounds of these metals. The wet oxidation treatment is performed under the supply of a gas containing the necessary amount of oxygen (step A). (B) The treated water that has passed through the step A is subjected to a biooxidation treatment with a biota containing marine bacteria in a state where the inorganic salt concentration is 30 g or more per liter (step B).

The present invention will be described in detail. The photographic processing waste liquid used in the method of the present invention is a processing liquid generated when a silver halide photographic light-sensitive material is developed. The silver halide light-sensitive material mentioned here includes a color light-sensitive material and a black-and-white light-sensitive material. Examples of the color light-sensitive material include color paper, color reversal paper, color negative film for photography, color reversal film, negative or positive film for movie, direct positive color light-sensitive material, and black-and-white light-sensitive material include X ray film, Examples thereof include a photosensitive material for printing, a microfilm, and a black and white film for photographing.

Usually, the used processing waste liquid discharged by these processing contains a large amount of silver ions eluted from the silver halide photographic light-sensitive material into the processing liquid for the purpose of recovering silver which is a valuable metal (silver-containing material). (Systems) and others (non-silver containing systems). Generally, used processing waste solutions from the fixing processing in black and white development and bleaching processing in color development, fixing processing and bleach-fixing processing are classified as silver-containing, and used processing waste solutions from the developing processing in color development and black and white development are not included. It is classified as silver-based. Spent processing effluents from water washing and stabilization treatments in color development and black and white development are classified into silver-containing or non-silver-containing, respectively, depending on the concentration of silver ions contained, and silver-containing waste is treated to recover silver. Those treated with are treated as silver recovery waste liquids, and non-silver-containing waste liquids as development waste liquids. In the present invention, any of these silver recovery system waste liquid, developing system waste liquid, and mixed waste liquid thereof can be applied.

Next, each step in the present invention will be described. (A) Step A: In this wet oxidation treatment, the waste liquid and oxygen are brought into contact with each other in the presence of heating, pressurization and a catalyst, whereby the components in the waste liquid are oxidized in the liquid phase. In this step, the photographic waste liquid is subjected to a wet oxidation treatment to oxidatively decompose organic and inorganic components having a COD load. As a result, the index of the pollution load of waste liquid such as BOD and COD can be lowered efficiently at low cost. In this process, the photographic waste liquid is wet-oxidized at a high concentration, so the reaction is inhibited by a large amount of inorganic salts in the waste liquid, especially bromide ions, and the organic components remain, but most of these organic components are acetic acid, etc. , Which is a low molecular weight compound, and is capable of efficiently decomposing persistent components such as EDTA.

The catalyst active ingredient used in the present invention is
Iron, cobalt, manganese, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten, and oxides thereof, and also chlorides such as ruthenium dichloride and platinum dichloride, ruthenium sulfide, rhodium sulfide. Examples thereof include insoluble or sparingly soluble compounds such as sulfides in water, and one or more of these compounds are supported on a carrier. The active ingredient of the catalyst is alumina,
Granular carrier such as silica, silica-alumina, titania, zirconia, activated carbon or nickel, nickel-chromium,
It is used in a state of being supported on a metal porous granular carrier such as nickel-chromium-iron. In the present invention, the catalyst can be used in various shapes such as pellets, cylinders, honeycombs, crushed pieces, powders, etc. in addition to particles. The amount of the catalytically active component supported is usually 0.05 of the carrier weight.
Is about 25%, more preferably about 0.5% to 3%. The reactor used is of a fixed bed type, and the volume thereof is such that the space velocity of the liquid is about 0.3 to 12 liters / hour (empty tower standard), more preferably 1.0 to 4 liters / hour (empty tower). It is good to make it about (standard).

The structure in which the honeycomb carrier is used may have any shape such as a square, a pentagon, a hexagon and a circle. The area per unit capacity, the aperture ratio, etc. are not particularly limited, but usually an area per unit capacity of about 200 to 800 m ² / m ³ and an aperture ratio of about 40 to 80% is used. As the material of the honeycomb structure,
Examples include titania and zirconia.

The oxygen-containing gas used in the present invention is air, oxygen-enriched air, oxygen or the like. The amount of these gases fed is such that the organic and inorganic substances contained in the waste liquid and ammonia are nitrogen, carbon dioxide,
It can be calculated from the theoretical amount of oxygen required for oxidative decomposition into water, sulfuric acid and the like. Generally, 1.0 to 3.0 times, more preferably 1.05 to 2.2 times the theoretical oxygen amount is used. The oxygen-containing gas may be supplied all at once or may be supplied in multiple times.

The temperature during the reaction is usually 100 to 370 ° C, preferably 220 to 350 ° C. The pressure during the reaction may be at least the minimum pressure at which the waste liquid maintains a liquid phase at a predetermined reaction temperature, and the operation is preferably performed in the pressure range of 50 kg / cm ² to 170 kg / cm ² . The reaction time is 5 to 300 minutes, preferably 15 to 180 minutes.

The reactor used in the wet oxidation treatment of the present invention may be either a batch type using an autoclave or a flow type using a reaction tower, as long as it can withstand the temperature and pressure during the reaction. Since the photographic waste liquid generally has a strong property of corroding metals, it is preferable that the reactor is made of a material having excellent corrosion resistance such as a corrosion resistant alloy (SUS316 or the like) or a titanium material.
It is preferable that each of the reactors has a stirring means such as a stirring blade or a baffle plate so that the oxygen and the water to be treated are sufficiently brought into contact with each other.

When a waste liquid containing silver ions such as a silver recovery waste liquid is treated, precipitation of iron oxide or the like may occur,
In such a case, the iron content can be removed from the waste liquid by separating it by filtration. At this time, a polymer flocculant may be used to accelerate sedimentation separation. The pH of the waste liquid that has undergone the wet oxidation process is lower than that of the original waste liquid due to the oxidation of the components, and in many cases, it is strongly acidic. In such a case, an alkali is added to adjust the pH to 5-9. When iron ions still remain in the liquid after the previous step, they may be precipitated as iron hydroxide or the like, but in this case as well, the iron content can be removed by filtering and separating. Also in this case, a polymer flocculant may be used, or the precipitate generated in the previous step may be separated by filtration together with the precipitate generated in this step.

As the alkali to be added, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate or the like can be used. Further, these alkalis may be added in advance in an amount necessary to bring them into the pH range after the wet oxidation treatment before the treatment. The polymer flocculants that can be used in the present invention include those having anionic, nonionic or cationic charges. They neutralize the surface charge of suspended particles in water that are charged with opposite ions and destabilize individual particles to promote the aggregation phenomenon. Then, the active functional groups cause adsorption to the particles, and the interparticle crosslinking effect promotes the aggregation of the suspended particles and promotes the formation of giant blocks. As a material for the polymer flocculant, a material obtained by copolymerizing acrylamide or acrylic acid is generally used, and for example, DIC-A500 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) or the like can be used. (B) Step B: The treated water that has been subjected to the step A is subjected to a biooxidation treatment with a biota containing marine bacteria in a state where the inorganic salt concentration is 30 g or more per liter. As a result, the components still remaining after the wet oxidation treatment can be decomposed without dilution or with low dilution, so that the environmental load can be reduced extremely efficiently. Psevdomonas genus, Zo used in general sewage treatment plants
In a biota containing microorganisms such as Ogloea, a liquid containing an inorganic salt concentration of 30 g or more per liter cannot dissolve sludge in the biota.

In the treated water that has been subjected to the wet oxidation treatment, the organic matter is decomposed into a substance having a low molecular weight and good biodegradability, such as acetic acid, so that the biological treatment is promptly and efficiently performed.
Materials with poor biodegradability such as chelating agents such as EDTA are hardly treated by biological treatment, but can be biodegraded by performing wet oxidation treatment. That is, by adopting the constitution of the present invention, the drawbacks of the wet oxidation treatment (the biodegradable component BOD remains) and the drawbacks of the biological oxidation treatment (E
(There are some components that cannot be decomposed, such as DTA). This is an effect that cannot be obtained by performing each of the treatments independently.

As biota, Alcaligenes,
Aeromanas, Photobacterium,
Alteromonas, Micrococcus, F
Treatment is carried out with a biota containing marine bacteria such as the genus Lavobacterium. Marine bacteria may be collected from sea mud, sea sand, the surface of a seawater fish and shellfish aquaculture tank or its water purification device, and gradually added to the process A treated water at a low dilution rate with seawater for acclimatization. By this acclimation, the waste liquid having a high salt concentration can be stably treated. At this time, DO
(Dissolved oxygen) controller, DO 0.1
When the concentration is controlled to 0.5 mg / liter, nitrification and denitrification can be performed simultaneously due to the coexistence of marine nitrifying bacteria and facultative anaerobic denitrifying bacteria.

When the salt concentration is about 3%, a photosynthetic bacterium such as purple sulfur bacterium (for example, Chromatum vinosam) or purple red sulfur-free bacterium (for example, Rhodopseudomonas capsilatas) is used instead of the marine bacterium of the present invention. Itakoku Sho 45-12631, 50-27668 and 55
-13800, "Water and Drainage", Vol. 27, N
o. 11, 40-45 (1985), "Soil and microorganisms",
No. 17, 37-46 (1975), Japanese Journal of Soil Fertilizer Science, Vol. 46, No. 3, 101-109 (197).
5), the No. 4, 148-156 (1975), and aerated with 0.005～0.05M ³ air / m ³ wastewater / min etc. by biological wastewater treatment process performed while aeration Can be processed. In this case, the photosynthetic bacterium may coexist with a symbiotic bacterium. The treatment may be performed in a single tank or a plurality of treatment tanks, and usually a continuous activated sludge method may be used. The pH in the aeration tank is preferably 6 to 8.5, the photosynthetic bacterial cell yield is 0.5 to 5.0 g / liter, the average retention time of the liquid is 1 to 5 days, and the amount of dissolved oxygen in the waste liquid in the range of aeration conditions. Can be performed at 0.1 to 5 ppm.

When the waste liquid lacks the phosphorus content, phosphate (eg, KH ₂ PO ₄ , K ₂ HPO ₄ , NaH ₂ PO ₄ , 2) is added so that the phosphorus content is 0.5% to 3% of the COD value.
It is preferable to add H ₂ O and Na ₂ HPO ₄ ) before the treatment, because the biota becomes stable. Also, it is preferable to keep the pH during the treatment near neutral in order to keep the biota healthy,
The preferred pH range is 5.5 to 8.5. Furthermore, when a biota containing marine bacteria is used, it is 6.5 to 8.0.
Is particularly preferable. The pH is preferably kept as constant as possible by using a pH controller or the like when used.

Examples of the method for biooxidizing treatment in the present invention include an activated sludge method lagoon method, a filter bed method, a rotating disk method, and the like, but any method may be used if it is aerobically aerated or brought into contact with air or oxygen. Anything can be used. For more specific methods of these biological treatments, "Maintenance and management technology of activated sludge method" Toshiro Sakurai, Ryuichi Sudo author (Chemical Technology Development Center), "New activated sludge method" Sho Hashimoto, Ryuichi Sudo (industrial water survey Published).

Regarding the treatment method using marine bacteria and the acclimatization method of biota, pp. 183 (1991) of the Journal of Research on Hygiene Engineering, and "Ecology and Ecotechnology of Estuarine and Coastal Areas" edited by Yasushi Kurihara, Tokai University Press, page 259, etc. The photographic processing waste liquid applied to the present invention is mainly composed of the photographic processing liquid component, and the photographic processing waste liquid includes not only the materials added to the photographic processing liquid but also the oxidized product of the developing agent generated in the photographic processing process. , Sulfates, halides and other reaction products, trace amounts of gelatin dissolved from the light-sensitive material, and components such as surfactants.

The photographic processing liquid includes a color processing liquid, a black-and-white processing liquid, a depressurizing liquid for plate-making work, a development processing tank cleaning liquid, and the like. A black-and-white developing liquid, a color developing liquid, a fixing liquid, a bleaching liquid,
Examples thereof include a bleach-fixing solution and an image stabilizing solution. The color developing solution usually contains an aromatic primary amine color developing agent as a main component. It is mainly a p-phenylenediamine derivative, representative examples of which are N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-methyl-4- [N-ethyl-N- (β- Hydroxyethyl) amino] aniline, N-ethyl-N-
(Β-Methanesulfonamidoethyl) -3-methyl-4
-Aminoaniline. Further, these p-phenylenediamine derivatives are salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The content of the aromatic primary amine developing agent is about 0.5 per liter of developing solution.
The range is from g to about 10 g.

Further, 1-phenyl-3 is contained in the black and white developer.
-Pyrazolidone, 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone, N-methyl-p-aminophenol and its sulfate, hydroquinone and its sulfonate, etc. are included. Color and black and white developers usually contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite as preservatives, and carbonyl sulfite adducts. The content of these is 0 g to 5 g per liter of the developing solution.

Color and black-and-white developing solutions contain various hydroxylamines as preservatives. Hydroxylamines may be substituted or unsubstituted. Examples of the substituent include hydroxylamines in which the nitrogen atom is substituted with a lower alkyl group, particularly N, N-dialkyl-substituted hydroxylamines substituted with two alkyl groups (for example, 1 to 3 carbon atoms). Be done. Also used are combinations of N, N-dialkyl substituted hydroxylamines and alkanolamines such as triethanolamine. The content of hydroxylamines is 0 to 5 g per liter of developer.

The color and black and white developers have a pH of 9-12. Various buffers are used to maintain the above pH. As the buffer, carbon salt, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,5-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1,3-propanediol salt, valine salt, proline salt, trishydrocyaminomethane salt, lysine salt and the like can be used. Particularly, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in a high pH range of pH 9.0 or higher, and even if added to a developing solution, they adversely affect photographic performance. These buffers are often used because they have the advantages of being free from (fogging, etc.) and being inexpensive. The amount of the buffering agent added to the developer is usually 0.1 mol to 1 mol per liter of the developer.

In addition, various chelating agents are added to the developing solution as a precipitation preventing agent for calcium and magnesium or for improving the stability of the developing solution. As typical examples thereof, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, nitrilo-N, N, N-trimethylenemethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3-diamino-2. -Propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, 1,3-
Diaminopropane tetraacetic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid etc. can be mentioned. Two or more of these chelating agents may be used in combination as necessary.

The developing solution contains various development accelerators.
As the development accelerator, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-
Aminophenols, amine compounds, polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, thione compounds, imidazoles and the like.

Many color developing solutions for color paper are
It contains alkylene glycols and benzyl alcohols together with the above color developing agents, sulfites, hydroxylamine salts, carbonates, water softeners and the like. On the other hand, color negative developers, color positive developers, and some color paper developers do not contain these alcohols.

The developing solution often contains bromine ions for the purpose of preventing fogging, but a developing solution containing no bromine ions may be used for a light-sensitive material mainly containing silver chloride. is there. In addition, a compound that gives chlorine ions such as NaCl or KCl may be contained as an inorganic antifoggant. In addition, it often contains various organic antifoggants. The organic antifoggant may contain, for example, adenines, benzimidazoles, benztriazoles and tetrazoles.
The content of these antifoggants is 0.010 to 2 g per liter of the developing solution. These antifoggants include those which are eluted from the light-sensitive material during processing and accumulated in the developing solution. Particularly, in the present invention, the total halogen ion concentration such as bromine ion and chlorine ion as described above is the mixed solution 1
It is possible to effectively treat even a waste liquid having a concentration of 1 mmol or more per liter. It is particularly effective when the bromine ion concentration is 1 mmol or more per liter of the mixed solution.

The developer contains various surfactants such as alkylphosphonic acid, arylphosphonic acid, fatty acid carboxylic acid and aromatic carboxylic acid. In black-and-white photographic processing, fixing processing is performed after development processing. In color photographic processing, a bleaching process is usually performed between the developing process and the fixing process, and the bleaching process may be performed by bleach-fixing (brix) at the same time as the fixing process.
The bleaching solution contains iron (III) or Co (II) as an oxidizing agent.
I) EDTA, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-propanetetraacetic acid salt, phosphonocarboxylic acid salt, as well as persulfate and quinones are included. In addition, alkali bromide, a rehalogenating agent such as ammonium bromide, borate salts, carbonates, and nitrates may be optionally contained. For fixers and bleach-fixers, thiosulfate (sodium salt, ammonium salt),
It contains acetate, borate, ammonium or potassium alum sulfite.

In the processing of silver halide photographic light-sensitive materials, it is common to carry out a fixing process or a bleach-fixing process, followed by washing with water and / or a stabilizing process. In the water-washing process, there are cases in which bacteria propagate in the processing tank and the floating substances formed adhere to the photosensitive material. As a solution to such a problem, it is possible to use washing water with calcium ions described in JP-A-61-131632.
A method of reducing magnesium ions can be used. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-57-8542, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the bactericides described in "Technology for Sterilization, Sterilization, and Antifungal of Microorganisms" edited by the Society of Hygiene and Technology, and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents.

Following the washing treatment with such washing water, or in place of the washing treatment, a stabilizing treatment with a stabilizing bath may be performed. An example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The method according to the present invention can also be applied to a processing waste liquid generated during the development processing of a PS plate (photosensitive lithographic plate) used as a printing plate. Further, these may be a mixed waste liquid with the waste liquid of the silver halide photographic light-sensitive material.

[0039]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. [Explanation of Waste Liquid Used] Commercially available photographed multilayer color negative film, Fuji Color SUPER HG (hereinafter, referred to as SHG
-) 100, SHG-200, SHG-400, SHG
-1600, REALA (hereinafter, trade name, manufactured by Fuji Photo Film Co., Ltd.), Kodacolor GOLD (hereinafter, GOLD-) 1
00, GOLD-200, GOLD-400, GOLD
-1600, Ector 25, Ector 125, Ecter 1000 (all trade names, manufactured by Eastman Kodak Company),
Konica Color GX (hereinafter GX-) 100, GX-20
0, GX-400, GX-3200, Konica Color GX
II (hereinafter, GXII-) 100, GX-100M (hereinafter, trade name, manufactured by Konica), without any particular distinction, by mixing them in succession and sequentially using a minilab film processor F
P900AL (trade name, manufactured by Fuji Photo Film Co., Ltd.) was used as a processing solution, and CN-16Q (trade name, manufactured by Fuji Photo Film Co., Ltd.) was used for development processing for color negative. At this time, the overflow solution of the developing bath and the washing bath was used as the color negative developing system waste solution, and the overflow solution of the bleaching bath and the fixing bath were used as the color negative bleaching / fixing system waste solution. Commercially available color paper (Fuji color paper SUPER, F
A, Fuji Photo Film Co., Ltd.) is printed and printed from the color negative, and Fuji Mini Lab Champion FA-1
70 printer processors PP1800B (trade name,
Fuji Photo Film Co., Ltd.) and treated CP-43FA (trade name, manufactured by Fuji Photo Film Co.) for color paper as a treatment liquid. The overflow solution of the developing bath at this time was used as a color paper developing system waste solution, and the overflow solutions of the bleach-fixing bath and the washing bath were used as a color paper bleach-fixing system waste solution.

A 1: 1 mixture of a color negative developing system waste solution and a color paper developing system waste solution is used as a color developing system waste solution, and a color negative bleaching / fixing system waste solution and a color paper bleaching / fixing system waste solution are mixed 1: 1. Was used as a color bleaching / fixing system waste liquid. Commercially available black-and-white negative film Neovan SS, Neovan 400 PRESTO, Neovan 1600 SUPER PRESTO (these product names, made by Fuji Photo Film Co., Ltd.) are mixed in various ways and the developer Fujidor and the fixer Fujifix (or more products) 5 liters of waste liquid treated with Fuji Photo Film Co., Ltd.) and a commercial black-and-white paper (Fuji Pro WP Fuji Photo Film Co., Ltd.) are printed from the negative, and the developer collector and fixer Fuji Fix are printed. (Hereinafter, trade name, manufactured by Fuji Photo Film Co., Ltd.), each containing 5 liters of waste liquid, medical X-ray sensitive material, MI-SF and MI-SFI
I (above product name, made by Fuji Photo Film Co., Ltd.)
-3 and a fixing solution Fuji-F (these product names, manufactured by Fuji Photo Film Co., Ltd.) each containing 10 liters of waste solution and a developing solution GR-D1 and a fixing solution GR- of the printing material system Fuji GRADEX series. 10 liters of each of the waste liquids of F1 (trade name, manufactured by Fuji Photo Film Co., Ltd.) are divided into a developing solution and a fixing solution, and mixed, respectively.
The volume was set to 0 liter, and this was used as a black-and-white developing system waste liquid and a black-and-white fixing system waste liquid.

The color developing system waste liquid and the black and white developing system waste liquid were mixed at a ratio of 1: 1 to obtain a developing system waste liquid. Also, color bleaching / fixing system waste liquid and black-and-white fixing system waste liquid are mixed at 1: 1,
The silver recovery system waste liquid was subjected to the silver recovery process. In this embodiment, a processing solution obtained by mixing the developing system waste solution and the silver recovery system waste solution in a ratio of 1: 1 was used. The analysis results of this mixed solution are shown in Table 1.
Shown in. The concentration of inorganic salts in this liquid was 12%. The TOD value, which is an index as a theoretical oxygen amount required for oxidative decomposition, was 82000 mg per liter of waste liquid.

Example 1 (a) The waste water was treated with a space velocity of 0.67 Hr ^-1 (vacant tower standard).
As the lower part of the cylindrical reaction tower (made of titanium clad). The mass velocity of the liquid is 5.7 tons / m ² · hour. On the other hand, an oxygen-containing gas is supplied to the lower part of the cylindrical reaction tower as a space velocity of 100 Hr ^-1 (blank column reference, standard state conversion).
These were adjusted so that 1.5 times the theoretical amount of oxygen was supplied. Ruthenium 2 was used as the titania carrier in the reactor.
It is filled with a spherical catalyst having a diameter of 5 mm and supporting wt%.

Inside the reaction tower, the temperature is 270 ° C. and the pressure is 86 kg.
The reaction was carried out while maintaining the temperature at / cm ² . The gas-liquid mixed phase after completion of the catalytic reaction was sequentially withdrawn from the upper part of the reaction tower, introduced into a gas-liquid separator, and the separated gas phase and liquid phase were cooled and then taken out of the system. The separated liquid phase was treated water 1, and the analysis results are shown in Table 1. (B) The treated water that had been subjected to the same operation (step A) as in (a) was subjected to a biological oxidation treatment by the following operation (step B).

Phosphorus in the form of dipotassium hydrogen phosphate was added to the treated water after the preceding step in an amount corresponding to 1% of the COD value, and 10% of seawater was added to supplement the deficient nutrient salt. The biological tank separated from the submerged filter in the purifier of seawater fish tank is planted and placed in the aeration tank, and the above waste liquid is used, and the average residence time is shortened every 20 days to 20 days, 10 days, 5 days. The sludge was acclimated by the continuous activated sludge method. The pH in the aeration tank is 8.0 ± 0.1 and the DO is 0.5 mg.
/ Liter. Inorganic salt concentration of waste liquid is 13%
The C value was 3800 ppm and the COD value was 1350 ppm. The sludge concentration (MLSS) was 30,000 ppm. At this time, when the contained organisms were fixed, Alter
Omonas haloplanktis was detected. Further, the retention time of the waste liquid is set to 2 days, and the treated water after the continuous biological treatment has reached a steady state is treated water 2 of step (B), and is shown in Table 2.

Example 2 Treated water which had been subjected to the same operation as in Example 1 (a) was diluted by a factor of 2 and treated in the same manner as in Example 1 (b) to obtain treated water. This treated water is referred to as treated water 3 and is shown in Table 2. Regarding treated water 1, TOC and COD components remain, but treated water 2,
For 3, the TOC and COD components were removed very efficiently.

Ammonia and TN could also be removed at the same time. [Comparative Example] The same operation as in (a) of Example 1 was performed. The treated water was subjected to the following biological oxidation treatment.
That is, the treated water is diluted 1 time, 2 times, 5 times with tap water, and phosphorus is in the form of dipotassium hydrogen phosphate at 1% of the COD value, and calcium ion and magnesium ion are added at 10 pp each.
m was added so that the concentration would be 2 ppm. Seed sludge is activated sludge used in sewage treatment plants (Zooloolea genus, Ps
bacterium of the genus Eudomonas is contained). The waste liquid was acclimated to the activated sludge by gradually shortening the average residence time. The treatment was based on the continuous activated sludge method. PH in the aeration tank is 7.0 ± 0.1, DO is 0.5
It was kept at mg / l. The treated waters obtained by this biological treatment are designated as treated waters 4, 5 and 6, respectively, and shown in Table 2.

Since the salt concentrations of the treated waters 4 and 5 were too high, the sludge was dismantled and treatment became impossible. The treated water 6 had a salt concentration of 2.6%, but the sludge was somewhat dismantled and suspended substances in the treated water increased. For this reason, it is necessary to dilute at least 5 times or more in the usual activated sludge treatment, and there is a concern that the equipment will increase. Example 3 The reaction was performed in the same manner as in Example 1 (a) except that the reaction was performed at a space velocity of 1.0 Hr ⁻¹ . This treated water is referred to as treated water 7. Using this treated water, treated water 8 was obtained by performing the same operation except that the residence time in Example 1 (b) was set to 5 days. Further, treated water 9 was obtained by the same operation except that the residence time in Example 2 was changed to 5 days. Table 1 shows the treated water 7, and Table 3 shows the treated waters 8 and 9. With this treatment, it was possible to obtain the same water quality as in Example 1 with respect to the removal of COD components. The sludge condition was good in all treatments.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

EFFECTS OF THE INVENTION By using the processing method of the present invention, the COD value, TOC value and ammonia nitrogen content of a photographic waste liquid containing both organic and inorganic COD components and ammonia can be reduced economically at a very high removal rate. be able to.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsuko Takahashi 210 Nakanishuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Inventor Hiroshi Ishizuka, 210 Nakanuma, Minami Ashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Inventor Kiyotaka Hori 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A photographic waste liquid containing an organic substance and an inorganic substance, having an inorganic salt concentration of 30 g or more per liter of waste liquid and a bromide ion concentration of 1 g or more per liter, of the following (A) and (B). A method for treating a photographic waste liquid, which comprises performing the treatment in the order of. (A) Iron, cobalt, manganese, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten while keeping the photographic waste liquid at a temperature of 100 to 370 ° C. and a pressure at which the waste liquid holds a liquid phase. In addition, in the presence of a catalyst body carrying at least one of these water-insoluble or sparingly soluble compounds of metals, the amount of oxygen necessary for decomposing ammonia, organic substances and inorganic substances in the waste liquid is reduced. Wet oxidation is performed under the supply of the contained gas (step A). (B) The treated water that has been subjected to the step A is subjected to a biooxidation treatment with a biota containing marine bacteria in a state where the inorganic salt concentration is 30 g or more per liter (step B).