JPS63143992A - Treatment of waste liquid from photographic process and apparatus thereof - Google Patents

Abstract

PURPOSE:To effectively remove offensive odor, by heating, evaporating and concentrating waste liquid under the existence of metal such as Fe, Ba, Zn and Ni or oxide and salt thereof. CONSTITUTION:Waste liquid is fed to an evaporation tank 3 via a feed pipe 1A thereof and metal such as Fe, Ba, Zn, Ni and Cu or oxide such as FeO, ZnO, NiO and CuO or metallic salt such as FeCl3, ZnCl2, NiCl2 and CuSO4 is added at 0.0001-3.0mol/l expressed in terms of metal. The mixture is heated and evaporated in such a state that the pH of waste liquid is maintained at 3.0-11.0. A pH regulating agent is fed from a tank 13 thereof with a pump 14 for the pH regulating agent. As a heating means, an electric heater or the like is preferably provided to the inside of the evaporation tank 3. Thereby the load of secondary treatment can be remarkably decreased.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention aims to eliminate bad odors during heating and evaporation treatment of waste liquid (herein referred to as photographic processing waste liquid or waste liquid) generated during the processing of photographic light-sensitive materials using automatic photographic processors. The present invention relates to methods and devices suitable for effective suppression. [Background of the invention] In recent years, stabilization treatments have been used to reduce the amount of replenishment and replace washing with water.
With the spread of photographic processing using so-called waterless automatic processors that do not substantially require water washing, the amount of waste liquid has been significantly reduced. However, even with such low-replenishment and water-free photographic processing, even relatively small-scale processing is possible, for example, in the processing of X-ray photosensitive materials, the amount of 1 O exchange per day is about 1, and in the processing of photosensitive materials for printing plate making, it is about 1
Approximately 301 waste liquids are generated per day, and approximately 50 waste liquids are generated per day in the processing of color photosensitive materials, and their disposal becomes a problem. The inventor has discovered that a small amount and a high concentration (e.g. BOD 20,00
0-30. OOOppm, NH4' 20,000
N40. We discovered that the evaporation method is an excellent way to efficiently treat photographic processing waste liquid (approximately OOppm), and have made various proposals (Japanese Patent Application No. 80-2511001~
259010, Japanese Patent Application No. 81-132098, Japanese Patent Application No. 61-185099, Japanese Patent Application No. 81-185100, etc.). However, in this heating/evaporation method, sulfur dioxide gas, hydrogen sulfide gas, sulfur gas, etc.
There was a problem in that a bad odor was generated due to ammonia gas, etc., and the process could not be completed unless this problem was solved. As a conventional measure against such bad odors, Japanese Utility Model Application Publication No. 80-70841 proposes a method in which an adsorption treatment section is provided in the 4J trachea. However, this method is based on the same technical concept as conventional exhaust gas treatment in that it attempts to treat the emitted foul-smelling gas at the end (immediately before it is emitted outside the system; the same applies hereinafter). 1. It was inappropriate as a gas treatment facility to be added to a small-scale waste liquid treatment facility such as the one of the present invention. In other words, it is generally thought that malodorous gases can be treated with equipment such as adsorption if the problem of condensation is solved (although this varies depending on the components), but the concentration of malodorous gases in the exhaust gas that is evaporated from photographic waste liquid is extremely high. Attempting to adsorb and treat this highly concentrated foul-smelling gas would quickly saturate the adsorbent, incurring huge running costs, and requiring frequent replacement of the adsorbent, making it extremely complicated. Furthermore, in order to reduce the replacement work, it is necessary to increase the size of the adsorption tower, resulting in an increase in equipment cost. [Object of the Invention] The present invention solves the drawbacks of the prior art. The purpose of the present invention is to provide a method and a device for efficiently suppressing bad odors without increasing costs or requiring complicated work. [Means for solving problems] The present inventors have made extensive studies to achieve the above object, and as a result, have arrived at the present invention. That is, the method for treating photographic processing waste liquid according to the present invention is: The following metals (1) to (3) (hereinafter referred to as the metal of the present invention), a method for processing a photographic processing waste liquid is characterized by heating, evaporating and concentrating the photographic processing waste liquid in the presence of at least one of the following. [Total bending etc.] (1) Fe , Ha, Zn, Ni, [:u, Sn
, Bi, Co, Cr, Ce. ? (2) Oxides of the above metals (3) Salts of the above metals In a preferred embodiment of the present invention, the photographic processing waste solution contains thiosulfate ions (for example ammonium thiosulfate). and further contains silver ions in addition to thiosulfate ions. Further, the processing apparatus for photographic processing waste liquid according to the present invention has a means for supplying the photographic processing waste liquid, an evaporation tank for receiving the waste liquid, and a heating means for heating the waste liquid in the evaporation tank, and includes heating means for heating the waste liquid in the evaporation tank. In a processing device for photographic processing waste liquid that evaporates and evaporates,
It is characterized in that it has a means for making the photographic processing waste liquid contain at least one kind of metal or the like of the present invention. [Function] The present invention is a technical idea based on an idea completely opposite to the conventional technical idea of treating emitted malodorous gas at the end,
Focusing on the source of the odor, the present invention provides a method of countermeasures against odor that has almost never been attempted before. That is, the photographic processing waste liquid contains a large amount of salts of sulfur compounds (particularly thiosulfate ions, etc.), and the foul odor of H2S is generated during the evaporation concentration process and from the distillate. Furthermore, H2S eventually sulfurizes and becomes S, which can clog pipes or make the distillate cloudy. Furthermore, if the pH of the distillate increases, there will be a foul odor from amines and ammonia. The inventors of the present invention have conducted extensive studies to solve problems such as bad odors, and have found that H2S, S It has been found that the odor associated with ammonia can be suppressed, and problems such as thirst associated with S can be solved. The cause of this is not clear, but the metals unique to the present invention produce hydroxides in the heated waste liquid, resulting in H2S. This is presumed to be because it exhibits the effect of suppressing the generation of S gas, forms a complex salt with ammonia to suppress the outflow of ammonia gas, and further forms sulfides to suppress the outflow of S. [Example] Hereinafter, an example of the method of suppressing a bad odor will be described based on the accompanying drawings. FIG. 1 is a conceptual diagram showing an example of a method for suppressing bad odor. In the figure, 1 is a supply means for photographic processing waste liquid, and LA is a waste liquid supply pipe used in the supply means 1. 2 is a preheater for preheating the photographic processing waste liquid before heating; 3
is an evaporation tank; 4 is a heating means, such as a heater; 5 is a steam exhaust pipe for discharging steam generated when the waste liquid in the evaporation tank 3 is heated to the outside of the evaporation tank 3; and 6 is for cooling the nozzle air. gas cooler. 7 is a gas cooler fan, 8 is a distillate tank for storing the distillate obtained by cooling the incoming air, 9 is a circulation fan for returning the dehumidified gas to the evaporation tank, and A is the main body. It is a means for containing the metal etc. of the invention, for example, a metal etc. dissolution tank lO2 metal etc. dissolution supply pump 11. It consists of a metal etc. supply pipe 12 and the like. B is a means for supplying a pH adjuster to the photographic processing waste liquid; for example, p) I adjuster tank 13, pH 2g1;
Regulatory pump +4. p) Consists of l regulator supply pipe 15, pH controller PHC, etc. TO is a temperature controller. To explain the outline of the heating and evaporation process using the above-mentioned device, the waste liquid is passed through the waste liquid supply pipe IA to the evaporation tank 3.
The metal of the present invention and the like are added thereto, and heated and evaporated by the heater 4. During this time, the pH of the concentrate was 3.0~
It is preferably maintained at 11.0, more preferably between 4.0 and 8.0, and even more preferably between 5.0 and 7.0. The heating temperature is appropriately adjusted by a temperature controller TC. 7 Popular is heat exchange with waste liquid in preheater 2, gas cooler 6
It is cooled and humidity-controlled, and the distillate is separated. The distilled liquid is stored in the distilled liquid tank 8, so that it does not give off a bad odor.
Furthermore, since it satisfies wastewater regulation values such as ROD, COD, and SS, it can be discharged into rivers or reused as necessary. The gas from which the distillate is separated does not give off a bad odor and does not contain any problematic components, so it can be discharged from the system. On the other hand, the volume of the waste liquid in the developing tank decreases with the passage of heating and evaporation time, and elIi'! be done. The heater 4 for heating is stopped by the operation of a timer, for example, and the heating is completed. The remaining 'cwj liquid is discharged outside the system. Next, a method for suppressing bad odor, which is an embodiment of the present invention, will be specifically described. As the metal of the present invention, at least one selected from the following metals (1) to (3) is used. [Metals, etc.] (1) Fe, Ba, Zn, Ni, Cu, Sn, Bi,
Go, Or, Ce, Ti. Metals consisting of Zr, Mo, and W (2) Oxides of the above metals (3) Salts of the above metals (e.g. chlorides, sulfates, nitrates, carbonates, phosphoric acids, etc.) of the above (+) to (3) Among metals, Fe, Zn,
Mi. Metal oxides and metal salts of Cu are preferred, and metal oxides and metal salts of Fe and Zn are more preferred. As a specific example of the metal oxide in (2) above, for example, 1fF
e203. Fen, ZnO, Nip, Cuo,
Cu70. Sno. Bi2O+, Cod, Cr21h, CI! 203
．． 7in? , ZrO;
SOs)3. FeC12, Fe5Os, ZnC12
゜ZnSO4, NiC12, N15Oa, CuSO4
,Cu2'JOa, 5nC12゜Bi(413,Co
CJl 2. Cr(NOz)x, Cez(SO4)
3. Ti09O4゜Zr(SOs)2. Na2M03
Examples include 0+e, Na+oW+20a+, and the like. The amount of metal etc. added in the present invention is 0.0001 to 3.0■
ol/i (as metal) is preferred, more preferably 0.001 to 2.0+sol/JL, particularly preferably 0.005 to 1.0 aol/4. The metal etc. of the present invention may be added in advance to the waste liquid supplied to the evaporation tank, or may be added after being supplied to the evaporation tank, or when added into the evaporation tank, heating and evaporation start. In addition, the metal of the present invention may be placed in the evaporation tank and then the photographic processing waste liquid may be supplied. In this case, the metal of the present invention is filled in a mesh container and placed in the evaporation tank. You can also leave it hanging. When adding externally to the evaporation tank 1 When the metal etc. of the present invention is a liquid, it can be added separately from the waste liquid using the metal etc. supply pump 1K from the metal etc. dissolution tank 1G as shown in Fig. 1. Also, when the metal of the present invention is a solid such as a powder, it may be added directly to the evaporation tank, or it may be added as a solution after being dissolved once in the tank 10 shown in FIG. 1. When using two or more types of metals, etc. of the present invention, it is preferable to provide multiple tanks for each additive metal, hA, etc., when externally adding them from a tank as shown in Figure 1. However, depending on the physical properties of the metals, etc. may be shared in one tank. In the present invention, the pH of the waste liquid (concentrated liquid) is preferably 3.
．． 0-11.0. By heating and evaporating while maintaining the temperature more preferably at 4.0 to 8.0, particularly preferably 5.0 to 7.0, malodors can be suppressed more effectively. Normally, the pH of waste liquid varies depending on the type of waste liquid, but if it is a fixer containing thiosulfate ions (e.g. ammonium thiosulfate) or sulfite ions (e.g. ammonium sulfite) and has a low pH, the pH may be quite low (e.g. p
H3 to 4), and if a color developing solution with a high pH is mixed in, the pH of this mixed waste solution will be slightly higher than neutral (
For example, it is considered to be at a pH of about 7 to 8). When these waste liquids are heated in the evaporator Mas, they cause pH fluctuations (mainly decreases), and pH regulators are used to control this pH fluctuation. The pH adjusting agent that can be used in the present invention is a adjusting agent in a broad sense, and is not necessarily clearly classified, but includes, for example, (I) a compound that imparts buffering properties to the waste liquid against pH fluctuations, (■) Examples include compounds that control (mainly increase) the pH by external addition in response to fluctuations (mainly decrease) in p)I during the evaporation process. Examples of compounds in (1) above include (1) metal oxides, metal hydroxides, or metal salts such as (1) Ca, Mg, AIL, Fe, Zn, etc.

Compound (2) which liberates p
Compounds that dissolve and become alkaline as H decreases (
3) Buffers such as organic m (e.g. citric acid, etc.) and their salts (0) Buffers such as inorganic m (e.g. boric acid, phosphoric acid, etc.) and their salts (5) E [7 Minocarboxylic acids such as TA Chelating agent (8) 1-tnitroxyethylidene-1,1-diphosphonic acid and the like can be mentioned, and one or more of these can be used in combination. Further, as the compound (II) above, for example ( 1) N
a0)1. Hydroxide of alkali metal or alkaline earth metal such as KOH, Ca(OH)2, etc. (2) Carbonate (3) Silicate (e.g. sodium silicate etc.) (4) Phosphate (5) Boric acid Salt (8) (Alkaline earth metal salts such as a salt and N8 salt (7)
Examples include various acids such as organic acids and inorganic acids (used when pH increases), and these acids can be used alone or in combination of two or more. In the present invention, where is the pH adjuster added? In the case of the compound (I) above, it is sufficient that it is added in advance before heating, so it may be contained in the waste liquid before being supplied to the evaporation tank 3, or after being supplied to the evaporation tank.
It may be added externally before the start of heating, and the above (■
), it goes without saying that it is supplied to the evaporation tank 3 from the outside. p) When supplying the adjuster from the outside, it may be supplied from the pHyA adjuster tank 13 with the pH adjuster pump 14 as shown in FIG. 1, or it may be supplied without using the pH adjuster pump 14. Alternatively, the tank 13 may be installed above the evaporation tank 3 to supply water with head pressure. In the present invention, when the p)l regulator is a liquid, it can be added, for example, as shown in Figure 1, but when it is a solid, the solid may be added directly to the waste liquid or concentrated liquid. Alternatively, it may be dissolved in a tank in advance and added as shown in the m1 diagram. When using two or more types of PH adjusters in the present invention, the first
As shown in the figure, when adding externally from a tank, it is preferable to provide a plurality of tanks for each additive compound, but depending on the physical properties of the compound, one tank may be used in common. In the present invention, as shown in FIG. 1, when externally adding a pHX18J regulator, the amount of addition can be controlled by a pH controller (7) signal.
When the pH within the tank decreases with the passage of heating and evaporation time, the pump 13 is turned on by a signal from the controller,
A pHI modifier can be provided. In addition, when the pump 13 is of a stroke adjustable type, the stroke can also be automatically adjusted. How to effectively suppress bad odor in the present invention. It is preferable to adjust the amount of heat supplied from the heater 4 in the evaporation tank 3. In other words, if the amount of heat applied per unit time is increased, the thiosulfate will crystallize before it decomposes and will not be released to the outside. Offensive odors can be suppressed, but on the other hand, when the amount of 8 added is small, decomposition is promoted and the outflow of substances that cause offensive odors is activated. Although an example of a method for suppressing a bad odor and a device thereof has been described above, the present invention is not limited thereto, and the scope of the present invention includes various embodiments, and the main embodiments thereof are listed below. Note that aspects other than the following may be applied to existing applications (for example, Japanese Patent Application No. 259
No. 001 to No. 25i3010, patent application No. 81-13209
No. 8, Patent Application No. 1881-1850H, Patent Application No. 1885-1983
100 etc.) can be referred to. (1) The present invention works particularly effectively when the photographic processing waste solution of the present invention contains thiosulfate ions (for example, ammonium thiosulfate), and the concentration of the thiosulfate ions is 5 to 500% in the case of ammonium thiosulfate. Examples of the types of waste liquids for which gin is preferable include mixed waste liquids of a color developing solution and a bleach-fixing solution or a stabilizing solution, or waste liquids of a bleach-fixing solution or a fixing solution alone. The present invention works particularly effectively when the waste liquid contains silver ions, and the concentration thereof is preferably in the range of 0.01 to 50 g/ml. In addition, the present invention is preferably applied to the treatment of small-volume waste liquids such as waterless automatic processors, etc. Here, small capacity refers to J! It is used as a precaution, and refers to a particular number (/i, although not limited to 1, for example, about 1/D to 1000M/D. (2) In the present invention, waste liquid is supplied to the evaporation tank 3. Possible means include pumping up and supplying from a waste liquid tank (not shown), supplying using head pressure, and other methods of supplying by hand. Also, waste liquid can be supplied either continuously or discontinuously. This often depends on whether the evaporation process is continuous or batchwise.Furthermore, the waste liquid may be supplied in liquid form, or may be supplied in spray form.(3) In the present invention, evaporation 41!I3 is not supplied. This is a tank that heats the waste liquid and evaporates a part of it to concentrate the waste liquid and reduce the amount of waste liquid to be disposed of. In this specification, concentration means to reduce the volume of waste liquid after evaporation to the value of the evaporation curve. The volume should be reduced to 1/4 or less, preferably 1/5 or less, and most preferably 1/10.In addition, the present invention is applicable when all (including substantially all) of the waste liquid is evaporated to dryness. The form of the evaporation tank 3 is not particularly limited, but the outer tank (
It is preferable that it has a double structure of an outer pot (outer pot) and an inner tank (inner pot), and the inner tank is removably formed, for example, by a resin bag. ) is preferably provided, and a hinged opening/closing lid is preferably provided at the top of the evaporation tank 3. (4) In the present invention, the heating means is not particularly limited, and FIG. 1 shows a heater heating method as an example thereof. Heaters include, for example, electric heaters, nichrome wire heaters with built-in quartz tubes, ceramic heaters, etc., and it is preferable to install these inside the evaporation tank 3 as shown in the figure. It is also possible to employ a dielectric heating method as described above, or a combination of these methods may be used. Note that the heating by the heater may be stopped by operating a timer, but is not limited to this. For example, the liquid level of the concentrated liquid may be detected by a level sensor. Heating may be stopped based on the detection signal. (5) In the present invention, the evaporated gas is cooled using, for example, a gas cooler 6, but any cooling means may be used. In order to achieve the purpose of the present invention, forced cooling is not a wood-based requirement; distillate is generated by natural cooling,
The scope of the present invention also includes cases where the product is discarded. In the present invention, after cooling, a distillate that is not cloudy, has no problems such as odor, and contains ammonium salts such as ammonium sulfite is obtained, and can be used as a photographic processing solution (for example, water dissolved in a replenisher) in an automatic processor. In addition to water submersion), it can also be reused as fertilizer, etc. (6) After cooling and humidity conditioning, the gas is suppressed to the extent that almost no foul odor is felt, but in order to eliminate the foul odor more completely, it is also preferable to use an adsorbent such as activated carbon. This method is advantageous in that it does not require the conventional method of processing high-concentration malodorous gases (e.g., saturation occurs quickly, the complexity of replacement work, etc.), and it also has the advantage of eliminating the above-mentioned malodor control. It is excellent in that it functions effectively as a pretreatment such as adsorption treatment where the means is provided at the end. [Experimental Example] The following experimental example was conducted using the photographic processing waste liquid shown below. (Negative Film Processing) After exposing SR-V100 film (manufactured by Konishiroku Photo Industry Co., Ltd.), the negative film was continuously processed using the following processing steps and processing liquid. Processing process Processing temperature Processing time Color development 38℃ 3 minutes 15 seconds bleaching
White 38℃ constant for 3 minutes 15 seconds
Arrive 38℃ 3 minutes 15 seconds 1st
Stability 1st tank 32℃~38℃ 1 minute 1st stability 2nd
Tank 32℃~38℃ 1 minute second stabilization
Dry at 38℃ for about 1 minute 4
5℃～65℃ [Color developer] Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite
5g1-hydroxyethylidene-
! , l-diphosphonic acid (80%) 1.0g Sodium bromide 1.3g Potassium iodide 2sg Hydroxylamine sulfate 2.5g Sodium chloride
0.6 g 4-amino-3-methyl-ethylate (β-hydroxylethyl) aniline sulfate 4.8 g potassium hydroxide 1.2 g ，
Adjust to 08. [Color developer replenisher] Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.9g! -Hydroxyethylidene-1.1- Diphosphonic acid (60%) 1.2g Hydroxylamine sulfate a! 3.1g 4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl) Aniline sulfate kM 8.0g Potassium hydroxide 2g Add water to make 11, and use potassium hydroxide or 20% sulfuric acid to make p
Adjust to H10,12. [Bleach solution] Iron ammonium ethylenediaminetetraacetate 180g Disodium ethylenediaminetetraacetate 10g Ammonium bromide 150g Glacial acetic acid
Add 101 ml of water to make 1 ml and adjust to p)l 5.8 using aqueous ammonia or glacial acetic acid. [l)j White replenisher] Iron ammonium ethylenediaminetetraacetate 170g Disodium ethylenediaminetetraacetate 12g Ammonium culture 178g Glacial acetic acid
Add 21m water to make 11, and use ammonia water or glacial acetic acid to make p)+5. Adjust to fi. [Fixer] Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate 0.5g Sodium carbonate 10g Add water to make 11,
Adjust p)I to 7.0 using aqueous ammonia or glacial acetic acid. [Joseki replenisher] Ammonium thiosulfate 300g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Ethylenedi7mine disodium tetraacetate 0.8g Sodium carbonate 14g Add water to make one sentence, and adjust to pH 7.5 using aqueous ammonia or glacial acetic acid. adjust. [First stable solution and first stable replenisher] 5-chloro-2-methyl-4-isothiazolin-3-one Q, 02° 2-year old cutyl-4-inthiazolin-3-one 0.02g ethylene glycol 1 Make up to 1 sentence with .0g water and adjust the pH to 7.0 with 20% sulfuric acid. [Second Stable Solution and Second Stable Replenisher] Formalin (37% aqueous solution) Add 2 m of Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) and make 1 solution. The color developer replenisher is used for color negative film 1oOcrn'
Replenish the color developing bath with 13.5++ per 100 crn of color negative film, and the bleach replenisher is 5.5+ per 100 crn' of color negative film.
JL is replenished into the bleach bath, the fixing replenishment wave replenishes the fixing bath with 8 layers per 100 crn of color negative film, and the first stable replenisher replenishes the fixing bath with 8 layers per 100 crn of color negative film.
The first stabilizing bath was replenished with 81 grams per 100 crrf of color negative film, and the second stabilizing bath was replenished with +50 aJL R per 100 crrf of color negative film. (Paper Processing) Next, after printing on Sakura Color SR Paper (manufactured by Konishiroku Photo Industry Co., Ltd.), continuous processing was performed using the following processing steps and processing liquid. (Semi-processing step (+) Color development 38°C 3 minutes 30 seconds (2) Bleaching room -
;77 38°C 1 minute 30 seconds (3) Stabilization treatment 25°C to 35°C 3 minutes (4) Drying 75°C
～100℃ for about 2 minutes Processing solution composition [Color developing tank solution] Benzyl alcohol 15-layer ethylene glycol 15-layer potassium sulfite 2.0g Potassium bromide
1.3g sodium chloride
0-. 2g potassium carbonate
24.0゜3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate a! 4.5゜Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) (trade name Keikol PK-Conc (manufactured by Shin Nisso Kako Co., Ltd.)) 1.0g Hydroxylamine sulfate 3.0g 1-Hydroxyethylidene -1,1- Niphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride Φ hexahydrate 0.7g 1.2-Hydroxybenzene-3,5-disulfonic acid disodium salt
Add 0.28 water to make one sentence, and adjust the pH to 10.20 with potassium hydroxide and sulfuric acid. [Color developer replenisher] Benzyl alcohol 20. Ethylene glycol 20mM potassium sulfite 3.0g potassium carbonate
30.0g hydroxylamine sulfate
4.0g3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline VL Butysalt 8.0g
Fluorescent brightener (4,4”-diaminostilbenzsulfone # derivative) (trade name Keikol P Niichikonku (manufactured by Shinro Sokako Co., Ltd.)) 2.5g 1-Hydroxyethylidene-1,1-niphosphonic acid 0.5g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride hexahydrate 0.8g 1.2-Hydroxybenzene-3:5-disulfonic acid disodium [0,
Add 3g of water to make the solution 11, and adjust the pH to 10 with potassium hydroxide.
70. [Bleach-fix tank solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 6G, 0g ethylenediaminetetraacetic acid 3.0g ammonium thiosulfate (70% solution) 100.0% Ammonium sulfite (40% solution) 27.5 Add the total amount to 1 sentence, and adjust the pH to 7 with potassium carbonate or glacial acetic acid.
, 1. [Bleach-fixing replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 2B0.0g Potassium carbonate 42.0g Add water to bring the total volume to 11. The pH of this solution is 6.7±0.1. [Bleach-fix replenisher B] Ammonium thiosulfate (70% solution) 500.0 Layered ammonium butyrite (40% solution) 250.0
Layered ethylenediaminetetraacetic acid 17.0g
Add aqueous acetic acid 85°0■ Imperial water to bring the total volume to 141. The pH of this solution is 5.3±0.1. [Water-washing stable tank solution and replenishment solution] Ethylene glycol 1.0g 1-hydroxyethylidene-1,l-niphosphonic acid (60% aqueous solution) 1.0g ammonia water (ammonium hydroxide 25% aqueous solution) 2.0g ill with water and bring it to p)l 7.0 with sulfuric acid. Fill an automatic processor with the above color developing tank liquid, bleaching qualitative tank liquid and stabilizing tank liquid, and add the above color developing replenisher and bleach-fixing replenisher A every 3 minutes while processing the Sakura Color SN paper sample. , A running test was conducted while replenishing B and stable replenisher through the fixed stitch cup. The amount of replenishment is 190 mL per color paper to the color developing tank, 50 ml each of Bleach Constant Replenishment Solution A and B to the bleach-fixing tank, and 50 ml of each of bleach fixing solutions A and B to the stabilizing tank. 250 sets of stable replenisher were replenished. The stabilization tanks of the automatic processor are the first to third tanks in the direction of sample flow, and the final tank is replenished and the overflow liquid from the final tank is allowed to flow into the previous tank. Furthermore, a multi-tank countercurrent system was adopted in which this overflow liquid also flows into the preceding tank. Continuous processing was carried out until the total amount of water washing substitute stabilizing solution replenished was three times the capacity of the stabilizing tank. All of the photographic processing waste liquids produced by the above processing were mixed and subjected to the following processing. Experimental Example 1 The photographic processing waste liquid of 5 sentences was received into the apparatus shown in Fig. 1,
Evaporation treatment was performed. After adding 30 g/l of the metals shown in Table 1 below to the waste liquid,
Adjust to pos, s with HCI and NaOH, and evaporate to 50 s in an evaporator.
The diameter was reduced to 0 ttrl, and the initial NH3 gas concentration at the top of the distillate was measured. After that, when the distillate becomes cloudy and a bad odor begins to occur (when 2 out of 5 monitors feel the odor)
concentrated to. Table 1 As is clear from Table 1, when the metals of the present invention were not added or comparative metals were added, a bad odor (possibly from H2S) was generated when the concentration was reduced to 1/3, and the residue Although the liquid became cloudy, it was found that when the metal of the present invention was added, the concentration could be further advanced, which is very preferable. Experimental Example 2 The following three samples were prepared. (1) Sample (A) in which 80 g/l of Fe5Oz was added to the waste liquid used in Experimental Example 1 (2) Cu7SO4Bog/l was added to the waste liquid used in Experimental Example 1
Added sample (B) (3) Sample in which nothing was added to the waste liquid used in Experimental Example 1 (C) The above samples (A) to (C) were adjusted to the pH shown in Table 2.3 before starting heating. p) 1wA regulator) 1(4
and NaOH were used. Evaporation and concentration were started, and the pH was adjusted as shown in Tables 2 and 3 every 100 times. Evaporate and ewi until it reaches 50oII, cool the evaporated gas, and make the distillate 111. When the temperature of the distillate was 25°C, the appearance of the distillate was examined. The results are shown in Table 2. Also, the ammonium concentration in the distillate (
NH4') was measured. The results are shown in Table 3. Table 2 Table 3 NH4'' concentration (g/vertical) As is clear from Table 2, in the absence of the addition of the metals of the present invention, moisture in the distilled solution with a pH of 4.0 or less is observed in the waste solution. 1. When the metals of the present invention are added, the waste liquid p
No turbidity is observed even when H is 3.0 or less. Furthermore, as is clear from Table 3, when one of the metals of the present invention is added, the ammonium concentration in the distillate changes over a wide range of pH.
It can be seen that it is low across the region. Experimental Example 3 A color developing waste solution containing no thiosulfate was designated as Mo, 13, a waste solution obtained by adding 30% by volume of a bleaching waste solution not containing thiosulfate to the color developing waste solution was designated as Mo, 14, and Mo.
The waste liquid obtained by adding 50 g/l of ammonium thiosulfate to the waste liquid from Mo. The waste liquid to which 30% volume of the qualitative waste liquid was added was designated as Mo, 17. Fe! 110420g/41,
A mixture of ZIISO420g/4 and CuSO420g/i was added, and the pH was adjusted with HCI and NaOH, respectively.
The concentration was adjusted to 4.0 and concentrated by evaporation. The ammonium concentration and hydrogen sulfide concentration in the distillate and the appearance of the distillate were investigated. The results are shown in Table 4. Table 4 As is clear from Table 4, when the metal of the present invention was mixed, the ammonium concentration and hydrogen sulfide concentration in the distillate decreased considerably, and the appearance of the distillate also became colorless and transparent without turbidity. I know that there is. [Effects of the Invention] According to the present invention, the presence of metals and the like unique to the present invention in the heated waste liquid suppresses the generation of H2S and S gases, completely suppresses the outflow of ammonia gas, and further The outflow of S can be suppressed. For example, even if 12S and S gases exist on the gas side at the top of the distillate, and H2S, NH3, and SO2 exist in the distillate, their concentrations are low, so as a secondary treatment for each of the gas and liquid, for example, gas It can be completely removed by installing activated carbon treatment equipment for treatment and liquid treatment. Therefore, the load on secondary processing is greatly reduced, the amount of adsorbent consumed is reduced, and the complexity required for replacing the adsorbent is eliminated. Further, according to the present invention, turbidity of the distillate is eliminated, and not only is there no problem with disposal, but also reuse is possible, and an extremely versatile process can be provided. Note that the present invention can be applied to purposes other than the above-described suppression of bad odors and prevention of turbidity of distillate.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a conceptual diagram showing an example of a method for suppressing bad odor, which is an embodiment of the present invention. 1: Waste liquid supply means 2: Preheater 3: 7M generation tank 4: Heating means, heater 5: Steam discharge pipe 6: Gas cooler 7: Gas cooler fan 8: Distillate tank 9: Circulation fan 1O: Total bending equal melting Tank 11: Full bending supply pump 12: Metal etc. supply pipe [: pH adjuster tank 14: pH adjuster pump 15: pH adjuster supply pipe

Claims (1)

[Scope of Claims] (1) A method for processing a photographic processing waste liquid, which comprises heating, evaporating, and concentrating the photographic processing waste liquid in the presence of at least one of the following metals (1) to (3). [Metals, etc.] (1) Fe, Ba, Zn, Ni, Cu, Sn, Bi, C
(2) Oxides of the above metals (3) Salts of the above metals (2) A patent characterized in that the photographic processing waste liquid contains thiosulfate ions A method for treating photographic processing waste liquid according to claim 1. (3) The method for treating photographic processing waste liquid according to claim 2, wherein the photographic processing waste liquid contains silver ions. (4) The photograph according to any one of claims 1 to 3, wherein the photographic processing waste liquid is heated, evaporated, and concentrated while maintaining the pH of the photographic processing waste liquid at 3.0 to 11.0. Processing method for processing waste liquid. (5) A processing device for photographic processing waste liquid that has a supply means for photographic processing waste liquid, an evaporation tank that receives the waste liquid, and a heating means that heats the waste liquid in the evaporation tank, and that heats, evaporates, and concentrates the waste liquid. , the following (1) to (3) are added to the photographic processing waste liquid.
A processing apparatus for photographic processing waste liquid, characterized in that it has means for containing at least one metal such as metal. [Metals, etc.] (1) Fe, Ba, Zn, Ni, Cu, Sn, Bi, C
o, Cr, Ce, Ti, Zr, Mo, W (2) Oxide of the above metal (3) Salt of the above metal