JPS63147594A - Method and device for treating waste photographic processing liquid - Google Patents

Abstract

PURPOSE:To efficiently suppress malodors without entailing a cost increase and without requiring laborious work by subjecting a waste photographic processing liquid to heating, evaporating and concentrating in the presence of an oxidizing agent which can oxidize the thiosulfuric acid ions in the waste photographic processing liquid. CONSTITUTION:The waste photographic processing liquid contg. thiosulfuric acid ions, silver ions, etc., is heated and evaporated in the state of maintaining pH at 3.0-11.0 in the presence of the oxidizing agent (e.g., sodium persulfate, potassium perchlorate) which can oxidize the thiosulfuric acid ions in the waste photographic processing liquid at the time of heating, evaporating and concentrating said waste liquid. As a result, amine and ammonia odors can be suppressed and the malodors arising from gaseous H2S, SO2 and S and other mercapto gases, etc., are suppressed. The malodors are thus efficiently suppressed without entailing the cost increase and without requiring the troublesome work.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the 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 an automatic photographic processor. The present invention relates to a method suitable for effectively suppressing bad odors during heating and evaporation treatment.

[Background of the invention] In recent years, stabilization treatment that replaces the amount of replenishment and washing with water has been used.
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 waterless washing method photographic processing, even relatively small-scale processing is possible, for example, about 10 JI per day for processing X-ray photosensitive materials, and about 30 JI per day for processing photosensitive materials for printing plate making. , 50 per day in processing color photosensitive materials.
About i of waste liquid is generated, and its disposal becomes a problem.

The inventor has discovered that small amounts of high concentrations (e.g. BOD 20.00
0~30,000ppm, N)Is・20,000~
We discovered that the evaporation method is excellent for efficiently treating photographic processing waste liquid with a concentration of about 40,000 ppm (approx.
No. 9010, Patent Application No. 1981-132098, Patent Application No. 1981
-185099, Japanese Patent Application No. 165100/1981, etc.).

However, in this heating/evaporation method, sulfur dioxide gas, hydrogen sulfide gas, sulfur gas, etc.
There is a problem with the generation of bad odors due to ammonia gas, etc., and unless this problem is resolved, the process will not be complete.

Conventionally, as a countermeasure against such bad odors, Japanese Utility Model Application No. 80-70841 proposes a method of providing an adsorption treatment section in the exhaust pipe section.

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). , it was inappropriate as a gas treatment facility to be added to a small-scale waste liquid treatment facility such as the present invention.

In other words, it is thought that foul-smelling gases can generally be treated with adsorption equipment if the problem of condensation is solved (although this varies depending on the components), but the concentration of foul-smelling gases in the exhaust gas obtained by evaporating photographic waste liquid is extremely high. When attempting to adsorb this highly concentrated foul-smelling gas, the adsorbent quickly becomes saturated.
The running cost is enormous, and the adsorbent has to be replaced frequently, which is extremely complicated. Furthermore, in order to reduce the number of replacement operations, it is necessary to increase the size of the adsorption tower, which has the disadvantage of increasing equipment costs.

[Objective of the Invention] The purpose of the present invention is to solve the drawbacks of the prior art and to provide a method and equipment for efficiently suppressing bad odors without increasing costs or requiring complicated work. do.

[Means for Solving the 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 involves heating and evaporating photographic processing waste liquid containing at least thiosulfate ions.
The evaporation processing method according to the present invention is characterized in that heating and evaporation are carried out in the presence of an oxidizing agent (hereinafter referred to as the oxidizing agent of the present invention) capable of oxidizing thiosulfate ions in the photographic processing waste liquid.

In a preferred embodiment of the present invention, the photographic processing waste solution contains silver ions, and furthermore, the p)l of the concentrated solution is 3
．． It is to maintain it between 0 and 11.0.

Further, there is a processing apparatus for photographic processing waste liquid according to the present invention.

A processing device for photographic processing waste liquid, which comprises a supply means for 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 evaporates and concentrates the waste liquid by adding p%φ. , characterized in that it has means for supplying an oxidizing agent capable of oxidizing thiosulfate ions to the photographic processing waste liquid.

[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 thiosulfate (particularly ammonium thiosulfate, etc.), and the foul odor of H2S and SO2 is generated during the evaporation and 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 made extensive studies to solve problems such as bad odor, and have found that by heating and evaporating in the presence of the oxidizing agent of the present invention, amine and ammonia odor can be reduced, and 12S, SO2 It has been found that the odor associated with S gas and other mercapto gases can be suppressed, and problems such as turbidity associated with S can be solved.

The reason for this is not certain, but it is presumed that when the oxidizing agent of the present invention is present in the heated waste liquid, volatile reducing components in the waste liquid are oxidized and stabilized. By being oxidized and producing stable species such as 5042-, )I2S, SO2, 3 gas and other mercapto gases are not generated, and
The inventors have discovered that by reacting with ammonia and amines to form salts and stabilizing them, it is possible to suppress the bad odors of ammonia, amines, and the like, leading to the present invention.

[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 means for supplying photographic processing waste liquid.

IA 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, and 5 is a waste liquid in the evaporation tank 3. A steam exhaust pipe for discharging the steam generated from the heated gas to the outside of the evaporation tank 3, 6 a gas cooler for cooling the gas, 7 a fan for the gas cooler, and 8 a gas cooler for cooling the steam. 9 is a circulation fan for returning the dehumidified gas to the evaporation tank; A is a means for supplying the oxidizing agent of the present invention to the photographic processing waste liquid;
It consists of an oxidant dissolving tank 1O1, an oxidant supply pump 11, an oxidant supply pipe 12, etc. B is a means for supplying a p)l adjuster to the photographic processing waste liquid, and for example, if pH adjuster tank 1.
3. pH21I! ! Regulatory pump 14. l1lH21!
J preparation supply pipe 15. Consists of pH controller PHC etc.

TC 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 oxidizing agent of the present invention is added thereto, and heated and evaporated by the heater 4. During this time, the pH of the waste liquid (concentrated liquid) is preferably maintained at 3.0 to 11.0, more preferably 4.0 to 8.0, more preferably 5.0 to 7.0.
It is to be maintained at 0.

The heating temperature is appropriately adjusted by a temperature controller TC.

The steam exchanges heat with the waste liquid in the preheater 2, is sent to the gas cooler 6, where it is cooled and humidity-controlled, and the distillate is separated. The distilled liquid is stored in the distilled liquid tank 8, and as it does not give off a bad odor and satisfies wastewater regulation values such as BOD, C0II, and SS, it can be discharged into rivers or reused as necessary. It is. 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 evaporation tank decreases and becomes concentrated as the heating ψ evaporation time passes. The heater 4 for heating is stopped by the operation of a timer, for example, and the heating is completed. The remaining concentrated 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 oxidizing agent of the present invention, (1) at least one kind selected from peroxides (2)
At least one selected from halogen oxides (3) At least 18N selected from total oxides.

Examples of the peroxide (1) include sodium persulfate,
Persulfate salts such as potassium persulfate and ammonium persulfate, hydrogen peroxide, sodium peroxo-sulfate, persulfate
Potassium sulfate, beroxo-sulfates such as bero-oxo-ammonium sulfate, potassium percarbonate, sodium percarbonate and other acid salts, ammonium perborate, potassium perborate, sodium perborate, magnesium perborate, benzoyl peroxide, Examples include peracetic acid, calcium peroxide, soda peroxide, barium peroxide, manganese peroxide, lithium peroxide, and at least one of these can be used.

(2) Examples of nohalogen acids include perchloric acid, potassium perchlorate, sodium perchlorate, barium perchlorate,
Magnesium perchlorate, +1! Examples include potassium chlorate, sodium chlorate, potassium bromate, potassium iodate, potassium hydrogen iodate, sodium iodate, and at least one of these can be used.

Examples of the metal oxides in (3) above include Fe2O3゜Fe5G*, FeO, ZnQ, old Q, Cub, MI
I02. KMnG*, C1120°Pb30a,
SnO, Bi2O3, Can, Cr2O3, K2Cr
2O7゜KCr04. Ce20x, Ti(12,Z
Examples include rO2, and at least one of these can be used.

Preferred among the oxidizing agents of the present invention are peroxide oxidizing agents.

The amount of the oxidizing agent added in the present invention is Q, OO1 to 2 mol/!
l is preferable, more preferably o, oos to 1+*ol
/fL, particularly preferably 0.01 to 0.5 liters/fL.

The oxidizing agent of the present invention may be added in advance to the waste liquid supplied to the concentration tank, or may be added after being supplied to the concentration tank, and when added into the concentration tank, heating and evaporation start. Doesn't matter before or after.

When externally adding the oxidizer to the concentration tank, a single oxidant supply means is used, and when the oxidizer of the present invention is a liquid, as shown in FIG.
If the oxidizing agent of the present invention is a solid such as a powder, it may be added directly to the e-ray type, or the tank shown in Figure 1 may be added separately from the waste liquid. It may be added as a solution after being dissolved once every 10 days.

When using two or more types of oxidizing agents of the present invention, it is preferable to provide a plurality of tanks for each added oxidizing agent if they are added externally from a tank as shown in Figure 1, but depending on the physical properties of the oxidizing agent, In some cases, one tank can be used in common.

In the present invention, the pH of the waste liquid (concentrated liquid) is set to 3.0 to 11.
, C1 is preferably 4.0 to 8.0, more preferably 5.
By maintaining the ratio between 0 and 7.0, malodors can be suppressed more effectively.

When the photographic processing waste liquid of the present invention is heated in the hansatsu tank 3,
pH modifiers are used to control this pH fluctuation, which causes pH fluctuations (mainly decreases).

The pHTA regulator that can be used in the present invention is a regulator in a broad sense, and is not necessarily clearly classified;
For example, there are CI), compounds that buffer the waste liquid against pH fluctuations, and (II) compounds that control pH (mainly increases) by external addition in response to pH fluctuations (mainly decreases) during the evaporation process. .

The compounds of (I) above include (1) metal oxides, metal hydroxides, or metal salts such as Ca, Ng, /Ill, Fe, Zn, etc. Compounds with buffering properties (2) Solid carbon salts (such as CaC03)
A compound that dissolves and becomes alkaline with a decrease in l (
3) Buffers such as organic acids (e.g. citric acid, etc.) and their salts (4) Buffers such as inorganic acids (e.g. boric acid, phosphoric acid, etc.) and their salts (5) Aminocarboxylic acids such as EDTA Chelating agent (
6) l-Hydroxyethylidene-1,1-diphosphonic acid and the like can be mentioned, and one type or a combination of two or more types of these can be used.

In addition, the above-mentioned compounds (n) include (1) hydroxides of alkali metals such as NaOH, KOH, Ca(OH)2, or alkaline earth metals (2) carbonates (3) silicates (e.g. Sodium silicate, etc.) (4) Phosphates (5) Borates (8) Alkaline earth metal salts such as Ca salts, M salts, etc. (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, the pH adjuster is added at the CI
), it is sufficient if 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 it may be added after being supplied to the evaporation tank but before the start of heating. In the case of the compound (n), it is of course supplied to the evaporation tank 3 from the outside.

When supplying the pH adjuster from the outside, as shown in FIG.
4, or the tank 13 may be provided above the evaporation tank 3 without using the pH adjuster pump 14, and the pH adjuster may be supplied using head pressure.

In the present invention, when the pHg14 adjuster is a liquid,
For example, it can be added as shown in Figure 1, but if it is a solid, it can be added directly to the waste liquid or concentrated liquid, or it can be dissolved in a tank beforehand and added as shown in Figure 1. You may.

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, when a pH adjuster is externally added as shown in Figure 1, the amount of addition can be controlled by a signal from a pH controller. When the pH decreases, the pump 13 can be turned on by a signal from the controller to supply the pH adjuster. In addition, when the pump 13 is of a stroke adjustable type, the stroke can also be automatically adjusted.

In order to effectively suppress bad odor in the present invention, the evaporation tank 3
It is preferable to adjust the amount of heat supplied from the heater 4 within. 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, suppressing the bad odor.On the other hand, if the amount of heat applied is small, the decomposition will be accelerated and the cause of the bad odor. The outflow of substances is activated.

Although an example of a method and a device for suppressing a bad odor has been described above, the scope of the present invention includes various embodiments without being limited thereto, and the main embodiments thereof are listed below. For aspects other than those listed below, please refer to existing applications (for example, Japanese Patent Application No. 80-259).
No. 001 to No. 259010, patent application Sho 8l-x32osa
No., Special Application No. 1981-165099, Special Patent Application No. 1981-185
100 etc.) can be referred to.

(1) The photographic processing waste solution of the present invention contains thiosulfate ions, and when the thiosulfate ions are ammonium thiosulfate, the present invention is preferably carried out when the concentration of ammonium thiosulfate is, for example, 5 to 500 gin. Applicable. Examples of the waste liquid include a mixed waste liquid of a color developer and a bleach-fixer or a stabilizer, a waste liquid of a certified white fixer or a fixer alone, and the like. In addition, it is preferable that the waste liquid contains silver ions, and the concentration thereof is 0.01 to
Preferably it is in the range of 50 g/l.

Furthermore, the present invention is preferably applied to the treatment of small-volume waste liquids, such as those from waterless automatic processors, etc. The term "small capacity" here is used as a concept for large-capacity factory waste liquids, etc. , for example, about 1 M/D to 1001/D, although there is no particular numerical limitation.

(2) In the present invention, the means for supplying the waste liquid to the evaporation tank 3 include a method of pumping it up from a waste liquid tank (not shown), a method of supplying it using head pressure, and a method of supplying it manually. be.

Furthermore, the waste liquid may be supplied either continuously or discontinuously, depending on whether the evaporation process is continuous or batchwise.

Further, the waste liquid may be supplied in liquid form, or may be supplied in spray form.

(3) In the present invention, the evaporation tank 3 is a tank that heats the supplied waste liquid and evaporates a part of it to concentrate the waste liquid and reduce the amount of waste liquid to be disposed of. i! 5 reduction means to reduce the volume of waste liquid after evaporation to one-fourth or less, preferably one-fifth or less, and most preferably one-tenth of the volume before evaporation. Note that the present invention can also be applied to cases where all (including substantially all) of the waste liquid is evaporated to dryness.

The form of the evaporation tank 3 is not particularly limited, but may be an outer tank (
It has a double structure of an outer pot (outer pot) and an inner tank (inner pot), and it is preferable that the inner tank is formed with a removable plastic bag, for example. 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. Examples of the heater include an electric heater, a nichrome wire heater with a built-in stone tube, a ceramic heater, etc., and it is preferable to install these inside the evaporation tank 3 as shown in the figure. It is also possible to adopt a dielectric heating method such as, or a combination of these methods may be used.Heating by a heater may be stopped by the operation of a timer, but is not limited to this, for example. The liquid level of the concentrated liquid may be detected by a level sensor, and the 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 odor, and contains ammonium salts such as ammonium sulfite can be obtained, and can be used as a photographic processing solution in an automatic processor (for example, water dissolved in a replenisher, or In addition to washing water (washing water), 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 superior in that it does not have the problems (for example, early saturation, complicated replacement work, etc.) that occur when treating high-concentration malodorous gases as in the conventional method, and furthermore, the malodor control of the present invention is effective. The method is excellent in that it can be effectively used as a pretreatment for malodor prevention means such as adsorption treatment 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°C 3 minutes 15 seconds Bleaching 38°C 3 minutes 15 seconds Fixing 38°C 3 minutes 15 seconds 1st stable 1st tank 32°C to 38°C 1 minute 1st stable 2nd tank 32℃～38℃ 1 minute 2nd stable
Dry for 1 minute at 38℃
45℃～65℃ [Color developer] Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 1.0g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate ffi 2.5g sodium chloride
0.684-amino-3-methyl-N-ethyl-N=(β-hydroxylethyl) Aniline sulfate 4.88Potassium hydroxide 1.2g was added to make 11, and potassium hydroxide or 20% sulfuric acid was added. using pHlo
, adjust to OB.

[Color developer replenisher] Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.9g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 1.2g hydroxylamine sulfate 3.1g 4-amino-
3-Methyl-N-ethyl-N-(β-hydroxylethyl) Aniline sulfate 6.0g Potassium hydroxide 2g Add water to make 141, and use potassium hydroxide or 20% sulfuric acid to make p) 110
．． Adjust to 12.

[Bleach solution] Iron ammonium ethylenediaminetetraacetate 160g Disodium ethylenediaminetetraacetate 10g Ammonium bromide 150g Glacial acetic acid
Add 10+s water to make ti, and adjust to P) 15.8 using aqueous ammonia or glacial acetic acid.

[Bleach replenisher] Iron ammonium ethylenediaminetetraacetate 170g Disodium ethylenediaminetetraacetate 12g Ammonium bromide 178g Glacial acetic acid
Add 21+m bunsui to make it 141,
Adjust the pH to 5.8 using aqueous ammonia or glacial acetic acid.

[Fixer] Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate 0.5g Sodium carbonate 10g Water was added to make IfL, and the pH was adjusted to 7.0 using aqueous ammonia or glacial acetic acid. do.

[Fixer replenisher] Ammonium thiosulfate 300g Anhydrous sodium bisulfite 15° Sodium metabisulfite 3g Ethylenediaminetetraacetic acid? Sodium 0.8g Sodium carbonate 14g Add water to make one sentence, and adjust the pH to 7.5 using aqueous ammonia or glacial acetic acid.

[First stable solution and first stable replenisher] 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-octyl-4-thiazolin-3-one 0.02° ethylene glycol 1.0 g Add water and adjust to pi 7.0 with 20% sulfuric acid.

[Second Stable Liquid and Second Stable Replenisher] Formalin (37% aqueous solution) 2 Double Bound Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 5 ■ of sample water to make one sentence.

The color development replenisher was added to the color development bath at an amount of 13.5 cm per 100 cm of color negative film, and the bleach replenisher was
Replenish the bleaching bath with 5.5 mJ1 per IQO cm of color negative film, and add fixing replenisher to 100 mJ of color negative film.
The fixing bath is replenished with 8yal per cm of color negative film, and the first stable replenisher is replenished with 8yal per 100cm of color negative film, and the second stable replenisher is added with 100crn of color negative film in the second stable bath. '150 layers per serving.

(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.

Standard processing step (1) Color development 38°C 3 minutes 30 seconds (2)
Bleach fixing 38℃ 1 minute 30 seconds (3) Stabilization treatment 25℃~35℃ 3 minutes (4) Drying 75
℃～100℃ Approximately 2 minutes Processing liquid composition [Color developing tank liquid] Benzyl alcohol 15M ethylene glycol 151IfL Potassium sulfite 2.0g Potassium bromide
1.3g sodium chloride
0.2g potassium carbonate
24.0g3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) aniline sulfate 4.5gFluorescent brightener (4,4'-diaminostilbenzsulfonic acid visiting conductor) (product 1.0g Hydroxylamine sulfate 3.0g 1-Hydroxyethylidene-1,
1-Niphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride/6 water fi 0.7g 1.2-Hydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Water was added to make a monomer. , adjust the pH to 10.20 with potassium hydroxide and sulfuric acid.

[Color developer replenisher] Benzyl alcohol 2h ethylene glycol 20ral potassium sulfite 3.0g potassium carbonate
30.0g hydroxylamine as an acid salt 4,0g 3-methyl-4-amino-N
-Ethyl-H-(β-methanesulfonamide ethyl) Aniline sulfate 6.0g Fluorescent brightener (4,4”-diaminostilbenzsulfonic acid derivative) (Product name Keikol PK-Nink (Shin Nisso Kako 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-di sodium salt
Add 0.3g of water to make one sentence, and add potassium hydroxide to P.
Let it be H10,70.

[Bleach-fix tank solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 80.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0+Jl Ammonium sulfite (40% solution) 27.5+ajL
Add water to bring the total volume to one level, and adjust the pH to 7.1 with potassium carbonate or glacial acetic acid.

[Bleach-fixing replenisher A] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 2B0.0g Potassium charcoal butyrate 42. Q.

Add water to bring the total volume to one level.

The pH of this solution is 8.7±0.1.

[Bleach-fix replenisher B] Ammonium thiosulfate (70% solution), 500.0
+JL ammonium sulfite (40% solution) 25Q
,hu ethylenediaminetetraacetic acid 17.0
Add 85 degrees of glacial acetic acid and 9 degrees of water to bring the total volume to 1! Let it be l.

The pH of this solution is 5.3±0.1.

[Water wash alternative stable tank fluid and replenisher] Ethylene glycol 1.0g 1-hydroxyethylidene-1,1-niphosphonic acid (60% aqueous solution) 1.0g ammonia water (ammonium hydroxide 25% aqueous solution) 2.0g 1 sentence with water and adjust the pH to 7.0 with sulfuric acid.

Fill an automatic processor with the above color developer tank solution, bleach pre-tank solution and stability tank solution, and add the above color developer replenisher and bleach-fixer replenisher every 3 minutes while processing the Sakura Color SR paper sample. A running test was conducted while replenishing A, B and stable replenisher through a metering cup. The replenishment amount is 190 + * i as the replenishment amount to the color developing tank per rn' of color paper, 50Il1 each of bleach-fixing replenisher A and B as the replenishment amount to the bleach-fixing tank, and water washing substitute as the replenishment amount to the stabilization tank Stable replenisher 25
0+a was replenished again. In addition, the stabilization tanks of the automatic developing machine are the fj41 tank to tank 3 in the direction of the flow of the sample,
Most P: A multi-tank countercurrent system was adopted in which replenishment was performed from the tank, and the overflow liquid from the final tank was allowed to flow into the tank at the previous stage, and this overflow liquid also flowed into the tank at the previous stage.

Continuous processing was performed until the total amount of replenishment of the water washing alternative stabilizing solution became 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 fifth processing.

Experimental Example 1 This photographic processing waste liquid 51 (waste liquid No. 1) was received into the apparatus shown in FIG. 1 and subjected to evaporation treatment.

It was evaporated and concentrated until the concentration was 2.51, and the evaporated gas was cooled to obtain a distillate.

When the temperature of the distillate is 25°C, NH3 in the gas on the surface of the distillate
Gas, )12S gas, and S02 gas were quantitatively determined, and the appearance of the distillate was examined. The results are shown in Table 1.

Next, five waste liquids Nos. 2 to 10 each containing 10 g of each of the various oxidizing agents shown in Table 1 were prepared, and the same experiment was repeated. The results are shown in Table 1.

Table 1 As is clear from Table 1, in the comparative waste liquid No. 1 in which the oxidizing agent of the present invention was not added, not only the NH3 gas and H2S gas concentrations were high, but also the distillate became significantly cloudy. When the oxidizing agent of the present invention is added, the distillate becomes colorless and transparent, and less NH3 gas and H2S gas are generated.

In particular, it can be seen that No. 2 to B to which a peroxide oxidizing agent was added showed particularly good results.

Experimental example 2 Waste liquid No. 1 used in Experimental Example 1 and stored over time.

Furthermore, 20 g/exchange of potassium persulfate was added to waste liquid No. 1.
The pH of 1 was adjusted with H2SO4 and KO)I as shown in Table 2. Start evaporation, p every 5001 sentences evaporated
H was adjusted as shown in Table 2. The mixture was concentrated by evaporation until the concentration reached 2.01, and the evaporated gas was cooled to obtain a distillate, which was evaluated in the same manner as in Experimental Example 1.

Table 2 As is clear from Table 2, with the addition of potassium persulfate, the generation of NH3 gas and especially toxic H2S gas is reduced, and the occurrence of turbidity of the distillate is also reduced, but especially at p)l 3.0~
It can be seen that good results are obtained within the range of 11.0.

Experimental Example 3 Comparative waste solution No. 12, in which 30% by volume of color development waste solution was added to bleach waste solution, was mixed with H2SOs and NaOH to pH 2.0.8,
Waste liquid adjusted to 0, 12, 0, waste liquid No. 12, with 50 g/ammonium thiosulfate added to the waste liquid No. 13
50 g/i of ammonium thiosulfate and 5 g/fL of AgBr were added to the waste liquid No. 12 whose pH was adjusted in the same way.
Waste liquid No. 14 with added pt + adjusted in the same way,
A waste liquid No. 15 was prepared by adding 30% by volume of fixing waste liquid to the waste liquid No. 12 and pH-adjusted in the same manner.

Next, 10 g/l of potassium peroxo-sulfate was added to the waste solutions of >io, 12 to 15 to produce waste solutions No. 18 to 15.
No. 19 was prepared and the pH was adjusted in the same manner.

All of the above waste liquids, 5 layers each, were received into the apparatus shown in Figure 1 and subjected to evaporation e12i, and the results are shown in Table 3. However, adjustments were made so that 500 layers were evaporated, and e! i
I did i.

Table 3 As is clear from Table 3, in all cases, the waste liquid containing Veroquin-potassium sulfate has less bad odor, effectively prevents H2S gas, which is likely to be generated due to the inclusion of thiosulfate ions, and is especially effective when containing silver. Waste liquid No. 18
and H2S in the waste liquid whose pH was adjusted to 8.0 within 19.
Gas is completely prevented.

[Effects of the Invention] According to the present invention, since there is an oxidizing agent that can oxidize thiosulfate ions when waste liquid is evaporated, the amine odor and ammonia odor of the distillate are suppressed, and the generation of H2S gas etc. can be suppressed. Further, even if activated carbon treatment or the like is provided as a secondary treatment, the load of the secondary treatment 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 in terms of disposal, but also reuse is possible, and it is possible to provide an extremely versatile process and apparatus.

Note that the present invention can be applied to purposes other than the above-described suppression of bad odors.

[Brief explanation of the drawing]

FIG. 1 is a conceptual diagram showing an example of a method for suppressing bad odor according to the present invention. 1: Waste liquid supply means 2: Preheater 3: Evaporation tank 4: Heating means, heater 5: Steam discharge pipe 6: Gas cooler 7: Gas cooler fan 8: Distillate tank 9: Circulation fan 10: Oxidizing agent dissolution tank 11 : Oxidizing agent supply pump 12: Oxidizing agent supply pipe 13: pH adjuster tank +4: pH adjuster pump 15: PH adjuster supply pipe

Claims (4)

[Claims] (1) An evaporation treatment method for heating, evaporating, and concentrating a photographic processing waste liquid containing at least thiosulfate ions, characterized by heating and evaporating in the presence of an oxidizing agent capable of oxidizing the thiosulfate ions in the photographic processing waste liquid. A method for treating photographic processing waste liquid. (2) The method for treating photographic processing waste liquid according to claim 1, wherein the photographic processing waste liquid contains silver ions. (3) A method for treating photographic processing waste liquid according to claim 1 or 2, characterized in that the photographic processing waste liquid is heated and evaporated while maintaining the pH of the photographic processing waste liquid at 3.0 to 11.0. . (4) 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. A processing apparatus for photographic processing waste liquid, characterized in that it has means for supplying an oxidizing agent capable of oxidizing thiosulfate ions to the photographic processing waste liquid.