JPS63143993A - Treatment of waste liquid from photographic process and apparatus thereof - Google Patents

Abstract

PURPOSE:To effectively remove offensive odor, by heating, a evaporating and concentrating waste liquid under the existence of a compd. capable of discharging sulfite ion. CONSTITUTION:Waste liquid is fed to an evaporation tank 3 via a feed pipe 1A thereof. A compd. capable of discharging sulfite ion (i.e. K2SO3, Na2SO3, (NH4)2SO3 and NaHSO3 or the like) is added to the evaporation tank 3 at 5X10<-4> g-ion/l expressed in terms of sulfite ion. 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. Further as a heating means, an electric heater and a ceramic heater, etc., are 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 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 and apparatus suitable for effectively suppressing bad odors during heating and evaporation treatment.

[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, about 10 out of 10 when processing X-ray photosensitive materials, and about 1 out of 10 when processing photosensitive materials for printing plate making.
30 a day! 50 per day for color photosensitive material processing
A waste liquid of approximately fL is generated, and its disposal becomes a problem.

The inventor has discovered that a small amount and a high concentration (e.g. BOD 20,00
0-30,000ppm, N)14' 20,000
~40. We discovered that the evaporation method is an excellent way to efficiently treat treated waste liquid (approximately OOppm), and have made various proposals (Japanese Patent Application No. 80-259001~
259010, Japanese Patent Application No. 81-132098, Japanese Patent Application No. 81-185099, Japanese Patent Application No. 81-165100, etc.).

However, in this addition method, there is a problem in that the evaporated gas or distillate generates a bad odor based on sulfur dioxide gas, hydrogen sulfide gas, sulfur gas, ammonia gas, amine gas, etc., and this problem cannot be solved. as long as
It was not a complete process.

Conventional measures against such bad odors include: 1. Jikaisho Go-70841
No. 1 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). 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 considered that malodorous gases can be agglomerated using equipment such as adsorption if the problem of condensation is solved (although this varies depending on the component), but the concentration of malodorous gases in the exhaust gas obtained by evaporating photographic waste liquid is extremely low. If you try to adsorb and treat this high concentration of foul-smelling gas, the adsorbent will quickly become 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.

Purpose of IJI from E] The purpose of the present invention is to solve the shortcomings of the prior art and provide a method and device for efficiently suppressing bad odors without increasing costs or requiring complicated work. do.

[Means for Solving the Problems] The present inventors have conducted 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 characterized in that the photographic processing waste liquid is subjected to heating-evaporation/am treatment in the presence of at least sulfite ions and a compound capable of releasing sulfite ions.

In a preferred embodiment of the present invention, the photographic processing waste solution contains thiosulfate ions, further contains silver ions in addition to the thiosulfate ions, and furthermore, the pH of the photographic processing waste solution is adjusted to 3.0. It is heated and evaporated while maintaining the temperature at ~11.0.

[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, since the photographic processing waste liquid contains amines and ammonium n1, it generates amine and ammonia odors, and if the waste liquid contains thiosulfate ions, it is heated and decomposed at high temperatures, generating Has gas. Eventually, it sulfurizes and generates S gas, which generates a bad odor.

The present inventors conducted extensive research to suppress such malodors;,=
As a result of stacking 1 ft of waste fluid, we found that depending on the type and composition of the waste fluid, there may or may not be an amine odor or ammonia odor.Furthermore, in the case of waste fluid containing sulfite ions, we found that It was found that amine odor and ammonia odor were significantly reduced. Furthermore, when thiosulfate ions are present in the waste liquid, in the case of a waste liquid containing sulfite ions.

It was found that the generation of hydrogen sulfide and sulfur gas was significantly reduced.

The present invention was made based on this knowledge, and if sulfite ions are present during heating, the amine odor and ammonia odor of the distillate can be suppressed, and the generation of H2S and S gas can be prevented.

It is presumed that amine and ammonia odors can be suppressed because amines and ammonia are trapped with water vapor and coagulate with sulfurous acid, and the generation of H2S and S gas can be prevented due to the decomposition reaction of thiosulfate ions caused by heating. It is assumed that this is because sulfite ions effectively prevent this.

[Example] An example of the method for 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 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
4 is a heating means such as a heater; 5 is a steam discharge pipe 26 for discharging steam generated when the waste liquid in the evaporation tank 3 is heated to the outside of the evaporation tank 3; 4 is a gas for cooling the steam; cooler.

7 is a gas cooler fan, 8 is a distillate tank for storing the distillate obtained by cooling the vapor, 9 is a circulation fan for returning the dehumidified gas to the evaporation tank, and A is a photographic processing waste liquid. This is a device for supplying a compound capable of releasing sulfite ions and 6jL acid ions to the system, and consists of a sulfite-containing compound tank 10, a sulfite-containing compound pump II, and a sulfite-containing compound supply pipe 12. B is the pH of the photographic processing waste liquid.
A means for supplying the adjusting agent, such as a pH adjusting agent tank 13, a pH adjusting agent pump 14. pH: A adjustment agent supply pipe 1
5. 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.
and is heated and evaporated by the heater 4. This heating-evaporation is carried out in the presence of sulfite ions and compounds capable of releasing sulfite ions. Further, heating and evaporation are preferably performed while the pH of the photographic processing solution is maintained at 3.0-11.0, more preferably 4.0.
~8.0. Particularly preferably, the temperature is maintained at 5.0 to 7.0. The heating temperature is appropriately adjusted by a temperature controller TG.

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 distillate is stored in the distillate tank 8 and does not give off any bad odor and satisfies wastewater regulation values such as BOO, COD, SS, etc., so it can be discharged into rivers or reused as necessary. Department. 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 φ evaporation time elapses. The heating heater 4 is stopped, for example, by the operation of a timer, and the heating is completed. Residual e-brain fluid is drained out of the system.

Next, a method for suppressing bad odor, which is an embodiment of the present invention, will be specifically described.

Among photographic processing waste solutions, color developing solutions and bleach-fixing solutions contain sulfite ions, but bleaching solutions do not contain sulfite ions. Therefore, when only bleaching solution is evaporated, , the method of the present invention is effective.

Furthermore, even waste liquid containing sulfite ions decreases and disappears over time. Especially in the case of mixed waste liquid, the rate of decrease is fast;
Since it disappears after storage for several days, even in such cases,
The method of the invention is effective.

In Endpoint 1, "heating and evaporating in the presence of sulfite ions" means that if the waste liquid received in the evaporation tank contains sulfite ions, it is not necessary to add new ions or If the waste liquid does not contain sulfite ions, or if the sulfite ions in the waste liquid have disappeared due to storage, or if they have disappeared during the heating process, it is preferable to add new sulfite ions to the waste liquid. The process involves heating and evaporating the substance while allowing it to exist in the atmosphere.

I+ [Compounds capable of releasing sulfate ions and sulfite ions may be present in the waste liquid in the evaporation tank in advance, may be added continuously or intermittently during the heating evaporation process, or may be present in the collected waste liquid. The waste liquid may be continuously or intermittently replenished into the evaporation tank.

In the present invention, sulfite ions (SO32-) in the evaporation tank
should be present at least 5X 1G-' Durham ion/gram, preferably IX 10-3 Gram ion/gram.
or more, preferably 5X 1G-3g ion/
The presence of U or more has the effect of suppressing bad odors.

Furthermore, if the amount of sulfite ions present is too large, problems such as the generation of S02 gas will occur, so it is preferably less than 4 grams ions/9.0 grams, more preferably 2 grams ions/9. below,
Particularly preferably, it is 0.5 gram ion/cross or less.

In the present invention, a "compound capable of releasing sulfite ions (SO32-)" refers to a compound that releases sulfite ions (SO32-) by hydrolysis in an evaporation tank or by heating/decomposition.

Specifically, the following compounds may be mentioned.

First, 2SO3, Na2SO3, (884)2SO3,
NaHSOx.

KHSOx, Na? Examples include inorganic sulfites such as 520s, 2S20s, etc., and one or more of these can be selected and used. This is a compound that is added to the evaporator and mainly hydrodissociates to release 5032-.

Further, bisulfite adducts represented by the following general formula [II or [II]] may be mentioned, and at least one compound selected from these can be used.

General formula [II R2-C-0)1 03M In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and R2 has 1 to 4 carbon atoms.
B preferably represents an alkyl group of 1 to 4, and 1M represents an alkali group or an ammonium group.

One of the preferable carbonyl bisulfite adducts represented by the general formula [II is one in which R1 is a hydrogen atom and R2 is an alkyl group having 1 to 4 carbon atoms, and the other is one in which R1 and Each R2 is an alkyl group having 1 to 4 carbon atoms.

General formula [111 In the formula, R3 and R4 are each a hydrogen atom or a carbon a
1-8. Preferably represents 1 to 2 alkyl groups, N represents an alkali total or ammonium group, n is 0 to 8,
Preferably represents an integer of 1 to 4.

One of the preferable carbonyl bis-bisulfite adducts represented by the general formula [■] is one in which R3 and R4 are each a hydrogen atom, and n is 1 to 4, and the other is one in which R3 and R4 are each an alkyl group having 1 to 2 carbon atoms, and n is an integer of 1 to 4.

Specific examples of the bisulfite adduct represented by the above general formula [11 or [nl] will be shown below, but the invention is not limited to these.

Exemplary bisulfite adduct of general formula [II I-(1) Acetaldehyde sodium bisulfite I-(
2) Propionaldehyde sodium bisulfite I-(3
) Butyraldehyde sodium bisulfite I-(4) Acetone sodium bisulfite 1-(5) Butanone sodium bisulfite I-(6) Pentanone sodium bisulfite Illustrative bisulfite adduct of general formula [11] n-(t) Succinic aldehyde sodium bisulfite 1 l - (2) Glutaraldehyde bis sodium bisulfite n - (3) β-Methylglutaraldehyde sodium bis bisulfite H - (4) Maleic acid dialdehyde sodium bis bisulfite 1 l - (5 ) 2.4-pentanedione sodium bisulfite The above bisulfite adducts may be used alone or in combination with 2.
More than one species may be used in combination.

As a compound other than the above, it can be decomposed by heating to 503
Examples of compounds that release 2- include compounds represented by the following general formula [AI] in addition to the above.

General formula [A] In the above formula, R5 and R6 each represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted acyl group, or an optionally substituted carbamoyl group. represents, also R
5. R6 may be linked to each other to form a ring.

In R5 or R6, the alkyl group which may have a substituent is preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and examples of the unsubstituted alkyl group include methyl group, ethyl group, etc. Examples of the substituted alkyl group include an alkyl group substituted with a hydroxy group (for example, a 2-hydroxyethyl group) and an alkyl group substituted with an alkoxy group. Here, examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and the like. Further, the acyl group or carbamoyl group which may have a substituent is preferably an aliphatic group or an aliphatic group, (
In addition to unsubstituted acyl groups such as acetyl groups, 7-minoacetyl groups (also known as glycylno, 0 Kasa's Examples include substituted acyl groups, and in addition to unsubstituted carbamoyl groups, examples with substituents include N-methylcarbamoyl groups, N,
Substituted carbamoyl groups such as N-dimethylcarbamoyl 71u and N,N-tetramethylenecarbamoyl group can be mentioned.

Examples of the ring formed by connecting R5 and R6 include a morpholine ring, a piperazine ring, and a pyrrolidine ring T. Preferred as R5 and R6 are a hydrogen atom, a methyl group, and an ethyl group, and a hydrogen atom is particularly preferred.

xl, x7 and x3 represent a hydrogen atom or an alkyl group which may have a substituent.

The alkyl group which may have 1iii substituent in x1 to
Propyl group, i-propyl group, n-butyl group, 1so-
In addition to unsubstituted alkyl groups such as butyl group and 5ee-butyl group, examples of one substituent include hydroxy group.

Hydroxymethyl group with carboxy group, etc.

3-hydroxyethyl group, 2-hydroxyethyl group.

Carboxymethyl group, 2-carboxyethyl group.

Examples include substituted alkyl groups such as 3-carboxyproyl group and 2-hydroxy-4-carboxybutyl group.

Xl. X? and X) are preferably hydrogen atoms,
Among these are a methyl group, an ethyl group, and a hydroxy-substituted methyl group, and particularly preferred is a hydrogen atom.

represents a hydrogen atom or an alkali (e.g. sodium, potassium, etc.). (2) represents an integer of 0 to 2, preferably 0 or 1, particularly preferably 0.

Specific examples of the compound represented by the general formula [A] used in the present invention are shown below, but the present invention is not limited thereto.

[Exemplary compound] A-(+) Nll, CII2SO□11A-(2)
NlI□C 11 2C II□SO, IIA-(
16) NlI□CII□CII, CII□SO:
1llA-(17) C113-NIICIIItCI
ItSO, IIA-(21) Vq-cnrsosn υ-The above compounds may be added to the waste liquid alone, or two or more of them may be added to the waste liquid.
;Can also be added in combination.

The location of addition of the compound that releases the so-co'- in the ending '11 is! It may be contained in the waste liquid before being supplied to the evaporation tank 3, or it may be added from the outside after being supplied to the evaporation tank and before or after the start of heating.

When the compound that releases 5Oz2- is supplied from the outside, as shown in FIG.
1, or the tank 10 may be placed above the evaporation tank 3 without using the pump 11, and the water may be supplied using head pressure.

If the compound capable of releasing 5032- in unreleased 11 is a liquid, it can be added as shown in Figure 1, but if it is a solid, the solid can be added directly to the waste liquid or concentrated liquid. Alternatively, it may be dissolved in the tank in advance and added as shown in FIG.

In the present invention, when two or more compounds capable of releasing 5032- are used, it is preferable to provide a plurality of tanks for each additive compound when externally added from a tank as shown in FIG. In some cases, one tank can be used in common.

In the present invention, the pH of the waste liquid (ella liquid) is set to 3.0~
11.0. Preferably 4.0 to 8.0. More preferably, malodor can be suppressed more effectively by heating and emitting while maintaining the temperature at 5.0 to 7.0.

Normally, p)l of waste liquid varies depending on the type of waste liquid, but if it is a joseki liquid containing thiosulfate ions (e.g. ammonium thiosulfate) or sulfite ions (e.g. ammonium sulfite) and has a low pH, the pH is low (e.g. pH7～
3), or P in the case of color developer or black and white developer)
l is considered to be high (for example, around pH 14 to 8).

When these waste liquids are heated in the evaporation tank 3, they cause pH fluctuations, so a pH adjuster is used to control this pH fluctuation.

The pH2g1 adjuster that can be used in the present invention is a adjuster in a broad sense, and is not necessarily clearly classified, but includes, for example, (I) a compound that makes the waste liquid resistant to pH fluctuations, (II) ) 7A Compounds that control pH fluctuations during the development process by external addition are listed.

Examples of the compound (I) above include (+) metal oxides such as (+) Ca, Mg, An, Fe, Zn, etc., as well as total hydroxides or metal salts that reduce [0)1-]' Compound (2) with ff1E& and slow Ii property 1. <Acid acid solids (e.g. CaC0
3) Compounds that dissolve and become alkaline as the pH decreases (3) Buffers such as organic acids (e.g. citric acid, etc.) and their salts (4) Inorganic acids (e.g. boric acid, phosphoric acid, etc.) and Buffers such as salts thereof (5) Aminocarboxylic acid chelating agents such as EDTA (6) l-hydroxyethylidene-1,1-diphosphonic acid, etc., and these may be used alone or in combination of two or more. can.

Further, as the compound (II) above, for example, (1)
Alkali such as NaOH, KOH, Ca(DH)2,
or alkaline earth metal hydroxide (2) carbonate (3) silicate (e.g. sodium silicate) (4) phosphate (5) borate (8) alkali such as Ca salt or Mg salt Earth metal 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 above p) 17A conditioning agent added?

In the case of the compound of ``-2 (1), 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 to the evaporation tank 3. After that, it may be added externally before the start of heating.
In the case of the compound II), it goes without saying that it is supplied to the Tsum development tank 3 from the outside.

P)! When supplying the adjuster from the outside, as shown in FIG.
4 may be supplied.

pH: Evaporate tank 13 without using Affi agent pump 14 I! The supply may be provided above II3 using head pressure.

In the present invention, pH3J? ! 1 if the agent 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.

In the present invention, when two or more types of pH 3J regulators are used, it is preferable to provide a plurality of tanks for each catfish compound when adding them externally from a tank as shown in Figure 1. However, depending on the physical properties of the compound, In some cases, one tank can be used in common.

In the present invention, when adding pHmff1 agent externally as shown in FIG.
When the pH value decreases with the elapse of the heating book evaporation time, the pump 14 can be turned on by a signal from the controller to supply the pH adjusting agent. Furthermore, pump 1
4 is a stroke adjustable type, the stroke can also be automatically adjusted.

As mentioned above, when the pH of the concentrated liquid is maintained at 3.0 to 11.0, the content of components that can cause bad odor in the evaporated gas, especially H2S and S gas, is small, and the amine odor from the distillate is reduced. No ammonia odor.

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 the range, i.e., the amount of heat added per unit time f)'l L'':
When increasing the amount, thiosulfate crystallizes before it decomposes,
It suppresses bad odors without being released to the outside; on the other hand, it adds heat; when there is little heat, 1) decomposition is accelerated, and the outflow of substances that cause bad odors is activated.

Although an example of a method and a device for suppressing bad odor 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. 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 No. Sho F31-13209
No. 8, Patent Application No. 11081-185099, Patent Application Closed 81-
165100 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). Preferred types of waste solution include, for example, a mixed waste solution of a color developing solution and a bleach-fixing solution or a stabilizing solution, or a waste solution of a bleach fixing solution alone, a fixing solution alone, a stabilizing solution alone, and the like. The present invention is particularly effective when the waste liquid contains silver ions, and the concentration thereof is preferably in the range of 0.01 to 50 g/J1.

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. , is not limited to a particular number, but is, for example, about 11/rJ to 1000 or /D.

(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 using head pressure, and other methods of manually supplying the liquid. .

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 heats the supplied waste liquid and evaporates a part of it to ellipse the waste liquid.
(This is a tank that reduces the amount of waste liquid that must be disposed of.)
In the Jl Specification, "concentration" refers to reducing the volume of waste liquid after evaporation to 1/4 or less, preferably 1/5 or less, and most preferably 1/10 of the volume of the evaporation surface. 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
It is preferable that it has a double structure of a J (outer pot) and an inner tank (inner pot), and that the inner tank is made of a resin bag, for example, and is removable. For example, a glass wool mat) is preferably provided, and the upper part of the evaporation tank 3 is preferably provided with a hinged opening/closing lid.

(In the invention, the heating means is not particularly limited, and the heating means is
The diagram shows a heater heating method as an example. 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 shown in FIG.

Note that the heating by the heater may be stopped by the operation of a timer, but is not limited to this.

For example, the liquid level of the e-line method can be measured using 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, the gas cooler 6, but any cooling means may be used. Note that in order to achieve the purpose of the present invention, forced cooling is not an essential requirement; the distillate is generated by natural cooling,
The scope of the present invention also includes cases where the product is discarded.

In addition, in the present invention, there are no problems such as odor after cooling,
In addition, a distillate containing ammonium salts such as ammonium sulfite can be obtained, and in addition to being used as a photographic processing solution in automatic processing machines (for example, water for dissolving replenisher or washing water), it can also be reused as fertilizer, etc. I will go to work.

(6) After cooling and humidity conditioning, the gas is suppressed to the extent that almost no foul odor is felt, but to further completely eliminate the foul odor, it is also preferable to use a youth absorbing agent such as activated carbon.

This method is advantageous in that it does not have the problems (for example, early saturation, complicated replacement work, etc.) that occur when treating high-concentration foul-smelling gases as in the past, and furthermore, the present invention's foul-smelling control is effective. It is excellent in that it functions effectively as a pretreatment for malodor prevention means such as youth absorption treatment, which is provided at the end of the treatment.

[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
Young 38℃ 3 minutes 15 seconds 1st
Stability 1st tank 32℃~38℃ 1 minute 1st stability 2nd
Tank 32℃~38℃ 1 minute second stabilization
38℃ for about 1 minute 4
5°C to 65°C [Color developer] j Potassium resistance 30g Carbonated water; Sodium 2.5g Potassium sulfite 5g 1-Hydroxyethylidene-1,1-diphosphone # (60%) 1.0g Sodium bromide 1.3g Iodine Potassium chloride 2mg Hydroxylamine sulfate IH2, 5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl root (β-hydroxylethyl) Aniline sulfate Ji! 4,8 g
Potassium hydroxide 1.2g Add water to make an ill, and adjust the pH to 10.08 using potassium hydroxide or 20% sulfuric acid.

[Color developer replenisher] Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.8g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 1.2g hydroxylamine sulfate 3.114-amino-
3-Methyl-N-ethyl-N-(β-hydroxylethyl) Aniline sulfuric acid 11!8.0g Potassium hydroxide 2g Add water to make one sentence, 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 lO Marofumi Tachiki to bring the solution to 11, and adjust the pH to 5.8 using aqueous ammonia or glacial acetic acid.

[L); White replenisher] Iron ammonium ethylenediaminetetraacetate 170g Disodium ethylenediaminetetraacetate 12g Ammonium bromide 178g Glacial acetic acid
Add 2111 water to make IJI, and adjust to PI (5, 8) using aqueous ammonia or glacial acetic acid.

[Fixer] Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate 0.58 Sodium carbonate 10g Add water to make IJL, and adjust to pH 7.0 using aqueous ammonia or glacial acetic acid. do.

[Fixer replenisher] Ammonium thiosulfate 300g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetraacetate 0.88 Sodium carbonate 14g Add wood to make 11, and adjust to pH 7.5 using ammonia water or glacial acetic acid. .

[First stable solution and first stable replenisher] 5-chloro-2-methyltoisothiazolin-3-one 0.02g 2-chloro-4-isothiazolin-3-one 0.02g
Ethylene glycol Make one sentence with 1.0g wood and adjust to p) 17.0 with 20% m acid.

[Second Stable Solution and Second Stable Replenisher] Add 2 samples of formalin (37% aqueous solution) and 51 samples of Konishiroku Photo Industry Co., Ltd. to make 1 Jl.

The color development replenisher is added to the color development bath at 13.5ml per 100cm of color negative film, and the bleaching replenisher is
Replenish the bleach bath with 5.5 mi per 100 cm of color negative film, and add fixing replenisher to 100 cm of color negative film.
The fixing bath is replenished with 811 sentences per 00crtI', and the first stable replenisher is replenished with 8-1 per IQOcm' of color negative film, and the second stable replenisher is added to the second stable bath. 150 current was generated per 100 cm of 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.

ノ、ti Semi-processing step (1) Color development 38℃ 3 minutes 30 seconds (2)
Bleach fixing 38°C 1 minute 30 seconds (3) Stabilization treatment 2
5℃~35℃ 3 minutes (4) Drying 75℃~10
0°C for about 2 minutes Processing liquid composition [Color developing tank liquid] Benzyl alcohol 15 ml ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide
1.3g sodium chloride
0.2g potassium carbonate
24.0g 3-Methyl-4-amino-ethyl-N-(β-methanesulfonamidoethyl) aniline sulfate 4.5g optical brightener (4,4゛-diaminostilbenzsulfone M
, J conductor) (trade name Keikoru PK-Conc (manufactured by Shinnichiba Kako Co., Ltd.)) 1.0 g Hydroxylamine sulfate 3.0 g 1-hydroxyethylidene-1,l-niphosphonic acid 0.4 g Hydroxyethylimino diacetic acid 1 %j 5. Og Magnesium chloride 6 water Jfi O, 7°1.2
-Hydroxybenzene-3,5-disulfonic acid disodium II! Add 0,2 g water to make one sentence, and add potassium hydroxide and sulfuric acid to P)! 10.20.

[9, Color developer replenisher 1 Benzyl alcohol 2h Cross enalene glycol 20+s Potassium sulfite 3.0g) Potassium pentate
30.0g hydroxylamine sulfate
l 4.0g3-methyl-4-amino-N
-Ethyl-N-(β-methanesulfonamide ethyl) Aniline sulfate 11!8.0g Fluorescent brightener (4,4゛-diaminostilbenzsulfonic acid derivative) (Product name: Keikol PK-Conc (Nippon Soka Kogyo) ) 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 salt
Add 0.3 g of wood to make the solution 141, and adjust the pH to 10.70 with potassium hydroxide.

[Fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium diwater jlj 60.0g
Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0g + Ammonium thiosulfite (40% solution) 27.5iJ
Add L water to make the total volume IIL, and adjust the pH to 7.1 with potassium carbonate or wood vinegar to 31! ! ! do.

[Bleach-fixing replenisher A] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 2B0.0g Potassium carbonate 42.0g Add water to make the total volume 1/2.

The pH of this solution is 6.7±0.1.

[Bleach-fix replenisher B] Ammonium thiosulfate (70% solution) 500.0-
Ammonium persulphite (40% solution) 250.0
Enteric ethylenediaminetetraacetic acid 17.0g
Add glacial acetic acid 85.0+s Bunsui to bring the total volume to 1 Bun.

The pH of this solution is 5.3±0.1.

[Water washing allowance () Stable tank liquid and replenisher] Ethylene glycol 1.0g 1-hydroxyethylidene-1,1-niphosphon m (80% aqueous solution) 1.0g ammonia water (ammonium hydroxide 25% aqueous solution) 2.0g with water IJl and P)I 7.0 with sulfuric acid.

Fill an automatic developing machine with the above color developing tank solution, bleach fixing tank solution and stabilizing tank solution, and add the above mentioned color developing replenisher and bleach fixing tank solution every 3 minutes while processing the Sakura Color SR Paper Sample 1. A running test was conducted while replenishing solutions A, B, and a stable replenisher through a metering cup.

The amount of replenishment is 190 layers per rn' of color paper to the color development tank, 50 layers each of Bleach and Qualitative Replenisher A and B to the bleach-fixing tank, and 50 μl of each of Bleach Qualitative Replenishers A and B to the stabilizing tank. Fill with substitute stabilizing liquid 2501
I looked at it and replenished it. 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 first processing.

Experimental Example 1 After storing the above photographic processing waste solution for 5 days, the So
32-c degree was determined by iodometry.
It was 4.5 Xl0I gram ion/cross.

Moreover, the pH was 8.0. Five volumes of this photographic processing waste liquid were received into the apparatus shown in FIG. 1 and subjected to evaporation treatment.

The mixture was evaporated and concentrated until it became 2.5 grams, and the evaporated gas was cooled to obtain a distillate.

When the temperature of the distillate is 25°C, N83 in the gas on the surface of the distillate
Gas, H2S gas, and S02 gas were quantified, and the appearance of the distillate was examined. The results are shown in Table 1.

Next, sodium sulfite was added, and the same experiment was repeated by changing the 5 degrees of sulfite ion (SO32-) in the waste liquid as shown in Table 1. The results are shown in Table 1.

However, here we start evaporation fist concentration, and 500peng fL7~
I adjusted S(h"5 degrees to the initial elf to emit.

Table 1 From Table 1, it is clear that if the 5O32-C degree in the waste liquid is in the range of 5X 10-4 to 4 gram ions/vertical, the distillate will not become cloudy, and N83 gas, )12S gas and SO? Less gas and preferred, especially 5X 1G-3
When the concentration is in the range of gram ion/cross to 0.5 gram ion/cross, the distillate becomes clear and colorless, and less NH3 gas, H, S gas, and S02 gas are generated.

On the other hand, if the 5 (h2-5 degree) in the waste liquid is less than 5X 10-4 gram ions/vertical, the generation of NH3 gas and H?S gas will be significant, and if it exceeds 4 grams ions/vertical The generation of SO2 gas becomes significant.

Experimental Example 2 After adding 100g of the compounds shown in Table 2 to the waste liquid 5J1 used in Experimental Example 1 after storage over time, H2SOs and NaOHTEPH were added.
After adjusting the temperature to 8.0 and reducing the temperature to 2.51 in the evaporator, the N)+3 gas, H2S gas and SO2 gas were determined in the same manner as in Experimental Example 1, and the appearance of the distillate was examined. Concentration 1ii@, when the compounds in each concentrate were quantified, all were 5g/1
It turns out that there are more. The results are shown in Table 2.

Table 2 As is clear from Table 2, the use of the compound capable of releasing sulfite ions of the present invention had almost the same effect as the sodium sulfite used in Experimental Example 1.

Experimental example 3 Waste liquid No. 1 used in Experimental Example 1 and stored over time.

Furthermore, 20g/sL of potassium bisulfite was added to waste liquid No.
, 23 was adjusted with H2SO4 and KOH as shown in Table 3. Evaporation was started, and p)l was adjusted as shown in Table 1 every 500+ seconds. Evaporation and e-condensation were performed until the concentration reached 2.51, and the evaporated gas was cooled to obtain a distillate, which was evaluated in the same manner as in Experimental Example 1. In addition, the S in the evaporation tank after the end of the experiment
o 32-5 degrees were all 5X 10-3 gram ions/vertical or higher. Table 3 As is clear from Table 3, sulfite ions (S032-)
Due to the addition of
It can be seen that good results are obtained for fII in the range of H3.0 to 11.0.

Experimental Example 4 Color developing waste solution No. 24 that does not contain thiosulfate was converted into H2
The pH was adjusted to 2, 0, 8, 0, 12, 0 with SO4 and NaOH, and 30% by volume of a bleach waste solution containing no thiosulfate was added to the color development waste solution.
It was adjusted.

In addition, 55% of ammonium thiosulfate was added to the waste liquid of No. 25.
The pH of No. 28 was adjusted in the same way as the waste liquid to which 0g/41 was added.

Waste liquid No. 27 and N are obtained by adding 50 g/l of ammonium thiosulfate and 5 g/l of AgBr to the waste liquid of No. 25.
Waste liquid No. o, 30% volume of fixing waste liquid was added to the waste liquid of No. 25.
, 28 was similarly pH-adjusted.

When these waste solutions were stored for one week and the sulfite ion concentrations in the waste solutions were measured, they were all less than 4.5×10 −4 gram ions/concentration.

Next, 108/l of sodium sulfite was added to these time-preserved waste liquids of Nos. 24 to 28 to prepare waste liquids of Nos. 29 to 33, and the pH was adjusted to 2.0.8.0.12.0 in the same way. did.

2. Receive all of the above waste liquids, each with 5 volumes, into the apparatus shown in Figure 1. Evaporation concentration was performed until it became 0. 500 again
■Corrected to the initial pH after each exchange evaporation.

What is the sulfite ion concentration in the waste liquids Nos. 29 to 33 after evaporation and concentration? , 94 Xl0-3 gram ions/view.

The above results are shown in Table 4.

Table 4 As is clear from Table 4, in all cases, the waste liquid containing sulfite ions has less bad odor, and in particular, sulfite ions effectively prevent Has gas, which is likely to be generated due to the inclusion of M thiosulfate ions. Has gas was completely prevented in the waste liquids No. 32 and 33 that contained waste liquids with a pH of 6.0.

[Effects of IJ1] According to IJ1, since sulfite ions are present when waste liquid is evaporated, it is possible to suppress the amine odor and ammonia odor of the distillate, and to suppress the generation of H2S gas and the like. 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.

It should be noted that Seikan IJ1 can be applied to purposes other than the above-mentioned malodor suppression.

[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 1O: Sulfite-containing compound tank 11 : Sulfite-containing compound pump 12: Sulfite-containing compound supply pipe 13: pH adjuster tank 142 P) I regulator pump 15: p) I regulator supply pipe

Claims (5)

[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 sulfite ions and a compound capable of releasing sulfite ions. (2) The method for treating photographic processing waste liquid according to claim 1, wherein the photographic processing waste liquid contains thiosulfate ions. (3) The method for treating photographic processing waste liquid according to claim 2, wherein the photographic processing waste liquid contains silver ions. (4) The photographic processing waste liquid according to any one of claims 1 to 3, wherein 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. processing method. (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. A processing apparatus for photographic processing waste liquid, characterized in that it has means for supplying sulfite ions and a compound capable of releasing sulfite ions to the photographic processing waste liquid.